# Electronic Supplementary Material (ESI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_1

_audit_creation_method           SHELXL-2012
_chemical_name_systematic        
(2Z)-3-carboxy-1-hydroxy-2-pyridinium-1-ylprop-2-1-olate
_chemical_name_common            \1
_chemical_melting_point          473.15
_chemical_formula_moiety         'C9 H7 N O4'
_chemical_formula_sum            'C9 H7 N O4'
_chemical_formula_weight         193.16

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'x+1/2, -y+1/2, -z'
'-x, y+1/2, -z+1/2'

_cell_length_a                   7.968(4)
_cell_length_b                   8.368(5)
_cell_length_c                   12.570(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     838.1(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    2550
_cell_measurement_theta_min      2.92
_cell_measurement_theta_max      27.48

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.531
_exptl_crystal_F_000             400
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.384
_exptl_crystal_size_mid          0.351
_exptl_crystal_size_min          0.104
_exptl_absorpt_coefficient_mu    0.123
_shelx_estimated_absorpt_T_min   0.954
_shelx_estimated_absorpt_T_max   0.987
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.9358
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   'SADABS, 2012'

_exptl_special_details           ?

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area -detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            5158
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_av_R_equivalents  0.0207
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.924
_diffrn_reflns_theta_max         27.552
_diffrn_reflns_theta_full        27.000
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             1888
_reflns_number_gt                1800
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.677
_reflns_Friedel_fraction_max     0.956
_reflns_Friedel_fraction_full    0.993

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
 
;

_computing_data_collection       'APEX2 (Bruker, 2012)'
_computing_cell_refinement       'SAINT (Bruker, 2012)'
_computing_data_reduction        'SAINT (Bruker, 2012)'
_computing_structure_solution    'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_molecular_graphics    
'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)'
_computing_publication_material  ?

_refine_special_details          
;
 The acidic proton was located using electron density maps and was confirmed
 by measuring the C-O bond distances. 
 [∼ 1.2 Å = C\\dbO; ∼ 1.3 Å = C---O]
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 w=1/[σ²(Fo²)+(0.0473P)²+0.2208P]
 where P=(Fo²+2Fc²)/3
;
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 700 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   ?
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1888
_refine_ls_number_parameters     131
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0371
_refine_ls_R_factor_gt           0.0347
_refine_ls_wR_factor_ref         0.0855
_refine_ls_wR_factor_gt          0.0841
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_restrained_S_all      1.056
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
O1 O 0.54385(19) 0.14738(18) 0.36312(13) 0.0181(3) Uani 1 1 d . . . . .
C1 C 0.5551(3) 0.2914(3) 0.37954(16) 0.0137(4) Uani 1 1 d . . . . .
O2 O 0.4365(2) 0.38983(17) 0.39371(13) 0.0180(3) Uani 1 1 d . . . . .
C2 C 0.7290(3) 0.3659(2) 0.38106(16) 0.0132(4) Uani 1 1 d . . . . .
O3 O 1.0616(2) 0.49985(18) 0.32158(14) 0.0221(4) Uani 1 1 d . . . . .
C3 C 0.8674(3) 0.2895(3) 0.35509(17) 0.0143(4) Uani 1 1 d . . . . .
H3 H 0.8582 0.1798 0.3367 0.017 Uiso 1 1 calc R U . . .
O4 O 1.15449(19) 0.26654(17) 0.38554(12) 0.0159(3) Uani 1 1 d . . . . .
C4 C 1.0393(3) 0.3640(3) 0.35254(17) 0.0142(4) Uani 1 1 d . . . . .
H4 H 1.266(4) 0.319(4) 0.383(3) 0.047(10) Uiso 1 1 d . . . . .
N5 N 0.7341(2) 0.53417(19) 0.41120(14) 0.0122(4) Uani 1 1 d . . . . .
C6 C 0.6937(3) 0.6440(3) 0.33779(18) 0.0191(5) Uani 1 1 d . . . . .
H6 H 0.6636 0.6115 0.2679 0.023 Uiso 1 1 calc R U . . .
C7 C 0.6958(3) 0.8038(3) 0.36371(19) 0.0201(5) Uani 1 1 d . . . . .
H7 H 0.6691 0.8822 0.3118 0.024 Uiso 1 1 calc R U . . .
C8 C 0.7369(3) 0.8487(2) 0.46585(19) 0.0192(5) Uani 1 1 d . . . . .
H8 H 0.7386 0.9585 0.4849 0.023 Uiso 1 1 calc R U . . .
C9 C 0.7757(3) 0.7337(3) 0.54028(19) 0.0247(5) Uani 1 1 d . . . . .
H9 H 0.8027 0.7636 0.6112 0.030 Uiso 1 1 calc R U . . .
C10 C 0.7750(3) 0.5756(3) 0.51122(18) 0.0211(5) Uani 1 1 d . . . . .
H10 H 0.8034 0.4956 0.5617 0.025 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1 C1 1.226(3) . ?
C1 O2 1.266(3) . ?
C1 C2 1.520(3) . ?
C2 C3 1.316(3) . ?
C2 N5 1.459(3) . ?
O3 C4 1.214(3) . ?
C3 C4 1.505(3) . ?
C3 H3 0.9500 . ?
O4 C4 1.296(3) . ?
O4 H4 0.99(3) . ?
N5 C6 1.342(3) . ?
N5 C10 1.344(3) . ?
C6 C7 1.376(3) . ?
C6 H6 0.9500 . ?
C7 C8 1.377(3) . ?
C7 H7 0.9500 . ?
C8 C9 1.377(3) . ?
C8 H8 0.9500 . ?
C9 C10 1.373(3) . ?
C9 H9 0.9500 . ?
C10 H10 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 C1 O2 127.5(2) . . ?
O1 C1 C2 118.17(19) . . ?
O2 C1 C2 114.33(18) . . ?
C3 C2 N5 120.69(18) . . ?
C3 C2 C1 124.18(18) . . ?
N5 C2 C1 115.11(17) . . ?
C2 C3 C4 124.51(19) . . ?
C2 C3 H3 117.7 . . ?
C4 C3 H3 117.7 . . ?
C4 O4 H4 110.1(19) . . ?
O3 C4 O4 126.0(2) . . ?
O3 C4 C3 121.87(19) . . ?
O4 C4 C3 112.13(18) . . ?
C6 N5 C10 121.66(19) . . ?
C6 N5 C2 118.42(18) . . ?
C10 N5 C2 119.91(17) . . ?
N5 C6 C7 120.0(2) . . ?
N5 C6 H6 120.0 . . ?
C7 C6 H6 120.0 . . ?
C6 C7 C8 119.2(2) . . ?
C6 C7 H7 120.4 . . ?
C8 C7 H7 120.4 . . ?
C9 C8 C7 119.8(2) . . ?
C9 C8 H8 120.1 . . ?
C7 C8 H8 120.1 . . ?
C10 C9 C8 119.5(2) . . ?
C10 C9 H9 120.3 . . ?
C8 C9 H9 120.3 . . ?
N5 C10 C9 119.9(2) . . ?
N5 C10 H10 120.1 . . ?
C9 C10 H10 120.1 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 C1 C2 C3 7.3(3) . . . . ?
O2 C1 C2 C3 -171.2(2) . . . . ?
O1 C1 C2 N5 -174.30(19) . . . . ?
O2 C1 C2 N5 7.1(2) . . . . ?
N5 C2 C3 C4 -0.6(3) . . . . ?
C1 C2 C3 C4 177.67(19) . . . . ?
C2 C3 C4 O3 -38.0(3) . . . . ?
C2 C3 C4 O4 142.6(2) . . . . ?
C3 C2 N5 C6 99.2(2) . . . . ?
C1 C2 N5 C6 -79.3(2) . . . . ?
C3 C2 N5 C10 -82.3(3) . . . . ?
C1 C2 N5 C10 99.3(2) . . . . ?
C10 N5 C6 C7 0.9(3) . . . . ?
C2 N5 C6 C7 179.5(2) . . . . ?
N5 C6 C7 C8 -1.1(3) . . . . ?
C6 C7 C8 C9 0.2(4) . . . . ?
C7 C8 C9 C10 0.9(4) . . . . ?
C6 N5 C10 C9 0.1(4) . . . . ?
C2 N5 C10 C9 -178.4(2) . . . . ?
C8 C9 C10 N5 -1.0(4) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C3 H3 O3 0.95 2.58 3.336(3) 137.2 4_745
O4 H4 O1 0.99(3) 2.65(3) 3.271(3) 121(2) 1_655
O4 H4 O2 0.99(3) 1.49(3) 2.474(2) 172(3) 1_655
C6 H6 O1 0.95 2.35 3.156(3) 142.0 4_655
C7 H7 O1 0.95 2.52 3.120(3) 121.4 1_565
C10 H10 O1 0.95 2.45 3.250(3) 142.1 3_556
C10 H10 O4 0.95 2.58 3.287(3) 131.4 3_456

_refine_diff_density_max         0.349
_refine_diff_density_min         -0.184
_refine_diff_density_rms         0.047

_shelxl_version_number           2012-9

_database_code_depnum_ccdc_archive 'CCDC 987540'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_2

_audit_creation_method           SHELXL-2012
_chemical_name_systematic        
(2Z)-3-carboxy-1-hydroxy-2-isoquinolinium-2-ylprop-2-en-1-olate
_chemical_name_common            \2
_chemical_melting_point          461.15
_chemical_formula_moiety         'C13 H9 N O4'
_chemical_formula_sum            'C13 H9 N O4'
_chemical_formula_weight         243.21

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   11.119(3)
_cell_length_b                   8.057(2)
_cell_length_c                   12.839(3)
_cell_angle_alpha                90
_cell_angle_beta                 113.549(3)
_cell_angle_gamma                90
_cell_volume                     1054.4(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    2737
_cell_measurement_theta_min      3.06
_cell_measurement_theta_max      27.37

_exptl_crystal_description       block
_exptl_crystal_colour            brown
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.532
_exptl_crystal_F_000             504
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.546
_exptl_crystal_size_mid          0.366
_exptl_crystal_size_min          0.244
_exptl_absorpt_coefficient_mu    0.116
_shelx_estimated_absorpt_T_min   0.940
_shelx_estimated_absorpt_T_max   0.972
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.8853
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   'SADABS, 2012'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area -detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            6107
_diffrn_reflns_av_unetI/netI     0.0227
_diffrn_reflns_av_R_equivalents  0.0179
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         2.055
_diffrn_reflns_theta_max         28.374
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.913
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.913
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.913
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             2414
_reflns_number_gt                2008
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX2 (Bruker, 2012)'
_computing_cell_refinement       'SAINT (Bruker, 2012)'
_computing_data_reduction        'SAINT (Bruker, 2012)'
_computing_structure_solution    'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_molecular_graphics    
'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)'
_computing_publication_material  ?

_refine_special_details          
;
  The acidic proton was located using electron density maps and was confirmed
 by measuring the C-O bond distances. 
 [∼ 1.2 Å = C\\dbO; ∼ 1.3 Å = C---O]
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 w=1/[σ²(Fo²)+(0.0616P)²+0.4630P]
 where P=(Fo²+2Fc²)/3
;
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2414
_refine_ls_number_parameters     167
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0501
_refine_ls_R_factor_gt           0.0409
_refine_ls_wR_factor_ref         0.1174
_refine_ls_wR_factor_gt          0.1107
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_restrained_S_all      1.052
_refine_ls_shift/su_max          0.011
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
O1 O 0.67776(11) 0.46411(13) 0.56480(9) 0.0246(3) Uani 1 1 d . . . . .
C1 C 0.61837(15) 0.46473(17) 0.62764(12) 0.0187(3) Uani 1 1 d . . . . .
O2 O 0.58689(11) 0.34127(12) 0.67279(9) 0.0240(3) Uani 1 1 d . . . . .
C2 C 0.57614(14) 0.63162(17) 0.65784(12) 0.0181(3) Uani 1 1 d . . . . .
O3 O 0.47092(11) 0.96948(13) 0.67537(10) 0.0255(3) Uani 1 1 d . . . . .
C3 C 0.59209(15) 0.77407(17) 0.61405(12) 0.0192(3) Uani 1 1 d . . . . .
H3 H 0.6308 0.7683 0.5602 0.023 Uiso 1 1 calc R U . . .
O4 O 0.62810(11) 1.05748(12) 0.61904(9) 0.0231(3) Uani 1 1 d . . . . .
C4 C 0.55585(15) 0.94397(17) 0.63986(12) 0.0190(3) Uani 1 1 d . . . . .
H4 H 0.608(3) 1.168(4) 0.638(2) 0.076(8) Uiso 1 1 d . . . . .
N5 N 0.51603(12) 0.62754(14) 0.74033(10) 0.0189(3) Uani 1 1 d . . . . .
C6 C 0.39753(15) 0.54542(18) 0.71088(13) 0.0223(3) Uani 1 1 d . . . . .
H6 H 0.3602 0.4878 0.6406 0.027 Uiso 1 1 calc R U . . .
C7 C 0.33487(16) 0.5474(2) 0.78245(14) 0.0249(3) Uani 1 1 d . . . . .
H7 H 0.2538 0.4906 0.7621 0.030 Uiso 1 1 calc R U . . .
C8 C 0.38945(15) 0.63370(19) 0.88760(13) 0.0227(3) Uani 1 1 d . . . . .
C9 C 0.32871(16) 0.6411(2) 0.96592(14) 0.0285(4) Uani 1 1 d . . . . .
H9 H 0.2464 0.5890 0.9488 0.034 Uiso 1 1 calc R U . . .
C10 C 0.39028(17) 0.7246(2) 1.06674(14) 0.0308(4) Uani 1 1 d . . . . .
H10 H 0.3498 0.7290 1.1193 0.037 Uiso 1 1 calc R U . . .
C11 C 0.51188(18) 0.8038(2) 1.09382(14) 0.0304(4) Uani 1 1 d . . . . .
H11 H 0.5521 0.8608 1.1641 0.036 Uiso 1 1 calc R U . . .
C12 C 0.57279(17) 0.7996(2) 1.01986(14) 0.0284(4) Uani 1 1 d . . . . .
H12 H 0.6547 0.8535 1.0383 0.034 Uiso 1 1 calc R U . . .
C13 C 0.51190(15) 0.71382(18) 0.91558(13) 0.0218(3) Uani 1 1 d . . . . .
C14 C 0.57225(16) 0.70698(18) 0.83825(13) 0.0210(3) Uani 1 1 d . . . . .
H14 H 0.6545 0.7600 0.8564 0.025 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1 C1 1.2300(18) . ?
C1 O2 1.2688(17) . ?
C1 C2 1.5246(19) . ?
C2 C3 1.321(2) . ?
C2 N5 1.4612(18) . ?
O3 C4 1.2190(18) . ?
C3 C4 1.5009(19) . ?
C3 H3 0.9500 . ?
O4 C4 1.3133(18) . ?
O4 H4 0.97(3) . ?
N5 C14 1.3241(19) . ?
N5 C6 1.385(2) . ?
C6 C7 1.357(2) . ?
C6 H6 0.9500 . ?
C7 C8 1.421(2) . ?
C7 H7 0.9500 . ?
C8 C13 1.417(2) . ?
C8 C9 1.419(2) . ?
C9 C10 1.374(2) . ?
C9 H9 0.9500 . ?
C10 C11 1.407(3) . ?
C10 H10 0.9500 . ?
C11 C12 1.369(2) . ?
C11 H11 0.9500 . ?
C12 C13 1.416(2) . ?
C12 H12 0.9500 . ?
C13 C14 1.404(2) . ?
C14 H14 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 C1 O2 127.94(13) . . ?
O1 C1 C2 118.10(12) . . ?
O2 C1 C2 113.95(12) . . ?
C3 C2 N5 120.41(12) . . ?
C3 C2 C1 123.42(13) . . ?
N5 C2 C1 116.17(12) . . ?
C2 C3 C4 127.23(13) . . ?
C2 C3 H3 116.4 . . ?
C4 C3 H3 116.4 . . ?
C4 O4 H4 111.5(16) . . ?
O3 C4 O4 125.94(13) . . ?
O3 C4 C3 123.56(13) . . ?
O4 C4 C3 110.50(12) . . ?
C14 N5 C6 121.79(13) . . ?
C14 N5 C2 119.88(12) . . ?
C6 N5 C2 118.26(12) . . ?
C7 C6 N5 119.95(14) . . ?
C7 C6 H6 120.0 . . ?
N5 C6 H6 120.0 . . ?
C6 C7 C8 120.59(14) . . ?
C6 C7 H7 119.7 . . ?
C8 C7 H7 119.7 . . ?
C13 C8 C9 118.83(14) . . ?
C13 C8 C7 117.78(14) . . ?
C9 C8 C7 123.39(15) . . ?
C10 C9 C8 119.29(15) . . ?
C10 C9 H9 120.4 . . ?
C8 C9 H9 120.4 . . ?
C9 C10 C11 121.50(15) . . ?
C9 C10 H10 119.2 . . ?
C11 C10 H10 119.2 . . ?
C12 C11 C10 120.65(15) . . ?
C12 C11 H11 119.7 . . ?
C10 C11 H11 119.7 . . ?
C11 C12 C13 119.07(15) . . ?
C11 C12 H12 120.5 . . ?
C13 C12 H12 120.5 . . ?
C14 C13 C12 120.32(14) . . ?
C14 C13 C8 119.01(14) . . ?
C12 C13 C8 120.67(14) . . ?
N5 C14 C13 120.84(14) . . ?
N5 C14 H14 119.6 . . ?
C13 C14 H14 119.6 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 C1 C2 C3 4.8(2) . . . . ?
O2 C1 C2 C3 -175.58(14) . . . . ?
O1 C1 C2 N5 -174.90(13) . . . . ?
O2 C1 C2 N5 4.76(19) . . . . ?
N5 C2 C3 C4 0.7(2) . . . . ?
C1 C2 C3 C4 -178.93(14) . . . . ?
C2 C3 C4 O3 -24.7(3) . . . . ?
C2 C3 C4 O4 155.20(15) . . . . ?
C3 C2 N5 C14 -61.15(19) . . . . ?
C1 C2 N5 C14 118.52(14) . . . . ?
C3 C2 N5 C6 116.09(16) . . . . ?
C1 C2 N5 C6 -64.24(17) . . . . ?
C14 N5 C6 C7 1.1(2) . . . . ?
C2 N5 C6 C7 -176.07(13) . . . . ?
N5 C6 C7 C8 0.2(2) . . . . ?
C6 C7 C8 C13 -1.3(2) . . . . ?
C6 C7 C8 C9 179.73(15) . . . . ?
C13 C8 C9 C10 -0.4(2) . . . . ?
C7 C8 C9 C10 178.59(15) . . . . ?
C8 C9 C10 C11 0.4(3) . . . . ?
C9 C10 C11 C12 -0.1(3) . . . . ?
C10 C11 C12 C13 -0.2(3) . . . . ?
C11 C12 C13 C14 -179.81(15) . . . . ?
C11 C12 C13 C8 0.2(2) . . . . ?
C9 C8 C13 C14 -179.90(14) . . . . ?
C7 C8 C13 C14 1.1(2) . . . . ?
C9 C8 C13 C12 0.1(2) . . . . ?
C7 C8 C13 C12 -178.94(14) . . . . ?
C6 N5 C14 C13 -1.3(2) . . . . ?
C2 N5 C14 C13 175.81(13) . . . . ?
C12 C13 C14 N5 -179.79(14) . . . . ?
C8 C13 C14 N5 0.2(2) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O4 H4 O2 0.97(3) 1.51(3) 2.4833(15) 176(3) 1_565
C6 H6 O1 0.95 2.53 3.296(2) 137.9 3_666
C14 H14 O1 0.95 2.39 3.287(2) 157.9 2_656

_refine_diff_density_max         0.377
_refine_diff_density_min         -0.247
_refine_diff_density_rms         0.052

_shelxl_version_number           2012-9

_database_code_depnum_ccdc_archive 'CCDC 987541'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_3

_audit_creation_method           SHELXL-2012
_chemical_name_systematic        
(2Z)-3-carboxy-1-hydroxy-2-(3-hydroxypyridinium-1-yl)prop-2-en-1-olate
_chemical_name_common            \3
_chemical_melting_point          457.15
_chemical_formula_moiety         'C9 H7 N O5, H2 O'
_chemical_formula_sum            'C9 H9 N O6'
_chemical_formula_weight         227.17

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   10.444(3)
_cell_length_b                   8.094(2)
_cell_length_c                   12.306(4)
_cell_angle_alpha                90
_cell_angle_beta                 110.376(6)
_cell_angle_gamma                90
_cell_volume                     975.2(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    2182
_cell_measurement_theta_min      3.27
_cell_measurement_theta_max      27.07

_exptl_crystal_description       rod
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.547
_exptl_crystal_F_000             472
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.322
_exptl_crystal_size_mid          0.162
_exptl_crystal_size_min          0.108
_exptl_absorpt_coefficient_mu    0.133
_shelx_estimated_absorpt_T_min   0.958
_shelx_estimated_absorpt_T_max   0.986
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.7926
_exptl_absorpt_correction_T_max  0.8621
_exptl_absorpt_process_details   'TWINABS, 2009'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area -detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            4218
_diffrn_reflns_av_unetI/netI     0.0513
_diffrn_reflns_av_R_equivalents  0.0412
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         2.080
_diffrn_reflns_theta_max         27.727
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             2235
_reflns_number_gt                1677
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX2 (Bruker, 2012)'
_computing_cell_refinement       'SAINT (Bruker, 2012)'
_computing_data_reduction        'SAINT (Bruker, 2012)'
_computing_structure_solution    'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_molecular_graphics    
'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)'
_computing_publication_material  ?

_refine_special_details          
;
 The acidic proton was located using electron density maps and was confirmed
 by measuring the C-O bond distances. 
 [∼ 1.2 Å = C\\dbO; ∼ 1.3 Å = C---O]
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 w=1/[σ²(Fo²)+(0.0661P)²+0.6329P]
 where P=(Fo²+2Fc²)/3
;
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2235
_refine_ls_number_parameters     163
_refine_ls_number_restraints     127
_refine_ls_R_factor_all          0.0739
_refine_ls_R_factor_gt           0.0519
_refine_ls_wR_factor_ref         0.1392
_refine_ls_wR_factor_gt          0.1301
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_restrained_S_all      1.221
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
O1 O 0.40046(14) 0.47485(18) 0.09384(12) 0.0158(3) Uani 1 1 d . U . . .
N1 N 0.74231(16) 0.6412(2) 0.22966(14) 0.0122(4) Uani 1 1 d . U . . .
C1 C 0.5268(2) 0.4773(2) 0.13963(16) 0.0125(4) Uani 1 1 d . U . . .
H1 H 0.546(3) 1.178(4) 0.137(3) 0.051(9) Uiso 1 1 d . . . . .
O2 O 0.60541(14) 0.35382(17) 0.17082(13) 0.0169(3) Uani 1 1 d . U . . .
C2 C 0.59708(19) 0.6445(2) 0.16078(17) 0.0121(4) Uani 1 1 d . U . . .
O3 O 0.71654(14) 0.98021(18) 0.16276(14) 0.0208(4) Uani 1 1 d . U . . .
C3 C 0.5331(2) 0.7849(2) 0.12072(17) 0.0134(4) Uani 1 1 d . U . . .
H3 H 0.4384 0.7779 0.0766 0.016 Uiso 1 1 calc R U . . .
O4 O 0.50088(14) 1.06795(18) 0.12323(12) 0.0147(3) Uani 1 1 d . U . . .
C4 C 0.5956(2) 0.9531(2) 0.13826(17) 0.0137(4) Uani 1 1 d . U . . .
C5 C 0.8296(2) 0.5779(3) 0.18142(19) 0.0178(5) Uani 1 1 d . U . . .
H10 H 0.7970 0.5384 0.1039 0.021 Uiso 1 1 calc R U . . .
O6 O 0.78229(17) 0.2215(2) 0.38529(16) 0.0243(4) Uani 1 1 d . . . . .
C6 C 0.9671(2) 0.5715(3) 0.24688(19) 0.0207(5) Uani 1 1 d D U . . .
H6 H 1.0297 0.5259 0.2146 0.025 Uiso 1 1 calc DR U . . .
O7 O 0.95617(18) 0.7664(3) 0.51195(16) 0.0378(5) Uani 1 1 d D U . . .
C7 C 1.0142(2) 0.6312(3) 0.3593(2) 0.0211(5) Uani 1 1 d . U . . .
H7 H 1.1086 0.6262 0.4046 0.025 Uiso 1 1 calc R U . . .
C8 C 0.9215(2) 0.6988(3) 0.40548(19) 0.0192(5) Uani 1 1 d . U . . .
C9 C 0.7843(2) 0.7003(3) 0.33879(18) 0.0155(4) Uani 1 1 d . U . . .
H9 H 0.7196 0.7429 0.3699 0.019 Uiso 1 1 calc R U . . .
H4 H 0.749(4) 0.264(5) 0.324(3) 0.057(11) Uiso 1 1 d . . . . .
H2 H 0.736(4) 0.134(6) 0.389(3) 0.074(13) Uiso 1 1 d . . . . .
H11 H 1.0594(19) 0.773(4) 0.552(3) 0.062(10) Uiso 1 1 d D . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1 C1 1.241(2) . ?
N1 C9 1.347(3) . ?
N1 C5 1.350(3) . ?
N1 C2 1.458(2) . ?
C1 O2 1.266(2) . ?
C1 C2 1.518(3) . ?
C2 C3 1.323(3) . ?
O3 C4 1.213(2) . ?
C3 C4 1.493(3) . ?
C3 H3 0.9500 . ?
O4 C4 1.322(2) . ?
O4 H1 0.99(3) . ?
C5 C6 1.382(3) . ?
C5 H10 0.9500 . ?
O6 H4 0.79(4) . ?
O6 H2 0.87(5) . ?
C6 C7 1.384(3) . ?
C6 H6 0.9500 . ?
O7 C8 1.348(3) . ?
O7 H11 1.020(18) . ?
C7 C8 1.393(3) . ?
C7 H7 0.9500 . ?
C8 C9 1.381(3) . ?
C9 H9 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C9 N1 C5 122.54(17) . . ?
C9 N1 C2 119.00(16) . . ?
C5 N1 C2 118.46(17) . . ?
O1 C1 O2 126.85(19) . . ?
O1 C1 C2 117.81(17) . . ?
O2 C1 C2 115.34(17) . . ?
C3 C2 N1 121.38(18) . . ?
C3 C2 C1 123.37(18) . . ?
N1 C2 C1 115.25(16) . . ?
C2 C3 C4 126.22(18) . . ?
C2 C3 H3 116.9 . . ?
C4 C3 H3 116.9 . . ?
C4 O4 H1 108.6(18) . . ?
O3 C4 O4 124.83(19) . . ?
O3 C4 C3 124.48(18) . . ?
O4 C4 C3 110.69(17) . . ?
N1 C5 C6 118.81(19) . . ?
N1 C5 H10 120.6 . . ?
C6 C5 H10 120.6 . . ?
H4 O6 H2 110(3) . . ?
C5 C6 C7 120.30(19) . . ?
C5 C6 H6 119.8 . . ?
C7 C6 H6 119.8 . . ?
C8 O7 H11 112(2) . . ?
C6 C7 C8 119.3(2) . . ?
C6 C7 H7 120.3 . . ?
C8 C7 H7 120.3 . . ?
O7 C8 C9 116.48(19) . . ?
O7 C8 C7 124.47(19) . . ?
C9 C8 C7 119.0(2) . . ?
N1 C9 C8 119.97(19) . . ?
N1 C9 H9 120.0 . . ?
C8 C9 H9 120.0 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C9 N1 C2 C3 71.4(3) . . . . ?
C5 N1 C2 C3 -109.0(2) . . . . ?
C9 N1 C2 C1 -108.5(2) . . . . ?
C5 N1 C2 C1 71.2(2) . . . . ?
O1 C1 C2 C3 -8.4(3) . . . . ?
O2 C1 C2 C3 171.24(19) . . . . ?
O1 C1 C2 N1 171.42(17) . . . . ?
O2 C1 C2 N1 -9.0(2) . . . . ?
N1 C2 C3 C4 0.1(3) . . . . ?
C1 C2 C3 C4 179.90(18) . . . . ?
C2 C3 C4 O3 21.5(3) . . . . ?
C2 C3 C4 O4 -158.6(2) . . . . ?
C9 N1 C5 C6 0.8(3) . . . . ?
C2 N1 C5 C6 -178.82(19) . . . . ?
N1 C5 C6 C7 -0.9(3) . . . . ?
C5 C6 C7 C8 -0.4(3) . . . . ?
C6 C7 C8 O7 -177.2(2) . . . . ?
C6 C7 C8 C9 1.8(3) . . . . ?
C5 N1 C9 C8 0.6(3) . . . . ?
C2 N1 C9 C8 -179.80(18) . . . . ?
O7 C8 C9 N1 177.2(2) . . . . ?
C7 C8 C9 N1 -1.9(3) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O4 H1 O2 0.99(3) 1.55(4) 2.539(2) 171(3) 1_565
C3 H3 O6 0.95 2.55 3.309(3) 137.2 2_655
C5 H10 O1 0.95 2.59 3.430(3) 148.0 3_665
C6 H6 O3 0.95 2.58 3.184(3) 121.8 2_745
C7 H7 O3 0.95 2.54 3.164(3) 123.1 2_745
C9 H9 O1 0.95 2.38 3.235(3) 148.8 2_655
O6 H4 O2 0.79(4) 2.09(4) 2.851(2) 162(3) .
O6 H2 O1 0.87(5) 1.99(4) 2.835(2) 165(4) 2_645
O7 H11 O6 1.020(18) 1.562(18) 2.582(3) 179(3) 3_766

_refine_diff_density_max         0.732
_refine_diff_density_min         -0.369
_refine_diff_density_rms         0.072

_shelxl_version_number           2012-9

_database_code_depnum_ccdc_archive 'CCDC 987542'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_4

_audit_creation_method           SHELXL-2012
_chemical_name_systematic        
(2Z)-3-carboxy-2-(4-cyanopyridinium-1-yl)-1-hydroxyprop-2-en-1-olate
_chemical_name_common            \4
_chemical_melting_point          460.15
_chemical_formula_moiety         'C10 H6 N2 O4'
_chemical_formula_sum            'C10 H6 N2 O4'
_chemical_formula_weight         218.17

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   7.097(3)
_cell_length_b                   19.995(8)
_cell_length_c                   7.478(3)
_cell_angle_alpha                90
_cell_angle_beta                 112.227(5)
_cell_angle_gamma                90
_cell_volume                     982.3(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    2168
_cell_measurement_theta_min      3.101
_cell_measurement_theta_max      27.26

_exptl_crystal_description       shard
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.475
_exptl_crystal_F_000             448
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.468
_exptl_crystal_size_mid          0.253
_exptl_crystal_size_min          0.170
_exptl_absorpt_coefficient_mu    0.117
_shelx_estimated_absorpt_T_min   0.947
_shelx_estimated_absorpt_T_max   0.980
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.939
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   'SADABS, 2012'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area -detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            6115
_diffrn_reflns_av_unetI/netI     0.0300
_diffrn_reflns_av_R_equivalents  0.0244
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         2.037
_diffrn_reflns_theta_max         27.953
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.945
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             2232
_reflns_number_gt                1788
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX2 (Bruker, 2012)'
_computing_cell_refinement       'SAINT (Bruker, 2012)'
_computing_data_reduction        'SAINT (Bruker, 2012)'
_computing_structure_solution    'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_molecular_graphics    
'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)'
_computing_publication_material  ?

_refine_special_details          
;
 The acidic proton was located using electron density maps and was confirmed
 by measuring the C-O bond distances. 
 [∼ 1.2 Å = C\\dbO; ∼ 1.3 Å = C---O]
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 w=1/[σ²(Fo²)+(0.0540P)²+0.2489P]
 where P=(Fo²+2Fc²)/3
;
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2232
_refine_ls_number_parameters     153
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0524
_refine_ls_R_factor_gt           0.0411
_refine_ls_wR_factor_ref         0.1104
_refine_ls_wR_factor_gt          0.1028
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_restrained_S_all      1.055
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
O1 O 0.33747(15) 0.43334(5) 0.24036(14) 0.0218(3) Uani 1 1 d . . . . .
N1 N 0.59630(17) 0.37600(6) 0.73111(16) 0.0176(3) Uani 1 1 d . . . . .
C1 C 0.4694(2) 0.40313(7) 0.3813(2) 0.0189(3) Uani 1 1 d . . . . .
O2 O 0.61819(18) 0.37130(6) 0.38316(16) 0.0313(3) Uani 1 1 d . . . . .
N2 N 1.1799(2) 0.26250(8) 1.3238(2) 0.0384(4) Uani 1 1 d . . . . .
C2 C 0.4363(2) 0.40863(7) 0.57045(19) 0.0185(3) Uani 1 1 d . . . . .
O3 O 0.10356(17) 0.47988(6) 0.78076(16) 0.0300(3) Uani 1 1 d . . . . .
C3 C 0.2833(2) 0.44009(8) 0.5940(2) 0.0223(3) Uani 1 1 d . . . . .
H3 H 0.186(3) 0.4622(8) 0.485(3) 0.023(4) Uiso 1 1 d . . . . .
H4 H 0.361(4) 0.4250(12) 1.048(4) 0.062(7) Uiso 1 1 d . . . . .
O4 O 0.37890(19) 0.41701(7) 0.92568(16) 0.0382(3) Uani 1 1 d . . . . .
C4 C 0.2465(2) 0.44775(8) 0.7782(2) 0.0226(3) Uani 1 1 d . . . . .
C5 C 0.5881(2) 0.30944(7) 0.7538(2) 0.0217(3) Uani 1 1 d . . . . .
H5 H 0.4793 0.2842 0.6652 0.026 Uiso 1 1 calc R U . . .
C6 C 0.7366(2) 0.27796(8) 0.9048(2) 0.0237(3) Uani 1 1 d . . . . .
H6 H 0.7327 0.2310 0.9219 0.028 Uiso 1 1 calc R U . . .
C7 C 0.8932(2) 0.31654(8) 1.0324(2) 0.0211(3) Uani 1 1 d . . . . .
C8 C 0.8990(2) 0.38470(8) 1.0064(2) 0.0228(3) Uani 1 1 d . . . . .
H8 H 1.0058 0.4110 1.0935 0.027 Uiso 1 1 calc R U . . .
C9 C 0.7470(2) 0.41377(8) 0.8517(2) 0.0211(3) Uani 1 1 d . . . . .
H9 H 0.7489 0.4606 0.8305 0.025 Uiso 1 1 calc R U . . .
C10 C 1.0534(2) 0.28567(8) 1.1943(2) 0.0272(4) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1 C1 1.2672(17) . ?
N1 C9 1.3410(19) . ?
N1 C5 1.346(2) . ?
N1 C2 1.4583(17) . ?
C1 O2 1.2285(18) . ?
C1 C2 1.523(2) . ?
N2 C10 1.141(2) . ?
C2 C3 1.323(2) . ?
O3 C4 1.2068(18) . ?
C3 C4 1.504(2) . ?
C3 H3 0.954(18) . ?
O4 C4 1.3010(18) . ?
O4 H4 0.98(3) . ?
C5 C6 1.372(2) . ?
C5 H5 0.9500 . ?
C6 C7 1.392(2) . ?
C6 H6 0.9500 . ?
C7 C8 1.379(2) . ?
C7 C10 1.448(2) . ?
C8 C9 1.377(2) . ?
C8 H8 0.9500 . ?
C9 H9 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C9 N1 C5 122.26(12) . . ?
C9 N1 C2 118.47(12) . . ?
C5 N1 C2 119.27(11) . . ?
O2 C1 O1 128.15(13) . . ?
O2 C1 C2 117.46(12) . . ?
O1 C1 C2 114.39(12) . . ?
C3 C2 N1 121.73(13) . . ?
C3 C2 C1 125.50(13) . . ?
N1 C2 C1 112.76(12) . . ?
C2 C3 C4 127.30(14) . . ?
C2 C3 H3 118.4(10) . . ?
C4 C3 H3 114.3(10) . . ?
C4 O4 H4 114.0(14) . . ?
O3 C4 O4 125.46(14) . . ?
O3 C4 C3 120.46(13) . . ?
O4 C4 C3 114.09(13) . . ?
N1 C5 C6 120.07(13) . . ?
N1 C5 H5 120.0 . . ?
C6 C5 H5 120.0 . . ?
C5 C6 C7 118.39(14) . . ?
C5 C6 H6 120.8 . . ?
C7 C6 H6 120.8 . . ?
C8 C7 C6 120.64(13) . . ?
C8 C7 C10 118.88(13) . . ?
C6 C7 C10 120.48(14) . . ?
C9 C8 C7 118.68(14) . . ?
C9 C8 H8 120.7 . . ?
C7 C8 H8 120.7 . . ?
N1 C9 C8 119.96(14) . . ?
N1 C9 H9 120.0 . . ?
C8 C9 H9 120.0 . . ?
N2 C10 C7 178.65(18) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C9 N1 C2 C3 -80.61(18) . . . . ?
C5 N1 C2 C3 99.26(17) . . . . ?
C9 N1 C2 C1 98.28(15) . . . . ?
C5 N1 C2 C1 -81.85(16) . . . . ?
O2 C1 C2 C3 -179.07(15) . . . . ?
O1 C1 C2 C3 1.6(2) . . . . ?
O2 C1 C2 N1 2.10(18) . . . . ?
O1 C1 C2 N1 -177.24(11) . . . . ?
N1 C2 C3 C4 -0.2(2) . . . . ?
C1 C2 C3 C4 -178.89(14) . . . . ?
C2 C3 C4 O3 177.45(16) . . . . ?
C2 C3 C4 O4 -2.9(2) . . . . ?
C9 N1 C5 C6 0.3(2) . . . . ?
C2 N1 C5 C6 -179.59(13) . . . . ?
N1 C5 C6 C7 0.3(2) . . . . ?
C5 C6 C7 C8 -0.4(2) . . . . ?
C5 C6 C7 C10 179.89(14) . . . . ?
C6 C7 C8 C9 -0.1(2) . . . . ?
C10 C7 C8 C9 179.65(14) . . . . ?
C5 N1 C9 C8 -0.8(2) . . . . ?
C2 N1 C9 C8 179.11(13) . . . . ?
C7 C8 C9 N1 0.6(2) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C3 H3 O3 0.954(18) 2.534(18) 3.483(2) 172.8(14) 3_566
O4 H4 O1 0.98(3) 1.52(3) 2.5008(17) 177(2) 1_556
C6 H6 O2 0.95 2.18 3.088(2) 159.8 4_566
C8 H8 O1 0.95 2.23 3.094(2) 150.1 1_656
C9 H9 O1 0.95 2.22 3.141(2) 164.3 3_666

_refine_diff_density_max         0.320
_refine_diff_density_min         -0.208
_refine_diff_density_rms         0.047

_shelxl_version_number           2012-9

_database_code_depnum_ccdc_archive 'CCDC 987543'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_5

_audit_creation_method           SHELXL-2012
_chemical_name_systematic        
(2Z)-3-carboxy-2-(4-carboxypyridinium-1-yl)-1-hydroxyprop-2-en-1-olate
_chemical_name_common            \5
_chemical_melting_point          473.15
_chemical_formula_moiety         'C20 H14 N2 O12'
_chemical_formula_sum            'C20 H14 N2 O12'
_chemical_formula_weight         474.33

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   7.189(5)
_cell_length_b                   7.500(5)
_cell_length_c                   9.557(7)
_cell_angle_alpha                82.788(7)
_cell_angle_beta                 87.499(7)
_cell_angle_gamma                64.972(7)
_cell_volume                     463.2(5)
_cell_formula_units_Z            1
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    4381
_cell_measurement_theta_min      3.02
_cell_measurement_theta_max      23.24

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.700
_exptl_crystal_F_000             244
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.773
_exptl_crystal_size_mid          0.319
_exptl_crystal_size_min          0.290
_exptl_absorpt_coefficient_mu    0.144
_shelx_estimated_absorpt_T_min   0.897
_shelx_estimated_absorpt_T_max   0.959
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.9472
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   'SADABS, 2012'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area -detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            5436
_diffrn_reflns_av_unetI/netI     0.0179
_diffrn_reflns_av_R_equivalents  0.0189
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.148
_diffrn_reflns_theta_max         28.432
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.908
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.908
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.908
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             2117
_reflns_number_gt                2031
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX2 (Bruker, 2012)'
_computing_cell_refinement       'SAINT (Bruker, 2012)'
_computing_data_reduction        'SAINT (Bruker, 2012)'
_computing_structure_solution    'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_molecular_graphics    
'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)'
_computing_publication_material  ?

_refine_special_details          
;
  The acidic proton was located using electron density maps and was confirmed
 by measuring the C-O bond distances. 
 [∼ 1.2 Å = C\\dbO; ∼ 1.3 Å = C---O]
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 w=1/[σ²(Fo²)+(0.0433P)²+0.2297P]
 where P=(Fo²+2Fc²)/3
;
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2117
_refine_ls_number_parameters     166
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0321
_refine_ls_R_factor_gt           0.0311
_refine_ls_wR_factor_ref         0.0851
_refine_ls_wR_factor_gt          0.0841
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_restrained_S_all      1.046
_refine_ls_shift/su_max          0.035
_refine_ls_shift/su_mean         0.002

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
O1 O 0.33724(11) 1.23559(11) 0.63163(8) 0.01230(17) Uani 1 1 d . . . . .
N1 N 0.60144(13) 0.71640(12) 0.76568(9) 0.00980(18) Uani 1 1 d . . . . .
C1 C 0.47451(16) 1.08047(15) 0.69365(11) 0.0115(2) Uani 1 1 d . . . . .
O2 O 0.62669(13) 1.06907(12) 0.75813(10) 0.0206(2) Uani 1 1 d . . . . .
C2 C 0.44687(15) 0.89167(14) 0.68617(10) 0.0104(2) Uani 1 1 d . . . . .
O3 O 0.10689(13) 0.72374(12) 0.53538(9) 0.01857(19) Uani 1 1 d . . . . .
C3 C 0.29455(16) 0.88453(15) 0.61610(10) 0.0113(2) Uani 1 1 d . . . . .
H3 H 0.195(2) 1.006(2) 0.5685(15) 0.014(3) Uiso 1 1 d . . . . .
O4 O 0.38793(12) 0.53980(11) 0.66862(8) 0.01480(18) Uani 1 1 d . . . . .
C4 C 0.25376(16) 0.70709(15) 0.60291(11) 0.0117(2) Uani 1 1 d . . . . .
H4 H 0.362(3) 0.432(3) 0.655(2) 0.047(5) Uiso 1 1 d . . . . .
H10 H 1.156(3) 0.098(3) 1.173(2) 0.041(5) Uiso 1 1 d . . . . .
O5 O 1.03075(12) 0.20196(11) 1.13388(8) 0.01348(17) Uani 1 1 d . . . . .
C5 C 0.58299(15) 0.69252(15) 0.90766(11) 0.0111(2) Uani 1 1 d . . . . .
H5 H 0.4743 0.7902 0.9532 0.013 Uiso 1 1 calc R U . . .
O6 O 1.17374(12) 0.07466(11) 0.93448(8) 0.01683(19) Uani 1 1 d . . . . .
C6 C 0.72320(16) 0.52536(15) 0.98582(11) 0.0110(2) Uani 1 1 d . . . . .
H6 H 0.7126 0.5073 1.0855 0.013 Uiso 1 1 calc R U . . .
C7 C 0.88056(15) 0.38337(15) 0.91643(11) 0.0106(2) Uani 1 1 d . . . . .
C8 C 0.89627(16) 0.41275(15) 0.77058(11) 0.0123(2) Uani 1 1 d . . . . .
H8 H 1.0030 0.3168 0.7225 0.015 Uiso 1 1 calc R U . . .
C9 C 0.75444(16) 0.58339(15) 0.69649(11) 0.0121(2) Uani 1 1 d . . . . .
H9 H 0.7648 0.6068 0.5971 0.014 Uiso 1 1 calc R U . . .
C10 C 1.04362(15) 0.20140(15) 0.99592(11) 0.0113(2) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1 C1 1.2590(14) . ?
N1 C9 1.3476(14) . ?
N1 C5 1.3544(16) . ?
N1 C2 1.4585(14) . ?
C1 O2 1.2452(15) . ?
C1 C2 1.5212(17) . ?
C2 C3 1.3317(16) . ?
O3 C4 1.2143(15) . ?
C3 C4 1.4994(17) . ?
C3 H3 0.958(15) . ?
O4 C4 1.3152(14) . ?
O4 H4 0.93(2) . ?
O5 C10 1.3181(16) . ?
O5 H10 0.96(2) . ?
C5 C6 1.3809(15) . ?
C5 H5 0.9500 . ?
O6 C10 1.2097(14) . ?
C6 C7 1.3950(15) . ?
C6 H6 0.9500 . ?
C7 C8 1.3909(17) . ?
C7 C10 1.5092(15) . ?
C8 C9 1.3821(15) . ?
C8 H8 0.9500 . ?
C9 H9 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C9 N1 C5 122.40(9) . . ?
C9 N1 C2 119.53(9) . . ?
C5 N1 C2 118.06(9) . . ?
O2 C1 O1 126.33(10) . . ?
O2 C1 C2 118.58(9) . . ?
O1 C1 C2 115.09(10) . . ?
C3 C2 N1 122.20(10) . . ?
C3 C2 C1 123.92(9) . . ?
N1 C2 C1 113.86(9) . . ?
C2 C3 C4 127.93(9) . . ?
C2 C3 H3 118.2(9) . . ?
C4 C3 H3 113.8(9) . . ?
C4 O4 H4 112.3(12) . . ?
O3 C4 O4 124.90(10) . . ?
O3 C4 C3 120.48(10) . . ?
O4 C4 C3 114.62(10) . . ?
C10 O5 H10 106.4(11) . . ?
N1 C5 C6 119.58(9) . . ?
N1 C5 H5 120.2 . . ?
C6 C5 H5 120.2 . . ?
C5 C6 C7 119.14(10) . . ?
C5 C6 H6 120.4 . . ?
C7 C6 H6 120.4 . . ?
C8 C7 C6 119.93(10) . . ?
C8 C7 C10 118.17(9) . . ?
C6 C7 C10 121.82(10) . . ?
C9 C8 C7 119.10(10) . . ?
C9 C8 H8 120.4 . . ?
C7 C8 H8 120.4 . . ?
N1 C9 C8 119.82(10) . . ?
N1 C9 H9 120.1 . . ?
C8 C9 H9 120.1 . . ?
O6 C10 O5 125.57(10) . . ?
O6 C10 C7 121.25(10) . . ?
O5 C10 C7 113.15(9) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C9 N1 C2 C3 77.41(13) . . . . ?
C5 N1 C2 C3 -101.61(12) . . . . ?
C9 N1 C2 C1 -103.69(11) . . . . ?
C5 N1 C2 C1 77.30(12) . . . . ?
O2 C1 C2 C3 -177.51(10) . . . . ?
O1 C1 C2 C3 2.23(15) . . . . ?
O2 C1 C2 N1 3.61(14) . . . . ?
O1 C1 C2 N1 -176.65(8) . . . . ?
N1 C2 C3 C4 -0.95(17) . . . . ?
C1 C2 C3 C4 -179.74(9) . . . . ?
C2 C3 C4 O3 179.66(11) . . . . ?
C2 C3 C4 O4 -0.58(16) . . . . ?
C9 N1 C5 C6 -0.88(15) . . . . ?
C2 N1 C5 C6 178.10(9) . . . . ?
N1 C5 C6 C7 -0.48(15) . . . . ?
C5 C6 C7 C8 0.92(15) . . . . ?
C5 C6 C7 C10 177.53(9) . . . . ?
C6 C7 C8 C9 -0.05(15) . . . . ?
C10 C7 C8 C9 -176.78(9) . . . . ?
C5 N1 C9 C8 1.78(15) . . . . ?
C2 N1 C9 C8 -177.19(9) . . . . ?
C7 C8 C9 N1 -1.28(15) . . . . ?
C8 C7 C10 O6 -6.85(15) . . . . ?
C6 C7 C10 O6 176.48(10) . . . . ?
C8 C7 C10 O5 171.00(9) . . . . ?
C6 C7 C10 O5 -5.67(14) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C3 H3 O3 0.959(15) 2.402(15) 3.3434(19) 167.1(12) 2_576
O4 H4 O1 0.93(2) 1.60(2) 2.5258(19) 175.1(19) 1_545
O5 H10 O2 0.96(2) 1.64(2) 2.5926(16) 176.7(19) 2_767
C5 H5 O6 0.95 2.30 3.150(2) 148.5 1_465
C6 H6 O4 0.95 2.46 3.388(3) 167.3 2_667
C8 H8 O1 0.95 2.37 3.177(2) 142.6 1_645
C9 H9 O1 0.95 2.34 3.235(2) 157.1 2_676

_refine_diff_density_max         0.362
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.053

_shelxl_version_number           2012-9

_database_code_depnum_ccdc_archive 'CCDC 987544'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_5a

_audit_creation_method           SHELXL-2012
_chemical_name_systematic        
;
4-carboxypyridinium, carboxy-propynoate hydrate
;
_chemical_name_common            \5a
_chemical_melting_point          410
_chemical_formula_moiety         'C6 H6 N O2, C4 H O4, H2 O'
_chemical_formula_sum            'C10 H9 N O7'
_chemical_formula_weight         255.18

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   7.344(5)
_cell_length_b                   7.851(5)
_cell_length_c                   9.780(6)
_cell_angle_alpha                91.428(7)
_cell_angle_beta                 94.012(7)
_cell_angle_gamma                106.401(7)
_cell_volume                     539.0(6)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    2776
_cell_measurement_theta_min      2.71
_cell_measurement_theta_max      27.84

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.572
_exptl_crystal_F_000             264
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.722
_exptl_crystal_size_mid          0.296
_exptl_crystal_size_min          0.141
_exptl_absorpt_coefficient_mu    0.136
_shelx_estimated_absorpt_T_min   0.908
_shelx_estimated_absorpt_T_max   0.981
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.4354
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_process_details   'SADABS, 2012'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area -detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            5894
_diffrn_reflns_av_unetI/netI     0.0440
_diffrn_reflns_av_R_equivalents  0.0352
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.090
_diffrn_reflns_theta_max         28.280
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 0.910
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.910
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.910
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             2439
_reflns_number_gt                2088
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX2 (Bruker, 2012)'
_computing_cell_refinement       'SAINT (Bruker, 2012)'
_computing_data_reduction        'SAINT (Bruker, 2012)'
_computing_structure_solution    'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_molecular_graphics    
'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)'
_computing_publication_material  ?

_refine_special_details          
;
 The acidic proton was located using electron density maps and was confirmed
 by measuring the C-O bond distances. 
 [∼ 1.2 Å = C\\dbO; ∼ 1.3 Å = C---O]
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 w=1/[σ²(Fo²)+(0.0648P)²+0.0818P]
 where P=(Fo²+2Fc²)/3
;
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2439
_refine_ls_number_parameters     183
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0488
_refine_ls_R_factor_gt           0.0421
_refine_ls_wR_factor_ref         0.1187
_refine_ls_wR_factor_gt          0.1152
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_restrained_S_all      1.087
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
H7B H 0.180(4) 0.528(3) 1.093(3) 0.058(7) Uiso 1 1 d . . . . .
O1A O 0.00423(15) 0.33562(14) 0.32236(10) 0.0178(3) Uani 1 1 d . . . . .
O2A O 0.30664(15) 0.39696(14) 0.41272(11) 0.0219(3) Uani 1 1 d . . . . .
O3A O 0.16732(17) -0.26946(14) 0.16560(10) 0.0242(3) Uani 1 1 d . . . . .
O4A O 0.04697(16) -0.34109(14) 0.36883(10) 0.0208(3) Uani 1 1 d . . . . .
C1A C 0.1585(2) 0.29475(19) 0.36136(14) 0.0167(3) Uani 1 1 d . . . . .
C2A C 0.1417(2) 0.1057(2) 0.33591(14) 0.0178(3) Uani 1 1 d . . . . .
C3A C 0.1333(2) -0.0462(2) 0.31219(14) 0.0168(3) Uani 1 1 d . . . . .
C4A C 0.1154(2) -0.23453(19) 0.27890(14) 0.0158(3) Uani 1 1 d . . . . .
H1A H 0.024(3) 0.469(4) 0.334(3) 0.062(7) Uiso 1 1 d . . . . .
H2C H 0.719(4) 0.317(3) 0.467(3) 0.062(8) Uiso 1 1 d . . . . .
O5B O 0.33037(17) 0.58428(15) 0.89431(11) 0.0245(3) Uani 1 1 d . . . . .
O6B O 0.19775(17) 0.42558(15) 1.06828(10) 0.0236(3) Uani 1 1 d . . . . .
N1B N 0.33557(18) -0.03005(17) 0.77224(12) 0.0180(3) Uani 1 1 d . . . . .
C2B C 0.2716(2) -0.0359(2) 0.89786(15) 0.0200(3) Uani 1 1 d . . . . .
H2B H 0.2402 -0.1443 0.9438 0.024 Uiso 1 1 calc R U . . .
H1C H 0.526(3) 0.305(3) 0.423(2) 0.033(5) Uiso 1 1 d . . . . .
H1B H 0.353(3) -0.130(3) 0.725(2) 0.042(6) Uiso 1 1 d . . . . .
C3B C 0.2519(2) 0.1175(2) 0.95945(14) 0.0180(3) Uani 1 1 d . . . . .
H3B H 0.2074 0.1158 1.0484 0.022 Uiso 1 1 calc R U . . .
C4B C 0.2980(2) 0.27459(19) 0.88987(14) 0.0161(3) Uani 1 1 d . . . . .
C5B C 0.3652(2) 0.2756(2) 0.76022(14) 0.0184(3) Uani 1 1 d . . . . .
H5B H 0.3984 0.3822 0.7120 0.022 Uiso 1 1 calc R U . . .
C6B C 0.3828(2) 0.1192(2) 0.70278(14) 0.0196(3) Uani 1 1 d . . . . .
H6B H 0.4283 0.1173 0.6143 0.023 Uiso 1 1 calc R U . . .
C7B C 0.2772(2) 0.4460(2) 0.95067(14) 0.0170(3) Uani 1 1 d . . . . .
O1C O 0.60877(17) 0.24748(15) 0.42662(10) 0.0200(3) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1A C1A 1.2976(19) . ?
O1A H1A 1.02(3) . ?
O2A C1A 1.2206(19) . ?
O3A C4A 1.2456(18) . ?
O4A C4A 1.2598(19) . ?
C1A C2A 1.468(2) . ?
C2A C3A 1.193(2) . ?
C3A C4A 1.473(2) . ?
O5B C7B 1.2067(19) . ?
O6B C7B 1.3189(19) . ?
O6B H7B 0.88(3) . ?
N1B C6B 1.341(2) . ?
N1B C2B 1.343(2) . ?
N1B H1B 0.94(2) . ?
C2B C3B 1.382(2) . ?
C2B H2B 0.9500 . ?
C3B C4B 1.392(2) . ?
C3B H3B 0.9500 . ?
C4B C5B 1.392(2) . ?
C4B C7B 1.509(2) . ?
C5B C6B 1.381(2) . ?
C5B H5B 0.9500 . ?
C6B H6B 0.9500 . ?
O1C H2C 0.90(3) . ?
O1C H1C 0.86(2) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C1A O1A H1A 110.7(14) . . ?
O2A C1A O1A 126.22(14) . . ?
O2A C1A C2A 120.89(14) . . ?
O1A C1A C2A 112.88(13) . . ?
C3A C2A C1A 177.62(16) . . ?
C2A C3A C4A 177.50(15) . . ?
O3A C4A O4A 127.95(14) . . ?
O3A C4A C3A 116.56(13) . . ?
O4A C4A C3A 115.48(13) . . ?
C7B O6B H7B 107.7(17) . . ?
C6B N1B C2B 122.99(13) . . ?
C6B N1B H1B 114.0(13) . . ?
C2B N1B H1B 123.0(13) . . ?
N1B C2B C3B 119.24(14) . . ?
N1B C2B H2B 120.4 . . ?
C3B C2B H2B 120.4 . . ?
C2B C3B C4B 119.37(14) . . ?
C2B C3B H3B 120.3 . . ?
C4B C3B H3B 120.3 . . ?
C3B C4B C5B 119.70(13) . . ?
C3B C4B C7B 121.96(13) . . ?
C5B C4B C7B 118.35(13) . . ?
C6B C5B C4B 118.92(14) . . ?
C6B C5B H5B 120.5 . . ?
C4B C5B H5B 120.5 . . ?
N1B C6B C5B 119.78(14) . . ?
N1B C6B H6B 120.1 . . ?
C5B C6B H6B 120.1 . . ?
O5B C7B O6B 125.60(13) . . ?
O5B C7B C4B 121.55(13) . . ?
O6B C7B C4B 112.85(13) . . ?
H2C O1C H1C 110(2) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C6B N1B C2B C3B 0.3(2) . . . . ?
N1B C2B C3B C4B 0.3(2) . . . . ?
C2B C3B C4B C5B -0.8(2) . . . . ?
C2B C3B C4B C7B 179.19(13) . . . . ?
C3B C4B C5B C6B 0.7(2) . . . . ?
C7B C4B C5B C6B -179.29(13) . . . . ?
C2B N1B C6B C5B -0.4(2) . . . . ?
C4B C5B C6B N1B -0.1(2) . . . . ?
C3B C4B C7B O5B 174.50(14) . . . . ?
C5B C4B C7B O5B -5.5(2) . . . . ?
C3B C4B C7B O6B -5.25(19) . . . . ?
C5B C4B C7B O6B 174.71(13) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O1A H1A O4A 1.02(3) 1.48(3) 2.494(2) 173(2) 1_565
O1C H2C O1A 0.90(3) 2.58(3) 3.044(2) 113.2(19) 1_655
O1C H2C O2A 0.90(3) 2.57(3) 3.052(2) 114.1(19) 2_666
O1C H2C O4A 0.90(3) 2.23(3) 3.017(2) 146(2) 2_656
C2B H2B O3A 0.95 2.43 3.245(2) 143.2 1_556
C2B H2B O5B 0.95 2.45 3.131(3) 128.5 1_545
O1C H1C O2A 0.86(2) 1.93(2) 2.785(2) 170.3(19) .
N1B H1B O1C 0.94(2) 1.81(2) 2.6839(19) 152.8(19) 2_656
C6B H6B O1C 0.95 2.42 3.299(2) 154.3 .

_refine_diff_density_max         0.350
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.060

_shelxl_version_number           2012-9

_database_code_depnum_ccdc_archive 'CCDC 987545'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_6_H2O

_audit_creation_method           SHELXL-2012
_chemical_name_systematic        
'(2Z)-3-carboxy-1-hydroxy-2-(4-phenylpyridinium-1-yl)prop-2-en-1-olate hydrate'
_chemical_name_common            \6H2O
_chemical_melting_point          453.15
_chemical_formula_moiety         'C15 H11 N O4, 0.21(H4 O2), 1.29(H2 O)'
_chemical_formula_sum            'C15 H14.42 N O5.71'
_chemical_formula_weight         300.01

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 2/c'
_space_group_name_Hall           '-C 2yc'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'

_cell_length_a                   13.856(6)
_cell_length_b                   8.011(3)
_cell_length_c                   25.655(11)
_cell_angle_alpha                90
_cell_angle_beta                 92.488(7)
_cell_angle_gamma                90
_cell_volume                     2845(2)
_cell_formula_units_Z            8
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    1271
_cell_measurement_theta_min      2.94
_cell_measurement_theta_max      21.14

_exptl_crystal_description       rod
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.401
_exptl_crystal_F_000             1257
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.722
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.090
_exptl_absorpt_coefficient_mu    0.109
_shelx_estimated_absorpt_T_min   0.926
_shelx_estimated_absorpt_T_max   0.990
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9121
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   'SADABS, 2012'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area -detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            8536
_diffrn_reflns_av_unetI/netI     0.0517
_diffrn_reflns_av_R_equivalents  0.0411
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_theta_min         1.589
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.968
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             3169
_reflns_number_gt                1962
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX2 (Bruker, 2012)'
_computing_cell_refinement       'SAINT (Bruker, 2012)'
_computing_data_reduction        'SAINT (Bruker, 2012)'
_computing_structure_solution    'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_molecular_graphics    
'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)'
_computing_publication_material  ?

_refine_special_details          
;
 The acidic proton was located using electron density maps and was confirmed
 by measuring the C-O bond distances. 
 [∼ 1.2 Å = C\\dbO; ∼ 1.3 Å = C---O]
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 w=1/[σ²(Fo²)+(0.0578P)²]
 where P=(Fo²+2Fc²)/3
;
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3169
_refine_ls_number_parameters     352
_refine_ls_number_restraints     544
_refine_ls_R_factor_all          0.0884
_refine_ls_R_factor_gt           0.0472
_refine_ls_wR_factor_ref         0.1236
_refine_ls_wR_factor_gt          0.1037
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_restrained_S_all      0.934
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
O2 O 0.14578(10) 0.14917(16) 0.28526(5) 0.0310(3) Uani 1 1 d D U . . .
O4 O 0.14683(10) 0.86738(17) 0.24711(5) 0.0310(3) Uani 1 1 d . U . . .
O1 O 0.11010(9) 0.26442(15) 0.20668(4) 0.0315(3) Uani 1 1 d . U . . .
O5 O 0.46409(12) 0.5227(2) 0.36363(5) 0.0421(4) Uani 1 1 d . . . . .
O3 O 0.08378(11) 0.77419(16) 0.32076(5) 0.0409(4) Uani 1 1 d . U . . .
N4A N 0.1518(14) 0.450(3) 0.3376(6) 0.022(2) Uani 0.530(18) 1 d . U P A 1
N4B N 0.1394(17) 0.430(3) 0.3349(8) 0.025(3) Uani 0.470(18) 1 d . U P A 2
C13B C 0.1967(12) 0.455(3) 0.6115(6) 0.054(3) Uani 0.470(18) 1 d . U P A 2
H13B H 0.2021 0.4628 0.6485 0.064 Uiso 0.470(18) 1 calc R U P A 2
C14B C 0.2679(12) 0.5223(19) 0.5825(6) 0.044(2) Uani 0.470(18) 1 d . U P A 2
H14B H 0.3241 0.5714 0.5985 0.053 Uiso 0.470(18) 1 calc R U P A 2
C15A C 0.2758(10) 0.5605(16) 0.5223(5) 0.047(2) Uani 0.530(18) 1 d . U P A 1
H15A H 0.3193 0.6176 0.5010 0.056 Uiso 0.530(18) 1 calc R U P A 1
C10A C 0.2001(9) 0.4675(17) 0.5001(4) 0.029(2) Uani 0.530(18) 1 d . U P A 1
C11A C 0.1388(9) 0.3830(19) 0.5321(5) 0.042(2) Uani 0.530(18) 1 d . U P A 1
H11A H 0.0854 0.3226 0.5172 0.051 Uiso 0.530(18) 1 calc R U P A 1
C12A C 0.1548(9) 0.3858(19) 0.5868(5) 0.054(2) Uani 0.530(18) 1 d . U P A 1
H12A H 0.1146 0.3229 0.6086 0.065 Uiso 0.530(18) 1 calc R U P A 1
C2 C 0.12997(13) 0.4400(2) 0.28004(6) 0.0251(4) Uani 1 1 d . U . . .
C4 C 0.11537(13) 0.7521(2) 0.27748(7) 0.0270(4) Uani 1 1 d . U . . .
C1 C 0.12836(13) 0.2701(2) 0.25456(6) 0.0254(4) Uani 1 1 d . U . . .
C3 C 0.11943(13) 0.5819(2) 0.25396(7) 0.0259(4) Uani 1 1 d . U . . .
H3 H 0.1139 0.5748 0.2170 0.031 Uiso 1 1 calc R U . . .
C6A C 0.0998(9) 0.392(2) 0.4196(6) 0.035(2) Uani 0.530(18) 1 d . U P A 1
H6A H 0.0519 0.3471 0.4409 0.042 Uiso 0.530(18) 1 calc R U P A 1
C7B C 0.1608(10) 0.430(2) 0.4448(5) 0.023(2) Uani 0.470(18) 1 d . U P A 2
C10B C 0.1726(10) 0.4358(18) 0.5039(5) 0.026(2) Uani 0.470(18) 1 d . U P A 2
C5B C 0.0609(9) 0.403(2) 0.3661(7) 0.0242(19) Uani 0.470(18) 1 d . U P A 2
H5B H -0.0009 0.3820 0.3500 0.029 Uiso 0.470(18) 1 calc R U P A 2
C13A C 0.2290(10) 0.480(2) 0.6084(5) 0.055(3) Uani 0.530(18) 1 d . U P A 1
H13A H 0.2404 0.4842 0.6451 0.066 Uiso 0.530(18) 1 calc R U P A 1
C9B C 0.2267(7) 0.4509(17) 0.3603(4) 0.033(2) Uani 0.470(18) 1 d . U P A 2
H9B H 0.2818 0.4638 0.3399 0.040 Uiso 0.470(18) 1 calc R U P A 2
C8A C 0.2508(6) 0.5217(12) 0.4091(3) 0.0319(15) Uani 0.530(18) 1 d . U P A 1
H8A H 0.3094 0.5687 0.4229 0.038 Uiso 0.530(18) 1 calc R U P A 1
C15B C 0.2534(9) 0.5153(18) 0.5273(5) 0.036(2) Uani 0.470(18) 1 d . U P A 2
H15B H 0.2994 0.5656 0.5058 0.043 Uiso 0.470(18) 1 calc R U P A 2
C8B C 0.2402(7) 0.4541(17) 0.4135(4) 0.034(2) Uani 0.470(18) 1 d . U P A 2
H8B H 0.3028 0.4726 0.4291 0.041 Uiso 0.470(18) 1 calc R U P A 2
C11B C 0.1067(11) 0.362(2) 0.5350(6) 0.041(2) Uani 0.470(18) 1 d . U P A 2
H11B H 0.0537 0.3011 0.5197 0.049 Uiso 0.470(18) 1 calc R U P A 2
C12B C 0.1179(11) 0.375(2) 0.5886(6) 0.059(3) Uani 0.470(18) 1 d . U P A 2
H12B H 0.0703 0.3293 0.6100 0.071 Uiso 0.470(18) 1 calc R U P A 2
C14A C 0.2867(12) 0.569(2) 0.5756(6) 0.061(3) Uani 0.530(18) 1 d . U P A 1
H14A H 0.3359 0.6382 0.5907 0.073 Uiso 0.530(18) 1 calc R U P A 1
C6B C 0.0711(9) 0.406(2) 0.4203(7) 0.032(2) Uani 0.470(18) 1 d . U P A 2
H6B H 0.0160 0.3910 0.4406 0.038 Uiso 0.470(18) 1 calc R U P A 2
C7A C 0.1851(10) 0.4629(17) 0.4429(5) 0.0258(19) Uani 0.530(18) 1 d . U P A 1
C9A C 0.2351(6) 0.5153(11) 0.3564(3) 0.0287(15) Uani 0.530(18) 1 d . U P A 1
H9A H 0.2819 0.5563 0.3337 0.034 Uiso 0.530(18) 1 calc R U P A 1
C5A C 0.0866(9) 0.389(2) 0.3665(6) 0.034(3) Uani 0.530(18) 1 d . U P A 1
H5A H 0.0295 0.3415 0.3510 0.041 Uiso 0.530(18) 1 calc R U P A 1
O6C O -0.0193(4) 0.0761(9) 0.46835(16) 0.052(2) Uani 0.415(9) 1 d D U P B -3
O7D O -0.0656(5) 0.1673(9) 0.4580(2) 0.033(2) Uani 0.294(8) 1 d D U P C -4
H4 H 0.132(3) 0.968(6) 0.2631(15) 0.017(10) Uiso 0.5 1 d . . P D -5
H6 H 0.514(2) 0.457(4) 0.3502(11) 0.098(11) Uiso 1 1 d . . . . .
H7C H -0.011(6) 0.047(9) 0.5045(10) 0.08(2) Uiso 0.415(9) 1 d D . P B -3
H5 H 0.446(2) 0.603(4) 0.3359(11) 0.103(11) Uiso 1 1 d . . . . .
H6C H -0.011(5) 0.030(9) 0.4338(14) 0.08(2) Uiso 0.415(9) 1 d D . P B -3
H7D H -0.048(6) 0.103(9) 0.428(2) 0.05(2) Uiso 0.294(8) 1 d D . P C -4
H2 H 0.151(6) 0.045(5) 0.267(3) 0.12(4) Uiso 0.5 1 d D . P E -5
H8D H -0.105(6) 0.263(8) 0.453(3) 0.10(4) Uiso 0.294(8) 1 d D . P C -4


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O2 C1 1.265(2) . ?
O2 H2 0.96(2) . ?
O4 C4 1.296(2) . ?
O4 H4 0.93(5) . ?
O1 C1 1.244(2) . ?
O5 H6 0.95(3) . ?
O5 H5 0.98(3) . ?
O3 C4 1.224(2) . ?
N4A C5A 1.29(2) . ?
N4A C9A 1.340(18) . ?
N4A C2 1.496(15) . ?
N4B C9B 1.36(2) . ?
N4B C5B 1.39(3) . ?
N4B C2 1.41(2) . ?
C13B C12B 1.372(14) . ?
C13B C14B 1.373(14) . ?
C13B H13B 0.9500 . ?
C14B C15B 1.425(18) . ?
C14B H14B 0.9500 . ?
C15A C14A 1.370(17) . ?
C15A C10A 1.389(10) . ?
C15A H15A 0.9500 . ?
C10A C11A 1.385(10) . ?
C10A C7A 1.472(15) . ?
C11A C12A 1.411(18) . ?
C11A H11A 0.9500 . ?
C12A C13A 1.372(13) . ?
C12A H12A 0.9500 . ?
C2 C3 1.324(2) . ?
C2 C1 1.510(2) . ?
C4 C3 1.493(2) . ?
C3 H3 0.9500 . ?
C6A C5A 1.37(2) . ?
C6A C7A 1.419(13) . ?
C6A H6A 0.9500 . ?
C7B C6B 1.382(14) . ?
C7B C8B 1.405(13) . ?
C7B C10B 1.517(17) . ?
C10B C11B 1.374(11) . ?
C10B C15B 1.400(11) . ?
C5B C6B 1.39(2) . ?
C5B H5B 0.9500 . ?
C13A C14A 1.381(12) . ?
C13A H13A 0.9500 . ?
C9B C8B 1.370(13) . ?
C9B H9B 0.9500 . ?
C8A C9A 1.361(11) . ?
C8A C7A 1.368(12) . ?
C8A H8A 0.9500 . ?
C15B H15B 0.9500 . ?
C8B H8B 0.9500 . ?
C11B C12B 1.38(2) . ?
C11B H11B 0.9500 . ?
C12B H12B 0.9500 . ?
C14A H14A 0.9500 . ?
C6B H6B 0.9500 . ?
C9A H9A 0.9500 . ?
C5A H5A 0.9500 . ?
O6C H7C 0.96(2) . ?
O6C H6C 0.97(2) . ?
O7D H7D 0.96(2) . ?
O7D H8D 0.95(2) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C1 O2 H2 113(5) . . ?
C4 O4 H4 105(2) . . ?
H6 O5 H5 105(2) . . ?
C5A N4A C9A 123.7(13) . . ?
C5A N4A C2 115.6(13) . . ?
C9A N4A C2 120.7(14) . . ?
C9B N4B C5B 116.4(16) . . ?
C9B N4B C2 120.8(18) . . ?
C5B N4B C2 122.8(16) . . ?
C12B C13B C14B 121.9(12) . . ?
C12B C13B H13B 119.0 . . ?
C14B C13B H13B 119.0 . . ?
C13B C14B C15B 116.7(11) . . ?
C13B C14B H14B 121.7 . . ?
C15B C14B H14B 121.7 . . ?
C14A C15A C10A 119.0(8) . . ?
C14A C15A H15A 120.5 . . ?
C10A C15A H15A 120.5 . . ?
C11A C10A C15A 119.3(9) . . ?
C11A C10A C7A 121.0(8) . . ?
C15A C10A C7A 119.6(8) . . ?
C10A C11A C12A 120.5(9) . . ?
C10A C11A H11A 119.7 . . ?
C12A C11A H11A 119.7 . . ?
C13A C12A C11A 119.5(9) . . ?
C13A C12A H12A 120.3 . . ?
C11A C12A H12A 120.3 . . ?
C3 C2 N4B 123.8(11) . . ?
C3 C2 N4A 117.9(9) . . ?
C3 C2 C1 123.78(15) . . ?
N4B C2 C1 112.4(11) . . ?
N4A C2 C1 118.2(9) . . ?
O3 C4 O4 125.81(17) . . ?
O3 C4 C3 121.34(17) . . ?
O4 C4 C3 112.84(16) . . ?
O1 C1 O2 127.73(17) . . ?
O1 C1 C2 117.31(16) . . ?
O2 C1 C2 114.96(15) . . ?
C2 C3 C4 125.79(16) . . ?
C2 C3 H3 117.1 . . ?
C4 C3 H3 117.1 . . ?
C5A C6A C7A 120.1(11) . . ?
C5A C6A H6A 120.0 . . ?
C7A C6A H6A 120.0 . . ?
C6B C7B C8B 118.0(11) . . ?
C6B C7B C10B 121.0(11) . . ?
C8B C7B C10B 120.9(9) . . ?
C11B C10B C15B 119.1(9) . . ?
C11B C10B C7B 121.4(9) . . ?
C15B C10B C7B 119.4(8) . . ?
C6B C5B N4B 121.6(13) . . ?
C6B C5B H5B 119.2 . . ?
N4B C5B H5B 119.2 . . ?
C12A C13A C14A 118.8(11) . . ?
C12A C13A H13A 120.6 . . ?
C14A C13A H13A 120.6 . . ?
N4B C9B C8B 124.0(12) . . ?
N4B C9B H9B 118.0 . . ?
C8B C9B H9B 118.0 . . ?
C9A C8A C7A 122.3(8) . . ?
C9A C8A H8A 118.8 . . ?
C7A C8A H8A 118.8 . . ?
C10B C15B C14B 121.4(8) . . ?
C10B C15B H15B 119.3 . . ?
C14B C15B H15B 119.3 . . ?
C9B C8B C7B 119.4(9) . . ?
C9B C8B H8B 120.3 . . ?
C7B C8B H8B 120.3 . . ?
C10B C11B C12B 119.7(10) . . ?
C10B C11B H11B 120.2 . . ?
C12B C11B H11B 120.2 . . ?
C13B C12B C11B 121.0(10) . . ?
C13B C12B H12B 119.5 . . ?
C11B C12B H12B 119.5 . . ?
C15A C14A C13A 122.7(11) . . ?
C15A C14A H14A 118.6 . . ?
C13A C14A H14A 118.6 . . ?
C7B C6B C5B 120.5(12) . . ?
C7B C6B H6B 119.7 . . ?
C5B C6B H6B 119.7 . . ?
C8A C7A C6A 115.8(10) . . ?
C8A C7A C10A 123.6(8) . . ?
C6A C7A C10A 120.6(9) . . ?
N4A C9A C8A 118.1(10) . . ?
N4A C9A H9A 120.9 . . ?
C8A C9A H9A 120.9 . . ?
N4A C5A C6A 120.0(12) . . ?
N4A C5A H5A 120.0 . . ?
C6A C5A H5A 120.0 . . ?
H7C O6C H6C 141(6) . . ?
H7D O7D H8D 119(7) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C12B C13B C14B C15B 4(3) . . . . ?
C14A C15A C10A C11A -1(2) . . . . ?
C14A C15A C10A C7A 177.6(14) . . . . ?
C15A C10A C11A C12A -2(2) . . . . ?
C7A C10A C11A C12A 178.9(14) . . . . ?
C10A C11A C12A C13A 3(2) . . . . ?
C9B N4B C2 C3 -84(2) . . . . ?
C5B N4B C2 C3 94(2) . . . . ?
C9B N4B C2 N4A -34(11) . . . . ?
C5B N4B C2 N4A 145(15) . . . . ?
C9B N4B C2 C1 99(2) . . . . ?
C5B N4B C2 C1 -83(2) . . . . ?
C5A N4A C2 C3 115.9(16) . . . . ?
C9A N4A C2 C3 -65(2) . . . . ?
C5A N4A C2 N4B -17(11) . . . . ?
C9A N4A C2 N4B 161(15) . . . . ?
C5A N4A C2 C1 -68.3(19) . . . . ?
C9A N4A C2 C1 110.6(17) . . . . ?
C3 C2 C1 O1 -4.6(3) . . . . ?
N4B C2 C1 O1 172.6(10) . . . . ?
N4A C2 C1 O1 180.0(9) . . . . ?
C3 C2 C1 O2 175.65(18) . . . . ?
N4B C2 C1 O2 -7.2(11) . . . . ?
N4A C2 C1 O2 0.2(9) . . . . ?
N4B C2 C3 C4 -0.2(12) . . . . ?
N4A C2 C3 C4 -7.9(9) . . . . ?
C1 C2 C3 C4 176.62(17) . . . . ?
O3 C4 C3 C2 -29.6(3) . . . . ?
O4 C4 C3 C2 151.37(18) . . . . ?
C6B C7B C10B C11B 23(2) . . . . ?
C8B C7B C10B C11B -158.6(15) . . . . ?
C6B C7B C10B C15B -158.0(16) . . . . ?
C8B C7B C10B C15B 20(2) . . . . ?
C9B N4B C5B C6B 3(3) . . . . ?
C2 N4B C5B C6B -175.3(18) . . . . ?
C11A C12A C13A C14A -1(2) . . . . ?
C5B N4B C9B C8B -3(3) . . . . ?
C2 N4B C9B C8B 175.4(13) . . . . ?
C11B C10B C15B C14B -1(2) . . . . ?
C7B C10B C15B C14B -179.4(15) . . . . ?
C13B C14B C15B C10B -3(2) . . . . ?
N4B C9B C8B C7B 2.1(19) . . . . ?
C6B C7B C8B C9B -0.9(18) . . . . ?
C10B C7B C8B C9B -178.9(11) . . . . ?
C15B C10B C11B C12B 4(3) . . . . ?
C7B C10B C11B C12B -177.4(16) . . . . ?
C14B C13B C12B C11B 0(3) . . . . ?
C10B C11B C12B C13B -4(3) . . . . ?
C10A C15A C14A C13A 4(2) . . . . ?
C12A C13A C14A C15A -3(3) . . . . ?
C8B C7B C6B C5B 1(2) . . . . ?
C10B C7B C6B C5B 179.1(15) . . . . ?
N4B C5B C6B C7B -2(3) . . . . ?
C9A C8A C7A C6A 0.9(16) . . . . ?
C9A C8A C7A C10A 179.8(11) . . . . ?
C5A C6A C7A C8A -1(2) . . . . ?
C5A C6A C7A C10A 179.9(13) . . . . ?
C11A C10A C7A C8A -169.6(14) . . . . ?
C15A C10A C7A C8A 12(2) . . . . ?
C11A C10A C7A C6A 9(2) . . . . ?
C15A C10A C7A C6A -169.6(15) . . . . ?
C5A N4A C9A C8A -2(3) . . . . ?
C2 N4A C9A C8A 179.6(12) . . . . ?
C7A C8A C9A N4A 0.4(16) . . . . ?
C9A N4A C5A C6A 1(3) . . . . ?
C2 N4A C5A C6A -179.8(14) . . . . ?
C7A C6A C5A N4A 0(2) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C5B H5B O1 0.95 2.26 3.155(15) 157.0 2
C9B H9B O4 0.95 2.60 3.395(9) 141.9 4_545
C9B H9B O5 0.95 2.62 3.336(11) 133.0 .
C9A H9A O1 0.95 2.50 3.392(9) 157.5 4
C9A H9A O5 0.95 2.62 3.171(9) 117.3 .
C5A H5A O1 0.95 2.46 3.392(13) 166.3 2
O4 H4 O2 0.93(5) 1.57(5) 2.461(2) 160(4) 1_565
O5 H6 O3 0.95(3) 1.93(3) 2.843(2) 162(3) 3_545
O5 H5 O1 0.98(3) 1.84(3) 2.811(2) 167(3) 4
O2 H2 O4 0.96(2) 1.51(3) 2.461(2) 168(8) 1_545

_refine_diff_density_max         0.193
_refine_diff_density_min         -0.222
_refine_diff_density_rms         0.047

_shelxl_version_number           2012-9

_database_code_depnum_ccdc_archive 'CCDC 987546'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
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data_6_MeOH

_audit_creation_method           SHELXL-2012
_chemical_name_systematic        
;
(2Z)-3-carboxy-1-hydroxy-2-(4-phenylpyridinium-1-yl)prop-2-en-1-olate 
methanol solvate
;
_chemical_name_common            \6MeOH
_chemical_melting_point          447.15
_chemical_formula_moiety         ?
_chemical_formula_sum            'C16 H15 N O5'
_chemical_formula_weight         301.29

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   13.746(5)
_cell_length_b                   7.408(2)
_cell_length_c                   14.216(5)
_cell_angle_alpha                90
_cell_angle_beta                 90.223(4)
_cell_angle_gamma                90
_cell_volume                     1447.7(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    3116
_cell_measurement_theta_min      2.87
_cell_measurement_theta_max      28.25

_exptl_crystal_description       plate
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.382
_exptl_crystal_F_000             632
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.504
_exptl_crystal_size_mid          0.500
_exptl_crystal_size_min          0.140
_exptl_absorpt_coefficient_mu    0.104
_shelx_estimated_absorpt_T_min   0.950
_shelx_estimated_absorpt_T_max   0.986
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6902
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_process_details   'SADABS, 2012'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area -detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            8666
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_av_R_equivalents  0.0179
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.057
_diffrn_reflns_theta_max         28.403
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.922
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.922
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.922
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3349
_reflns_number_gt                2628
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX2 (Bruker, 2012)'
_computing_cell_refinement       'SAINT (Bruker, 2012)'
_computing_data_reduction        'SAINT (Bruker, 2012)'
_computing_structure_solution    'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_molecular_graphics    
'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)'
_computing_publication_material  ?

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 w=1/[σ²(Fo²)+(0.0452P)²+0.2726P]
 where P=(Fo²+2Fc²)/3
;
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3349
_refine_ls_number_parameters     328
_refine_ls_number_restraints     495
_refine_ls_R_factor_all          0.0495
_refine_ls_R_factor_gt           0.0363
_refine_ls_wR_factor_ref         0.0957
_refine_ls_wR_factor_gt          0.0882
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_restrained_S_all      0.971
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
O1 O 1.24230(6) -0.16615(11) 0.63342(6) 0.0292(2) Uani 1 1 d . U . A 5
O2 O 1.08195(6) -0.13303(11) 0.60835(7) 0.0388(3) Uani 1 1 d . U . . .
O3 O 1.36875(6) 0.45112(11) 0.65905(7) 0.0380(2) Uani 1 1 d . U . . .
O4 O 1.21445(7) 0.50841(12) 0.62246(7) 0.0370(2) Uani 1 1 d . U . B -5
N4 N 1.08862(7) 0.22994(12) 0.64603(6) 0.0215(2) Uani 1 1 d . U . . .
C1 C 1.16305(8) -0.07547(15) 0.62585(8) 0.0250(3) Uani 1 1 d . U . . .
C2 C 1.17752(8) 0.12569(14) 0.63813(7) 0.0208(2) Uani 1 1 d . U . . .
C3 C 1.26372(8) 0.20494(14) 0.63822(8) 0.0221(2) Uani 1 1 d . U . . .
H3 H 1.3184 0.1265 0.6362 0.027 Uiso 1 1 calc R U . . .
C4 C 1.28614(8) 0.40336(15) 0.64106(8) 0.0224(2) Uani 1 1 d . U . . .
C5 C 1.02745(8) 0.24184(15) 0.57190(8) 0.0244(3) Uani 1 1 d . U . . .
H5 H 1.0363 0.1703 0.5171 0.029 Uiso 1 1 calc R U . C 1
C10B C 0.8513(5) 0.5961(11) 0.6433(5) 0.0258(12) Uani 0.517(14) 1 d . U P D 2
C11B C 0.7653(5) 0.5630(11) 0.5948(4) 0.0387(12) Uani 0.517(14) 1 d . U P D 2
H11B H 0.7548 0.4492 0.5657 0.046 Uiso 0.517(14) 1 calc R U P D 2
C12B C 0.6949(5) 0.6963(14) 0.5889(4) 0.0559(16) Uani 0.517(14) 1 d . U P D 2
H12B H 0.6358 0.6736 0.5561 0.067 Uiso 0.517(14) 1 calc R U P D 2
C13B C 0.7106(6) 0.8623(14) 0.6306(4) 0.0564(18) Uani 0.517(14) 1 d . U P D 2
H13B H 0.6627 0.9541 0.6253 0.068 Uiso 0.517(14) 1 calc R U P D 2
C14B C 0.7951(6) 0.8958(10) 0.6799(4) 0.0474(14) Uani 0.517(14) 1 d . U P D 2
H14B H 0.8051 1.0097 0.7091 0.057 Uiso 0.517(14) 1 calc R U P D 2
C15B C 0.8658(5) 0.7618(10) 0.6866(4) 0.0340(11) Uani 0.517(14) 1 d . U P D 2
H15B H 0.9241 0.7838 0.7209 0.041 Uiso 0.517(14) 1 calc R U P D 2
C17D C 0.5518(4) 0.2236(6) 0.5099(4) 0.0391(11) Uani 0.410(4) 1 d . U P E 4
H17A H 0.6192 0.1857 0.4993 0.059 Uiso 0.410(4) 1 calc R U P E 4
H17B H 0.5505 0.3202 0.5570 0.059 Uiso 0.410(4) 1 calc R U P E 4
H17C H 0.5237 0.2680 0.4508 0.059 Uiso 0.410(4) 1 calc R U P E 4
O6C O 0.50498(14) 0.2086(3) 0.58591(14) 0.0451(7) Uani 0.590(4) 1 d . U P E 3
C6A C 0.9471(11) 0.370(2) 0.5796(11) 0.024(2) Uani 0.483(14) 1 d . U P D 1
H6A H 0.9001 0.3753 0.5305 0.029 Uiso 0.483(14) 1 calc R U P D 1
C7A C 0.9372(11) 0.486(2) 0.6586(11) 0.032(2) Uani 0.483(14) 1 d . U P D 1
C8A C 1.0046(13) 0.460(3) 0.7323(12) 0.030(2) Uani 0.483(14) 1 d . U P D 1
H8A H 1.0015 0.5351 0.7861 0.036 Uiso 0.483(14) 1 calc R U P D 1
C9A C 1.0701(10) 0.336(2) 0.7285(10) 0.031(2) Uani 0.483(14) 1 d . U P D 1
H9A H 1.1083 0.3140 0.7831 0.038 Uiso 0.483(14) 1 calc R U P D 1
C10A C 0.8740(6) 0.6389(11) 0.6569(6) 0.0284(13) Uani 0.483(14) 1 d . U P D 1
C11A C 0.7871(5) 0.6258(11) 0.6064(5) 0.0386(13) Uani 0.483(14) 1 d . U P D 1
H11A H 0.7710 0.5166 0.5750 0.046 Uiso 0.483(14) 1 calc R U P D 1
C12A C 0.7235(6) 0.7730(13) 0.6019(5) 0.0509(18) Uani 0.483(14) 1 d . U P D 1
H12A H 0.6634 0.7633 0.5690 0.061 Uiso 0.483(14) 1 calc R U P D 1
C13A C 0.7488(8) 0.9316(12) 0.6455(5) 0.058(2) Uani 0.483(14) 1 d . U P D 1
H13A H 0.7063 1.0324 0.6415 0.070 Uiso 0.483(14) 1 calc R U P D 1
C14A C 0.8345(7) 0.9472(10) 0.6950(5) 0.0526(16) Uani 0.483(14) 1 d . U P D 1
H14A H 0.8508 1.0581 0.7247 0.063 Uiso 0.483(14) 1 calc R U P D 1
C15A C 0.8973(6) 0.8005(9) 0.7014(5) 0.0348(12) Uani 0.483(14) 1 d . U P D 1
H15A H 0.9562 0.8107 0.7362 0.042 Uiso 0.483(14) 1 calc R U P D 1
C16C C 0.5750(4) 0.2966(7) 0.5343(5) 0.097(2) Uani 0.590(4) 1 d . U P E 3
H16A H 0.5456 0.3460 0.4769 0.146 Uiso 0.590(4) 1 calc R U P E 3
H16B H 0.6266 0.2114 0.5175 0.146 Uiso 0.590(4) 1 calc R U P E 3
H16C H 0.6026 0.3952 0.5719 0.146 Uiso 0.590(4) 1 calc R U P E 3
O7D O 0.4995(2) 0.0822(4) 0.54096(19) 0.0485(10) Uani 0.410(4) 1 d D U P E 4
C6B C 0.9544(11) 0.351(2) 0.5691(11) 0.0272(18) Uani 0.517(14) 1 d . U P D 2
H6B H 0.9141 0.3569 0.5147 0.033 Uiso 0.517(14) 1 calc R U P D 2
C7B C 0.9355(9) 0.4588(17) 0.6456(9) 0.0239(16) Uani 0.517(14) 1 d . U P D 2
C8B C 0.9905(11) 0.435(2) 0.7262(11) 0.0256(18) Uani 0.517(14) 1 d . U P D 2
H8B H 0.9739 0.4947 0.7831 0.031 Uiso 0.517(14) 1 calc R U P D 2
C9B C 1.0741(7) 0.3174(19) 0.7212(8) 0.0212(16) Uani 0.517(14) 1 d . U P D 2
H9B H 1.1172 0.3057 0.7732 0.025 Uiso 0.517(14) 1 calc R U P D 2
H2 H 0.471(2) 0.293(4) 0.609(2) 0.057(9) Uiso 0.590(4) 1 d . . P E 3
H1 H 1.237(3) -0.281(6) 0.626(3) 0.052(11) Uiso 0.5 1 d . . P F 5
H7 H 0.474(4) -0.033(5) 0.520(4) 0.10(2) Uiso 0.410(4) 1 d D . P E 4
H4 H 1.230(2) 0.624(5) 0.628(2) 0.031(8) Uiso 0.5 1 d . . P G -5


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1 C1 1.2840(14) . ?
O1 H1 0.86(4) . ?
O2 C1 1.2184(14) . ?
O3 C4 1.2157(14) . ?
O4 C4 1.2825(14) . ?
O4 H4 0.89(4) . ?
N4 C9B 1.266(13) . ?
N4 C5 1.3485(15) . ?
N4 C9A 1.435(15) . ?
N4 C2 1.4503(14) . ?
C1 C2 1.5134(16) . ?
C2 C3 1.3224(16) . ?
C3 C4 1.5024(16) . ?
C3 H3 0.9500 . ?
C5 C6B 1.290(12) . ?
C5 C6A 1.459(13) . ?
C5 H5 0.9500 . ?
C10B C11B 1.387(6) . ?
C10B C15B 1.388(6) . ?
C10B C7B 1.542(12) . ?
C11B C12B 1.385(8) . ?
C11B H11B 0.9500 . ?
C12B C13B 1.382(8) . ?
C12B H12B 0.9500 . ?
C13B C14B 1.376(7) . ?
C13B H13B 0.9500 . ?
C14B C15B 1.393(8) . ?
C14B H14B 0.9500 . ?
C15B H15B 0.9500 . ?
C17D O7D 1.346(5) . ?
C17D H17A 0.9800 . ?
C17D H17B 0.9800 . ?
C17D H17C 0.9800 . ?
O6C C16C 1.376(5) . ?
O6C H2 0.84(3) . ?
C6A C7A 1.421(16) . ?
C6A H6A 0.9500 . ?
C7A C8A 1.41(2) . ?
C7A C10A 1.430(15) . ?
C8A C9A 1.28(2) . ?
C8A H8A 0.9500 . ?
C9A H9A 0.9500 . ?
C10A C15A 1.391(6) . ?
C10A C11A 1.395(7) . ?
C11A C12A 1.399(9) . ?
C11A H11A 0.9500 . ?
C12A C13A 1.373(8) . ?
C12A H12A 0.9500 . ?
C13A C14A 1.375(8) . ?
C13A H13A 0.9500 . ?
C14A C15A 1.391(8) . ?
C14A H14A 0.9500 . ?
C15A H15A 0.9500 . ?
C16C H16A 0.9800 . ?
C16C H16B 0.9800 . ?
C16C H16C 0.9800 . ?
O7D O7D 1.685(6) 3_656 ?
O7D H7 0.97(2) . ?
C6B C7B 1.374(15) . ?
C6B H6B 0.9500 . ?
C7B C8B 1.381(19) . ?
C8B C9B 1.45(2) . ?
C8B H8B 0.9500 . ?
C9B H9B 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C1 O1 H1 116(3) . . ?
C4 O4 H4 113(2) . . ?
C9B N4 C5 121.8(4) . . ?
C5 N4 C9A 119.4(5) . . ?
C9B N4 C2 118.2(4) . . ?
C5 N4 C2 119.82(10) . . ?
C9A N4 C2 120.5(5) . . ?
O2 C1 O1 127.55(11) . . ?
O2 C1 C2 119.20(10) . . ?
O1 C1 C2 113.23(10) . . ?
C3 C2 N4 121.26(10) . . ?
C3 C2 C1 123.68(10) . . ?
N4 C2 C1 115.01(9) . . ?
C2 C3 C4 128.17(10) . . ?
C2 C3 H3 115.9 . . ?
C4 C3 H3 115.9 . . ?
O3 C4 O4 125.67(11) . . ?
O3 C4 C3 118.80(10) . . ?
O4 C4 C3 115.52(10) . . ?
C6B C5 N4 123.2(7) . . ?
N4 C5 C6A 117.0(6) . . ?
N4 C5 H5 121.5 . . ?
C6A C5 H5 121.5 . . ?
C11B C10B C15B 119.9(5) . . ?
C11B C10B C7B 122.2(6) . . ?
C15B C10B C7B 117.9(6) . . ?
C12B C11B C10B 119.8(5) . . ?
C12B C11B H11B 120.1 . . ?
C10B C11B H11B 120.1 . . ?
C13B C12B C11B 120.1(4) . . ?
C13B C12B H12B 120.0 . . ?
C11B C12B H12B 120.0 . . ?
C14B C13B C12B 120.6(5) . . ?
C14B C13B H13B 119.7 . . ?
C12B C13B H13B 119.7 . . ?
C13B C14B C15B 119.6(5) . . ?
C13B C14B H14B 120.2 . . ?
C15B C14B H14B 120.2 . . ?
C10B C15B C14B 120.0(5) . . ?
C10B C15B H15B 120.0 . . ?
C14B C15B H15B 120.0 . . ?
O7D C17D H17A 109.5 . . ?
O7D C17D H17B 109.5 . . ?
H17A C17D H17B 109.5 . . ?
O7D C17D H17C 109.5 . . ?
H17A C17D H17C 109.5 . . ?
H17B C17D H17C 109.5 . . ?
C16C O6C H2 104(2) . . ?
C7A C6A C5 121.8(10) . . ?
C7A C6A H6A 119.1 . . ?
C5 C6A H6A 119.1 . . ?
C8A C7A C6A 116.1(12) . . ?
C8A C7A C10A 121.2(13) . . ?
C6A C7A C10A 121.8(11) . . ?
C9A C8A C7A 121.7(15) . . ?
C9A C8A H8A 119.1 . . ?
C7A C8A H8A 119.1 . . ?
C8A C9A N4 123.4(12) . . ?
C8A C9A H9A 118.3 . . ?
N4 C9A H9A 118.3 . . ?
C15A C10A C11A 119.3(6) . . ?
C15A C10A C7A 122.5(8) . . ?
C11A C10A C7A 118.2(8) . . ?
C10A C11A C12A 120.2(5) . . ?
C10A C11A H11A 119.9 . . ?
C12A C11A H11A 119.9 . . ?
C13A C12A C11A 119.3(5) . . ?
C13A C12A H12A 120.4 . . ?
C11A C12A H12A 120.4 . . ?
C12A C13A C14A 121.2(5) . . ?
C12A C13A H13A 119.4 . . ?
C14A C13A H13A 119.4 . . ?
C13A C14A C15A 119.9(5) . . ?
C13A C14A H14A 120.1 . . ?
C15A C14A H14A 120.1 . . ?
C10A C15A C14A 120.1(5) . . ?
C10A C15A H15A 120.0 . . ?
C14A C15A H15A 120.0 . . ?
O6C C16C H16A 109.5 . . ?
O6C C16C H16B 109.5 . . ?
H16A C16C H16B 109.5 . . ?
O6C C16C H16C 109.5 . . ?
H16A C16C H16C 109.5 . . ?
H16B C16C H16C 109.5 . . ?
C17D O7D O7D 109.3(3) . 3_656 ?
C17D O7D H7 141(4) . . ?
O7D O7D H7 32(4) 3_656 . ?
C5 C6B C7B 119.3(11) . . ?
C5 C6B H6B 120.4 . . ?
C7B C6B H6B 120.4 . . ?
C6B C7B C8B 118.6(11) . . ?
C6B C7B C10B 120.7(9) . . ?
C8B C7B C10B 120.6(11) . . ?
C7B C8B C9B 117.9(12) . . ?
C7B C8B H8B 121.0 . . ?
C9B C8B H8B 121.0 . . ?
N4 C9B C8B 118.6(9) . . ?
N4 C9B H9B 120.7 . . ?
C8B C9B H9B 120.7 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C9B N4 C2 C3 -64.1(7) . . . . ?
C5 N4 C2 C3 111.32(13) . . . . ?
C9A N4 C2 C3 -62.0(8) . . . . ?
C9B N4 C2 C1 118.4(7) . . . . ?
C5 N4 C2 C1 -66.19(13) . . . . ?
C9A N4 C2 C1 120.4(8) . . . . ?
O2 C1 C2 C3 -165.80(12) . . . . ?
O1 C1 C2 C3 12.52(16) . . . . ?
O2 C1 C2 N4 11.65(16) . . . . ?
O1 C1 C2 N4 -170.04(9) . . . . ?
N4 C2 C3 C4 -3.31(18) . . . . ?
C1 C2 C3 C4 173.99(10) . . . . ?
C2 C3 C4 O3 165.83(12) . . . . ?
C2 C3 C4 O4 -15.12(18) . . . . ?
C9B N4 C5 C6B 5.1(12) . . . . ?
C9A N4 C5 C6B 3.3(13) . . . . ?
C2 N4 C5 C6B -170.2(10) . . . . ?
C9B N4 C5 C6A 4.1(11) . . . . ?
C9A N4 C5 C6A 2.3(12) . . . . ?
C2 N4 C5 C6A -171.2(8) . . . . ?
C15B C10B C11B C12B 0.8(10) . . . . ?
C7B C10B C11B C12B -175.0(8) . . . . ?
C10B C11B C12B C13B 0.5(9) . . . . ?
C11B C12B C13B C14B -1.3(9) . . . . ?
C12B C13B C14B C15B 0.8(9) . . . . ?
C11B C10B C15B C14B -1.3(10) . . . . ?
C7B C10B C15B C14B 174.7(7) . . . . ?
C13B C14B C15B C10B 0.5(9) . . . . ?
C6B C5 C6A C7A -168(15) . . . . ?
N4 C5 C6A C7A 4.3(19) . . . . ?
C5 C6A C7A C8A -5(2) . . . . ?
C5 C6A C7A C10A 164.6(13) . . . . ?
C6A C7A C8A C9A -1(3) . . . . ?
C10A C7A C8A C9A -170.8(16) . . . . ?
C7A C8A C9A N4 8(3) . . . . ?
C9B N4 C9A C8A -157(26) . . . . ?
C5 N4 C9A C8A -9(2) . . . . ?
C2 N4 C9A C8A 164.7(14) . . . . ?
C8A C7A C10A C15A 26(2) . . . . ?
C6A C7A C10A C15A -143.3(14) . . . . ?
C8A C7A C10A C11A -155.8(13) . . . . ?
C6A C7A C10A C11A 35.0(19) . . . . ?
C15A C10A C11A C12A -1.0(11) . . . . ?
C7A C10A C11A C12A -179.3(9) . . . . ?
C10A C11A C12A C13A 1.7(10) . . . . ?
C11A C12A C13A C14A -1.3(9) . . . . ?
C12A C13A C14A C15A 0.0(9) . . . . ?
C11A C10A C15A C14A -0.3(10) . . . . ?
C7A C10A C15A C14A 177.9(9) . . . . ?
C13A C14A C15A C10A 0.8(9) . . . . ?
N4 C5 C6B C7B -2(2) . . . . ?
C6A C5 C6B C7B 7(13) . . . . ?
C5 C6B C7B C8B -6(2) . . . . ?
C5 C6B C7B C10B 177.6(12) . . . . ?
C11B C10B C7B C6B 33.9(17) . . . . ?
C15B C10B C7B C6B -142.0(13) . . . . ?
C11B C10B C7B C8B -142.9(12) . . . . ?
C15B C10B C7B C8B 41.2(16) . . . . ?
C6B C7B C8B C9B 9(2) . . . . ?
C10B C7B C8B C9B -174.2(12) . . . . ?
C5 N4 C9B C8B -1.2(15) . . . . ?
C9A N4 C9B C8B 32(23) . . . . ?
C2 N4 C9B C8B 174.1(10) . . . . ?
C7B C8B C9B N4 -6(2) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C5 H5 O2 0.95 2.42 3.0736(16) 125.4 3_756
C6B H6B O2 0.95 2.41 3.035(16) 122.9 3_756
O6C H2 O3 0.84(3) 1.97(3) 2.798(2) 167(3) 1_455
O1 H1 O4 0.86(4) 1.59(4) 2.4459(14) 171(4) 1_545

_refine_diff_density_max         0.248
_refine_diff_density_min         -0.179
_refine_diff_density_rms         0.035

_shelxl_version_number           2012-9

_database_code_depnum_ccdc_archive 'CCDC 987547'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
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#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_6a

_audit_creation_method           SHELXL-2012
_chemical_name_systematic        
;
bis(4-phenylpyridinium) carboxy-propynoate methanol solvate
;
_chemical_name_common            \6a
_chemical_melting_point          378
_chemical_formula_moiety         '2(C11 H10 N), C4 O4, C H4 O'
_chemical_formula_sum            'C27 H24 N2 O5'
_chemical_formula_weight         456.48

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   16.831(7)
_cell_length_b                   7.267(3)
_cell_length_c                   20.065(8)
_cell_angle_alpha                90
_cell_angle_beta                 110.560(6)
_cell_angle_gamma                90
_cell_volume                     2297.8(16)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    1950
_cell_measurement_theta_min      2.59
_cell_measurement_theta_max      26.73

_exptl_crystal_description       shard
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_F_000             960
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.352
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.151
_exptl_absorpt_coefficient_mu    0.092
_shelx_estimated_absorpt_T_min   0.968
_shelx_estimated_absorpt_T_max   0.986
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.9303
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   'SADABS, 2012'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area -detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            13887
_diffrn_reflns_av_unetI/netI     0.0716
_diffrn_reflns_av_R_equivalents  0.0535
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         1.957
_diffrn_reflns_theta_max         27.572
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             5190
_reflns_number_gt                3043
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX2 (Bruker, 2012)'
_computing_cell_refinement       'SAINT (Bruker, 2012)'
_computing_data_reduction        'SAINT (Bruker, 2012)'
_computing_structure_solution    'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_molecular_graphics    
'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)'
_computing_publication_material  ?

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 w=1/[σ²(Fo²)+(0.0625P)²]
 where P=(Fo²+2Fc²)/3
;
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         5190
_refine_ls_number_parameters     320
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1013
_refine_ls_R_factor_gt           0.0532
_refine_ls_wR_factor_ref         0.1408
_refine_ls_wR_factor_gt          0.1166
_refine_ls_goodness_of_fit_ref   0.976
_refine_ls_restrained_S_all      0.976
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
N1B N 0.41375(11) 0.5571(2) 0.36306(9) 0.0201(4) Uani 1 1 d . . . . .
C2B C 0.34684(13) 0.5908(3) 0.38265(11) 0.0215(5) Uani 1 1 d . . . . .
H2B H 0.3556 0.6161 0.4312 0.026 Uiso 1 1 calc R U . . .
C3B C 0.26523(12) 0.5892(3) 0.33340(10) 0.0197(5) Uani 1 1 d . . . . .
H3B H 0.2183 0.6135 0.3479 0.024 Uiso 1 1 calc R U . . .
C4B C 0.25240(12) 0.5519(3) 0.26228(10) 0.0166(4) Uani 1 1 d . . . . .
C5B C 0.32389(12) 0.5174(3) 0.24360(11) 0.0197(5) Uani 1 1 d . . . . .
H5B H 0.3174 0.4909 0.1956 0.024 Uiso 1 1 calc R U . . .
C6B C 0.40339(13) 0.5222(3) 0.29522(11) 0.0216(5) Uani 1 1 d . . . . .
H6B H 0.4518 0.5002 0.2824 0.026 Uiso 1 1 calc R U . . .
C7B C 0.16554(12) 0.5512(3) 0.20738(10) 0.0174(4) Uani 1 1 d . . . . .
C8B C 0.09565(13) 0.4962(3) 0.22459(11) 0.0219(5) Uani 1 1 d . . . . .
H8B H 0.1034 0.4551 0.2714 0.026 Uiso 1 1 calc R U . . .
O1A O 0.60453(8) 0.5962(2) 0.36200(7) 0.0270(4) Uani 1 1 d . . . . .
O2A O 0.56646(9) 0.5591(2) 0.45742(7) 0.0269(4) Uani 1 1 d . . . . .
O3A O 0.92226(9) 0.5675(2) 0.54680(7) 0.0263(4) Uani 1 1 d . . . . .
O4A O 0.88422(9) 0.7807(2) 0.61045(8) 0.0306(4) Uani 1 1 d . . . . .
C1A C 0.61898(12) 0.5906(3) 0.42678(11) 0.0200(5) Uani 1 1 d . . . . .
C2A C 0.70764(13) 0.6215(3) 0.47538(11) 0.0193(5) Uani 1 1 d . . . . .
C3A C 0.77944(13) 0.6412(3) 0.51401(10) 0.0196(5) Uani 1 1 d . . . . .
C4A C 0.86915(13) 0.6659(3) 0.56125(11) 0.0200(5) Uani 1 1 d . . . . .
C9B C 0.01473(13) 0.5014(3) 0.17334(11) 0.0275(5) Uani 1 1 d . . . . .
H9B H -0.0326 0.4623 0.1851 0.033 Uiso 1 1 calc R U . . .
C10B C 0.00264(14) 0.5631(3) 0.10530(12) 0.0290(5) Uani 1 1 d . . . . .
H10B H -0.0530 0.5680 0.0707 0.035 Uiso 1 1 calc R U . . .
C11B C 0.07150(13) 0.6176(3) 0.08748(11) 0.0249(5) Uani 1 1 d . . . . .
H11B H 0.0632 0.6598 0.0407 0.030 Uiso 1 1 calc R U . . .
C12B C 0.15263(13) 0.6104(3) 0.13816(10) 0.0215(5) Uani 1 1 d . . . . .
H12B H 0.1998 0.6462 0.1256 0.026 Uiso 1 1 calc R U . . .
N1C N 0.92249(11) 0.3616(2) 0.36884(9) 0.0197(4) Uani 1 1 d . . . . .
C2C C 0.85482(12) 0.4089(3) 0.38614(11) 0.0197(5) Uani 1 1 d . . . . .
H2C H 0.8627 0.4498 0.4330 0.024 Uiso 1 1 calc R U . . .
C3C C 0.77384(13) 0.3983(3) 0.33597(10) 0.0193(5) Uani 1 1 d . . . . .
H3C H 0.7263 0.4299 0.3487 0.023 Uiso 1 1 calc R U . . .
C4C C 0.76176(12) 0.3416(3) 0.26682(10) 0.0179(4) Uani 1 1 d . . . . .
C5C C 0.83379(12) 0.2908(3) 0.25139(10) 0.0184(4) Uani 1 1 d . . . . .
H5C H 0.8280 0.2494 0.2050 0.022 Uiso 1 1 calc R U . . .
C6C C 0.91301(13) 0.3010(3) 0.30366(10) 0.0202(5) Uani 1 1 d . . . . .
H6C H 0.9615 0.2644 0.2932 0.024 Uiso 1 1 calc R U . . .
C7C C 0.67639(12) 0.3394(3) 0.21016(10) 0.0179(4) Uani 1 1 d . . . . .
C8C C 0.60409(12) 0.2990(3) 0.22673(11) 0.0214(5) Uani 1 1 d . . . . .
H8C H 0.6093 0.2723 0.2744 0.026 Uiso 1 1 calc R U . . .
C9C C 0.52458(13) 0.2982(3) 0.17315(11) 0.0261(5) Uani 1 1 d . . . . .
H9C H 0.4756 0.2697 0.1844 0.031 Uiso 1 1 calc R U . . .
C10C C 0.51632(14) 0.3384(3) 0.10378(12) 0.0272(5) Uani 1 1 d . . . . .
H10C H 0.4619 0.3368 0.0674 0.033 Uiso 1 1 calc R U . . .
C11C C 0.58742(14) 0.3812(3) 0.08706(11) 0.0258(5) Uani 1 1 d . . . . .
H11C H 0.5816 0.4113 0.0395 0.031 Uiso 1 1 calc R U . . .
C12C C 0.66726(13) 0.3799(3) 0.14008(11) 0.0225(5) Uani 1 1 d . . . . .
H12C H 0.7160 0.4070 0.1283 0.027 Uiso 1 1 calc R U . . .
O1D O 0.80710(11) 0.1192(2) 0.57715(9) 0.0391(5) Uani 1 1 d . . . . .
C2D C 0.75466(16) 0.1273(3) 0.50541(13) 0.0476(7) Uani 1 1 d . . . . .
H2D1 H 0.7258 0.2467 0.4956 0.071 Uiso 1 1 calc R U . . .
H2D2 H 0.7124 0.0286 0.4952 0.071 Uiso 1 1 calc R U . . .
H2D3 H 0.7891 0.1123 0.4753 0.071 Uiso 1 1 calc R U . . .
H1 H 0.4773(19) 0.558(4) 0.4013(15) 0.072(9) Uiso 1 1 d . . . . .
H2 H 0.9880(18) 0.381(4) 0.4048(14) 0.069(9) Uiso 1 1 d . . . . .
H3 H 0.833(2) -0.004(5) 0.5887(16) 0.093(12) Uiso 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
N1B C6B 1.335(3) . ?
N1B C2B 1.339(3) . ?
N1B H1 1.08(3) . ?
C2B C3B 1.382(3) . ?
C2B H2B 0.9500 . ?
C3B C4B 1.393(3) . ?
C3B H3B 0.9500 . ?
C4B C5B 1.403(3) . ?
C4B C7B 1.490(3) . ?
C5B C6B 1.375(3) . ?
C5B H5B 0.9500 . ?
C6B H6B 0.9500 . ?
C7B C8B 1.396(3) . ?
C7B C12B 1.396(3) . ?
C8B C9B 1.389(3) . ?
C8B H8B 0.9500 . ?
O1A C1A 1.236(2) . ?
O2A C1A 1.262(2) . ?
O3A C4A 1.256(2) . ?
O4A C4A 1.248(2) . ?
C1A C2A 1.485(3) . ?
C2A C3A 1.193(3) . ?
C3A C4A 1.485(3) . ?
C9B C10B 1.382(3) . ?
C9B H9B 0.9500 . ?
C10B C11B 1.385(3) . ?
C10B H10B 0.9500 . ?
C11B C12B 1.388(3) . ?
C11B H11B 0.9500 . ?
C12B H12B 0.9500 . ?
N1C C6C 1.335(2) . ?
N1C C2C 1.347(3) . ?
N1C H2 1.09(3) . ?
C2C C3C 1.383(3) . ?
C2C H2C 0.9500 . ?
C3C C4C 1.392(3) . ?
C3C H3C 0.9500 . ?
C4C C5C 1.402(3) . ?
C4C C7C 1.487(3) . ?
C5C C6C 1.379(3) . ?
C5C H5C 0.9500 . ?
C6C H6C 0.9500 . ?
C7C C12C 1.391(3) . ?
C7C C8C 1.401(3) . ?
C8C C9C 1.392(3) . ?
C8C H8C 0.9500 . ?
C9C C10C 1.381(3) . ?
C9C H9C 0.9500 . ?
C10C C11C 1.387(3) . ?
C10C H10C 0.9500 . ?
C11C C12C 1.391(3) . ?
C11C H11C 0.9500 . ?
C12C H12C 0.9500 . ?
O1D C2D 1.401(3) . ?
O1D H3 0.98(3) . ?
C2D H2D1 0.9800 . ?
C2D H2D2 0.9800 . ?
C2D H2D3 0.9800 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C6B N1B C2B 120.79(18) . . ?
C6B N1B H1 118.0(15) . . ?
C2B N1B H1 121.2(15) . . ?
N1B C2B C3B 121.0(2) . . ?
N1B C2B H2B 119.5 . . ?
C3B C2B H2B 119.5 . . ?
C2B C3B C4B 119.45(19) . . ?
C2B C3B H3B 120.3 . . ?
C4B C3B H3B 120.3 . . ?
C3B C4B C5B 118.01(18) . . ?
C3B C4B C7B 121.13(18) . . ?
C5B C4B C7B 120.85(18) . . ?
C6B C5B C4B 119.56(19) . . ?
C6B C5B H5B 120.2 . . ?
C4B C5B H5B 120.2 . . ?
N1B C6B C5B 121.13(19) . . ?
N1B C6B H6B 119.4 . . ?
C5B C6B H6B 119.4 . . ?
C8B C7B C12B 118.97(18) . . ?
C8B C7B C4B 120.75(18) . . ?
C12B C7B C4B 120.26(18) . . ?
C9B C8B C7B 120.1(2) . . ?
C9B C8B H8B 120.0 . . ?
C7B C8B H8B 120.0 . . ?
O1A C1A O2A 127.25(19) . . ?
O1A C1A C2A 117.81(18) . . ?
O2A C1A C2A 114.93(18) . . ?
C3A C2A C1A 178.1(2) . . ?
C2A C3A C4A 179.2(2) . . ?
O4A C4A O3A 126.86(19) . . ?
O4A C4A C3A 117.66(18) . . ?
O3A C4A C3A 115.48(18) . . ?
C10B C9B C8B 120.4(2) . . ?
C10B C9B H9B 119.8 . . ?
C8B C9B H9B 119.8 . . ?
C9B C10B C11B 120.1(2) . . ?
C9B C10B H10B 120.0 . . ?
C11B C10B H10B 120.0 . . ?
C10B C11B C12B 119.8(2) . . ?
C10B C11B H11B 120.1 . . ?
C12B C11B H11B 120.1 . . ?
C11B C12B C7B 120.6(2) . . ?
C11B C12B H12B 119.7 . . ?
C7B C12B H12B 119.7 . . ?
C6C N1C C2C 121.05(17) . . ?
C6C N1C H2 115.8(14) . . ?
C2C N1C H2 123.0(14) . . ?
N1C C2C C3C 120.30(19) . . ?
N1C C2C H2C 119.9 . . ?
C3C C2C H2C 119.9 . . ?
C2C C3C C4C 120.23(19) . . ?
C2C C3C H3C 119.9 . . ?
C4C C3C H3C 119.9 . . ?
C3C C4C C5C 117.59(18) . . ?
C3C C4C C7C 121.93(18) . . ?
C5C C4C C7C 120.45(19) . . ?
C6C C5C C4C 119.87(19) . . ?
C6C C5C H5C 120.1 . . ?
C4C C5C H5C 120.1 . . ?
N1C C6C C5C 120.92(19) . . ?
N1C C6C H6C 119.5 . . ?
C5C C6C H6C 119.5 . . ?
C12C C7C C8C 119.18(18) . . ?
C12C C7C C4C 120.31(19) . . ?
C8C C7C C4C 120.51(19) . . ?
C9C C8C C7C 119.8(2) . . ?
C9C C8C H8C 120.1 . . ?
C7C C8C H8C 120.1 . . ?
C10C C9C C8C 120.5(2) . . ?
C10C C9C H9C 119.8 . . ?
C8C C9C H9C 119.8 . . ?
C9C C10C C11C 120.09(19) . . ?
C9C C10C H10C 120.0 . . ?
C11C C10C H10C 120.0 . . ?
C10C C11C C12C 119.9(2) . . ?
C10C C11C H11C 120.1 . . ?
C12C C11C H11C 120.1 . . ?
C11C C12C C7C 120.6(2) . . ?
C11C C12C H12C 119.7 . . ?
C7C C12C H12C 119.7 . . ?
C2D O1D H3 110.4(18) . . ?
O1D C2D H2D1 109.5 . . ?
O1D C2D H2D2 109.5 . . ?
H2D1 C2D H2D2 109.5 . . ?
O1D C2D H2D3 109.5 . . ?
H2D1 C2D H2D3 109.5 . . ?
H2D2 C2D H2D3 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C6B N1B C2B C3B 0.4(3) . . . . ?
N1B C2B C3B C4B 0.1(3) . . . . ?
C2B C3B C4B C5B -0.1(3) . . . . ?
C2B C3B C4B C7B -179.24(17) . . . . ?
C3B C4B C5B C6B -0.3(3) . . . . ?
C7B C4B C5B C6B 178.85(18) . . . . ?
C2B N1B C6B C5B -0.8(3) . . . . ?
C4B C5B C6B N1B 0.7(3) . . . . ?
C3B C4B C7B C8B -32.4(3) . . . . ?
C5B C4B C7B C8B 148.5(2) . . . . ?
C3B C4B C7B C12B 145.9(2) . . . . ?
C5B C4B C7B C12B -33.2(3) . . . . ?
C12B C7B C8B C9B -0.2(3) . . . . ?
C4B C7B C8B C9B 178.11(18) . . . . ?
C7B C8B C9B C10B -0.8(3) . . . . ?
C8B C9B C10B C11B 1.0(3) . . . . ?
C9B C10B C11B C12B -0.1(3) . . . . ?
C10B C11B C12B C7B -0.9(3) . . . . ?
C8B C7B C12B C11B 1.1(3) . . . . ?
C4B C7B C12B C11B -177.26(17) . . . . ?
C6C N1C C2C C3C -1.1(3) . . . . ?
N1C C2C C3C C4C -1.1(3) . . . . ?
C2C C3C C4C C5C 2.1(3) . . . . ?
C2C C3C C4C C7C -176.10(18) . . . . ?
C3C C4C C5C C6C -1.0(3) . . . . ?
C7C C4C C5C C6C 177.19(18) . . . . ?
C2C N1C C6C C5C 2.2(3) . . . . ?
C4C C5C C6C N1C -1.1(3) . . . . ?
C3C C4C C7C C12C 145.4(2) . . . . ?
C5C C4C C7C C12C -32.7(3) . . . . ?
C3C C4C C7C C8C -33.8(3) . . . . ?
C5C C4C C7C C8C 148.1(2) . . . . ?
C12C C7C C8C C9C 0.6(3) . . . . ?
C4C C7C C8C C9C 179.79(18) . . . . ?
C7C C8C C9C C10C -0.5(3) . . . . ?
C8C C9C C10C C11C -0.4(3) . . . . ?
C9C C10C C11C C12C 1.3(3) . . . . ?
C10C C11C C12C C7C -1.2(3) . . . . ?
C8C C7C C12C C11C 0.3(3) . . . . ?
C4C C7C C12C C11C -178.92(18) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C2B H2B O2A 0.95 2.51 3.213(3) 131.3 3_666
C3B H3B O1D 0.95 2.58 3.276(3) 130.1 3_666
C5B H5B O1D 0.95 2.46 3.399(3) 172.3 4_565
C6B H6B O1A 0.95 2.60 3.219(3) 123.0 .
C2C H2C O3A 0.95 2.31 3.231(3) 162.8 .
C3C H3C O1A 0.95 2.47 3.392(3) 162.8 .
C5C H5C O1A 0.95 2.33 3.148(3) 144.6 2_645
C6C H6C O4A 0.95 2.66 3.292(3) 124.7 3_766
N1B H1 O1A 1.08(3) 2.54(3) 3.231(3) 120.9(19) .
N1B H1 O2A 1.08(3) 1.53(3) 2.603(2) 178(3) .
N1C H2 O3A 1.09(3) 1.53(3) 2.618(2) 173(2) 3_766
N1C H2 O4A 1.09(3) 2.56(3) 3.298(3) 123.8(18) 3_766
O1D H3 O4A 0.98(3) 1.77(3) 2.752(2) 178(3) 1_545

_refine_diff_density_max         0.285
_refine_diff_density_min         -0.282
_refine_diff_density_rms         0.058

_shelxl_version_number           2012-9

_database_code_depnum_ccdc_archive 'CCDC 987548'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_7

_audit_creation_method           SHELXL-2012
_chemical_name_systematic        
(2Z)-2-(4-benzylpyridinium-1-yl-3-carboxy-1-hydroxyprop-2-en-1-olate
_chemical_name_common            \7
_chemical_melting_point          451.15
_chemical_formula_moiety         'C16 H13 N O4'
_chemical_formula_sum            'C16 H13 N O4'
_chemical_formula_weight         283.27

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'x+1/2, -y+1/2, -z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'-x-1/2, y-1/2, z'
'x, -y-1/2, z-1/2'

_cell_length_a                   15.1432(11)
_cell_length_b                   7.6866(5)
_cell_length_c                   22.3032(16)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2596.1(3)
_cell_formula_units_Z            8
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    6097
_cell_measurement_theta_min      2.69
_cell_measurement_theta_max      28.32

_exptl_crystal_description       plate
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.450
_exptl_crystal_F_000             1184
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.539
_exptl_crystal_size_mid          0.478
_exptl_crystal_size_min          0.184
_exptl_absorpt_coefficient_mu    0.105
_shelx_estimated_absorpt_T_min   0.945
_shelx_estimated_absorpt_T_max   0.981
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.943
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   'SADABS, 2012'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD area -detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            15206
_diffrn_reflns_av_unetI/netI     0.0172
_diffrn_reflns_av_R_equivalents  0.0222
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_theta_min         1.826
_diffrn_reflns_theta_max         28.410
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.939
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.939
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             3070
_reflns_number_gt                2711
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX2 (Bruker, 2012)'
_computing_cell_refinement       'SAINT (Bruker, 2012)'
_computing_data_reduction        'SAINT (Bruker, 2012)'
_computing_structure_solution    'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_molecular_graphics    
'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)'
_computing_publication_material  ?

_refine_special_details          
;
 The acidic proton was located using electron density maps and was confirmed
 by measuring the C-O bond distances. 
 [∼ 1.2 Å = C\\dbO; ∼ 1.3 Å = C---O]
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 w=1/[σ²(Fo²)+(0.0514P)²+1.2424P]
 where P=(Fo²+2Fc²)/3
;
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3070
_refine_ls_number_parameters     194
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0430
_refine_ls_R_factor_gt           0.0379
_refine_ls_wR_factor_ref         0.1011
_refine_ls_wR_factor_gt          0.0973
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_restrained_S_all      1.019
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
O1 O 0.15372(6) 0.75171(11) 0.31179(4) 0.0187(2) Uani 1 1 d . . . . .
N1 N 0.13438(6) 0.37364(12) 0.21570(4) 0.0147(2) Uani 1 1 d . . . . .
C1 C 0.13294(7) 0.66238(15) 0.26634(5) 0.0159(2) Uani 1 1 d . . . . .
O2 O 0.10528(6) 0.71486(11) 0.21743(4) 0.0211(2) Uani 1 1 d . . . . .
C2 C 0.14133(8) 0.46411(15) 0.27273(5) 0.0164(2) Uani 1 1 d . . . . .
O3 O 0.15941(7) 0.13929(13) 0.38812(4) 0.0274(2) Uani 1 1 d . . . . .
C3 C 0.15005(8) 0.38034(16) 0.32434(6) 0.0188(3) Uani 1 1 d . . . . .
H3 H 0.1550 0.4528 0.3587 0.023 Uiso 1 1 calc R U . . .
O4 O 0.14774(6) 0.08571(12) 0.28947(4) 0.0199(2) Uani 1 1 d . . . . .
C4 C 0.15330(8) 0.18854(16) 0.33684(5) 0.0181(2) Uani 1 1 d . . . . .
H4 H 0.1497(13) -0.027(3) 0.3015(9) 0.053(6) Uiso 1 1 d . . . . .
C5 C 0.05378(8) 0.33535(16) 0.19418(5) 0.0176(2) Uani 1 1 d . . . . .
H5 H 0.0029 0.3567 0.2179 0.021 Uiso 1 1 calc R U . . .
C6 C 0.04498(8) 0.26514(16) 0.13767(5) 0.0186(2) Uani 1 1 d . . . . .
H6 H -0.0120 0.2379 0.1226 0.022 Uiso 1 1 calc R U . . .
C7 C 0.11945(8) 0.23391(15) 0.10258(5) 0.0164(2) Uani 1 1 d . . . . .
C8 C 0.20195(8) 0.27272(16) 0.12691(5) 0.0185(2) Uani 1 1 d . . . . .
H8 H 0.2540 0.2494 0.1046 0.022 Uiso 1 1 calc R U . . .
C9 C 0.20809(8) 0.34471(16) 0.18320(5) 0.0182(2) Uani 1 1 d . . . . .
H9 H 0.2643 0.3741 0.1992 0.022 Uiso 1 1 calc R U . . .
C10 C 0.11112(9) 0.16719(16) 0.03935(5) 0.0194(3) Uani 1 1 d . . . . .
H10A H 0.1594 0.2179 0.0150 0.023 Uiso 1 1 calc R U . . .
H10B H 0.0546 0.2095 0.0225 0.023 Uiso 1 1 calc R U . . .
C11 C 0.11418(8) -0.02865(15) 0.03288(5) 0.0167(2) Uani 1 1 d . . . . .
C12 C 0.15661(8) -0.09767(17) -0.01737(5) 0.0195(3) Uani 1 1 d . . . . .
H12 H 0.1881 -0.0227 -0.0436 0.023 Uiso 1 1 calc R U . . .
C13 C 0.15321(9) -0.27456(17) -0.02937(6) 0.0233(3) Uani 1 1 d . . . . .
H13 H 0.1812 -0.3203 -0.0641 0.028 Uiso 1 1 calc R U . . .
C14 C 0.10866(9) -0.38416(17) 0.00957(6) 0.0263(3) Uani 1 1 d . . . . .
H14 H 0.1051 -0.5051 0.0011 0.032 Uiso 1 1 calc R U . . .
C15 C 0.06918(9) -0.31778(17) 0.06089(6) 0.0250(3) Uani 1 1 d . . . . .
H15 H 0.0405 -0.3941 0.0882 0.030 Uiso 1 1 calc R U . . .
C16 C 0.07141(8) -0.14018(16) 0.07249(5) 0.0201(3) Uani 1 1 d . . . . .
H16 H 0.0438 -0.0950 0.1074 0.024 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1 C1 1.2642(15) . ?
N1 C5 1.3441(15) . ?
N1 C9 1.3494(15) . ?
N1 C2 1.4534(14) . ?
C1 O2 1.2361(15) . ?
C1 C2 1.5359(16) . ?
C2 C3 1.3256(17) . ?
O3 C4 1.2082(15) . ?
C3 C4 1.5013(17) . ?
C3 H3 0.9500 . ?
O4 C4 1.3221(15) . ?
O4 H4 0.91(2) . ?
C5 C6 1.3774(16) . ?
C5 H5 0.9500 . ?
C6 C7 1.3935(17) . ?
C6 H6 0.9500 . ?
C7 C8 1.3944(17) . ?
C7 C10 1.5057(16) . ?
C8 C9 1.3752(17) . ?
C8 H8 0.9500 . ?
C9 H9 0.9500 . ?
C10 C11 1.5130(17) . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C11 C16 1.3909(17) . ?
C11 C12 1.3966(17) . ?
C12 C13 1.3867(18) . ?
C12 H12 0.9500 . ?
C13 C14 1.385(2) . ?
C13 H13 0.9500 . ?
C14 C15 1.388(2) . ?
C14 H14 0.9500 . ?
C15 C16 1.3899(18) . ?
C15 H15 0.9500 . ?
C16 H16 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C5 N1 C9 121.54(10) . . ?
C5 N1 C2 118.89(10) . . ?
C9 N1 C2 119.28(10) . . ?
O2 C1 O1 127.93(11) . . ?
O2 C1 C2 115.70(10) . . ?
O1 C1 C2 116.35(10) . . ?
C3 C2 N1 122.33(11) . . ?
C3 C2 C1 124.81(11) . . ?
N1 C2 C1 112.80(10) . . ?
C2 C3 C4 129.91(11) . . ?
C2 C3 H3 115.0 . . ?
C4 C3 H3 115.0 . . ?
C4 O4 H4 109.5(13) . . ?
O3 C4 O4 125.03(12) . . ?
O3 C4 C3 119.07(11) . . ?
O4 C4 C3 115.89(10) . . ?
N1 C5 C6 120.03(11) . . ?
N1 C5 H5 120.0 . . ?
C6 C5 H5 120.0 . . ?
C5 C6 C7 120.20(11) . . ?
C5 C6 H6 119.9 . . ?
C7 C6 H6 119.9 . . ?
C6 C7 C8 118.01(11) . . ?
C6 C7 C10 121.13(11) . . ?
C8 C7 C10 120.82(11) . . ?
C9 C8 C7 120.13(11) . . ?
C9 C8 H8 119.9 . . ?
C7 C8 H8 119.9 . . ?
N1 C9 C8 120.06(11) . . ?
N1 C9 H9 120.0 . . ?
C8 C9 H9 120.0 . . ?
C7 C10 C11 115.19(10) . . ?
C7 C10 H10A 108.5 . . ?
C11 C10 H10A 108.5 . . ?
C7 C10 H10B 108.5 . . ?
C11 C10 H10B 108.5 . . ?
H10A C10 H10B 107.5 . . ?
C16 C11 C12 119.33(11) . . ?
C16 C11 C10 122.57(11) . . ?
C12 C11 C10 117.94(11) . . ?
C13 C12 C11 120.69(12) . . ?
C13 C12 H12 119.7 . . ?
C11 C12 H12 119.7 . . ?
C14 C13 C12 119.55(12) . . ?
C14 C13 H13 120.2 . . ?
C12 C13 H13 120.2 . . ?
C13 C14 C15 120.20(12) . . ?
C13 C14 H14 119.9 . . ?
C15 C14 H14 119.9 . . ?
C14 C15 C16 120.26(12) . . ?
C14 C15 H15 119.9 . . ?
C16 C15 H15 119.9 . . ?
C15 C16 C11 119.90(12) . . ?
C15 C16 H16 120.1 . . ?
C11 C16 H16 120.1 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C5 N1 C2 C3 92.78(14) . . . . ?
C9 N1 C2 C3 -93.31(14) . . . . ?
C5 N1 C2 C1 -84.44(13) . . . . ?
C9 N1 C2 C1 89.46(13) . . . . ?
O2 C1 C2 C3 -163.95(12) . . . . ?
O1 C1 C2 C3 14.98(17) . . . . ?
O2 C1 C2 N1 13.19(14) . . . . ?
O1 C1 C2 N1 -167.87(10) . . . . ?
N1 C2 C3 C4 -1.0(2) . . . . ?
C1 C2 C3 C4 175.86(11) . . . . ?
C2 C3 C4 O3 -178.09(13) . . . . ?
C2 C3 C4 O4 0.90(19) . . . . ?
C9 N1 C5 C6 -0.11(18) . . . . ?
C2 N1 C5 C6 173.65(11) . . . . ?
N1 C5 C6 C7 -0.14(18) . . . . ?
C5 C6 C7 C8 1.19(18) . . . . ?
C5 C6 C7 C10 -176.35(11) . . . . ?
C6 C7 C8 C9 -2.01(18) . . . . ?
C10 C7 C8 C9 175.54(11) . . . . ?
C5 N1 C9 C8 -0.72(18) . . . . ?
C2 N1 C9 C8 -174.46(11) . . . . ?
C7 C8 C9 N1 1.80(18) . . . . ?
C6 C7 C10 C11 -92.20(14) . . . . ?
C8 C7 C10 C11 90.33(14) . . . . ?
C7 C10 C11 C16 41.05(17) . . . . ?
C7 C10 C11 C12 -143.55(11) . . . . ?
C16 C11 C12 C13 2.77(18) . . . . ?
C10 C11 C12 C13 -172.78(11) . . . . ?
C11 C12 C13 C14 -1.25(19) . . . . ?
C12 C13 C14 C15 -1.3(2) . . . . ?
C13 C14 C15 C16 2.2(2) . . . . ?
C14 C15 C16 C11 -0.7(2) . . . . ?
C12 C11 C16 C15 -1.79(18) . . . . ?
C10 C11 C16 C15 173.55(12) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O4 H4 O1 0.91(2) 1.72(2) 2.6167(12) 170.6(19) 1_545
C5 H5 O1 0.95 2.59 3.2101(14) 123.1 4_545
C5 H5 O2 0.95 2.44 3.2475(15) 142.9 4_545
C6 H6 O1 0.95 2.60 3.2149(15) 122.8 4_545
C9 H9 O2 0.95 2.36 3.0930(15) 133.7 7_655

_refine_diff_density_max         0.396
_refine_diff_density_min         -0.206
_refine_diff_density_rms         0.044

_shelxl_version_number           2012-9

_database_code_depnum_ccdc_archive 'CCDC 987549'
