# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 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
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#  data retrieval see:
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#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
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data_p21n

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C15 H10 Cu N4 O4'
_chemical_formula_weight         373.81

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'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   'P2(1)/n  '

loop_
_symmetry_equiv_pos_as_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                   9.046(3)
_cell_length_b                   11.876(4)
_cell_length_c                   14.006(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 108.792(4)
_cell_angle_gamma                90.00
_cell_volume                     1424.5(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    1140
_cell_measurement_theta_min      2.30
_cell_measurement_theta_max      22.61

_exptl_crystal_description       needle
_exptl_crystal_colour            brown
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.15
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.743
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             756
_exptl_absorpt_coefficient_mu    1.563
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  0.7349
_exptl_absorpt_correction_T_max  0.7993
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  MoKα
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            8608
_diffrn_reflns_av_R_equivalents  0.0580
_diffrn_reflns_av_unetI/netI     0.0803
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.93
_diffrn_reflns_theta_max         27.59
_reflns_number_total             3289
_reflns_number_gt                1904
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.1000P)²+0.2409P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3289
_refine_ls_number_parameters     217
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1065
_refine_ls_R_factor_gt           0.0538
_refine_ls_wR_factor_ref         0.1754
_refine_ls_wR_factor_gt          0.1410
_refine_ls_goodness_of_fit_ref   0.922
_refine_ls_restrained_S_all      0.922
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.24085(7) 0.52060(5) 0.84569(4) 0.0424(2) Uani 1 1 d . . .
O2 O 0.1961(4) 0.5329(3) 0.6976(3) 0.0505(9) Uani 1 1 d . . .
N1 N 0.2799(4) 0.5270(3) 0.9907(3) 0.0341(8) Uani 1 1 d . . .
N3 N 0.3871(4) 0.6493(3) 0.8818(3) 0.0387(9) Uani 1 1 d . . .
O3 O 0.3494(4) 0.3903(3) 0.7443(3) 0.0603(10) Uani 1 1 d . . .
N2 N 0.3756(4) 0.6004(3) 1.0440(3) 0.0412(9) Uani 1 1 d . . .
C7 C 0.4353(5) 0.6682(4) 0.9833(3) 0.0360(10) Uani 1 1 d . . .
N4 N 0.2767(5) 0.4538(4) 0.6749(3) 0.0454(10) Uani 1 1 d . . .
O1 O 0.1041(4) 0.3973(3) 0.8546(2) 0.0481(8) Uani 1 1 d . . .
C6 C 0.2018(5) 0.4510(4) 1.0271(3) 0.0358(10) Uani 1 1 d . . .
O4 O 0.2751(5) 0.4436(4) 0.5883(3) 0.0694(12) Uani 1 1 d . . .
C5 C 0.2000(5) 0.4349(4) 1.1293(3) 0.0360(10) Uani 1 1 d . . .
C11 C 0.4423(6) 0.7143(4) 0.8240(3) 0.0452(12) Uani 1 1 d . . .
H11 H 0.4100 0.7014 0.7548 0.054 Uiso 1 1 calc R . .
C8 C 0.5400(6) 0.7527(4) 1.0267(4) 0.0445(11) Uani 1 1 d . . .
H8 H 0.5728 0.7646 1.0961 0.053 Uiso 1 1 calc R . .
C1 C 0.1039(5) 0.3818(4) 0.9456(3) 0.0391(10) Uani 1 1 d . . .
C10 C 0.5463(6) 0.8005(4) 0.8638(4) 0.0490(12) Uani 1 1 d . . .
H10 H 0.5828 0.8453 0.8217 0.059 Uiso 1 1 calc R . .
C9 C 0.5948(6) 0.8193(4) 0.9643(4) 0.0495(13) Uani 1 1 d . . .
H9 H 0.6652 0.8771 0.9915 0.059 Uiso 1 1 calc R . .
C4 C 0.1030(5) 0.3490(4) 1.1466(4) 0.0418(11) Uani 1 1 d . . .
C3 C 0.0094(6) 0.2809(4) 1.0632(4) 0.0473(12) Uani 1 1 d . . .
H3 H -0.0531 0.2242 1.0755 0.057 Uiso 1 1 calc R . .
C2 C 0.0104(6) 0.2972(4) 0.9687(4) 0.0472(12) Uani 1 1 d . . .
H2 H -0.0517 0.2520 0.9171 0.057 Uiso 1 1 calc R . .
C12 C 0.0984(6) 0.3309(4) 1.2441(4) 0.0503(13) Uani 1 1 d . . .
H12 H 0.0336 0.2752 1.2553 0.060 Uiso 1 1 calc R . .
C15 C 0.2933(6) 0.4978(4) 1.2122(4) 0.0401(11) Uani 1 1 d . . .
H15 H 0.3596 0.5535 1.2030 0.048 Uiso 1 1 calc R . .
C14 C 0.2854(6) 0.4760(4) 1.3075(4) 0.0496(13) Uani 1 1 d . . .
H14 H 0.3473 0.5179 1.3618 0.060 Uiso 1 1 calc R . .
C13 C 0.1889(6) 0.3944(5) 1.3241(4) 0.0531(13) Uani 1 1 d . . .
H13 H 0.1846 0.3821 1.3887 0.064 Uiso 1 1 calc R . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1 0.0494(4) 0.0434(4) 0.0342(3) -0.0038(3) 0.0131(3) -0.0039(3)
O2 0.065(2) 0.046(2) 0.0378(18) -0.0048(15) 0.0121(17) 0.0083(18)
N1 0.0313(19) 0.0313(19) 0.038(2) -0.0035(16) 0.0092(16) -0.0001(16)
N3 0.041(2) 0.034(2) 0.039(2) -0.0002(17) 0.0100(17) -0.0036(17)
O3 0.055(2) 0.068(3) 0.056(2) 0.0180(19) 0.0145(18) 0.016(2)
N2 0.043(2) 0.044(2) 0.036(2) -0.0006(17) 0.0139(18) -0.0079(18)
C7 0.035(2) 0.038(2) 0.038(2) 0.0046(19) 0.0156(19) 0.006(2)
N4 0.042(2) 0.050(3) 0.045(3) -0.008(2) 0.015(2) -0.0022(19)
O1 0.052(2) 0.053(2) 0.0370(18) -0.0156(15) 0.0118(15) -0.0110(16)
C6 0.031(2) 0.041(3) 0.036(2) -0.0045(19) 0.0126(19) 0.0005(19)
O4 0.092(3) 0.083(3) 0.038(2) -0.002(2) 0.027(2) 0.024(2)
C5 0.036(2) 0.032(2) 0.044(3) 0.005(2) 0.019(2) 0.006(2)
C11 0.050(3) 0.048(3) 0.036(3) 0.008(2) 0.012(2) 0.005(2)
C8 0.042(3) 0.049(3) 0.042(3) -0.003(2) 0.012(2) -0.002(2)
C1 0.035(2) 0.041(3) 0.044(3) -0.002(2) 0.016(2) 0.000(2)
C10 0.049(3) 0.052(3) 0.046(3) 0.013(2) 0.016(2) -0.002(2)
C9 0.047(3) 0.038(3) 0.061(3) -0.001(2) 0.014(3) -0.004(2)
C4 0.040(3) 0.036(3) 0.054(3) 0.005(2) 0.022(2) 0.007(2)
C3 0.040(3) 0.041(3) 0.063(3) 0.000(2) 0.020(3) -0.009(2)
C2 0.041(3) 0.040(3) 0.058(3) -0.012(2) 0.013(2) -0.012(2)
C12 0.056(3) 0.047(3) 0.060(3) 0.014(3) 0.036(3) 0.002(3)
C15 0.041(3) 0.045(3) 0.039(3) -0.002(2) 0.020(2) -0.001(2)
C14 0.052(3) 0.058(3) 0.040(3) 0.000(2) 0.017(2) 0.002(3)
C13 0.062(3) 0.063(4) 0.045(3) 0.012(3) 0.033(3) 0.010(3)

_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
Cu1 O1 1.947(3) . ?
Cu1 N1 1.948(4) . ?
Cu1 N3 1.978(4) . ?
Cu1 O2 1.987(3) . ?
O2 N4 1.290(5) . ?
N1 N2 1.285(5) . ?
N1 C6 1.343(6) . ?
N3 C11 1.326(6) . ?
N3 C7 1.364(5) . ?
O3 N4 1.238(5) . ?
N2 C7 1.399(5) . ?
C7 C8 1.380(7) . ?
N4 O4 1.215(5) . ?
O1 C1 1.287(5) . ?
C6 C5 1.449(6) . ?
C6 C1 1.454(6) . ?
C5 C15 1.410(7) . ?
C5 C4 1.416(6) . ?
C11 C10 1.381(7) . ?
C8 C9 1.384(7) . ?
C1 C2 1.416(6) . ?
C10 C9 1.351(7) . ?
C4 C12 1.396(6) . ?
C4 C3 1.449(6) . ?
C3 C2 1.341(7) . ?
C12 C13 1.380(7) . ?
C15 C14 1.383(7) . ?
C14 C13 1.374(7) . ?

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 Cu1 N1 82.40(14) . . ?
O1 Cu1 N3 162.09(14) . . ?
N1 Cu1 N3 79.74(15) . . ?
O1 Cu1 O2 101.69(14) . . ?
N1 Cu1 O2 173.42(14) . . ?
N3 Cu1 O2 95.99(15) . . ?
N4 O2 Cu1 105.2(3) . . ?
N2 N1 C6 125.0(4) . . ?
N2 N1 Cu1 119.6(3) . . ?
C6 N1 Cu1 115.4(3) . . ?
C11 N3 C7 119.0(4) . . ?
C11 N3 Cu1 130.2(3) . . ?
C7 N3 Cu1 110.8(3) . . ?
N1 N2 C7 110.9(4) . . ?
N3 C7 C8 121.5(4) . . ?
N3 C7 N2 118.9(4) . . ?
C8 C7 N2 119.7(4) . . ?
O4 N4 O3 123.8(4) . . ?
O4 N4 O2 119.5(4) . . ?
O3 N4 O2 116.8(4) . . ?
C1 O1 Cu1 112.0(3) . . ?
N1 C6 C5 129.7(4) . . ?
N1 C6 C1 110.1(4) . . ?
C5 C6 C1 120.2(4) . . ?
C15 C5 C4 118.6(4) . . ?
C15 C5 C6 123.3(4) . . ?
C4 C5 C6 118.0(4) . . ?
N3 C11 C10 121.7(4) . . ?
C7 C8 C9 118.1(4) . . ?
O1 C1 C2 121.2(4) . . ?
O1 C1 C6 120.1(4) . . ?
C2 C1 C6 118.6(4) . . ?
C9 C10 C11 119.6(5) . . ?
C10 C9 C8 120.1(5) . . ?
C12 C4 C5 119.6(5) . . ?
C12 C4 C3 120.6(4) . . ?
C5 C4 C3 119.8(4) . . ?
C2 C3 C4 121.8(4) . . ?
C3 C2 C1 121.6(5) . . ?
C13 C12 C4 120.9(5) . . ?
C14 C15 C5 119.6(5) . . ?
C13 C14 C15 121.9(5) . . ?
C14 C13 C12 119.4(5) . . ?

_diffrn_measured_fraction_theta_max 0.995
_diffrn_reflns_theta_full        27.59
_diffrn_measured_fraction_theta_full 0.995
_refine_diff_density_max         0.428
_refine_diff_density_min         -0.646
_refine_diff_density_rms         0.089
_database_code_depnum_ccdc_archive 'CCDC 999899'
