# Electronic Supplementary Material (ESI) for Energy & Environmental Science.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
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data_p21_trial1
_database_code_depnum_ccdc_archive 'CCDC 1020368'
_audit_update_record             
;
2014-08-21 deposited with the CCDC.
2015-12-23 downloaded from the CCDC.
;
_audit_creation_date             2014-08-21
_audit_creation_method           
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_shelxl_version_number           2013-4
_chemical_name_common            ?
_chemical_name_systematic        
;
 ?
;
_chemical_formula_moiety         'C15 H16 N4, 4(H2 O)'
_chemical_formula_sum            'C15 H24 N4 O4'
_chemical_formula_weight         324.38
_chemical_absolute_configuration ?
_chemical_melting_point          ?
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'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_H-M_alt        'P 1 21 1'
_space_group_name_Hall           'P 2yb'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z'

_cell_length_a                   9.4300(19)
_cell_length_b                   4.7380(9)
_cell_length_c                   18.556(4)
_cell_angle_alpha                90
_cell_angle_beta                 91.27(3)
_cell_angle_gamma                90
_cell_volume                     828.9(3)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    ?
_cell_measurement_temperature    100
_cell_measurement_theta_max      ?
_cell_measurement_theta_min      ?
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.096
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   ?
_exptl_crystal_colour            'clear reddish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.300
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             348
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.004
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0524
_diffrn_reflns_av_unetI/netI     0.0418
_diffrn_reflns_Laue_measured_fraction_full 0.938
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            10069
_diffrn_reflns_point_group_measured_fraction_full 0.935
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.987
_diffrn_reflns_theta_min         1.098
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.938
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_device_type  'Australian Synchrotron'
_diffrn_measurement_method       'ω scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_special_details          
'Crystals were extremely thin and streaky diffraction spots were observed only at low angles.'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.762
_reflns_Friedel_fraction_full    0.932
_reflns_Friedel_fraction_max     0.957
_reflns_number_gt                2660
_reflns_number_total             2809
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       ?
_computing_data_collection       ?
_computing_data_reduction        ?
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_refine_diff_density_max         2.485
_refine_diff_density_min         -0.993
_refine_diff_density_rms         0.250
_refine_ls_abs_structure_details 
;
 Flack x determined using 1109 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.1(5)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.728
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     223
_refine_ls_number_reflns         2809
_refine_ls_number_restraints     131
_refine_ls_R_factor_all          0.2255
_refine_ls_R_factor_gt           0.2218
_refine_ls_restrained_S_all      2.678
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4964
_refine_ls_wR_factor_ref         0.5053
_refine_special_details          
'The structure could be solved with Direct mehtods, but the refinement converged at the R value of ~ 0.22. The high R value could be attributed to the diffraction data from ultra thin ribbon like crystals that bend easily like a blade of grass. The hydrogens on the four water molecules were modelled to make the H-bonding with the N atoms of the dye molecule and with each other. The residual electron density ~ 2 eA-3 may be attributed to the data from these crystals.'
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 H4WA-N2
 2.2 with sigma of 0.02
 H1WB-N3
 2 with sigma of 0.02
 H3WA-O4W
 1.9 with sigma of 0.02
 H2WB-O1W
 1.9 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.9A with sigma of 0.02 and sigma
for terminal atoms of 0.04
4.a Free rotating group:
 O1W(H1WA,H1WB), O3W(H3WA,H3WB), O2W(H2WA,H2WB), O4W(H4WA,H4WB)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C9(H9), C10(H10), C1(H1)
4.c X=CH2 refined with riding coordinates:
 N1(H1A,H1B)
4.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   ?
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
C2 C 1.0021(10) -0.630(2) 0.8470(6) 0.026(2) Uani 1 1 d . . . . .
C3 C 0.8977(11) -0.578(2) 0.9029(6) 0.028(2) Uani 1 1 d . . . . .
N4 N 0.4680(9) 0.6685(18) 0.6531(4) 0.026(2) Uani 1 1 d . . . . .
C4 C 0.7924(10) -0.366(2) 0.8879(5) 0.024(2) Uani 1 1 d . . . . .
H4 H 0.7258 -0.3228 0.9239 0.029 Uiso 1 1 calc R . . . .
C5 C 0.7841(10) -0.2208(19) 0.8220(6) 0.022(2) Uani 1 1 d . . . . .
C7 C 0.5726(12) 0.313(2) 0.7330(6) 0.031(2) Uani 1 1 d . . . . .
H7 H 0.5057 0.3562 0.7689 0.037 Uiso 1 1 calc R . . . .
C6 C 0.6795(11) 0.100(2) 0.7477(6) 0.025(2) Uani 1 1 d . . . . .
C8 C 0.5655(11) 0.455(2) 0.6677(6) 0.030(2) Uani 1 1 d . . . . .
C9 C 0.6694(13) 0.379(2) 0.6147(6) 0.032(3) Uani 1 1 d . . . . .
H9 H 0.6651 0.4712 0.5693 0.039 Uiso 1 1 calc R . . . .
N3 N 0.8811(9) -0.1638(19) 0.7048(5) 0.027(2) Uani 1 1 d D . . . .
C11 C 0.7788(11) 0.035(2) 0.6933(6) 0.026(2) Uani 1 1 d . . . . .
C10 C 0.7694(10) 0.189(2) 0.6258(5) 0.021(2) Uani 1 1 d . . . . .
H10 H 0.8360 0.1520 0.5893 0.026 Uiso 1 1 calc R . . . .
C13 C 1.1207(9) -0.829(2) 0.8643(5) 0.023(2) Uani 1 1 d . . . . .
H13A H 1.1743 -0.7608 0.9066 0.035 Uiso 1 1 calc GR . . . .
H13B H 1.1838 -0.8413 0.8231 0.035 Uiso 1 1 calc GR . . . .
H13C H 1.0820 -1.0168 0.8745 0.035 Uiso 1 1 calc GR . . . .
C12 C 0.8830(9) -0.302(2) 0.7673(5) 0.023(2) Uani 1 1 d . . . . .
C14 C 0.4385(13) 0.757(3) 0.5801(6) 0.042(3) Uani 1 1 d . . . . .
H14A H 0.5230 0.8474 0.5606 0.063 Uiso 1 1 calc GR . . . .
H14B H 0.3597 0.8921 0.5794 0.063 Uiso 1 1 calc GR . . . .
H14C H 0.4128 0.5927 0.5506 0.063 Uiso 1 1 calc GR . . . .
N2 N 0.6808(9) -0.0313(17) 0.8103(5) 0.025(2) Uani 1 1 d D . . . .
C15 C 0.3578(10) 0.692(2) 0.7054(5) 0.029(2) Uani 1 1 d . . . . .
H15A H 0.2881 0.5409 0.6975 0.044 Uiso 1 1 calc GR . . . .
H15B H 0.3108 0.8755 0.7002 0.044 Uiso 1 1 calc GR . . . .
H15C H 0.3994 0.6752 0.7541 0.044 Uiso 1 1 calc GR . . . .
O1W O 1.0434(6) -0.3182(13) 0.5858(3) 0.0191(16) Uani 1 1 d D . . . .
H1WA H 1.0862 -0.4755 0.5896 0.029 Uiso 1 1 d G . . . .
H1WB H 0.9820 -0.3054 0.6185 0.029 Uiso 1 1 d DG . . . .
O3W O 0.3607(7) -0.3236(17) 0.9517(4) 0.0267(18) Uani 1 1 d . . . . .
H3WA H 0.3934 -0.1588 0.9449 0.040 Uiso 1 1 d DG . . . .
H3WB H 0.4088 -0.4425 0.9281 0.040 Uiso 1 1 d G . . . .
O2W O 0.8497(7) -0.3131(14) 0.4677(3) 0.0232(17) Uani 1 1 d . . . . .
H2WA H 0.8747 -0.4555 0.4432 0.035 Uiso 1 1 d G . . . .
H2WB H 0.9020 -0.3010 0.5055 0.035 Uiso 1 1 d DG . . . .
O4W O 0.4963(6) 0.1687(16) 0.9159(3) 0.0267(18) Uani 1 1 d D . . . .
H4WA H 0.5523 0.2277 0.8840 0.040 Uiso 1 1 d DG . . . .
H4WB H 0.5404 0.1588 0.9563 0.040 Uiso 1 1 d G . . . .
N1 N 0.9072(8) -0.7031(19) 0.9664(4) 0.024(2) Uani 1 1 d . . . . .
H1A H 0.8482 -0.6571 1.0005 0.029 Uiso 1 1 calc R . . . .
H1B H 0.9725 -0.8326 0.9746 0.029 Uiso 1 1 calc R . . . .
C1 C 0.9899(12) -0.493(2) 0.7846(6) 0.029(2) Uani 1 1 d . . . . .
H1 H 1.0594 -0.5283 0.7495 0.034 Uiso 1 1 calc R . . . .


_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
C2 C3 1.467(15) . ?
C2 C13 1.494(13) . ?
C2 C1 1.330(16) . ?
C3 C4 1.434(14) . ?
C3 N1 1.321(14) . ?
N4 C8 1.390(14) . ?
N4 C14 1.440(12) . ?
N4 C15 1.442(13) . ?
C4 C5 1.404(14) . ?
C5 C12 1.445(13) . ?
C5 N2 1.339(12) . ?
C7 C6 1.447(16) . ?
C7 C8 1.386(16) . ?
C6 C11 1.427(14) . ?
C6 N2 1.318(15) . ?
C8 C9 1.448(17) . ?
C9 C10 1.317(15) . ?
N3 C11 1.362(14) . ?
N3 C12 1.331(13) . ?
C11 C10 1.449(13) . ?
C12 C1 1.389(14) . ?

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
C3 C2 C13 117.8(9) . . ?
C1 C2 C3 119.1(9) . . ?
C1 C2 C13 123.1(10) . . ?
C4 C3 C2 117.0(9) . . ?
N1 C3 C2 121.5(9) . . ?
N1 C3 C4 121.3(9) . . ?
C8 N4 C14 120.6(10) . . ?
C8 N4 C15 114.1(8) . . ?
C14 N4 C15 118.9(9) . . ?
C5 C4 C3 122.5(9) . . ?
C4 C5 C12 117.3(9) . . ?
N2 C5 C4 119.7(9) . . ?
N2 C5 C12 122.8(9) . . ?
C8 C7 C6 121.5(10) . . ?
C11 C6 C7 118.8(9) . . ?
N2 C6 C7 119.2(9) . . ?
N2 C6 C11 121.9(10) . . ?
N4 C8 C9 120.2(9) . . ?
C7 C8 N4 122.8(10) . . ?
C7 C8 C9 116.9(10) . . ?
C10 C9 C8 123.9(9) . . ?
C12 N3 C11 118.2(9) . . ?
C6 C11 C10 118.3(9) . . ?
N3 C11 C6 120.8(9) . . ?
N3 C11 C10 120.8(9) . . ?
C9 C10 C11 120.5(9) . . ?
N3 C12 C5 119.1(9) . . ?
N3 C12 C1 121.2(9) . . ?
C1 C12 C5 119.1(9) . . ?
C6 N2 C5 116.9(9) . . ?
C2 C1 C12 124.7(10) . . ?

_olex2_exptl_crystal_mounting_method 
'One of the extremely thin ribbon like crystals was mounted on the cryo loop with paraffin oil.'
_olex2_submission_original_sample_id 'Neutral Red Dye'
_olex2_submission_special_instructions 'No special instructions were received'
