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#$Date: 2024-10-06 10:30:52 +0300 (Sun, 06 Oct 2024) $
#$Revision: 295217 $
#$URL: file:///home/coder/svn-repositories/cod/cif/7/24/92/7249210.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_7249210
loop_
_publ_author_name
'Kalavalapudi, Likhitha'
'Palani, Sivanarayanan'
'Nechipadappu, Sunil Kumar'
_publ_section_title
;
 Serendipitous discovery of a novel polymorph of an immunosuppressant drug
 azathioprine: phase transformation, solubility, dissolution and stability
 study
;
_journal_issue                   37
_journal_name_full               CrystEngComm
_journal_page_first              5187
_journal_page_last               5201
_journal_paper_doi               10.1039/D4CE00589A
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety         'C9 H7 N7 O2 S'
_chemical_formula_sum            'C9 H7 N7 O2 S'
_chemical_formula_weight         277.28
_chemical_name_common            Azathioprine
_chemical_name_systematic        Azathioprine
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     difmap
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2019/3
_audit_update_record
;
2024-06-08 deposited with the CCDC.	2024-08-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.676(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.3738(7)
_cell_length_b                   8.3050(5)
_cell_length_c                   13.8405(9)
_cell_measurement_reflns_used    5250
_cell_measurement_temperature    294(2)
_cell_measurement_theta_max      29.22
_cell_measurement_theta_min      3.88
_cell_volume                     1158.61(13)
_computing_cell_refinement       'SAINT (Bruker, 2016)'
_computing_data_collection       'APEX3 (Bruker, 2016)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL2014 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      294(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker D8 QUEST PHOTON-III'
_diffrn_measurement_method       'ω and φ'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0330
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            14246
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.507
_diffrn_reflns_theta_min         2.883
_exptl_absorpt_coefficient_mu    0.291
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6562
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 SADABS 2016/2: Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
 J. Appl. Cryst. 48 (2015) 3-10
;
_exptl_crystal_density_diffrn    1.590
_exptl_crystal_description       block
_exptl_crystal_F_000             568
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: cyclohexanol + acetone'
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.130
_exptl_crystal_size_min          0.120
_refine_diff_density_max         0.380
_refine_diff_density_min         -0.302
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     177
_refine_ls_number_reflns         3468
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0751
_refine_ls_R_factor_gt           0.0432
_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)+(0.0599P)²+0.3207P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1107
_refine_ls_wR_factor_ref         0.1284
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2328
_reflns_number_total             3468
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            d4ce00589a2.cif
_cod_data_source_block           KB1306_0m
_cod_depositor_comments
'Adding full bibliography for 7249210--7249213.cif.'
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7249210
_shelx_shelxl_version_number     2019/3
_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.
;
_shelx_estimated_absorpt_t_min   0.958
_shelx_estimated_absorpt_t_max   0.966
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'
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
C1 C 0.33505(17) 0.7018(2) 0.13397(13) 0.0414(4) Uani 1 1 d . . . . .
H1 H 0.247019 0.732150 0.109824 0.050 Uiso 1 1 calc R U . . .
C2 C 0.52974(15) 0.6009(2) 0.13694(11) 0.0327(4) Uani 1 1 d . . . . .
C3 C 0.52352(15) 0.6606(2) 0.22977(11) 0.0320(4) Uani 1 1 d . . . . .
C4 C 0.63840(15) 0.6447(2) 0.30540(11) 0.0320(3) Uani 1 1 d . . . . .
C5 C 0.73962(17) 0.5267(3) 0.19393(12) 0.0435(5) Uani 1 1 d . . . . .
H5 H 0.816479 0.480255 0.182971 0.052 Uiso 1 1 calc R U . . .
C6 C 0.79257(16) 0.6801(2) 0.49336(11) 0.0345(4) Uani 1 1 d . . . . .
C7 C 0.91537(18) 0.7381(2) 0.49096(13) 0.0421(4) Uani 1 1 d . . . . .
C8 C 0.9498(2) 0.5866(3) 0.61452(16) 0.0583(6) Uani 1 1 d . . . . .
H8 H 0.991357 0.530219 0.671420 0.070 Uiso 1 1 calc R U . . .
C9 C 0.7229(2) 0.4855(3) 0.61369(16) 0.0638(6) Uani 1 1 d . . . . .
H9A H 0.666123 0.427583 0.560125 0.096 Uiso 1 1 calc R U . . .
H9B H 0.670227 0.555555 0.644063 0.096 Uiso 1 1 calc R U . . .
H9C H 0.769917 0.410671 0.662260 0.096 Uiso 1 1 calc R U . . .
N1 N 0.39996(14) 0.7245(2) 0.22700(11) 0.0409(4) Uani 1 1 d . . . . .
N2 N 0.40813(14) 0.6300(2) 0.07633(11) 0.0391(4) Uani 1 1 d . . . . .
H2N H 0.384(2) 0.592(3) 0.0153(17) 0.054(6) Uiso 1 1 d . . . . .
N3 N 0.63637(14) 0.5323(2) 0.11546(10) 0.0408(4) Uani 1 1 d . . . . .
N4 N 0.74681(13) 0.57954(19) 0.28658(10) 0.0382(4) Uani 1 1 d . . . . .
N5 N 0.81786(15) 0.5813(2) 0.57504(11) 0.0430(4) Uani 1 1 d . . . . .
N6 N 1.01287(16) 0.6783(3) 0.56521(14) 0.0584(5) Uani 1 1 d . . . . .
N7 N 0.9476(2) 0.8440(2) 0.41920(14) 0.0571(5) Uani 1 1 d . . . . .
O1 O 0.8577(2) 0.9057(2) 0.35719(13) 0.0728(5) Uani 1 1 d . . . . .
O2 O 1.0658(2) 0.8698(3) 0.42513(17) 0.1058(8) Uani 1 1 d . . . . .
S1 S 0.63196(4) 0.71350(7) 0.42440(3) 0.04402(16) Uani 1 1 d . . . . .
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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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
N1 C1 N2 114.12(15) . . ?
N1 C1 H1 122.9 . . ?
N2 C1 H1 122.9 . . ?
N3 C2 N2 129.24(15) . . ?
N3 C2 C3 125.26(14) . . ?
N2 C2 C3 105.49(14) . . ?
N1 C3 C2 110.90(13) . . ?
N1 C3 C4 132.93(15) . . ?
C2 C3 C4 116.17(14) . . ?
N4 C4 C3 120.30(14) . . ?
N4 C4 S1 122.50(11) . . ?
C3 C4 S1 117.21(12) . . ?
N3 C5 N4 128.32(16) . . ?
N3 C5 H5 115.8 . . ?
N4 C5 H5 115.8 . . ?
C7 C6 N5 103.46(15) . . ?
C7 C6 S1 135.08(15) . . ?
N5 C6 S1 121.37(13) . . ?
N6 C7 C6 112.61(18) . . ?
N6 C7 N7 119.94(17) . . ?
C6 C7 N7 127.39(17) . . ?
N6 C8 N5 113.31(18) . . ?
N6 C8 H8 123.3 . . ?
N5 C8 H8 123.3 . . ?
N5 C9 H9A 109.5 . . ?
N5 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
N5 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
C1 N1 C3 103.23(14) . . ?
C2 N2 C1 106.26(13) . . ?
C2 N2 H2N 122.8(14) . . ?
C1 N2 H2N 130.2(14) . . ?
C5 N3 C2 112.36(14) . . ?
C4 N4 C5 117.57(14) . . ?
C8 N5 C6 106.99(16) . . ?
C8 N5 C9 125.20(18) . . ?
C6 N5 C9 127.80(16) . . ?
C8 N6 C7 103.60(16) . . ?
O1 N7 O2 124.0(2) . . ?
O1 N7 C7 118.85(18) . . ?
O2 N7 C7 117.2(2) . . ?
C6 S1 C4 102.64(7) . . ?
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
C1 N1 1.318(2) . ?
C1 N2 1.361(2) . ?
C1 H1 0.9300 . ?
C2 N3 1.339(2) . ?
C2 N2 1.3613(19) . ?
C2 C3 1.393(2) . ?
C3 N1 1.379(2) . ?
C3 C4 1.394(2) . ?
C4 N4 1.328(2) . ?
C4 S1 1.7595(16) . ?
C5 N3 1.334(2) . ?
C5 N4 1.340(2) . ?
C5 H5 0.9300 . ?
C6 C7 1.370(2) . ?
C6 N5 1.372(2) . ?
C6 S1 1.7354(16) . ?
C7 N6 1.354(2) . ?
C7 N7 1.424(3) . ?
C8 N6 1.298(3) . ?
C8 N5 1.349(2) . ?
C8 H8 0.9300 . ?
C9 N5 1.462(3) . ?
C9 H9A 0.9600 . ?
C9 H9B 0.9600 . ?
C9 H9C 0.9600 . ?
N2 H2N 0.88(2) . ?
N7 O1 1.222(3) . ?
N7 O2 1.228(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
_geom_hbond_publ_flag
C1 H1 N6 0.93 2.48 3.401(2) 173.5 4_475 yes
C5 H5 O2 0.93 2.33 3.172(2) 150.2 2_745 yes
N2 H2N N3 0.88(2) 2.05(2) 2.915(2) 167(2) 3_665 yes
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
N3 C2 C3 N1 179.60(17) . . . . ?
N2 C2 C3 N1 0.5(2) . . . . ?
N3 C2 C3 C4 -0.7(3) . . . . ?
N2 C2 C3 C4 -179.85(16) . . . . ?
N1 C3 C4 N4 -178.69(19) . . . . ?
C2 C3 C4 N4 1.7(3) . . . . ?
N1 C3 C4 S1 1.5(3) . . . . ?
C2 C3 C4 S1 -178.11(13) . . . . ?
N5 C6 C7 N6 0.9(2) . . . . ?
S1 C6 C7 N6 177.35(16) . . . . ?
N5 C6 C7 N7 178.28(19) . . . . ?
S1 C6 C7 N7 -5.3(3) . . . . ?
N2 C1 N1 C3 -0.8(2) . . . . ?
C2 C3 N1 C1 0.2(2) . . . . ?
C4 C3 N1 C1 -179.4(2) . . . . ?
N3 C2 N2 C1 179.98(19) . . . . ?
C3 C2 N2 C1 -0.9(2) . . . . ?
N1 C1 N2 C2 1.2(2) . . . . ?
N4 C5 N3 C2 0.1(3) . . . . ?
N2 C2 N3 C5 178.77(19) . . . . ?
C3 C2 N3 C5 -0.2(3) . . . . ?
C3 C4 N4 C5 -1.8(3) . . . . ?
S1 C4 N4 C5 178.03(15) . . . . ?
N3 C5 N4 C4 0.9(3) . . . . ?
N6 C8 N5 C6 -0.9(3) . . . . ?
N6 C8 N5 C9 178.7(2) . . . . ?
C7 C6 N5 C8 -0.1(2) . . . . ?
S1 C6 N5 C8 -177.10(15) . . . . ?
C7 C6 N5 C9 -179.6(2) . . . . ?
S1 C6 N5 C9 3.4(3) . . . . ?
N5 C8 N6 C7 1.4(3) . . . . ?
C6 C7 N6 C8 -1.4(3) . . . . ?
N7 C7 N6 C8 -179.0(2) . . . . ?
N6 C7 N7 O1 -174.8(2) . . . . ?
C6 C7 N7 O1 8.1(3) . . . . ?
N6 C7 N7 O2 3.9(3) . . . . ?
C6 C7 N7 O2 -173.3(2) . . . . ?
C7 C6 S1 C4 63.7(2) . . . . ?
N5 C6 S1 C4 -120.36(15) . . . . ?
N4 C4 S1 C6 2.52(18) . . . . ?
C3 C4 S1 C6 -177.68(14) . . . . ?
