Polymorphs and stoichiometric variants of crown ether-based molecular complexes: exploring the landscape of conformational flexibility and supramolecular interactions
Winson, Cinu; Kandasamy, Saravanan; Divya, Indira S.; Wozniak, Krzysztof; Varughese, Sunil; CrystEngComm 27 (2025) 2698–2710; doi:10.1039/D5CE00025D

data_7250156
_publ_section_title
;
 Polymorphs and stoichiometric variants of crown ether-based molecular
 complexes: exploring the landscape of conformational flexibility and
 supramolecular interactions
;
_journal_issue                   17
_journal_name_full               CrystEngComm
_journal_page_first              2698
_journal_page_last               2710
_journal_paper_doi               10.1039/D5CE00025D
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C2 H4 N2 S2, C20 H36 O6'
_chemical_formula_sum            'C22 H40 N2 O6 S2'
_chemical_formula_weight         492.705
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_audit_creation_date             2024-03-09
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-12-23 deposited with the CCDC.	2025-03-20 downloaded from the CCDC.
;
_cell_angle_alpha                91.7000(19)
_cell_angle_beta                 105.5010(19)
_cell_angle_gamma                101.171(2)
_cell_formula_units_Z            3
_cell_length_a                   10.1460(2)
_cell_length_b                   14.1440(4)
_cell_length_c                   14.5050(3)
_cell_measurement_reflns_used    16103
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      77.3830
_cell_measurement_theta_min      3.2020
_cell_volume                     1960.51(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9996
_diffrn_measured_fraction_theta_max 0.9855
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -74.00 -42.00   0.50    0.05    --    0.00 140.00  -7.00   64
  2  \w    -70.00 -19.00   0.50    0.05    --    0.00 130.00 178.00  102
  3  \w    -50.00 -10.00   0.50    0.05    --    0.00 -77.00 -60.00   80
  4  \w     15.00  42.00   0.50    0.05    --    0.00  57.00 -60.00   54
  5  \w    -93.00 -42.00   0.50    0.05    --    0.00-178.00   0.00  102
  6  \w    -34.00  -9.00   0.50    0.05    --    0.00 -77.00-120.00   50
  7  \w    -85.00 -58.00   0.50    0.05    --    0.00 -77.00 -60.00   54
  8  \w    -86.00 -55.00   0.50    0.05    --    0.00 -77.00  60.00   62
  9  \w     54.00  80.00   0.50    0.05    --    0.00  57.00 -60.00   52
 10  \w    -52.00  -8.00   0.50    0.05    --    0.00 -77.00  60.00   88
 11  \w    -74.00 -38.00   0.50    0.05    --    0.00 -77.00-120.00   72
 12  \w    -35.00  -2.00   0.50    0.05    --    0.00  57.00 -60.00   66
 13  \w    -33.00   4.00   0.50    0.05    --   18.00 103.00  42.89   74
 14  \w    -49.00 -24.00   0.50    0.05    --   30.00 146.00  40.30   50
 15  \w     -1.00  24.00   0.50    0.08    --   50.00  95.00-107.50   50
 16  \w      2.00  27.00   0.50    0.08    --   54.00  96.00 107.67   50
 17  \w      8.00  34.00   0.50    0.08    --   58.00  93.00  18.19   52
 18  \w      8.00  34.00   0.50    0.08    --   58.00  93.00 -69.03   52
 19  \w     15.00  40.00   0.50    0.08    --   62.00  89.00 154.19   50
 20  \w     14.00  41.00   0.50    0.08    --   62.00  91.00 109.17   54
 21  \w     17.00  42.00   0.50    0.08    --   66.00  90.00 -86.96   50
 22  \w     17.00  42.00   0.50    0.08    --   66.00  90.00-112.05   50
 23  \w     17.00  42.00   0.50    0.08    --   66.00  90.00 -12.21   50
 24  \w     16.00  41.00   0.50    0.08    --   66.00  92.00  94.70   50
 25  \w     16.00  42.00   0.50    0.08    --   66.00  92.00-172.49   52
 26  \w     17.00  42.00   0.50    0.08    --   66.00  90.00  36.14   50
 27  \w     29.00 103.00   0.50    0.08    --   66.57 -77.00  90.00  148
 28  \w     -8.00 102.00   0.50    0.08    --   66.57 -61.00-180.00  220
 29  \w     52.00  79.00   0.50    0.08    --   66.57 -94.00   0.00   54
 30  \w    -22.00 135.00   0.50    0.08    --   66.57 -30.00 -30.00  314
 31  \w     -2.00  81.00   0.50    0.08    --   66.57 -61.00-120.00  166
 32  \w     53.00  98.00   0.50    0.08    --   66.57 -94.00 120.00   90
 33  \w     36.00 109.00   0.50    0.08    --   66.57 -77.00 -30.00  146
 34  \w     70.00 106.00   0.50    0.08    --   70.00  75.00 176.54   72
 35  \w     41.00 109.00   0.50    0.08    --   70.00  76.00   5.86  136
 36  \w     29.00  63.00   0.50    0.08    --   70.00  75.00 176.54   68
 37  \w     80.00 108.00   0.50    0.08    --   74.00  77.00  50.56   56
 38  \w     31.00  57.00   0.50    0.08    --   74.00  77.00  50.56   52
 39  \w     75.00 101.00   0.50    0.08    --   74.00  75.00 -30.27   52
 40  \w     36.00  63.00   0.50    0.08    --   74.00  75.00 -30.27   54
 41  \w     35.00  61.00   0.50    0.08    --   78.00  77.00 -92.80   52
 42  \w     36.00  62.00   0.50    0.08    --   78.00  77.00 123.64   52
 43  \w     76.00 109.00   0.50    0.08    --   78.00  77.00  79.76   66
 44  \w     35.00  66.00   0.50    0.08    --   78.00  77.00  79.76   62
 45  \w     84.00 109.00   0.50    0.08    --   78.00  77.00 -92.80   50
 46  \w     68.00 109.00   0.50    0.08    --   78.00  77.00 123.64   82
 47  \w     36.00  62.00   0.50    0.08    --   78.00  75.00 -62.83   52
 48  \w     40.00  66.00   0.50    0.08    --   82.00  75.00 138.57   52
 49  \w     84.00 109.00   0.50    0.08    --   82.00  76.00 -17.81   50
 50  \w     41.00  67.00   0.50    0.08    --   82.00  76.00 -17.81   52
 51  \w     83.00 109.00   0.50    0.08    --   82.00  75.00 138.57   52
 52  \w     40.00  70.00   0.50    0.08    --   82.00  76.00-117.42   60
 53  \w     44.00  70.00   0.50    0.08    --   86.00  77.00 159.68   52
 54  \w     45.00  71.00   0.50    0.08    --   86.00  74.00  22.03   52
 55  \w     69.00  95.00   0.50    0.08    --   86.00  77.00-148.18   52
 56  \w     43.00  68.00   0.50    0.08    --   86.00  77.00-148.18   50
 57  \w     84.00 109.00   0.50    0.08    --   86.00  77.00 -85.61   50
 58  \w     43.00  69.00   0.50    0.08    --   86.00  77.00 -85.61   52
 59  \w     49.00  75.00   0.50    0.08    --   90.00  76.00 172.82   52
 60  \w     80.00 109.00   0.50    0.08    --   90.00  77.00  63.86   58
 61  \w     47.00  72.00   0.50    0.08    --   90.00  77.00  63.86   50
 62  \w     48.00  75.00   0.50    0.08    --   90.00  76.00 -61.74   54
 63  \w     62.00  88.00   0.50    0.08    --   94.00  66.00-162.42   52
 64  \w    120.00 146.00   0.50    0.08    --   94.00  72.00  68.60   52
 65  \w     53.00  79.00   0.50    0.08    --   94.00  72.00  68.60   52
 66  \w     53.00  89.00   0.50    0.08    --   94.00  73.00-114.11   72
 67  \w    121.00 169.00   0.50    0.08    --   94.00  66.00-162.42   96
 68  \w     89.00 135.00   0.50    0.08    --   94.00  70.00 111.52   92
 69  \w     55.00  81.00   0.50    0.08    --   94.00  70.00 111.52   52
 70  \w     51.00  77.00   0.50    0.08    --   94.00  77.00  84.67   52
 71  \w     52.00  78.00   0.50    0.08    --   94.00  76.00 -12.05   52
 72  \w    138.00 175.00   0.50    0.08    --   94.00  70.00 111.52   74
 73  \w     56.00  81.00   0.50    0.08    --   98.00  75.00 149.12   50
 74  \w     56.00  81.00   0.50    0.08    --   98.00  77.00 -31.01   50
 75  \w     56.00  92.00   0.50    0.08    --   98.00  76.00 116.07   72
 76  \w     55.00 109.00   0.50    0.08    --   98.00  77.00  21.32  108
 77  \w    107.00 167.00   0.50    0.08    --   98.00  68.00 -79.05  120
 78  \w     61.00  87.00   0.50    0.08    --   98.00  68.00 -79.05   52
 79  \w     66.00 108.00   0.50    0.08    --  102.00  63.00-148.64   84
 80  \w     60.00  85.00   0.50    0.08    --  102.00  76.00 -72.22   50
 81  \w     64.00  89.00   0.50    0.08    --  106.00  75.00 154.93   50
 82  \w     64.00  89.00   0.50    0.08    --  106.00  76.00 -35.45   50
 83  \w    153.00 178.00   0.50    0.08    --  110.00  73.00-111.86   50
 84  \w     69.00  98.00   0.50    0.08    --  110.00  73.00-111.86   58
 85  \w    139.00 176.00   0.50    0.08    --  110.00  69.00 -20.70   74
 86  \w     73.00  99.00   0.50    0.08    --  110.00  69.00 -20.70   52
 87  \w     68.00 109.00   0.50    0.08    --  110.00  76.00  87.21   82
 88  \w    153.00 178.00   0.50    0.08    --  114.00  72.00 137.65   50
 89  \w     73.00 113.00   0.50    0.08    --  114.00  72.00 137.65   80
 90  \w    133.00 176.00   0.50    0.08    --  114.00  64.00 -57.58   86
 91  \w     79.00 118.00   0.50    0.08    --  114.00  64.00 -57.58   78
 92  \w    146.00 178.00   0.50    0.08    --  114.00  73.00   1.82   64
 93  \w    109.00 139.00   0.50    0.08    --  114.00  73.00   1.82   60
 94  \w     74.00 104.00   0.50    0.08    --  114.00  73.00   1.82   60
 95  \w    129.00 155.00   0.50    0.08    --  114.00  72.00-147.62   52
 96  \w     73.00 107.00   0.50    0.08    --  114.00  72.00-147.62   68
 97  \w    126.00 171.00   0.50    0.08    --  114.00  68.00  64.84   90
 98  \w     75.00 105.00   0.50    0.08    --  114.00  68.00  64.84   60
 99  \w     91.00 153.00   0.50    0.08    --  121.75  50.00  60.00  124
100  \w    121.00 178.00   0.50    0.08    --  121.75  63.00  90.00  114
101  \w     78.00 137.00   0.50    0.08    --  121.75  45.00 -92.50  118
102  \w     83.00 166.00   0.50    0.08    --  121.75  50.00-120.00  166
103  \w     62.00 106.00   0.50    0.08    --  121.75 -96.00  77.06   88
104  \w    125.00 151.00   0.50    0.08    --  121.75 -37.00-150.00   52
105  \w     85.00 152.00   0.50    0.08    --  121.75  63.00 120.00  134
106  \w     85.00 113.00   0.50    0.08    --  121.75  63.00  90.00   56
107  \w     46.00 103.00   0.50    0.08    --  121.75 -91.00 -90.00  114
108  \w     72.00 114.00   0.50    0.08    --  121.75 -37.00-150.00   84
109  \w     35.00  66.00   0.50    0.08    --  121.75 -37.00-150.00   62
110  \w     83.00 174.00   0.50    0.08    --  121.75  68.00 139.36  182
111  \w     81.00 107.00   0.50    0.08    --  121.75  77.00 156.97   52
112  \w     84.00 112.00   0.50    0.08    --  121.75-126.00 175.41   56
113  \w     89.00 177.00   0.50    0.08    --  121.75  63.00-180.00  176
114  \w     95.00 120.00   0.50    0.08    --  121.75-135.00  59.47   50
115  \w    127.00 170.00   0.50    0.08    --  121.75  68.00-169.49   86
116  \w     83.00 116.00   0.50    0.08    --  121.75  68.00-169.49   66
117  \w    126.00 178.00   0.50    0.08    --  121.75  48.00 -13.46  104
118  \w    124.00 168.00   0.50    0.08    --  121.75  63.00  30.00   88
119  \w     70.00 161.00   0.50    0.08    --  121.75 -50.00  30.00  182
120  \w     62.00 108.00   0.50    0.08    --  121.75-106.00 160.75   92
121  \w     46.00 103.00   0.50    0.08    --  121.75 -91.00 -60.00  114
122  \w     92.00 119.00   0.50    0.08    --  121.75  48.00 -13.46   54
123  \w     88.00 143.00   0.50    0.08    --  121.75  63.00 -90.00  110
124  \w    131.00 162.00   0.50    0.08    --  121.75 -77.00-150.00   62
125  \w     54.00 118.00   0.50    0.08    --  121.75 -77.00-150.00  128
126  \w    123.00 161.00   0.50    0.08    --  121.75 -12.00-150.00   76
127  \w     86.00 112.00   0.50    0.08    --  121.75  63.00  30.00   52
128  \w     30.00  82.00   0.50    0.08    --  121.75 -12.00-150.00  104
129  \w     51.00 105.00   0.50    0.08    --  121.75 -91.00  30.00  108
130  \w     56.00 106.00   0.50    0.08    --  121.75 -98.00-161.13  100
131  \w     53.00  79.00   0.50    0.08    --  121.75 -91.00-180.00   52
132  \w     80.00 106.00   0.50    0.08    --  121.75 -91.00-150.00   52
133  \w     85.00 151.00   0.50    0.08    --  121.75  50.00 -30.00  132
134  \w     47.00  78.00   0.50    0.08    --  121.75 -91.00 120.00   62
135  \w     87.00 162.00   0.50    0.08    --  121.75  50.00 120.00  150
136  \w     46.00  75.00   0.50    0.08    --  121.75 -91.00-150.00   58
137  \w     80.00 107.00   0.50    0.08    --  121.75  77.00 -88.42   54
138  \w     82.00 177.00   0.50    0.08    --  121.75  48.00  12.71  190
139  \w     38.00 174.00   0.50    0.08    --  121.75 -37.00 -30.00  272
140  \w     49.00 106.00   0.50    0.08    --  121.75 -91.00   0.00  114
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1164058000
_diffrn_orient_matrix_UB_12      -0.0534387000
_diffrn_orient_matrix_UB_13      -0.0875100000
_diffrn_orient_matrix_UB_21      -0.0816778000
_diffrn_orient_matrix_UB_22      -0.0486126000
_diffrn_orient_matrix_UB_23      0.0675653000
_diffrn_orient_matrix_UB_31      -0.0757969000
_diffrn_orient_matrix_UB_32      0.0848519000
_diffrn_orient_matrix_UB_33      -0.0038870000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0506
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.9996
_diffrn_reflns_Laue_measured_fraction_max 0.9855
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            47546
_diffrn_reflns_point_group_measured_fraction_full 0.9996
_diffrn_reflns_point_group_measured_fraction_max 0.9855
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         77.69
_diffrn_reflns_theta_min         4.31
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.160
_exptl_absorpt_correction_T_max  0.472
_exptl_absorpt_correction_T_min  0.064
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.57a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.252
_exptl_crystal_description       block
_exptl_crystal_F_000             802.474
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.4346
_refine_diff_density_min         -0.3622
_refine_diff_density_rms         0.0491
_refine_ls_d_res_high            0.7891
_refine_ls_d_res_low             10.2629
_refine_ls_goodness_of_fit_ref   1.0253
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    86
_refine_ls_number_parameters     456
_refine_ls_number_reflns         8228
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.0237
_refine_ls_R_factor_all          0.0449
_refine_ls_R_factor_gt           0.0416
_refine_ls_shift/su_max          -0.0003
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0665P)^2^+0.4219P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1125
_refine_ls_wR_factor_ref         0.1159
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              12
_reflns_limit_h_min              -12
_reflns_limit_k_max              17
_reflns_limit_k_min              -17
_reflns_limit_l_max              18
_reflns_limit_l_min              0
_reflns_number_gt                7384
_reflns_number_total             8228
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5ce00025d2.cif
_cod_data_source_block           exp_89_red1_abs1
_cod_depositor_comments
'Adding full bibliography for 7250152--7250159.cif.'
_cod_database_code               7250156
_chemical_oxdiff_formula         'C32 H48 S2 N2 F9 I1'
_chemical_oxdiff_usercomment     '100K '
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 H21a-N21
 0.89 with sigma of 0.04
 H21b-N21
 0.89 with sigma of 0.04
 S11-C11 \\sim S11-C11A
 with sigma of 0.02
 S12-C12 \\sim S12-C12A
 with sigma of 0.02
 N11-C11 \\sim N11-C11A
 with sigma of 0.02
 N11-C12 \\sim N11-C12A
 with sigma of 0.04
 N12-C12 \\sim N12-C12A
 with sigma of 0.02
 S11-C12 \\sim S11-C12A
 with sigma of 0.04
 C11-C12 \\sim C11A-C12A
 with sigma of 0.02
 S12-C11 \\sim S12-C11A
 with sigma of 0.04
 N12-C11 \\sim N12-C11A
 with sigma of 0.04
 S21-C21A \\sim S21-C21
 with sigma of 0.02
 N21-C21A \\sim N21-C21
 with sigma of 0.02
3. Others
 Sof(C11A)=Sof(C12A)=1-FVAR(1)
 Sof(C11)=Sof(C12)=FVAR(1)
 Sof(C21)=1-FVAR(2)
 Sof(C21A)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C33(H33), C38(H38), C51(H51), C56(H56), C61(H61), C66(H66)
4.b Secondary CH2 refined with riding coordinates:
 C31(H31a,H31b), C32(H32a,H32b), C34(H34a,H34b), C35(H35a,H35b), C36(H36a,
 H36b), C37(H37a,H37b), C39(H39a,H39b), C40(H40a,H40b), C52(H52a,H52b),
 C53(H53a,H53b), C54(H54a,H54b), C55(H55a,H55b), C57(H57a,H57b), C58(H58a,H58b),
  C62(H62a,H62b), C63(H63a,H63b), C64(H64a,H64b), C65(H65a,H65b), C67(H67a,
 H67b), C68(H68a,H68b), C69(H69a,H69b), C70(H70a,H70b), C59(H59a,H59b),
 C60(H60a,H60b)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.321
_oxdiff_exptl_absorpt_empirical_full_min 0.805