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_7250158
_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         '2(C H2 N S), C20 H36 O6, H2 O'
_chemical_formula_sum            'C22 H42 N2 O7 S2'
_chemical_formula_weight         510.720
_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'
_symmetry_Int_Tables_number      14
_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                90
_cell_angle_beta                 90.560(1)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.1890(1)
_cell_length_b                   14.7300(1)
_cell_length_c                   21.8560(2)
_cell_measurement_reflns_used    20432
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.3110
_cell_measurement_theta_min      3.6070
_cell_volume                     2636.23(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.70a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.70a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.70a (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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.0000
_diffrn_measured_fraction_theta_max 0.9900
_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    -43.00  41.00   0.50    0.05    --    0.00  87.00  75.00  168
  2  \w     47.00  85.00   0.50    0.05    --   66.57 -87.00 -42.00   76
  3  \w     44.00 169.00   0.50    0.05    --  121.75 -87.00 -42.00  250
  4  \w     48.00  83.00   0.50    0.05    --    0.00  77.00 150.00   70
  5  \w    -70.00 -11.00   0.50    0.05    --    0.00 -77.00 -30.00  118
  6  \w    -94.00 -40.00   0.50    0.05    --    0.00 178.00-150.00  108
  7  \w    -42.00  45.00   0.50    0.05    --    0.00  77.00 150.00  174
  8  \w    -94.00 -54.00   0.50    0.05    --    0.00-178.00 -60.00   80
  9  \w    -85.00 -12.00   0.50    0.05    --    0.00 -77.00  90.00  146
 10  \w    -16.00  19.00   0.50    0.05    --   38.00 101.00 -99.39   70
 11  \w    -12.00  13.00   0.50    0.05    --   42.00 101.00 110.33   50
 12  \w     -3.00  22.00   0.50    0.05    --   50.00  99.00  49.69   50
 13  \w     17.00  42.00   0.50    0.05    --   62.00  85.00-149.00   50
 14  \w     12.00  37.00   0.50    0.05    --   62.00  92.00 113.51   50
 15  \w     15.00  40.00   0.50    0.05    --   62.00  90.00  15.65   50
 16  \w     17.00  42.00   0.50    0.05    --   66.00  90.00 -48.69   50
 17  \w     17.00  42.00   0.50    0.05    --   66.00  90.00-111.46   50
 18  \w     16.00  41.00   0.50    0.05    --   66.00  92.00 -10.62   50
 19  \w     16.00  41.00   0.50    0.05    --   66.00  92.00  63.86   50
 20  \w     16.00  41.00   0.50    0.05    --   66.00  92.00 123.45   50
 21  \w    -17.00 110.00   0.50    0.05    --   66.57 -45.00 -90.00  254
 22  \w     -9.00 101.00   0.50    0.05    --   66.57 -61.00  30.00  220
 23  \w    -10.00  99.00   0.50    0.05    --   66.57 -61.00 120.00  218
 24  \w     61.00  94.00   0.50    0.05    --   66.57 -94.00 120.00   66
 25  \w     52.00  98.00   0.50    0.05    --   66.57 -94.00  30.00   92
 26  \w     60.00 106.00   0.50    0.05    --   66.57 -94.00-180.00   92
 27  \w     65.00 105.00   0.50    0.05    --   66.57 -94.00-150.00   80
 28  \w     64.00  90.00   0.50    0.05    --   74.00  74.00 132.09   52
 29  \w     65.00 106.00   0.50    0.05    --   74.00  76.00 -32.48   82
 30  \w     32.00  61.00   0.50    0.05    --   74.00  74.00 132.09   58
 31  \w     32.00  97.00   0.50    0.05    --   74.00  76.00-120.30  130
 32  \w     32.00  70.00   0.50    0.05    --   74.00  75.00 -92.56   76
 33  \w     32.00 109.00   0.50    0.05    --   74.00  77.00  60.74  154
 34  \w     80.00 108.00   0.50    0.05    --   74.00  75.00 -92.56   56
 35  \w     32.00  58.00   0.50    0.05    --   74.00  76.00 -32.48   52
 36  \w     75.00 109.00   0.50    0.05    --   78.00  76.00 151.39   68
 37  \w     84.00 109.00   0.50    0.05    --   78.00  76.00  -3.78   50
 38  \w     38.00  70.00   0.50    0.05    --   78.00  76.00 151.39   64
 39  \w     38.00  73.00   0.50    0.05    --   78.00  71.00  93.62   70
 40  \w     85.00 160.00   0.50    0.05    --   78.00  71.00  93.62  150
 41  \w     41.00  67.00   0.50    0.05    --   78.00  76.00  -3.78   52
 42  \w    139.00 165.00   0.50    0.05    --   86.00  73.00 -11.64   52
 43  \w     43.00  69.00   0.50    0.05    --   86.00  77.00   2.04   52
 44  \w     95.00 136.00   0.50    0.05    --   86.00  73.00 -11.64   82
 45  \w     83.00 109.00   0.50    0.05    --   86.00  77.00-111.50   52
 46  \w     44.00  73.00   0.50    0.05    --   86.00  77.00-111.50   58
 47  \w     44.00  69.00   0.50    0.05    --   86.00  74.00  33.15   50
 48  \w     45.00  70.00   0.50    0.05    --   86.00  73.00 -11.64   50
 49  \w     43.00  68.00   0.50    0.05    --   86.00  77.00-138.63   50
 50  \w     43.00  69.00   0.50    0.05    --   86.00  77.00 -79.97   52
 51  \w     48.00  88.00   0.50    0.05    --   90.00  76.00 156.31   80
 52  \w     49.00  95.00   0.50    0.05    --   90.00  76.00  46.89   92
 53  \w     48.00  83.00   0.50    0.05    --   90.00  76.00 171.14   70
 54  \w     52.00 101.00   0.50    0.05    --   94.00  74.00  78.46   98
 55  \w     52.00  78.00   0.50    0.05    --   94.00  74.00 133.08   52
 56  \w     83.00 109.00   0.50    0.05    --   94.00  77.00 -90.30   52
 57  \w     51.00  99.00   0.50    0.05    --   94.00  77.00-168.45   96
 58  \w     51.00  76.00   0.50    0.05    --   94.00  77.00 -90.30   50
 59  \w     53.00  78.00   0.50    0.05    --   94.00  73.00  61.89   50
 60  \w     51.00  79.00   0.50    0.05    --   94.00  77.00  -4.49   56
 61  \w     51.00  92.00   0.50    0.05    --   94.00  77.00 -71.17   82
 62  \w     53.00  79.00   0.50    0.05    --   94.00  75.00 177.87   52
 63  \w     52.00  78.00   0.50    0.05    --   94.00  75.00  89.63   52
 64  \w    147.00 173.00   0.50    0.05    --   94.00  73.00  61.89   52
 65  \w     99.00 125.00   0.50    0.05    --   94.00  73.00  61.89   52
 66  \w     55.00  80.00   0.50    0.05    --   98.00  77.00 101.83   50
 67  \w     56.00  81.00   0.50    0.05    --   98.00  74.00 -32.23   50
 68  \w     56.00  96.00   0.50    0.05    --   98.00  76.00-157.84   80
 69  \w     59.00  84.00   0.50    0.05    --  102.00  77.00 137.68   50
 70  \w     60.00  85.00   0.50    0.05    --  102.00  75.00  11.67   50
 71  \w     59.00 107.00   0.50    0.05    --  102.00  77.00 -61.97   96
 72  \w     59.00  84.00   0.50    0.05    --  102.00  77.00 104.25   50
 73  \w     66.00  91.00   0.50    0.05    --  106.00  70.00 -99.65   50
 74  \w    114.00 139.00   0.50    0.05    --  106.00  70.00 -99.65   50
 75  \w     64.00 107.00   0.50    0.05    --  106.00  76.00 -19.31   86
 76  \w    103.00 163.00   0.50    0.05    --  106.00  67.00-131.42  120
 77  \w     68.00 100.00   0.50    0.05    --  106.00  67.00-131.42   64
 78  \w     64.00 105.00   0.50    0.05    --  106.00  76.00 168.34   82
 79  \w     68.00 109.00   0.50    0.05    --  110.00  75.00  40.62   82
 80  \w     72.00 177.00   0.50    0.05    --  110.00  68.00 -77.30  210
 81  \w    114.00 161.00   0.50    0.05    --  110.00  63.00  27.11   94
 82  \w     74.00 100.00   0.50    0.05    --  110.00  63.00  27.11   52
 83  \w    113.00 177.00   0.50    0.05    --  114.00  61.00  -4.84  128
 84  \w     78.00 104.00   0.50    0.05    --  114.00  61.00  -4.84   52
 85  \w     74.00 100.00   0.50    0.05    --  114.00  73.00 -99.15   52
 86  \w    151.00 177.00   0.50    0.05    --  114.00  70.00 136.30   52
 87  \w    114.00 147.00   0.50    0.05    --  114.00  70.00 136.30   66
 88  \w     75.00 105.00   0.50    0.05    --  114.00  70.00 136.30   60
 89  \w    130.00 177.00   0.50    0.05    --  114.00  67.00  63.66   94
 90  \w     76.00 121.00   0.50    0.05    --  114.00  67.00  63.66   90
 91  \w     78.00 177.00   0.50    0.05    --  118.00  73.00 168.54  198
 92  \w     78.00 107.00   0.50    0.05    --  118.00  71.00 163.54   58
 93  \w    150.00 176.00   0.50    0.05    --  118.00  71.00 116.19   52
 94  \w     78.00 132.00   0.50    0.05    --  118.00  71.00 116.19  108
 95  \w     61.00 107.00   0.50    0.05    --  121.75-105.00-163.17   92
 96  \w     79.00 105.00   0.50    0.05    --  121.75 -91.00 -60.00   52
 97  \w    119.00 175.00   0.50    0.05    --  121.75  50.00 -30.00  112
 98  \w     88.00 114.00   0.50    0.05    --  121.75  50.00 -30.00   52
 99  \w     49.00  75.00   0.50    0.05    --  121.75 -91.00 -60.00   52
100  \w     64.00 108.00   0.50    0.05    --  121.75-109.00-107.86   88
101  \w     39.00  81.00   0.50    0.05    --  121.75  25.00 -60.00   84
102  \w    122.00 150.00   0.50    0.05    --  121.75 -63.00 -60.00   56
103  \w     47.00 104.00   0.50    0.05    --  121.75 -63.00 -60.00  114
104  \w     81.00 109.00   0.50    0.05    --  121.75  76.00 -80.17   56
105  \w    140.00 175.00   0.50    0.05    --  121.75  72.00  73.13   70
106  \w     80.00 134.00   0.50    0.05    --  121.75  72.00  73.13  108
107  \w     87.00 112.00   0.50    0.05    --  121.75  65.00  53.38   50
108  \w     62.00 108.00   0.50    0.05    --  121.75-108.00  51.97   92
109  \w     81.00 106.00   0.50    0.05    --  121.75 -93.00 -95.51   50
110  \w     50.00  76.00   0.50    0.05    --  121.75 -93.00 -95.51   52
111  \w     81.00 106.00   0.50    0.05    --  121.75 -91.00-120.00   50
112  \w     46.00  75.00   0.50    0.05    --  121.75 -91.00-120.00   58
113  \w     79.00 104.00   0.50    0.05    --  121.75  76.00  23.27   50
114  \w     46.00 104.00   0.50    0.05    --  121.75 -91.00 120.00  116
115  \w    151.00 176.00   0.50    0.05    --  121.75  73.00 139.53   50
116  \w    121.00 177.00   0.50    0.05    --  121.75  63.00   0.00  112
117  \w     93.00 118.00   0.50    0.05    --  121.75  25.00 -60.00   50
118  \w    152.00 177.00   0.50    0.05    --  121.75  25.00 -60.00   50
119  \w    116.00 146.00   0.50    0.05    --  121.75  73.00 139.53   60
120  \w     85.00 174.00   0.50    0.05    --  121.75  63.00  30.00  178
121  \w     85.00 114.00   0.50    0.05    --  121.75  63.00   0.00   58
122  \w    148.00 173.00   0.50    0.05    --  121.75  71.00-173.64   50
123  \w     84.00 127.00   0.50    0.05    --  121.75  71.00-173.64   86
124  \w     68.00 108.00   0.50    0.05    --  121.75-107.00 107.22   80
125  \w     81.00 110.00   0.50    0.05    --  121.75  73.00 139.53   58
126  \w     88.00 121.00   0.50    0.05    --  121.75  63.00-120.00   66
127  \w     79.00 104.00   0.50    0.05    --  121.75  76.00 -18.94   50
128  \w     85.00 143.00   0.50    0.05    --  121.75 -77.00  30.00  116
129  \w    135.00 175.00   0.50    0.05    --  121.75  50.00 120.00   80
130  \w     60.00 122.00   0.50    0.05    --  121.75 -50.00  90.00  124
131  \w    114.00 177.00   0.50    0.05    --  121.75  63.00 -90.00  126
;
_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      0.0867255000
_diffrn_orient_matrix_UB_12      0.0203817000
_diffrn_orient_matrix_UB_13      -0.0606963000
_diffrn_orient_matrix_UB_21      -0.1380490000
_diffrn_orient_matrix_UB_22      0.0661172000
_diffrn_orient_matrix_UB_23      -0.0180524000
_diffrn_orient_matrix_UB_31      0.0938025000
_diffrn_orient_matrix_UB_32      0.0784653000
_diffrn_orient_matrix_UB_33      0.0309717000
_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     0.0207
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 0.9900
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            60133
_diffrn_reflns_point_group_measured_fraction_full 1.0000
_diffrn_reflns_point_group_measured_fraction_max 0.9900
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         77.51
_diffrn_reflns_theta_min         3.62
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.188
_exptl_absorpt_correction_T_max  0.897
_exptl_absorpt_correction_T_min  0.286
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.70a (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    1.287
_exptl_crystal_description       block
_exptl_crystal_F_000             1110.175
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.4173
_refine_diff_density_min         -0.4988
_refine_diff_density_rms         0.0544
_refine_ls_d_res_high            0.7896
_refine_ls_d_res_low             12.2147
_refine_ls_goodness_of_fit_ref   1.0311
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    60
_refine_ls_number_parameters     324
_refine_ls_number_reflns         5565
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.0307
_refine_ls_R_factor_all          0.0343
_refine_ls_R_factor_gt           0.0319
_refine_ls_shift/su_max          0.0005
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0407P)^2^+0.9681P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0808
_refine_ls_wR_factor_ref         0.0826
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              10
_reflns_limit_h_min              -10
_reflns_limit_k_max              18
_reflns_limit_k_min              0
_reflns_limit_l_max              27
_reflns_limit_l_min              0
_reflns_number_gt                5139
_reflns_number_total             5565
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5ce00025d2.cif
_cod_data_source_block           47_C1_red1_abs1
_cod_depositor_comments
'Adding full bibliography for 7250152--7250159.cif.'
_cod_database_code               7250158
_chemical_oxdiff_formula         'C34 S2 N2 Br2 F6 H48'
_chemical_oxdiff_usercomment     '100K '
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
2. Restrained distances
 S11-C11A \\sim S11-C11
 with sigma of 0.02
 N11-C11A \\sim N11-C11
 with sigma of 0.02
3. Others
 Sof(C11)=1-FVAR(1)
 Sof(C11A)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C51(H51), C56(H56), C61(H61), C62(H62)
4.b Secondary CH2 refined with riding coordinates:
 C52(H52a,H52b), C53(H53a,H53b), C54(H54a,H54b), C55(H55a,H55b), C57(H57a,
 H57b), C58(H58a,H58b), C59(H59a,H59b), C60(H60a,H60b), C63(H63a,H63b),
 C64(H64a,H64b), C65(H65a,H65b), C66(H66a,H66b), C67(H67a,H67b), C68(H68a,H68b),
  C69(H69a,H69b), C70(H70a,H70b)
4.c X=CH2 refined with riding coordinates:
 N21(H21a,H21b)
;
_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 1.195
_oxdiff_exptl_absorpt_empirical_full_min 0.792