The role of water in the formation of crystal structures: a case study of valnemulin hydrochloride
Li, Shuyu; Wang, Ting; Huang, Xin; Zhou, Lina; Chen, Mingyu; Liu, Wanying; Zhang, Xiunan; Dong, Yuyuan; Hao, Hongxun; CrystEngComm 23 (2021) 47–55; doi:10.1039/D0CE01459A

data_7241922
_publ_section_title
;
 The role of water in the formation of crystal structures: a case study of
 valnemulin hydrochloride
;
_journal_issue                   1
_journal_name_full               CrystEngComm
_journal_page_first              47
_journal_page_last               55
_journal_paper_doi               10.1039/D0CE01459A
_journal_volume                  23
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C31 H53 N2 O5 S, Cl, 2(H2 O)'
_chemical_formula_sum            'C31 H57 Cl N2 O7 S'
_chemical_formula_weight         637.29
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-04-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-09-21 deposited with the CCDC.	2020-11-16 downloaded from the CCDC.
;
_cell_angle_alpha                105.9470(10)
_cell_angle_beta                 93.0280(10)
_cell_angle_gamma                108.1380(10)
_cell_formula_units_Z            3
_cell_length_a                   9.60590(10)
_cell_length_b                   15.35080(10)
_cell_length_c                   19.7270(2)
_cell_measurement_reflns_used    66284
_cell_measurement_temperature    160.00(10)
_cell_measurement_theta_max      76.2660
_cell_measurement_theta_min      2.3680
_cell_volume                     2627.33(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      160.00(10)
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.950
_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    -78.00  27.00   0.50    0.05    --  -46.12  94.00  81.00  210
  2  \w    -26.00  78.00   0.50    0.05    --   46.12 -94.00 -29.00  208
  3  \w   -173.00 -84.00   0.50    0.20    -- -100.00 -94.00 -29.00  178
  4  \w   -109.00 -27.00   0.50    0.20    -- -100.00  94.00  81.00  164
  5  \w     78.00 178.00   0.50    0.20    --  107.31  94.00  81.00  200
  6  \w    -24.00   3.00   0.50    0.05    --   12.00 102.00 152.36   54
  7  \w    -19.00   8.00   0.50    0.05    --   16.00 100.00-152.75   54
  8  \w    -12.00  30.00   0.50    0.05    --   20.00  94.00  79.37   84
  9  \w      5.00  36.00   0.50    0.05    --   36.00  92.00 -61.41   62
 10  \w      8.00  39.00   0.50    0.05    --   36.00  87.00 129.42   62
 11  \w     10.00  39.00   0.50    0.05    --   40.00  91.00-152.45   58
 12  \w    -95.00 -20.00   0.50    0.05    --  -46.12 125.00  60.00  150
 13  \w     31.00 122.00   0.50    0.05    --   46.12  19.00  60.00  182
 14  \w     23.00 118.00   0.50    0.05    --   46.12  77.00  60.00  190
 15  \w     23.00 121.00   0.50    0.05    --   48.00  81.00 128.28  196
 16  \w     22.00 121.00   0.50    0.05    --   48.00  83.00 -55.08  198
 17  \w     25.00 125.00   0.50    0.05    --   52.00  84.00 -26.19  200
 18  \w     25.00 125.00   0.50    0.05    --   52.00  84.00 -87.96  200
 19  \w   -128.00 -29.00   0.50    0.05    --  -56.00 -83.00  44.38  198
 20  \w     29.00 129.00   0.50    0.05    --   56.00  84.00  46.57  200
 21  \w     31.00 129.00   0.50    0.05    --   56.00  79.00 150.74  196
 22  \w   -132.00 -33.00   0.50    0.05    --  -60.00 -83.00 176.83  198
 23  \w   -132.00 -33.00   0.50    0.05    --  -60.00 -84.00-129.03  198
 24  \w     38.00 137.00   0.50    0.05    --   64.00  83.00-146.32  198
 25  \w     39.00 137.00   0.50    0.05    --   64.00  80.00 158.88  196
 26  \w     39.00 137.00   0.50    0.05    --   64.00  79.00 -31.00  196
 27  \w   -140.00 -41.00   0.50    0.05    --  -68.00 -83.00  16.92  198
 28  \w    -81.00 -43.00   0.50    0.05    --  -68.00 -81.00  59.67   76
 29  \w    -73.00 -42.00   0.50    0.05    --  -68.00 -81.00 117.19   62
 30  \w   -136.00-110.00   0.50    0.05    --  -68.00 -81.00 117.19   52
 31  \w    -75.00 -44.00   0.50    0.05    --  -68.00 -76.00  77.46   62
 32  \w    -66.00 -41.00   0.50    0.05    --  -68.00 -83.00  -4.64   50
 33  \w     43.00  68.00   0.50    0.05    --   68.00  79.00-118.08   50
 34  \w    -82.00 -45.00   0.50    0.05    --  -72.00 -83.00-173.09   74
 35  \w   -144.00-119.00   0.50    0.05    --  -72.00 -83.00-173.09   50
 36  \w    -77.00 -45.00   0.50    0.05    --  -72.00 -83.00 -55.92   64
 37  \w    -85.00 -53.00   0.50    0.20    --  -76.00 -75.00  34.97   64
 38  \w    -75.00 -49.00   0.50    0.20    --  -76.00 -83.00 -27.45   52
 39  \w    -84.00 -57.00   0.50    0.20    --  -80.00 -75.00-125.70   54
 40  \w    -80.00 -54.00   0.50    0.20    --  -80.00 -82.00  14.20   52
 41  \w    -80.00 -54.00   0.50    0.20    --  -80.00 -81.00 -73.19   52
 42  \w    -87.00 -57.00   0.50    0.20    --  -80.00 -82.00-140.05   60
 43  \w    -86.00 -53.00   0.50    0.20    --  -80.00 -83.00 -89.39   66
 44  \w    -81.00 -55.00   0.50    0.20    --  -80.00 -83.00-178.60   52
 45  \w   -148.00-122.00   0.50    0.20    --  -80.00 -83.00-178.60   52
 46  \w    -94.00 -61.00   0.50    0.20    --  -84.00 -74.00-174.00   66
 47  \w    -91.00 -61.00   0.50    0.20    --  -84.00 -74.00 125.06   60
 48  \w    -87.00 -62.00   0.50    0.20    --  -84.00 -73.00  65.50   50
 49  \w   -101.00 -58.00   0.50    0.20    --  -84.00 -81.00 165.46   86
 50  \w    -96.00 -57.00   0.50    0.20    --  -84.00 -84.00 -11.52   78
 51  \w    -91.00 -65.00   0.50    0.20    --  -88.00 -74.00 -58.82   52
 52  \w   -158.00-108.00   0.50    0.20    --  -88.00 -74.00 -58.82  100
 53  \w    -95.00 -70.00   0.50    0.20    --  -88.00 -63.00  32.85   50
 54  \w    -89.00 -63.00   0.50    0.20    --  -88.00 -79.00 121.89   52
 55  \w    -91.00 -64.00   0.50    0.20    --  -88.00 -76.00 -38.43   54
 56  \w   -157.00-101.00   0.50    0.20    --  -88.00 -79.00 121.89  112
 57  \w    -93.00 -65.00   0.50    0.20    --  -88.00 -75.00  87.22   56
 58  \w   -101.00 -65.00   0.50    0.20    --  -88.00 -74.00 103.11   72
 59  \w    -91.00 -65.00   0.50    0.20    --  -88.00 -74.00  27.70   52
 60  \w   -107.00 -75.00   0.50    0.20    --  -92.00 -60.00-167.67   64
 61  \w   -111.00 -72.00   0.50    0.20    --  -92.00 -68.00 -97.25   78
 62  \w   -141.00-116.00   0.50    0.20    --  -92.00 -68.00 -97.25   50
 63  \w   -169.00 -72.00   0.50    0.20    --  -96.00 -78.00 -36.49  194
 64  \w    -97.00 -72.00   0.50    0.20    --  -96.00 -76.00 -31.91   50
 65  \w   -133.00-107.00   0.50    0.20    --  -96.00 -76.00 -31.91   52
 66  \w   -168.00 -72.00   0.50    0.20    --  -96.00 -76.00   1.09  192
 67  \w   -168.00 -73.00   0.50    0.20    --  -96.00 -75.00  76.81  190
 68  \w   -167.00 -72.00   0.50    0.20    --  -96.00 -78.00-105.64  190
 69  \w   -159.00 -78.00   0.50    0.20    -- -100.00 -72.00  32.81  162
 70  \w   -165.00 -77.00   0.50    0.20    -- -100.00 -76.00-127.03  176
 71  \w   -101.00 -76.00   0.50    0.20    -- -100.00 -76.00-165.27   50
 72  \w   -171.00-119.00   0.50    0.20    -- -100.00 -76.00-165.27  104
 73  \w   -117.00 -82.00   0.50    0.20    -- -100.00 125.00 150.00   70
 74  \w   -104.00 -78.00   0.50    0.20    -- -100.00 -72.00 -70.01   52
 75  \w   -172.00-108.00   0.50    0.20    -- -100.00 -72.00 -70.01  128
 76  \w   -172.00 -79.00   0.50    0.20    -- -100.00 -71.00 161.78  186
 77  \w   -118.00 -82.00   0.50    0.20    -- -100.00 -65.00 113.71   72
 78  \w   -173.00-133.00   0.50    0.20    -- -100.00 -65.00 113.71   80
 79  \w   -173.00 -75.00   0.50    0.20    -- -100.00 -80.00  23.82  196
 80  \w   -142.00 -76.00   0.50    0.20    -- -100.00 -76.00  65.85  132
 81  \w   -172.00 -76.00   0.50    0.20    -- -100.00 -77.00-180.00  192
 82  \w     36.00 107.00   0.50    0.20    --  107.31 -94.00   0.00  142
 83  \w     55.00 125.00   0.50    0.20    --  107.31 -61.00 -30.00  140
 84  \w     35.00 131.00   0.50    0.20    --  107.31 -77.00-150.00  192
 85  \w     35.00 108.00   0.50    0.20    --  107.31 -94.00 150.00  146
 86  \w     47.00 115.00   0.50    0.20    --  107.31 -61.00-150.00  136
 87  \w     75.00 117.00   0.50    0.20    --  107.31-125.00 120.00   84
 88  \w     35.00 110.00   0.50    0.20    --  107.31 -61.00 120.00  150
 89  \w     63.00 107.00   0.50    0.20    --  107.31 -94.00 -29.00   88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0545
_diffrn_reflns_av_unetI/netI     0.0333
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            89550
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.888
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.546
_diffrn_reflns_theta_min         2.357
_exptl_absorpt_coefficient_mu    1.885
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89187
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45g (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.208
_exptl_crystal_description       needle
_exptl_crystal_F_000             1038
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.035
_refine_diff_density_min         -1.163
_refine_diff_density_rms         0.100
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.020(19)
_refine_ls_extinction_coef       0.0058(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1259
_refine_ls_number_reflns         19844
_refine_ls_number_restraints     22
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0807
_refine_ls_R_factor_gt           0.0745
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1752P)^2^+1.1472P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2107
_refine_ls_wR_factor_ref         0.2253
_reflns_Friedel_coverage         0.869
_reflns_Friedel_fraction_full    0.934
_reflns_Friedel_fraction_max     0.826
_reflns_number_gt                18462
_reflns_number_total             19844
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ce01459a2.cif
_cod_data_source_block           030824_lpy_ra
_cod_depositor_comments          'Adding full bibliography for 7241922.cif.'
_cod_database_code               7241922
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.912
_shelx_estimated_absorpt_t_min   0.834
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups,
  All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 C80-C81
 1.45 with sigma of 0.01
 C4BA-C3BA
 1.45 with sigma of 0.01
 C71A-C70A \\sim C71-C70
 with sigma of 0.04
 C68-C70A \\sim C68-C70
 with sigma of 0.04
 S2-C71A \\sim S2-C71
 with sigma of 0.04
 S2-C70A \\sim S2-C70
 with sigma of 0.04
 C68-C71A \\sim C68-C71
 with sigma of 0.04
 C66A-C63A \\sim C66-C63
 with sigma of 0.04
 C67-C65A \\sim C67-C65
 with sigma of 0.04
 C67-C66A \\sim C67-C66
 with sigma of 0.02
 C66A-C65A \\sim C66-C65
 with sigma of 0.02
 C66A-C64A \\sim C66-C64
 with sigma of 0.04
 C64A-C65A \\sim C64-C65
 with sigma of 0.02
 C65A-C63A \\sim C65-C63
 with sigma of 0.02
 C64A-C63A \\sim C64-C63
 with sigma of 0.04
 S2-C69A \\sim S2-C69
 with sigma of 0.02
 C68-C69A \\sim C68-C69
 with sigma of 0.02
 C69A-C71A \\sim C69-C71
 with sigma of 0.02
 C69A-C70A \\sim C69-C70
 with sigma of 0.02
 N4A-C66A \\sim N4-C66
 with sigma of 0.02
 C67-N4A \\sim C67-N4
 with sigma of 0.04
 N4A-C65A \\sim N4-C65
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(O21A) = Uanis(O21)
4. Others
 Sof(H68C)=Sof(H68D)=Sof(C69)=Sof(C71)=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C70)=
 Sof(H70D)=Sof(H70E)=Sof(H70F)=1-FVAR(1)
 Sof(H68A)=Sof(H68B)=Sof(C69A)=Sof(C71A)=Sof(H71A)=Sof(H71B)=Sof(H71C)=
 Sof(C70A)=Sof(H70A)=Sof(H70B)=Sof(H70C)=FVAR(1)
 Sof(C66)=Sof(H66)=Sof(C65)=Sof(H65)=Sof(C64)=Sof(H64D)=Sof(H64E)=Sof(H64F)=
 Sof(C63)=Sof(H63D)=Sof(H63E)=Sof(H63F)=Sof(N4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=1-
 FVAR(2)
 Sof(N4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=Sof(C66A)=Sof(H66A)=Sof(C64A)=
 Sof(H64A)=Sof(H64B)=Sof(H64C)=Sof(C65A)=Sof(H65A)=Sof(C63A)=Sof(H63A)=
 Sof(H63B)=Sof(H63C)=FVAR(2)
 Sof(O16A)=Sof(H16C)=Sof(H16D)=1-FVAR(3)
 Sof(O16)=Sof(H16A)=Sof(H16B)=FVAR(3)
 Sof(O21)=Sof(H21C)=Sof(H21D)=1-FVAR(4)
 Sof(O21A)=Sof(H21A)=Sof(H21B)=FVAR(4)
 Fixed X: O21A(0.205009) O19(0.278049) H19A(0.245509) H19B(0.253361)
 O16(0.466109) O16A(0.54529) H16C(0.59635) H16D(0.46372) O21(0.07026)
 H21C(0.06055) H21D(0.153201)
 Fixed Y: O21A(0.20476) O19(0.360841) H19A(0.38404) H19B(0.301021)
 O16(0.28094) O16A(0.26523) H16C(0.242129) H16D(0.25386) O21(0.17593)
 H21C(0.124721) H21D(0.21548)
 Fixed Z: O21A(0.473459) O19(0.6274) H19A(0.664981) H19B(0.62267) O16(0.53206)
 O16A(0.53186) H16C(0.55371) H16D(0.54823) O21(0.491469) H21C(0.45817)
 H21D(0.488999)
5.a Free rotating group:
 O20(H20A,H20B), O21A(H21A,H21B), O17(H17A,H17B), O18(H18A,H18B), O16(H16A,H16B)
5.b Ternary CH refined with riding coordinates:
 C2DA(H2DA), C9AA(H9AA), C87(H87), C3AA(H3AA), C5AA(H5AA), C46(H46),
 C0DA(H0DA), C54(H54), C1AA(H1AA), C43(H43), C91(H91), C49(H49), C0AA(H0AA),
 C74(H74), C33(H33), C93(H93), C35(H35), C47(H47), C83(H83), C66A(H66A),
 C65A(H65A), C66(H66), C65(H65)
5.c Secondary CH2 refined with riding coordinates:
 C2CA(H2CA,H2CB), C0BA(H0BA,H0BB), C37(H37A,H37B), C44(H44A,H44B), C6AA(H6AA,
 H6AB), C77(H77A,H77B), C56(H56A,H56B), C7AA(H7AA,H7AB), C41(H41A,H41B),
 C0CA(H0CA,H0CB), C85(H85A,H85B), C90(H90A,H90B), C52(H52A,H52B), C84(H84A,
 H84B), C55(H55A,H55B), C8BA(H8BA,H8BB), C51(H51A,H51B), C68(H68A,H68B),
 C68(H68C,H68D), C7BA(H7BA,H7BB), C89(H89A,H89B), C72(H72A,H72B)
5.d Aromatic/amide H refined with riding coordinates:
 N2(H2), N5(H5), N3(H3), C3BA(H3BA), C61(H61), C80(H80)
5.e X=CH2 refined with riding coordinates:
 C62(H62A,H62B), C4BA(H4BA,H4BB), C81(H81A,H81B)
5.f Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), N6(H6A,H6B,H6C), C5BA(H5BA,H5BB,H5BC), C1DA(H1DA,H1DB,H1DC),
 C59(H59A,H59B,H59C), C8AA(H8AA,H8AB,H8AC), C39(H39A,H39B,H39C), C7CA(H7CA,H7CB,
 H7CC), C34(H34A,H34B,H34C), C2BA(H2BA,H2BB,H2BC), C40(H40A,H40B,H40C),
 C58(H58A,H58B,H58C), C79(H79A,H79B,H79C), C76(H76A,H76B,H76C), C8CA(H8CA,H8CB,
 H8CC), C57(H57A,H57B,H57C), C9BA(H9BA,H9BB,H9BC), C32(H32A,H32B,H32C),
 N4A(H4AA,H4AB,H4AC), C92(H92A,H92B,H92C), C60(H60A,H60B,H60C), C64A(H64A,H64B,
 H64C), C9CA(H9CA,H9CB,H9CC), C63A(H63A,H63B,H63C), C82(H82A,H82B,H82C),
 C71A(H71A,H71B,H71C), C70A(H70A,H70B,H70C), C71(H71D,H71E,H71F), C70(H70D,H70E,
 H70F), C64(H64D,H64E,H64F), C63(H63D,H63E,H63F), N4(H4A,H4B,H4C)
5.g Idealised tetrahedral OH refined as rotating group:
 O11(H11), O7(H7), O2(H2A)
;
_shelx_res_checksum              96909
_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
;