Designing the structure and relevant properties of semiclathrate hydrates by partly asymmetric alkylammonium salts
Muromachi, Sanehiro; Kida, Masato; Morimoto, Masato; Yamane, Shogo; Takeya, Satoshi; Physical Chemistry Chemical Physics  (2022) –; doi:10.1039/D2CP02625B

data_7245199
_publ_section_title
;
 Designing the structure and relevant properties of semiclathrate hydrates
 by partly asymmetric alkylammonium salts
;
_journal_name_full               'Physical Chemistry Chemical Physics'
_journal_paper_doi               10.1039/D2CP02625B
_journal_year                    2022
_chemical_formula_moiety
'0.22(Br), 0.39(O), H9.16 O8.81, H0.25 O0.5, 0.25(C17 H38 N)'
_chemical_formula_sum            'C3.65 H16.27 Br0.21 N0.22 O9.66'
_chemical_formula_weight         234.73
_space_group_crystal_system      orthorhombic
_space_group_IT_number           51
_space_group_name_Hall           '-P 2a 2a'
_space_group_name_H-M_alt        'P m m a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-13
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2022-06-02 deposited with the CCDC.	2022-07-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.0695(10)
_cell_length_b                   12.6077(6)
_cell_length_c                   12.0415(6)
_cell_measurement_reflns_used    5064
_cell_measurement_temperature    90.00(16)
_cell_measurement_theta_max      31.3360
_cell_measurement_theta_min      1.9430
_cell_volume                     3198.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_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_environment      N~2~
_diffrn_ambient_temperature      90.00(16)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.826
_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    -36.00   0.00   0.50   17.74    --   -4.27 -76.00  57.00   72
  2  \w    -72.00 -43.00   0.50   17.74    --   -4.27 -76.00  57.00   58
  3  \w    -20.00  22.00   0.50   17.74    --   -4.27 -99.00 150.00   84
  4  \w    -28.00  -3.00   0.50   17.74    --   -4.27  79.00 -62.00   50
  5  \w    -20.00  40.00   0.50   17.74    --    6.85 -99.00 -60.00  120
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0141684000
_diffrn_orient_matrix_UB_12      0.0273815000
_diffrn_orient_matrix_UB_13      -0.0451027000
_diffrn_orient_matrix_UB_21      -0.0241813000
_diffrn_orient_matrix_UB_22      0.0390591000
_diffrn_orient_matrix_UB_23      0.0027247000
_diffrn_orient_matrix_UB_31      0.0186603000
_diffrn_orient_matrix_UB_32      0.0298332000
_diffrn_orient_matrix_UB_33      0.0377714000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0617
_diffrn_reflns_av_unetI/netI     0.0580
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.826
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            20300
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.826
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.024
_diffrn_reflns_theta_min         1.948
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.621
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96376
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.104a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.975
_exptl_crystal_description       prism
_exptl_crystal_F_000             995
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.715
_refine_diff_density_min         -0.457
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     307
_refine_ls_number_reflns         4514
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0825
_refine_ls_R_factor_gt           0.0573
_refine_ls_shift/su_max          0.062
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0718P)^2^+2.8456P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1549
_refine_ls_wR_factor_ref         0.1639
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3374
_reflns_number_total             4514
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cp02625b2.cif
_cod_data_source_block           20220328_sv20_mo_90k_auto_CCDC1
_cod_database_code               7245199
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         (C4H9)3C5H11NBr(H2O)38
_chemical_oxdiff_usercomment     'N4445-3-HYD hydrate'
_diffrn_oxdiff_digest_frames
;
01ea679cf95e7796c0116bd8c54f7acad3000251021
;
_diffrn_oxdiff_digest_hkl
;
0121ef92cb60643db8d402326c5ec9b91ed242
;
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups, All O(H,H,H)
  groups, All O(H,H,H,H) groups
2. Restrained distances
 O2-H2A = O2-H2B
 0.87 with sigma of 0.02
 O10-H10A = O10-H10B
 0.87 with sigma of 0.02
 O11-H11A = O11-H11B
 0.87 with sigma of 0.02
 O12-H12A = O12-H12B
 0.87 with sigma of 0.02
 O13-H13A = O13-H13B
 0.87 with sigma of 0.02
 O14-H14A = O14-H14B
 0.87 with sigma of 0.02
 O15-H15A = O15-H15B
 0.87 with sigma of 0.02
 O16-H16A = O16-H16B
 0.87 with sigma of 0.02
 O17-H17A = O17-H17B
 0.87 with sigma of 0.02
 H13A-H13B
 1.38 with sigma of 0.04
 H2A-H2B
 1.38 with sigma of 0.04
 H17A-H17B
 1.38 with sigma of 0.04
 H11A-H11B
 1.38 with sigma of 0.04
 H15A-H15B
 1.38 with sigma of 0.04
 H10A-H10B
 1.38 with sigma of 0.04
 H12A-H12B
 1.38 with sigma of 0.04
 H14A-H14B
 1.38 with sigma of 0.04
 H16A-H16B
 1.38 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uiso(C1B) = Uiso(C1D)
Uiso(C2B) = Uiso(C2D)
Uiso(C3B) = Uiso(C3D)
Uiso(C4B) = Uiso(C4D)
Uanis(C1A) = Uanis(C1C)
Uanis(C2A) = Uanis(C2C)
Uanis(C3A) = Uanis(C3C)
Uanis(C4A) = Uanis(C4C)
4. Others
 1*[Sof(O21A)+Sof(H21A)+Sof(H21B)]+1*[Sof(O21B)]=1 with esd of 0.1
 1*[Sof(O20A)]+1*[Sof(O20B)]=1 with esd of 0.1
 Sof(H21A)=Sof(H21B)=0.12495*FVAR(2)
 Sof(O21A)=0.5*FVAR(2)
 Fixed Sof: H18A(0.25) H18B(0.25) H20A(0.25) H2A(0.25) H2B(0.25) H2C(0.25)
 H2D(0.25) H10A(0.25) H10B(0.25) H10C(0.25) H10D(0.25) H11A(0.25) H11B(0.25)
 H11C(0.25) H11D(0.25) H12A(0.25) H12B(0.25) H12C(0.25) H12D(0.25) H13A(0.25)
 H13B(0.25) H13C(0.25) H14A(0.25) H14B(0.25) H14C(0.25) H14D(0.25) H15A(0.25)
 H15B(0.25) H15C(0.25) H16A(0.25) H16B(0.25) H16C(0.25) H17A(0.25) H17B(0.25)
 H17C(0.25) H19A(0.25) H19B(0.25) N1(0.25) C1A(0.25) H1AA(0.25) H1AB(0.25)
 C2A(0.25) H2AA(0.25) H2AB(0.25) C3A(0.25) H3AA(0.25) H3AB(0.25) C4A(0.25)
 H4AA(0.25) H4AB(0.25) H4AC(0.25) C1B(0.25) H1BA(0.25) H1BB(0.25) C2B(0.25)
 H2BA(0.25) H2BB(0.25) C3B(0.25) H3BA(0.25) H3BB(0.25) C4B(0.25) H4BA(0.25)
 H4BB(0.25) H4BC(0.25) C1C(0.25) H1CA(0.25) H1CB(0.25) C2C(0.25) H2CA(0.25)
 H2CB(0.25) C3C(0.25) H3CA(0.25) H3CB(0.25) C4C(0.25) H4CA(0.25) H4CB(0.25)
 H4CC(0.25) C1D(0.25) H1DA(0.25) H1DB(0.25) C2D(0.25) H2DA(0.25) H2DB(0.25)
 C3D(0.25) H3DA(0.25) H3DB(0.25) C4D(0.25) H4DA(0.25) H4DB(0.25) C5D(0.25)
 H5DA(0.25) H5DB(0.25) H5DC(0.25)
5.a Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C2A(H2AA,H2AB), C3A(H3AA,H3AB), C1B(H1BA,H1BB), C2B(H2BA,
 H2BB), C3B(H3BA,H3BB), C1C(H1CA,H1CB), C2C(H2CA,H2CB), C3C(H3CA,H3CB),
 C1D(H1DA,H1DB), C2D(H2DA,H2DB), C3D(H3DA,H3DB), C4D(H4DA,H4DB)
5.b Idealised Me refined as rotating group:
 C4A(H4AA,H4AB,H4AC), C4B(H4BA,H4BB,H4BC), C4C(H4CA,H4CB,H4CC), C5D(H5DA,H5DB,
 H5DC)
;
_shelx_res_checksum              56903
_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 1.136
_oxdiff_exptl_absorpt_empirical_full_min 0.885