Effects of organic ammonium cations on the isolation of {Ti<sub>4</sub>} cyclic clusters from water: an <sup>17</sup>O NMR study.
Liu, Weiming; Liu, Caiyun; Wu, Wenli; Zhang, Guanyun; Zhang, Jian; Tung, Chen-Ho; Wang, Yifeng; Dalton transactions (Cambridge, England : 2003) 49 (2020) 5957–5964; doi:10.1039/d0dt00165a

data_7703975
_publ_section_title
;
 Effects of organic ammonium cations on the isolation of {Ti<sub>4</sub>}
 cyclic clusters from water: an <sup>17</sup>O NMR study.
;
_journal_issue                   18
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              5957
_journal_page_last               5964
_journal_paper_doi               10.1039/d0dt00165a
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         '4(H16 O28 S4 Ti4), O32 S8, 8(C6 H16 N2)'
_chemical_formula_sum            'C48 H192 N16 O144 S24 Ti16'
_chemical_formula_weight         4834.00
_space_group_crystal_system      tetragonal
_space_group_IT_number           140
_space_group_name_Hall           '-I 4 2c'
_space_group_name_H-M_alt        'I 4/m c m'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-03-25
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-04-01 deposited with the CCDC.	2020-04-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   13.7675(2)
_cell_length_b                   13.7675(2)
_cell_length_c                   20.9391(4)
_cell_measurement_reflns_used    3451
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      76.0270
_cell_measurement_theta_min      6.1530
_cell_volume                     3968.88(11)
_computing_cell_refinement       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.25a (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    'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.958
_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   -120.00 -55.00   1.00    0.30    --  -48.45-173.00  89.00   65
  2  \w   -154.00 -83.00   1.00    0.95    --  -86.25-114.00-130.00   71
  3  \w    111.00 177.00   1.00    0.95    --  106.49  19.00-133.00   66
  4  \w   -105.00 -70.00   1.00    0.30    --  -48.45-125.00   0.00   35
  5  \w   -112.00 -80.00   1.00    0.30    --  -48.45-125.00 -30.00   32
  6  \w     40.00  81.00   1.00    0.95    --  106.49 -94.00  30.00   41
  7  \w     94.00 158.00   1.00    0.95    --  106.49  15.00 -30.00   64
;
_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      0.0223046000
_diffrn_orient_matrix_UB_12      -0.1093630000
_diffrn_orient_matrix_UB_13      0.0059036000
_diffrn_orient_matrix_UB_21      -0.0173644000
_diffrn_orient_matrix_UB_22      -0.0126592000
_diffrn_orient_matrix_UB_23      -0.0721719000
_diffrn_orient_matrix_UB_31      0.1082545000
_diffrn_orient_matrix_UB_32      0.0205167000
_diffrn_orient_matrix_UB_33      -0.0127321000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0407
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            5055
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.289
_diffrn_reflns_theta_min         4.542
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.700
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57223
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.25a (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    2.022
_exptl_crystal_description       block
_exptl_crystal_F_000             2480
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.780
_refine_diff_density_min         -0.759
_refine_diff_density_rms         0.159
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.228
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     131
_refine_ls_number_reflns         1094
_refine_ls_number_restraints     108
_refine_ls_restrained_S_all      1.175
_refine_ls_R_factor_all          0.0901
_refine_ls_R_factor_gt           0.0858
_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^)+156.6020P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1855
_refine_ls_wR_factor_ref         0.1897
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1046
_reflns_number_total             1094
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt00165a2.cif
_cod_data_source_block           ti4-chexda
_cod_depositor_comments
'Adding full bibliography for 7703974--7703977.cif.'
_cod_original_cell_volume        3968.88(14)
_cod_database_code               7703975
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Ti O S'
_reflns_odcompleteness_completeness 99.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H,H,H,H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 C2B-C2B_$1
 1.5 with sigma of 0.02
 S1-O6 = S1-O7 = S1-O7 = S1-O9
 1.45 with sigma of 0.01
 C2B_$2-C2B_$3
 1.5 with sigma of 0.02
 C2B-C2B_$3
 2.3 with sigma of 0.02
 C2B_$1-C2B_$2
 2.3 with sigma of 0.02
 C2B-C1B
 1.5 with sigma of 0.02
 C2A-C2A_$1
 1.5 with sigma of 0.02
 C2A_$2-C2A_$3
 1.5 with sigma of 0.02
 C2A-C2A_$3
 2.3 with sigma of 0.02
 C2A_$2-C2A_$1
 2.3 with sigma of 0.02
 C1A-N1
 1.5 with sigma of 0.02
 C1A-C2A
 1.5 with sigma of 0.02
 S1-O7 \\sim S1-O6 \\sim S1-O8_$4 \\sim S1-O9
 with sigma of 0.02
 O6-O7 \\sim O6-O8_$4 \\sim O6-O9 \\sim O7-O8_$4 \\sim O7-O9 \\sim O8_$4-O9
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S1 \\sim O6 \\sim O7 \\sim O8 \\sim O9: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(S1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1B) \\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(C1B)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C1A) \\sim Ueq, Uanis(C2A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 S1, O6, O7, O8, O9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: S1(0.25) O6(0.25) O7(0.25) O8(0.25) O9(0.25) H1AA(0.25) H1AC(0.25)
 H1AB(0.25) H1BE(0.25) H1BF(0.25) H1BD(0.25) C1A(0.25) H1A(0.25) C1B(0.25)
 H1B(0.25) C2A(0.5) H2AA(0.5) H2AB(0.5) C2B(0.5) H2BA(0.5) H2BB(0.5)
6.a Rotating group:
 O5(H5A,H5B)
6.b Ternary CH refined with riding coordinates:
 C1A(H1A), C1B(H1B)
6.c Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C2B(H2BA,H2BB)
6.d Idealised Me refined as rotating group:
 N1(H1AA,H1AC,H1AB), N1(H1BE,H1BF,H1BD)
;
_shelx_res_checksum              2888
_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 1.416
_oxdiff_exptl_absorpt_empirical_full_min 0.778