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_7703977
_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
'2(H8 O40 S8 Ti4), 7(C8 H22 N2), 2(C8 H21 N2), 6(H2 O), 3(Cl), O4 S'
_chemical_formula_sum            'C72 H224 Cl3 N18 O90 S17 Ti8'
_chemical_formula_weight         3817.25
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_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
;
2020-03-28 deposited with the CCDC.	2020-04-06 downloaded from the CCDC.
;
_cell_angle_alpha                109.769(2)
_cell_angle_beta                 90.193(2)
_cell_angle_gamma                109.105(2)
_cell_formula_units_Z            1
_cell_length_a                   15.4295(4)
_cell_length_b                   17.3585(5)
_cell_length_c                   18.1126(4)
_cell_measurement_reflns_used    14657
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      75.7490
_cell_measurement_theta_min      2.5590
_cell_volume                     4278.2(2)
_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      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.941
_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    -80.00  22.00   1.00    0.20    --  -48.45  98.00-139.00  102
  2  \w     -8.00  78.00   1.00    0.20    --   48.45 -98.00 113.00   86
  3  \w    -71.00 -13.00   1.00    2.00    --  -86.25  98.00-139.00   58
  4  \w   -122.00 -82.00   1.00    2.00    --  -86.25 -98.00 113.00   40
  5  \w    103.00 147.00   1.00    2.00    --  106.49  98.00-139.00   44
  6  \w     42.00 109.00   1.00    2.00    --  106.49 -98.00 113.00   67
  7  \w    -63.00 -10.00   1.00    0.20    --  -48.45  57.00  60.00   53
  8  \w     -6.00  23.00   1.00    0.20    --  -48.45  57.00  60.00   29
  9  \w    -71.00  23.00   1.00    0.20    --  -48.45  77.00-180.00   94
 10  \w    -61.00  25.00   1.00    0.20    --  -48.45  37.00 150.00   86
 11  \w     36.00 116.00   1.00    2.00    --  106.49-125.00 120.00   80
 12  \w     86.00 178.00   1.00    2.00    --  106.49  77.00 -90.00   92
 13  \w     94.00 178.00   1.00    2.00    --  106.49  61.00-180.00   84
 14  \w     35.00 118.00   1.00    2.00    --  106.49 -45.00 -60.00   83
 15  \w     93.00 178.00   1.00    2.00    --  106.49  15.00-150.00   85
 16  \w     38.00 108.00   1.00    2.00    --  106.49 -94.00-180.00   70
 17  \w     42.00 123.00   1.00    2.00    --  106.49 -61.00-180.00   81
 18  \w     90.00 178.00   1.00    2.00    --  106.49  61.00 -60.00   88
 19  \w     34.00  60.00   1.00    2.00    --  106.49-125.00 -30.00   26
 20  \w     76.00 117.00   1.00    2.00    --  106.49-125.00 -30.00   41
 21  \w     35.00 119.00   1.00    2.00    --  106.49 -61.00 -90.00   84
;
_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      -0.0062193000
_diffrn_orient_matrix_UB_12      -0.0660323000
_diffrn_orient_matrix_UB_13      -0.0837102000
_diffrn_orient_matrix_UB_21      -0.0773304000
_diffrn_orient_matrix_UB_22      -0.0702734000
_diffrn_orient_matrix_UB_23      0.0193353000
_diffrn_orient_matrix_UB_31      -0.0730295000
_diffrn_orient_matrix_UB_32      0.0287923000
_diffrn_orient_matrix_UB_33      -0.0304010000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1331
_diffrn_reflns_av_unetI/netI     0.1130
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            42809
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.628
_diffrn_reflns_theta_min         2.614
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.253
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33223
_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    1.482
_exptl_crystal_description       block
_exptl_crystal_F_000             2001
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.653
_refine_diff_density_min         -1.256
_refine_diff_density_rms         0.209
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     987
_refine_ls_number_reflns         16946
_refine_ls_number_restraints     303
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1876
_refine_ls_R_factor_gt           0.1504
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0820P)^2^+182.8221P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3949
_refine_ls_wR_factor_ref         0.4155
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12571
_reflns_number_total             16946
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt00165a2.cif
_cod_data_source_block           ti4-ocda
_cod_depositor_comments
'Adding full bibliography for 7703974--7703977.cif.'
_cod_original_cell_volume        4278.1(2)
_cod_database_code               7703977
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Ti O C SN'
_shelx_estimated_absorpt_t_max   0.788
_shelx_estimated_absorpt_t_min   0.521
_reflns_odcompleteness_completeness 98.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 S1_1-O1_1 = S1_1-O2_1 = S1_1-O3_1 = S1_1-O4_1
 1.5 with sigma of 0.02
 C22-C21 = C23-C22 = C24-C23 = C25-C24 = C26-C25 = C27-C26 = C28-C27
 1.45 with sigma of 0.01
 C11-C10 = C9-C10 = C9-C8 = C5-C37 = N6-C5 = C7-C37
 1.45 with sigma of 0.01
 N5-C36 = C36-C35 = C35-C34 = C34-C33 = C33-C32 = C32-C31 = C31-C30 = C30-C29 =
  N4-C29
 1.45 with sigma of 0.01
 C2-C1 = C4-C3
 1.45 with sigma of 0.02
 C16-C15 = C19-C18
 1.45 with sigma of 0.02
 O1_1-O3_1 \\sim O2_1-O4_1 \\sim O1_1-O4_1 \\sim O2_1-O3_1 \\sim O1_1-O2_1
\\sim O3_1-O4_1
 with sigma of 0.04
 O1_1-O2_1 \\sim O3_1-O4_1
 Cl1_2-Cl1_2 \\sim Cl1_2-Cl1_2
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C21 \\sim N2 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim
C28 \\sim N3: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C11 \\sim C10 \\sim C9 \\sim C8 \\sim C7 \\sim C37 \\sim C5 \\sim N6 \\sim C12
\\sim N7: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
C36 \\sim C35 \\sim C34 \\sim C33 \\sim C32 \\sim C31 \\sim C30 \\sim C29 \\sim
N4: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(C28) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O33) \\sim Ueq, Uanis(O30) \\sim Ueq, Uanis(O13) \\sim Ueq: with sigma of
0.002 and sigma for terminal atoms of 0.004
Uanis(O28) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 S1_1, O1_1, O2_1, O3_1, O4_1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Cl3(0.5) Cl1(0.5) S1(0.5) O1(0.5) O2(0.5) O3(0.5) O4(0.5) Cl1(0.5)
6.a Riding coordinates:
 N6(H6A,H6B), O39(H39A,H39B), O38(H38A,H38B), O37(H37C,H37D)
6.b Free rotating group:
 O5(H5A,H5B)
6.c Rotating group:
 O25(H25A,H25B), O15(H15A,H15B), O32(H32A,H32B)
6.d Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C21(H21A,H21B), C13(H13A,H13B), C19(H19A,H19B), C36(H36A,
 H36B), C12(H12A,H12B), C18(H18A,H18B), C28(H28A,H28B), C17(H17A,H17B),
 C16(H16A,H16B), C15(H15C,H15D), C14(H14A,H14B), C11(H11A,H11B), C37(H37A,H37B),
  C22(H22A,H22B), C9(H9D,H9E), C7(H7D,H7E), C24(H24A,H24B), C25(H25C,H25D),
 C35(H35A,H35B), C8(H8D,H8E), C29(H29A,H29B), C27(H27A,H27B), C30(H30A,H30B),
 C32(H32C,H32D), C31(H31A,H31B), C10(H10A,H10B), C23(H23A,H23B), C26(H26A,H26B),
  C33(H33A,H33B), C1(H1D,H1E), C2(H2D,H2E), C3(H3D,H3E), C4(H4D,H4E), C34(H34A,
 H34B), C5(H5F,H5G)
6.e Idealised Me refined as rotating group:
 N8(H8A,H8B,H8C), N7(H7A,H7B,H7C), N9(H9A,H9B,H9C), N3(H3A,H3B,H3C), N2(H2A,
 H2B,H2C), N5(H5C,H5D,H5E), N4(H4A,H4B,H4C), N1(H1A,H1B,H1C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 76 electrons were
found in a volume of 222\%A^3 in 3 voids per unit cell.
This is consistent with the presence of 4[H2O] per Formula Unit 
which account for 80 electrons per unit cell.
;
_shelx_res_checksum              39225
_shelx_fab_checksum              35202
_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 1.814
_oxdiff_exptl_absorpt_empirical_full_min 0.304