A close-packed Ti6 and Ti12 nanocluster superstructure
Li, Huan; Cui, Xiaoqin; Li, Xin; Dong, Jing; Wang, Yuan; Zhang, Xian-Ming; CrystEngComm 25 (2023) 53–57; doi:10.1039/D2CE01198K

data_7245870
_publ_section_title
;
 A close-packed Ti6 and Ti12 nanocluster superstructure
;
_journal_issue                   1
_journal_name_full               CrystEngComm
_journal_page_first              53
_journal_page_last               57
_journal_paper_doi               10.1039/D2CE01198K
_journal_volume                  25
_journal_year                    2023
_chemical_formula_moiety         '3(C54 H72 N6 O24 Ti6), C54 H126 O32 Ti12'
_chemical_formula_sum            'C216 H342 N18 O104 Ti30'
_chemical_formula_weight         6292.06
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-07
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-11-08 deposited with the CCDC.	2022-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   30.0732(10)
_cell_length_b                   30.0732(10)
_cell_length_c                   29.0267(11)
_cell_measurement_reflns_used    6949
_cell_measurement_temperature    298(1)
_cell_measurement_theta_max      74.6180
_cell_measurement_theta_min      3.4380
_cell_volume                     22734.6(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      298(1)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.942
_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     84.00 163.00   0.50   35.00    --  101.00  41.00 -36.00  158
  2  \w     74.00 130.00   0.50   35.00    --  101.00 -72.00-124.00  112
  3  \w      4.00  34.00   0.50    0.80    --    0.00  82.00 150.00   60
  4  \w    -33.00  39.00   0.50    0.80    --    0.00  82.00 -90.00  144
  5  \w     98.00 152.00   0.50   35.00    --  101.00  81.00-132.00  108
  6  \w     77.00 174.00   0.50   35.00    --  101.00  77.00   0.00  194
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0116550667
_diffrn_orient_matrix_UB_12      0.0379454667
_diffrn_orient_matrix_UB_13      -0.0254343333
_diffrn_orient_matrix_UB_21      -0.0284109000
_diffrn_orient_matrix_UB_22      -0.0404126000
_diffrn_orient_matrix_UB_23      -0.0378052000
_diffrn_orient_matrix_UB_31      -0.0505882000
_diffrn_orient_matrix_UB_32      -0.0206036000
_diffrn_orient_matrix_UB_33      0.0271468000
_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  0.0622
_diffrn_reflns_av_unetI/netI     0.0763
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            21819
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.527
_diffrn_reflns_theta_min         3.486
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.012
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55734
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (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    1.379
_exptl_crystal_description       block
_exptl_crystal_F_000             9768
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.774
_refine_diff_density_min         -1.006
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.133
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     594
_refine_ls_number_reflns         10015
_refine_ls_number_restraints     185
_refine_ls_restrained_S_all      1.124
_refine_ls_R_factor_all          0.1774
_refine_ls_R_factor_gt           0.1178
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3109
_refine_ls_wR_factor_ref         0.3636
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5164
_reflns_number_total             10015
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ce01198k2.cif
_cod_data_source_block           ti12+ti6
_cod_depositor_comments          'Adding full bibliography for 7245870.cif.'
_cod_original_cell_volume        22734.6(17)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               7245870
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C O N H Ti'
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.127
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3A-C1A
 1.5 with sigma of 0.01
 C3A-C1A = C3B-C1B = C2B-C1B = C2A-C1A
 1.5 with sigma of 0.01
 C2A-C1A = C3A-C1A
 1.5 with sigma of 0.01
 C34-C36
 1.53 with sigma of 0.01
 C6B-C4 = C5B-C4
 1.5 with sigma of 0.01
 C14B-C13 = C13-C14A = C13-C15B = C15A-C13
 1.45 with sigma of 0.01
 O6-C1B
 1.36 with sigma of 0.01
 O1-C4
 1.38 with sigma of 0.01
 C6A-C4 = C5A-C4
 1.5 with sigma of 0.01
 O12-C13
 1.367 with sigma of 0.01
 C35-C34
 1.45 with sigma of 0.01
 O10-C34
 1.37 with sigma of 0.01
 O6-C1A
 1.32 with sigma of 0.01
 C12-C10
 1.5 with sigma of 0.01
 C3A-C2A
 2.52 with sigma of 0.04
 C5B-C6B
 2.52 with sigma of 0.04
 C15B-C14B
 2.4 with sigma of 0.04
 C6A-C5A
 2.52 with sigma of 0.04
 C2A-C3A \\sim C2B-C3B
 with sigma of 0.04
 C1A-C2A \\sim C1B-C2B
 with sigma of 0.02
 O6-C2A \\sim O6-C2B
 with sigma of 0.04
 C1A-C3A \\sim C1B-C3B
 with sigma of 0.02
 O6-C3A \\sim O6-C3B
 with sigma of 0.04
 C13-C15A \\sim C13-C14B
 with sigma of 0.02
 O6-C1A \\sim O6-C1B
 with sigma of 0.02
 C13-C14A \\sim C13-C15B
 with sigma of 0.02
3. Rigid bond restraints
 C5A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C36) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C7)
\\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C10) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C6B) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
Uanis(C1A) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C1B)
\\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(C3B) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C4) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C5B)
\\sim Ueq, Uanis(C6B) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C13) \\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C15B)
\\sim Ueq, Uanis(C14B) \\sim Ueq: with sigma of 0.1 and sigma for terminal
atoms of 0.2
Uanis(C5A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C1B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C1A) = Uanis(C2A) = Uanis(C3A)
Uanis(C5A) = Uanis(C5B) = Uanis(C4) = Uanis(C6A) = Uanis(C6B)
5. Others
 Sof(HB)=Sof(C5B)=Sof(HV)=Sof(HW)=Sof(HX)=Sof(C6B)=Sof(HY)=Sof(HZ)=Sof(H4)=1-
 FVAR(1)
 Sof(HA)=Sof(C5A)=Sof(HI)=Sof(HJ)=Sof(HK)=Sof(C6A)=Sof(HS)=Sof(HT)=Sof(HU)=
 FVAR(1)
 Sof(H13A)=Sof(C15B)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C14B)=Sof(H14D)=
 Sof(H14E)=Sof(H14F)=1-FVAR(2)
 Sof(H13)=Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15A)=Sof(H15A)=
 Sof(H15B)=Sof(H15C)=FVAR(2)
 Sof(C1B)=Sof(H5)=Sof(C2B)=Sof(H6)=Sof(H7)=Sof(H8)=Sof(C3B)=Sof(H9)=Sof(H11)=
 Sof(H12)=1-FVAR(3)
 Sof(C1A)=Sof(HL)=Sof(C2A)=Sof(HM)=Sof(HN)=Sof(HO)=Sof(C3A)=Sof(HP)=Sof(HQ)=
 Sof(HR)=FVAR(3)
6.a Riding coordinates:
 C2A(HM,HN,HO), C3A(HP,HQ,HR), C36(H36A,H36B,H36C), C6B(HY,HZ,H4), C14B(H14D,
 H14E,H14F), C2B(H6,H7,H8), C3B(H9,H11,H12)
6.b Ternary CH refined with riding coordinates:
 C10(H10), C7(H), C4(HA), C4(HB), C1A(HL), C34(H34), C13(H13), C13(H13A),
 C1B(H5)
6.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C27(H27), N1(H1), C24(H24), C33(H33), C18(H18), N3(H3), C30(H30),
 C32(H32), C26(H26), C25(H25), C21(H21), C19(H19), C31(H31), C20(H20)
6.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C11(H11A,H11B,H11C), C8(HC,HD,HE), C9(HF,HG,HH), C5A(HI,
 HJ,HK), C35(H35A,H35B,H35C), C6A(HS,HT,HU), C5B(HV,HW,HX), C14A(H14A,H14B,
 H14C), C15A(H15A,H15B,H15C), C15B(H15D,H15E,H15F)
;
_shelx_res_checksum              99536
_shelx_hkl_checksum              29320
_shelx_fab_checksum              72090
_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 1.786
_oxdiff_exptl_absorpt_empirical_full_min 0.330