Cluster <i>versus</i> coordination: the chemistry of cyclopentadienyl titanium and vanadium complexes with B- and C-functionalized carborane-thiols, [C<sub>2</sub>B<sub>10</sub>H<sub>12-<i>n</i></sub> (SH) <sub><i>n</i></sub> ] (<i>n</i> = 2 or 3).
Bairagi, Subhash; Patel, Deepak Kumar; Chatterjee, Debipada; Kučeráková, Monika; Macháček, Jan; Base, Tomas; Pradeep, Thalappil; Ghosh, Sundargopal; Chemical science 16 (2025) 14127–14139; doi:10.1039/d5sc03562g

data_1575075
_publ_section_title
;
 Cluster <i>versus</i> coordination: the chemistry of cyclopentadienyl
 titanium and vanadium complexes with B- and C-functionalized
 carborane-thiols, [C<sub>2</sub>B<sub>10</sub>H<sub>12-<i>n</i></sub>
 (SH) <sub><i>n</i></sub> ] (<i>n</i> = 2 or 3).
;
_journal_issue                   31
_journal_name_full               'Chemical science'
_journal_page_first              14127
_journal_page_last               14139
_journal_paper_doi               10.1039/d5sc03562g
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '2(C41.5 H65 B5 S7.5 Ti5)'
_chemical_formula_sum            'C83 H130 B10 S15 Ti10'
_chemical_formula_weight         2195.86
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-05-15
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-05-15 deposited with the CCDC.	2025-07-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.7370(14)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   22.5923(5)
_cell_length_b                   21.4585(9)
_cell_length_c                   12.9948(10)
_cell_measurement_reflns_used    9871
_cell_measurement_temperature    150
_cell_measurement_theta_max      24.396
_cell_measurement_theta_min      2.261
_cell_volume                     6256.3(6)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0822
_diffrn_reflns_av_unetI/netI     0.0450
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            118101
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.416
_diffrn_reflns_theta_min         1.969
_exptl_absorpt_coefficient_mu    0.885
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.904
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
Krause, L., Herbst-Irmer, R., Sheldrick, G. M., Stalke, D. (2015).
"Comparison of silver and molybdenum microfocus X-ray sources for
single-crystal structure determination"
J. Appl. Cryst. 48, 3-10.
doi:10.1107/S1600576714022985
;
_exptl_crystal_density_diffrn    1.166
_exptl_crystal_description       'polygon shape'
_exptl_crystal_F_000             2276
_exptl_crystal_size_max          0.102
_exptl_crystal_size_mid          0.054
_exptl_crystal_size_min          0.037
_refine_diff_density_max         1.331
_refine_diff_density_min         -0.948
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     666
_refine_ls_number_reflns         12788
_refine_ls_number_restraints     1849
_refine_ls_restrained_S_all      0.990
_refine_ls_R_factor_all          0.0977
_refine_ls_R_factor_gt           0.0763
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1419P)^2^+14.4095P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2219
_refine_ls_wR_factor_ref         0.2465
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9411
_reflns_number_total             12788
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03562g2.cif
_cod_data_source_block           ti5-standard-settingsolex
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Multi-Scan' was
changed to 'multi-scan' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1575071--1575076.cif.
;
_cod_database_code               1575075
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C4h-C3h \\sim C4g-C3g \\sim C4g-C5g \\sim C5h-C4h \\sim C5h-C49 \\sim C1h-C5g
\\sim C2h-C49 \\sim C1h-C2g
 \\sim C3g-C2g \\sim C2h-C3h
 with sigma of 0.02
 C5h-C10h \\sim C10g-C5g \\sim C4g-C9g \\sim C9h-C4h \\sim C3g-C8g \\sim
C8h-C3h \\sim C7g-C2h \\sim C7h-
 C2g \\sim C6h-C49 \\sim C1h-C6g
 with sigma of 0.02
 C4f-C3f \\sim C5f-C4f \\sim C5f-C1f \\sim C1f-C2f \\sim C3e-C2e \\sim C2f-C3f
\\sim C3e-C4e \\sim C5e-C4e
 \\sim C5e-C1e \\sim C2e-C1e
 with sigma of 0.02
 C4e-C9e \\sim C9f-C4f \\sim C5e-C10e \\sim C10f-C5f \\sim C6e-C1e \\sim
C6f-C1f \\sim C2e-C7e \\sim C7f-
 C2f \\sim C3e-C8e \\sim C8f-C3f
 with sigma of 0.02
 C2a-C1a \\sim C3a-C2a \\sim C2b-C1b \\sim C2b-C3b \\sim C3a-C4a \\sim C4b-C3b
\\sim C5b-C4b \\sim C4a-C5a
 \\sim C1b-C5b \\sim C1a-C5a
 with sigma of 0.02
 C7a-C2a \\sim C7b-C2b \\sim C8b-C3b \\sim C3a-C8a \\sim C9a-C4a \\sim C9b-C4b
\\sim C10a-C5a \\sim C10b-
 C5b \\sim C6a-C1a \\sim C6b-C1b
 with sigma of 0.02
 C5c-C1c \\sim C2c-C1c \\sim C5c-C4c \\sim C5d-C4d \\sim C4c-C3c \\sim C3d-C4d
\\sim C3d-C2d \\sim C2c-C3c
 \\sim C5d-C1d \\sim C2d-C1d
 with sigma of 0.02
 C10c-C5c \\sim C10d-C5d \\sim C6d-C1d \\sim C6c-C1c \\sim C7d-C2d \\sim
C7c-C2c \\sim C3d-C8d \\sim C8c-
 C3c \\sim C9c-C4c \\sim C9d-C4d
 with sigma of 0.02
 C4h-C9h \\sim C4g-C9g
 with sigma of 0.02
 C3g-C8g \\sim C8h-C3h
 with sigma of 0.02
 C3c-C5c \\sim C5h-C3h
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C8b) = Uanis(C8a)
Uanis(C9a) = Uanis(C9b)
Uanis(C10a) = Uanis(C10b)
Uanis(C6a) = Uanis(C6b)
Uanis(C7b) = Uanis(C7a)
Uanis(C5a) = Uanis(C5b)
Uanis(C1a) = Uanis(C1b)
Uanis(C2b) = Uanis(C2a)
Uanis(C3a) = Uanis(C3b)
Uanis(C3e) = Uanis(C3f)
Uanis(C4e) = Uanis(C4f)
Uanis(C5e) = Uanis(C5f)
Uanis(C1e) = Uanis(C1f)
Uanis(C2e) = Uanis(C2f)
Uanis(C8e) = Uanis(C8f)
Uanis(C9e) = Uanis(C9f)
Uanis(C7f) = Uanis(C7e)
Uanis(C6f) = Uanis(C6e)
Uanis(C10f) = Uanis(C10e)
Uanis(C5g) = Uanis(C5h)
Uanis(C4h) = Uanis(C4g)
Uanis(C3h) = Uanis(C3g)
Uanis(C2h) = Uanis(C2g)
Uanis(C7g) = Uanis(C7h)
Uanis(C8h) = Uanis(C8g)
Uanis(C9h) = Uanis(C9g)
Uanis(C10h) = Uanis(C10g)
Uanis(C6g) = Uanis(C6h)
Uanis(C7c) = Uanis(C7d)
Uanis(C6c) = Uanis(C6d)
Uanis(C10d) = Uanis(C10c)
Uanis(C9c) = Uanis(C9d)
Uanis(C8c) = Uanis(C8d)
Uanis(C2d) = Uanis(C2c)
Uanis(C1d) = Uanis(C1c)
Uanis(C49) = Uanis(C1h)
Uanis(C2b) = Uanis(C2a) = Uanis(C3b) = Uanis(C3a)
Uanis(C8h) = Uanis(C8g) = Uanis(C3h) = Uanis(C3g) = Uanis(C2h) = Uanis(C2g)
Uanis(C49) = Uanis(C1h) = Uanis(C5h) = Uanis(C5g) = Uanis(C6h) = Uanis(C6g) =
Uanis(C7g) = Uanis(C7h)
Uanis(C9h) = Uanis(C9g) = Uanis(C4h) = Uanis(C4g) = Uanis(C5h) = Uanis(C5g)
Uanis(C8f) = Uanis(C8e) = Uanis(C2f) = Uanis(C2e) = Uanis(C1f) = Uanis(C1e)
Uanis(B1) = Uanis(B4) = Uanis(B8) = Uanis(B9) = Uanis(B10) = Uanis(B3) =
Uanis(C4) = Uanis(C2) = Uanis(C1) = Uanis(C3) = Uanis(B6) = Uanis(B7) =
Uanis(B5) = Uanis(B2)
Uanis(C10h) = Uanis(C10g) = Uanis(C5g) = Uanis(C5h) = Uanis(C1h) = Uanis(C49)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Sof(C10g)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C3g)=Sof(C4g)=Sof(C1h)=Sof(C2g)=
 Sof(C9g)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C8g)=Sof(H12A)=Sof(H12B)=Sof(H12C)=
 Sof(C6g)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C7h)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C5g)=1-FVAR(1)
 Sof(C9h)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C10h)=Sof(H2AA)=Sof(H2AB)=
 Sof(H2AC)=Sof(C5h)=Sof(C3h)=Sof(C4h)=Sof(C49)=Sof(C2h)=Sof(C8h)=Sof(H52A)=
 Sof(H52B)=Sof(H52C)=Sof(C6h)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C7g)=Sof(H54A)=
 Sof(H54B)=Sof(H54C)=FVAR(1)
 Sof(C3f)=Sof(C2f)=Sof(C4f)=Sof(C1f)=Sof(C6f)=Sof(H76A)=Sof(H76B)=Sof(H76C)=
 Sof(C5f)=Sof(C7f)=Sof(H81A)=Sof(H81B)=Sof(H81C)=Sof(C8f)=Sof(H82A)=Sof(H82B)=
 Sof(H82C)=Sof(C10f)=Sof(H83A)=Sof(H83B)=Sof(H83C)=Sof(C9f)=Sof(H84A)=Sof(H84B)=
 Sof(H84C)=1-FVAR(2)
 Sof(C1e)=Sof(C6e)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C7e)=Sof(H41A)=Sof(H41B)=
 Sof(H41C)=Sof(C8e)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C10e)=Sof(H43A)=Sof(H43B)=
 Sof(H43C)=Sof(C9e)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C2e)=Sof(C4e)=Sof(C3e)=
 Sof(C5e)=FVAR(2)
 Sof(C5a)=Sof(C10a)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C1a)=Sof(C2a)=Sof(C6a)=
 Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C7a)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C4a)=
 Sof(C8a)=Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(C3a)=Sof(C9a)=Sof(H71A)=Sof(H71B)=
 Sof(H71C)=1-FVAR(3)
 Sof(C3b)=Sof(C4b)=Sof(C9b)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C8b)=Sof(H32A)=
 Sof(H32B)=Sof(H32C)=Sof(C5b)=Sof(C10b)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C1b)=
 Sof(C2b)=Sof(C6b)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C7b)=Sof(H74A)=Sof(H74B)=
 Sof(H74C)=FVAR(3)
 Sof(C8d)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C1d)=Sof(C2d)=Sof(C4d)=Sof(C5d)=
 Sof(C7d)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C6d)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(C9d)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C10d)=Sof(H24A)=Sof(H24B)=Sof(H24C)=
 Sof(C3d)=1-FVAR(4)
 Sof(C3c)=Sof(C8c)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C1c)=Sof(C2c)=Sof(C4c)=
 Sof(C5c)=Sof(C7c)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C6c)=Sof(H62A)=Sof(H62B)=
 Sof(H62C)=Sof(C9c)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C10c)=Sof(H64A)=Sof(H64B)=
 Sof(H64C)=FVAR(4)
 Fixed Sof: S7(0.5) S8(0.5) C1(0.5) C2(0.5) B1(0.5) H1(0.5) B2(0.5) H2(0.5)
 B3(0.5) H3(0.5) B4(0.5) H4(0.5) B5(0.5) H5(0.5) B6(0.5) H6(0.5) B7(0.5)
 H7(0.5) B8(0.5) H8(0.5) B9(0.5) H9(0.5) B10(0.5) H10(0.5) S9(0.25) S10(0.25)
 C3(0.25) C4(0.25)
6.a Idealised Me refined as rotating group:
 C9h(H1AA,H1AB,H1AC), C10h(H2AA,H2AB,H2AC), C8h(H52A,H52B,H52C), C6h(H53A,H53B,
 H53C), C7g(H54A,H54B,H54C), C10g(H6A,H6B,H6C), C9g(H11A,H11B,H11C), C8g(H12A,
 H12B,H12C), C6g(H13A,H13B,H13C), C7h(H14A,H14B,H14C), C6e(H36A,H36B,H36C),
 C7e(H41A,H41B,H41C), C8e(H42A,H42B,H42C), C10e(H43A,H43B,H43C), C9e(H44A,H44B,
 H44C), C6f(H76A,H76B,H76C), C7f(H81A,H81B,H81C), C8f(H82A,H82B,H82C),
 C10f(H83A,H83B,H83C), C9f(H84A,H84B,H84C), C9b(H31A,H31B,H31C), C8b(H32A,H32B,
 H32C), C10b(H66A,H66B,H66C), C6b(H73A,H73B,H73C), C7b(H74A,H74B,H74C),
 C10a(H26A,H26B,H26C), C6a(H33A,H33B,H33C), C7a(H34A,H34B,H34C), C8a(H67A,H67B,
 H67C), C9a(H71A,H71B,H71C), C8c(H56A,H56B,H56C), C7c(H61A,H61B,H61C), C6c(H62A,
 H62B,H62C), C9c(H63A,H63B,H63C), C10c(H64A,H64B,H64C), C8d(H16A,H16B,H16C),
 C7d(H21A,H21B,H21C), C6d(H22A,H22B,H22C), C9d(H23A,H23B,H23C), C10d(H24A,H24B,
 H24C)
6.b Boron cage BH refined with riding coordinates:
 B1(H1), B2(H2), B3(H3), B4(H4), B5(H5), B6(H6), B7(H7), B8(H8), B9(H9),
 B10(H10)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              89583
_shelx_fab_checksum              12741
_olex2_submission_special_instructions 'No special instructions were received'