Heterodinuclear Cu(I)/Mo(VI) chemistry with bifunctional dibenzobarrelene ligands.
Chandima, A. M. Buddhika; Sgro, Griffyn; Hilditch, Sierra M.; Kaluarachchige Don, Umesh I.; Ward, Cassandra L.; Anderson, Dennis P.; Herman, Limor; Gelman, Dmitri; Lord, Richard L.; Groysman, Stanislav; Dalton transactions (Cambridge, England : 2003) 54 (2025) 14716–14727; doi:10.1039/d5dt01337b

data_1575689
_publ_section_title
;
 Heterodinuclear Cu(I)/Mo(VI) chemistry with bifunctional dibenzobarrelene
 ligands.
;
_journal_issue                   39
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14716
_journal_page_last               14727
_journal_paper_doi               10.1039/d5dt01337b
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety
'C88 H84 Cu2 Mo O10 P4 S2, 0.809(H2 O), 0.5(C2 H6 O S), 2.5[C2H6SO]'
_chemical_formula_sum            'C94 H103.62 Cu2 Mo O13.81 P4 S5'
_chemical_formula_weight         1961.52
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-28
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-06-04 deposited with the CCDC.	2025-09-10 downloaded from the CCDC.
;
_cell_angle_alpha                87.912(3)
_cell_angle_beta                 76.933(3)
_cell_angle_gamma                75.879(3)
_cell_formula_units_Z            2
_cell_length_a                   16.0253(14)
_cell_length_b                   17.1157(14)
_cell_length_c                   18.2784(15)
_cell_measurement_reflns_used    5195
_cell_measurement_temperature    101.00
_cell_measurement_theta_max      24.988
_cell_measurement_theta_min      2.288
_cell_volume                     4735.2(7)
_computing_cell_refinement       'SAINT V8.41 (?, 2016)'
_computing_data_reduction        'SAINT V8.41 (?, 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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      101.00
_diffrn_detector                 'Photon III'
_diffrn_detector_type            'CPAD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device       '\k--geometry diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    '0.8 mm pinhole collimator'
_diffrn_radiation_monochromator  'multilayer mirror'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.2344
_diffrn_reflns_av_unetI/netI     0.1404
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            17450
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.502
_diffrn_reflns_theta_min         1.951
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\mS'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.813
_exptl_absorpt_correction_T_max  0.745212
_exptl_absorpt_correction_T_min  0.346720
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1423 before and 0.0950 after correction.
 
For component 2:
 wR2(int) was 0.1387 before and 0.0945 after correction.
 
For component 3:
 wR2(int) was 0.1486 before and 0.0928 after correction.
 The Ratio of minimum to maximum transmission is 0.47.

Final HKLF 4 output contains 203208 reflections, Rint = 0.2344
 (26800 with I > 3sig(I), Rint = 0.1200)
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_description       block
_exptl_crystal_F_000             2036
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         2.081
_refine_diff_density_min         -0.678
_refine_diff_density_rms         0.185
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.998
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1215
_refine_ls_number_reflns         17450
_refine_ls_number_restraints     805
_refine_ls_restrained_S_all      0.981
_refine_ls_R_factor_all          0.1717
_refine_ls_R_factor_gt           0.1110
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1903P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2781
_refine_ls_wR_factor_ref         0.3127
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9239
_reflns_number_total             17450
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01337b3.cif
_cod_data_source_block           sag69
_cod_depositor_comments
'Adding full bibliography for 1575687--1575689.cif.'
_cod_database_code               1575689
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.888
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, 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
2. Restrained distances
 O11-S3
 1.69 with sigma of 0.02
 S3-C1A = S3-C1B
 1.89 with sigma of 0.02
 O11-C1A = O11-C1B
 2.79 with sigma of 0.04
 Mo1-O4 \\sim Mo1-O3 \\sim Mo1-O4B \\sim Mo1-O3B
 with sigma of 0.02
 C45B-C44B \\sim C44-C45 \\sim C43B-C44B \\sim C44-C43 \\sim C48B-C43B \\sim
C48B-C47B \\sim C47B-C46B
 \\sim C45B-C46B \\sim C46-C45 \\sim C47-C46 \\sim C47-C48 \\sim C48-C43
 with sigma of 0.02
 C8B-C7B \\sim C11B-C12B \\sim C7B-C12B \\sim C12-C7 \\sim C11-C12 \\sim
C11B-C10B \\sim C11-C10 \\sim C9B-
 C10B \\sim C10-C9 \\sim C8B-C9B \\sim C9-C8 \\sim C7-C8
 with sigma of 0.02
 P1-C7B \\sim P1-C7 \\sim P3-C43B \\sim P3-C43
 with sigma of 0.02
 C21B-C20 \\sim C21-C20 \\sim C23-C22 \\sim C63B-C62 \\sim C63-C62 \\sim
C65-C64 \\sim C64-C65B
 with sigma of 0.02
 O7-C63 \\sim O7B-C63B \\sim O8-C65 \\sim O5-C21 \\sim O5B-C21B \\sim O6-C23
\\sim O8B-C65B
 with sigma of 0.02
 S3-C1A \\sim S3-C1B
 with sigma of 0.02
 C1A-O11 \\sim C1B-O11
 with sigma of 0.04
3. Restrained planarity
 C43B, C44B, C45B, C46B, C47B, C48B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C48B \\sim C47B \\sim C46B \\sim C44B \\sim C43B \\sim C45B \\sim C44 \\sim C43
\\sim C48 \\sim C47 \\sim C46 \\sim C45 \\sim P3 \\sim C63B \\sim O7B \\sim O7
\\sim C63 \\sim C62 \\sim C64 \\sim C65 \\sim O8 \\sim C12 \\sim C11 \\sim C11B
\\sim C12B \\sim C7 \\sim C8 \\sim C8B \\sim C9 \\sim C10 \\sim C10B \\sim C9B
\\sim C7B \\sim P1 \\sim O1B \\sim O1 \\sim O6 \\sim C23 \\sim C22 \\sim O5
\\sim O5B \\sim C21B \\sim C21 \\sim C20 \\sim C19 \\sim C24 \\sim Cu2 \\sim
Cu1 \\sim C61 \\sim C66 \\sim Mo1 \\sim O4 \\sim O4B \\sim O3 \\sim O3B \\sim
C65B \\sim O8B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.01 within 2A
O11 \\sim S3 \\sim C1A \\sim C1B: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
5. Rigid body (RIGU) restrains
 O11, S3, C1A, C1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H20A)=Sof(H62A)=Sof(H64A)=Sof(C63B)=Sof(H63C)=Sof(H63D)=Sof(C21B)=
 Sof(H21C)=Sof(H21D)=Sof(O5B)=Sof(H5B)=Sof(O7B)=Sof(H7B)=Sof(O8B)=Sof(H8BA)=
 Sof(C65B)=Sof(H65C)=Sof(H65D)=1-FVAR(1)
 Sof(O5)=Sof(H5)=Sof(O7)=Sof(H7)=Sof(O8)=Sof(H8)=Sof(H20)=Sof(C21)=Sof(H21A)=
 Sof(H21B)=Sof(H62)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H64)=Sof(C65)=Sof(H65A)=
 Sof(H65B)=Sof(O1W)=Sof(H1WA)=Sof(H1WB)=FVAR(1)
 Sof(C43B)=Sof(C44B)=Sof(H44B)=Sof(C45B)=Sof(H45B)=Sof(C46B)=Sof(H46B)=
 Sof(C47B)=Sof(H47B)=Sof(C48B)=Sof(H48B)=1-FVAR(2)
 Sof(C43)=Sof(C44)=Sof(H44)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46)=Sof(C47)=
 Sof(H47)=Sof(C48)=Sof(H48)=FVAR(2)
 Sof(O1B)=Sof(O3B)=Sof(O4B)=1-FVAR(3)
 Sof(O1)=Sof(O3)=Sof(O4)=FVAR(3)
 Sof(C7B)=Sof(C8B)=Sof(H8B)=Sof(C9B)=Sof(H9B)=Sof(C10B)=Sof(H10B)=Sof(C11B)=
 Sof(H11B)=Sof(C12B)=Sof(H12B)=1-FVAR(4)
 Sof(C7)=Sof(C8)=Sof(H8A)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=
 Sof(C12)=Sof(H12)=FVAR(4)
 Fixed Sof: O11(0.5) S3(0.5) C1A(0.5) H1AA(0.5) H1AB(0.5) H1AC(0.5) C1B(0.5)
 H1BA(0.5) H1BB(0.5) H1BC(0.5)
7.a Riding coordinates:
 O5B(H5B), O7B(H7B)
7.b Free rotating group:
 O1W(H1WA,H1WB)
7.c Ternary CH refined with riding coordinates:
 C19(H19), C20(H20), C20(H20A), C22(H22), C24(H24), C61(H61), C62(H62),
 C62(H62A), C64(H64), C64(H64A), C66(H66)
7.d Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C23(H23A,H23B), C63(H63A,H63B), C65(H65A,H65B), C63B(H63C,
 H63D), C21B(H21C,H21D), C65B(H65C,H65D)
7.e Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5A), C6(H6A), C8(H8A), C9(H9), C10(H10), C11(H11),
  C12(H12), C14(H14), C15(H15), C16(H16), C26(H26), C27(H27), C28(H28),
 C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39), C40(H40),
  C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48),
 C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57), C58(H58),
  C68(H68), C69(H69), C70(H70), C74(H74), C75(H75), C76(H76), C77(H77),
 C78(H78), C80(H80), C81(H81), C82(H82), C83(H83), C84(H84), C8B(H8B), C9B(H9B),
  C10B(H10B), C11B(H11B), C12B(H12B), C44B(H44B), C45B(H45B), C46B(H46B),
 C47B(H47B), C48B(H48B)
7.f Tetrahedral OH refined with riding coordinates:
 O8(H8)
7.g Idealised Me refined as rotating group:
 C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C88(H88A,H88B,
 H88C), C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,H1BC)
7.h Idealised tetrahedral OH refined as rotating group:
 O5(H5), O6(H6), O7(H7), O8B(H8BA)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              84537
_shelx_fab_checksum              79863
_olex2_submission_special_instructions 'No special instructions were received'