Interplay of the Cu⋯Cu distance and coordination geometry as a factor affecting the quantum efficiency in dimeric copper(I) halide complexes with derivatives of 4-pyrazolylpyrimidine-2-thiol.
Skvortsova, Sofia V.; Verkhov, Fyodor K.; Nikolaenkova, Elena B.; Rakhmanova, Marianna I.; Kokina, Tatiana E.; Sukhikh, Taisiya S.; Shekhovtsov, Nikita A.; Bushuev, Mark B.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 9000–9015; doi:10.1039/d5dt00498e

data_7718558
_publ_section_title
;
 Interplay of the Cu&#x22ef;Cu distance and coordination geometry as a
 factor affecting the quantum efficiency in dimeric copper(I) halide
 complexes with derivatives of 4-pyrazolylpyrimidine-2-thiol.
;
_journal_issue                   22
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9000
_journal_page_last               9015
_journal_paper_doi               10.1039/d5dt00498e
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C32 H32 Cu2 I2 N8 S2'
_chemical_formula_sum            'C32 H32 Cu2 I2 N8 S2'
_chemical_formula_weight         973.65
_chemical_name_systematic
bis(2-(benzylthio)-4-(3,5-dimethyl-1H-pyrazol-1-yl)pyrimidine)-bis(mu2-iodo)-di-copper(I)
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-17
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7205)
;
_audit_update_record
;
2025-04-17 deposited with the CCDC.	2025-04-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.785(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.405(2)
_cell_length_b                   9.845(2)
_cell_length_c                   19.150(5)
_cell_measurement_reflns_used    7514
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      26.34
_cell_measurement_theta_min      2.33
_cell_volume                     1772.3(7)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.00
_diffrn_detector                 PIXEL
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON III area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture diffractometer'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Incoatec HELIOS multilayer mirrors'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0682
_diffrn_reflns_av_unetI/netI     0.0603
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            18304
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.407
_diffrn_reflns_theta_min         2.128
_diffrn_source                   'Incoatec IuS3.0 microfocus X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.095
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5057
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1297 before and 0.0666 after correction.
The Ratio of minimum to maximum transmission is 0.6784.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.825
_exptl_crystal_description       needle
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.239
_refine_diff_density_min         -1.730
_refine_diff_density_rms         0.185
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.300
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     319
_refine_ls_number_reflns         3619
_refine_ls_number_restraints     275
_refine_ls_restrained_S_all      1.257
_refine_ls_R_factor_all          0.1146
_refine_ls_R_factor_gt           0.0898
_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^)+40.6218P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2021
_refine_ls_wR_factor_ref         0.2117
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2795
_reflns_number_total             3619
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00498e2.cif
_cod_data_source_block           s60
_cod_depositor_comments
'Adding full bibliography for 7718557--7718562.cif.'
_cod_database_code               7718558
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.941
_shelx_estimated_absorpt_t_min   0.576
_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
2. Restrained distances
 C3-C2 = C3A-C2A = C7-C2 = C7A-C2A = C7-C6 = C7A-C6A = C6A-C5A = C6-C5 = C5-C4
 = C5A-C4A = C4A-C3A = C4-C3
 1.39 with sigma of 0.02
 C4A-C6A = C3A-C7A
 2.35 with sigma of 0.04
 C2A-C5A = C2-C5
 2.75 with sigma of 0.04
 C3-C7 = C4-C6
 2.35 with sigma of 0.04
 S1A-C11 \\sim S1B-C11A
 with sigma of 0.02
 S1A-C111 \\sim S1B-C1
 with sigma of 0.02
 N2A-C11A \\sim N2-C11
 with sigma of 0.02
 N1A-C11A \\sim N1-C11
 with sigma of 0.02
 N3-C12 \\sim N3-C12A
 with sigma of 0.02
 C2A-C1 \\sim C2-C111
 with sigma of 0.02
 C3A-C1 \\sim C1-C7A
 with sigma of 0.02
 C3-C111 \\sim C111-C7
 with sigma of 0.02
 N2A-C12A \\sim N2-C12
 with sigma of 0.02
 N1A-C14A \\sim N1-C14
 with sigma of 0.02
 C14-C13 \\sim C14A-C13A
 with sigma of 0.02
 C13-C12 \\sim C13A-C12A
 with sigma of 0.02
 C11A-C13A \\sim C11-C13
 with sigma of 0.02
3. Restrained planarity
 S1B, C12A, N2A, C11A, N1A, C14A, C13A
 with sigma of 0.1
 C1, C2A, C3A, C4A, C5A, C6A, C7A
 with sigma of 0.1
 C111, C2, C3, C4, C5, C6, C7
 with sigma of 0.1
 C12, N2, C11, N1, C14, C13, S1A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(S1B)
\\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C3A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C12) = Uanis(C12A)
Uanis(C13A) = Uanis(C13)
Uanis(N2A) = Uanis(N2)
5. Rigid body (RIGU) restrains
 C12, N2, C11, N1, C14, C13, S1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C111, C2, C3, C4, C5, C6, C7, S1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1B, C4A, C6A, C1, C5A, C2A, C7A, C3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1B, C12A, N2A, C11A, N1A, C14A, C13A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(S1B)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=
 Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C12A)=
 Sof(N2A)=Sof(C11A)=Sof(N1A)=Sof(C14A)=Sof(H14A)=Sof(C13A)=Sof(H13A)=1-FVAR(1)
 Sof(C12)=Sof(N2)=Sof(C11)=Sof(N1)=Sof(C14)=Sof(H14)=Sof(C13)=Sof(H13)=
 Sof(C111)=Sof(H11A)=Sof(H11B)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=
 Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=Sof(S1A)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C111(H11A,H11B), C1(H1A,H1B)
7.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C13(H13), C16(H16), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7),
 C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C14A(H14A), C13A(H13A)
7.c Idealised Me refined as rotating group:
 C151(H15A,H15B,H15C), C171(H17A,H17B,H17C)
;
_shelx_res_checksum              77710
_shelx_hkl_checksum              28702
_olex2_submission_special_instructions 'No special instructions were received'