Multinuclear copper(i) and silver(i) pyrazolates decorated with adamantyl substituents
Phan, Vo Quang Huy; Watson, Brandon T.; Noonikara-Poyil, Anurag; Duran, Katrina; Patterson, Monika R.; Dias, H. V. Rasika; CrystEngComm 27 (2025) 6987–6999; doi:10.1039/D5CE00912J

data_7250974
_publ_section_title
;
 Multinuclear copper(i) and silver(i) pyrazolates decorated with adamantyl
 substituents
;
_journal_issue                   43
_journal_name_full               CrystEngComm
_journal_page_first              6987
_journal_page_last               6999
_journal_paper_doi               10.1039/D5CE00912J
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C64 H92 Cu4 N8, 3(C H Cl3)'
_chemical_formula_sum            'C67 H95 Cl9 Cu4 N8'
_chemical_formula_weight         1585.71
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-09-12
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-09-12 deposited with the CCDC.	2025-10-08 downloaded from the CCDC.
;
_cell_angle_alpha                81.723(2)
_cell_angle_beta                 86.491(2)
_cell_angle_gamma                89.546(2)
_cell_formula_units_Z            2
_cell_length_a                   11.7131(15)
_cell_length_b                   12.9283(16)
_cell_length_c                   23.679(3)
_cell_measurement_reflns_used    9909
_cell_measurement_temperature    100.03
_cell_measurement_theta_max      30.36
_cell_measurement_theta_min      2.36
_cell_volume                     3541.7(8)
_computing_data_collection       'APEX3 Ver. 2016.5-0 (Bruker-AXS, 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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.03
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 8
_diffrn_detector_type            'Bruker ApexII'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker Smart ApexII'
_diffrn_measurement_method       '0.3\% \w and 0.3\% \f scans'
_diffrn_radiation_collimation    '0.6 mm double-pinhole'
_diffrn_radiation_detector       'Bruker ApexII'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0198
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            38568
_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         28.700
_diffrn_reflns_theta_min         1.592
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.570
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6785
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.487
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       blocks
_exptl_crystal_F_000             1644
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.17
_refine_diff_density_max         1.896
_refine_diff_density_min         -1.384
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1032
_refine_ls_number_reflns         18230
_refine_ls_number_restraints     393
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0576
_refine_ls_R_factor_gt           0.0455
_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^)+(0.0510P)^2^+5.5521P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1109
_refine_ls_wR_factor_ref         0.1181
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14778
_reflns_number_total             18230
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00912j2.cif
_cod_data_source_block           dia13_0m_a
_cod_depositor_comments
'Adding full bibliography for 7250974--7250981.cif.'
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               7250974
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.776
_shelx_estimated_absorpt_t_min   0.724
_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
 C1R-Cl10 = C1R-Cl11 = C1R-Cl12
 1.78 with sigma of 0.02
 C1A-C1B \\sim C1A-C1C \\sim C1A-C1D \\sim C1E-C1F \\sim C1F-C1G \\sim C1G-C1H
\\sim C1J-C1E \\sim C1C-C1G
 \\sim C1D-C1E
 with sigma of 0.02
 C1B-C1C \\sim C1C-C1D \\sim C1D-C1B \\sim C1G-C1E \\sim C1F-C1J \\sim C1F-C1H
\\sim C1H-C1J
 with sigma of 0.04
 C64-C62 \\sim C69-C68 \\sim C63-C62 \\sim C70-C69 \\sim C69-C51 \\sim C62-C51
 with sigma of 0.005
 C1I-C1K \\sim C1I-C1L \\sim C1I-C1M \\sim C1N-C1O \\sim C1O-C1P \\sim C1P-C1Q
\\sim C1S-C1N \\sim C1L-C1P
 \\sim C1M-C1N
 with sigma of 0.02
 C1K-C1L \\sim C1L-C1M \\sim C1M-C1K \\sim C1P-C1N \\sim C1O-C1S \\sim C1O-C1Q
\\sim C1Q-C1S
 with sigma of 0.04
 C1N-C1Q \\sim C1P-C1S \\sim C1E-C1H \\sim C1G-C1J
 with sigma of 0.05
 Cl10-Cl11 \\sim Cl11-Cl12 \\sim Cl12-Cl10
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C40 \\sim C44 \\sim C45 \\sim C1B \\sim C1H \\sim C1J: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.01 within 1.7A
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim
C29 \\sim C1I \\sim C1K \\sim C1L \\sim C1M \\sim C1N \\sim C1O \\sim C1P \\sim
C1Q \\sim C1S: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.01 within 1.7A
C1R \\sim C66: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.01 within 1.7A
4. Others
 Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C69)=Sof(H69)=Sof(C70)=Sof(H70A)=
 Sof(H70B)=Sof(H70C)=1-FVAR(1)
 Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C64)=Sof(H64A)=
 Sof(H64B)=Sof(H64C)=FVAR(1)
 Sof(C1A)=Sof(H1A)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(C1C)=Sof(H1CA)=Sof(H1CB)=
 Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(C1E)=Sof(H1E)=Sof(C1F)=Sof(H1FA)=Sof(H1FB)=
 Sof(C1G)=Sof(H1G)=Sof(C1H)=Sof(H1HA)=Sof(H1HB)=Sof(C1J)=Sof(H1JA)=Sof(H1JB)=1-
 FVAR(2)
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41)=Sof(C42)=Sof(H42A)=Sof(H42B)=
 Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=
 Sof(C46)=Sof(H46)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(C48)=Sof(H48A)=Sof(H48B)=
 FVAR(2)
 Sof(C1I)=Sof(H1I)=Sof(C1K)=Sof(H1KA)=Sof(H1KB)=Sof(C1L)=Sof(H1LA)=Sof(H1LB)=
 Sof(C1M)=Sof(H1MA)=Sof(H1MB)=Sof(C1N)=Sof(H1N)=Sof(C1O)=Sof(H1OA)=Sof(H1OB)=
 Sof(C1P)=Sof(H1P)=Sof(C1Q)=Sof(H1QA)=Sof(H1QB)=Sof(C1S)=Sof(H1SA)=Sof(H1SB)=1-
 FVAR(3)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23A)=Sof(H23B)=
 Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(H29A)=Sof(H29B)=
 FVAR(3)
 Sof(Cl10)=Sof(Cl11)=Sof(Cl12)=Sof(C1R)=Sof(H1R)=1-FVAR(4)
 Sof(Cl4)=Sof(Cl5)=Sof(Cl6)=Sof(C66)=Sof(H66)=FVAR(4)
5.a Ternary CH refined with riding coordinates:
 C6(H6), C8(H8), C11(H11), C14(H14), C30(H30), C36(H36), C54(H54), C56(H56),
 C59(H59), C22(H22), C24(H24), C27(H27), C41(H41), C43(H43), C46(H46), C62(H62),
  C1A(H1A), C1E(H1E), C1G(H1G), C1I(H1I), C1N(H1N), C1P(H1P), C69(H69),
 C65(H65), C67(H67), C66(H66), C1R(H1R)
5.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C7(H7A,H7B), C9(H9A,H9B), C10(H10A,H10B), C12(H12A,H12B),
 C13(H13A,H13B), C53(H53A,H53B), C55(H55A,H55B), C57(H57A,H57B), C58(H58A,H58B),
  C60(H60A,H60B), C61(H61A,H61B), C21(H21A,H21B), C23(H23A,H23B), C25(H25A,
 H25B), C26(H26A,H26B), C28(H28A,H28B), C29(H29A,H29B), C40(H40A,H40B),
 C42(H42A,H42B), C44(H44A,H44B), C45(H45A,H45B), C47(H47A,H47B), C48(H48A,H48B),
  C1B(H1BA,H1BB), C1C(H1CA,H1CB), C1D(H1DA,H1DB), C1F(H1FA,H1FB), C1H(H1HA,
 H1HB), C1J(H1JA,H1JB), C1K(H1KA,H1KB), C1L(H1LA,H1LB), C1M(H1MA,H1MB),
 C1O(H1OA,H1OB), C1Q(H1QA,H1QB), C1S(H1SA,H1SB)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C18(H18), C34(H34), C50(H50)
5.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C63(H63A,H63B,H63C), C64(H64A,
 H64B,H64C), C68(H68A,H68B,H68C), C70(H70A,H70B,H70C)
;
_shelx_res_checksum              65629
_olex2_submission_special_instructions 'No special instructions were received'