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_7250975
_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         'C92 H124 Cu4 N8, 3.5(C6 H6)'
_chemical_formula_sum            'C113 H145 Cu4 N8'
_chemical_formula_weight         1869.52
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_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                90
_cell_angle_beta                 95.2110(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.7596(17)
_cell_length_b                   16.0134(10)
_cell_length_c                   44.636(3)
_cell_measurement_reflns_used    9018
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      30.19
_cell_measurement_theta_min      2.58
_cell_volume                     19048(2)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       'APEX3 Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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      100.00
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 8
_diffrn_detector_type            'Bruker ApexII'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w 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  0.0339
_diffrn_reflns_av_unetI/netI     0.0297
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       57
_diffrn_reflns_limit_l_min       -57
_diffrn_reflns_number            93874
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         0.916
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_type              'KFF MO-2KC-90'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.935
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6898
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0652 before and 0.0480 after correction.
The Ratio of minimum to maximum transmission is 0.9245.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       blocks
_exptl_crystal_F_000             7960
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.21
_refine_diff_density_max         2.378
_refine_diff_density_min         -1.147
_refine_diff_density_rms         0.126
_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     1249
_refine_ls_number_reflns         21853
_refine_ls_number_restraints     851
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0937
_refine_ls_R_factor_gt           0.0774
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1025P)^2^+178.7461P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2009
_refine_ls_wR_factor_ref         0.2164
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17682
_reflns_number_total             21853
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00912j2.cif
_cod_data_source_block           dia27_0m_a
_cod_depositor_comments
'Adding full bibliography for 7250974--7250981.cif.'
_cod_original_sg_symbol_H-M      C2/c
_cod_database_code               7250975
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.828
_shelx_estimated_absorpt_t_min   0.712
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C62-C61
 1.52 with sigma of 0.02
 C1S-C1T \\sim C1S-C1U \\sim C1S-C1V \\sim C1W-C1X \\sim C1X-C1Y \\sim C1Y-C1Z
\\sim C1Z-C2A \\sim C2A-C2B
 \\sim C2B-C1W \\sim C1T-C2A \\sim C1U-C1Y \\sim C1V-C1W
 with sigma of 0.02
 C1T-C1U \\sim C1U-C1V \\sim C1V-C1T \\sim C1W-C2A \\sim C2A-C1Y \\sim C1Y-C1W
\\sim C1X-C2B \\sim C1X-C1Z
 \\sim C1Z-C2B
 with sigma of 0.04
 C1W-C1Z \\sim C1Y-C2B \\sim C2A-C1X
 with sigma of 0.05
 C66-C67 \\sim C66-C69 \\sim C66-C65 \\sim C64-C63 \\sim C63-C62 \\sim C62-C61
\\sim C61-C60 \\sim C60-C68
 \\sim C68-C64 \\sim C67-C60 \\sim C69-C62 \\sim C65-C64
 with sigma of 0.02
 C67-C69 \\sim C69-C65 \\sim C65-C67 \\sim C64-C60 \\sim C60-C62 \\sim C62-C64
\\sim C63-C68 \\sim C63-C61
 \\sim C61-C68
 with sigma of 0.04
 C64-C61 \\sim C62-C68 \\sim C60-C63
 with sigma of 0.05
 C49-C2A \\sim C49-C60
 with sigma of 0.02
 C38-C37 \\sim C45-C37 \\sim C44-C37
 with sigma of 0.005
 C39-C38 \\sim C44-C43 \\sim C45-C41 \\sim C46-C43 \\sim C43-C42 \\sim C42-C41
\\sim C41-C40 \\sim C40-C39
 \\sim C46-C39
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
C1S \\sim C1T \\sim C1U \\sim C1V \\sim C1W \\sim C1X \\sim C1Y \\sim C1Z \\sim
C2A \\sim C2B: within 2A with sigma of 0.003 and sigma for terminal atoms of
0.003 within 2A
C105 \\sim C110 \\sim C109 \\sim C108 \\sim C107 \\sim C114 \\sim C113 \\sim
C112 \\sim C111 \\sim C116: within 2A with sigma of 0.003 and sigma for
terminal atoms of 0.003 within 2A
C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim
C68 \\sim C69: within 2A with sigma of 0.003 and sigma for terminal atoms of
0.003 within 2A
Uanis(C101) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C100)
\\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C102) \\sim Ueq: with sigma of 0.005
and sigma for terminal atoms of 0.005
Uanis(C114) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C69)
\\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C68) \\sim Ueq,
Uanis(C115) \\sim Ueq, Uanis(C112) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C113)
\\sim Ueq, Uanis(C116) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C60) \\sim Ueq,
Uanis(C111) \\sim Ueq, Uanis(C67) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.003
Uanis(C45) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C41)
\\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C43) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C44) \\sim Ueq: with sigma of
0.008 and sigma for terminal atoms of 0.008
Uanis(C77) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C80)
\\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C76) \\sim Ueq: with sigma of 0.002 and
sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 C1S, C1T, C1U, C1V, C1W, C1X, C1Y, C1Z, C2A, C2B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C60, C61, C62, C63, C64, C65, C66, C67, C68, C69
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C60(0.6) C61(0.6) H61A(0.6) H61B(0.6) C62(0.6) H62(0.6) C63(0.6)
 H63A(0.6) H63B(0.6) C64(0.6) H64(0.6) C65(0.6) H65A(0.6) H65B(0.6) C66(0.6)
 H66(0.6) C67(0.6) H67A(0.6) H67B(0.6) C68(0.6) H68A(0.6) H68B(0.6) C69(0.6)
 H69A(0.6) H69B(0.6) C1S(0.4) H1S(0.4) C1T(0.4) H1TA(0.4) H1TB(0.4) C1U(0.4)
 H1UA(0.4) H1UB(0.4) C1V(0.4) H1VA(0.4) H1VB(0.4) C1W(0.4) H1W(0.4) C1X(0.4)
 H1XA(0.4) H1XB(0.4) C1Y(0.4) H1Y(0.4) C1Z(0.4) H1ZA(0.4) H1ZB(0.4) C2A(0.4)
 C2B(0.4) H2BA(0.4) H2BB(0.4) C114(0.55) H114(0.55) C113(0.55) H113(0.55)
 C112(0.55) H112(0.55) C111(0.55) H111(0.55) C116(0.55) H116(0.55) C115(0.55)
 H115(0.55) C1B(0.45) H1B(0.45) C1C(0.45) H1C(0.45) C1D(0.45) H1D(0.45)
 C1E(0.45) H1E(0.45) C1F(0.45) H1F(0.45) C1A(0.45) H1A(0.45) C101(0.5)
 H101(0.5) C100(0.5) H100(0.5) C99(0.5) H99(0.5) C104(0.5) H104(0.5) C103(0.5)
 H103(0.5) C102(0.5) H102(0.5)
6.a Ternary CH refined with riding coordinates:
 C6(H6), C8(H8), C10(H10), C16(H16), C18(H18), C20(H20), C29(H29), C31(H31),
 C33(H33), C39(H39), C41(H41), C43(H43), C52(H52), C54(H54), C56(H56), C75(H75),
  C77(H77), C79(H79), C85(H85), C87(H87), C90(H90), C62(H62), C64(H64),
 C66(H66), C1S(H1S), C1W(H1W), C1Y(H1Y)
6.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C7(H7A,H7B), C9(H9A,H9B), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B), C15(H15A,H15B), C17(H17A,H17B), C19(H19A,H19B), C21(H21A,H21B),
  C22(H22A,H22B), C23(H23A,H23B), C28(H28A,H28B), C30(H30A,H30B), C32(H32A,
 H32B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C38(H38A,H38B),
 C40(H40A,H40B), C42(H42A,H42B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B),
  C51(H51A,H51B), C53(H53A,H53B), C55(H55A,H55B), C57(H57A,H57B), C58(H58A,
 H58B), C59(H59A,H59B), C74(H74A,H74B), C76(H76A,H76B), C78(H78A,H78B),
 C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B), C84(H84A,H84B), C86(H86A,H86B),
  C88(H88A,H88B), C89(H89A,H89B), C91(H91A,H91B), C92(H92A,H92B), C61(H61A,
 H61B), C63(H63A,H63B), C65(H65A,H65B), C67(H67A,H67B), C68(H68A,H68B),
 C69(H69A,H69B), C1T(H1TA,H1TB), C1U(H1UA,H1UB), C1V(H1VA,H1VB), C1X(H1XA,H1XB),
  C1Z(H1ZA,H1ZB), C2B(H2BA,H2BB)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C25(H25), C48(H48), C71(H71), C93(H93), C94(H94), C95(H95), C96(H96),
 C97(H97), C98(H98), C106(H106), C105(H105), C110(H110), C109(H109), C108(H108),
  C107(H107), C114(H114), C113(H113), C112(H112), C111(H111), C116(H116),
 C115(H115), C1B(H1B), C1C(H1C), C1D(H1D), C1E(H1E), C1F(H1F), C1A(H1A),
 C101(H101), C100(H100), C99(H99), C104(H104), C103(H103), C102(H102)
6.d Fitted hexagon refined as free rotating group:
 C106(C105,C110,C109,C108,C107), C114(C113,C112,C111,C116,C115), C1B(C1C,C1D,
 C1E,C1F,C1A), C101(C100,C99,C104,C103,C102)
;
_shelx_res_checksum              19786
_olex2_submission_special_instructions 'No special instructions were received'