Base-mediated alkynyl-cubane to Cu<sub>8</sub>-alkynide cluster transformation.
Gupta, Arvind Kumar; Fayet, Océane Y O; Tian, Lei; Berger, Raphael J. F.; Lomoth, Reiner; Orthaber, Andreas; Chemical communications (Cambridge, England) 61 (2025) 18673–18676; doi:10.1039/d5cc00783f

data_7135099
_publ_section_title
;
 Base-mediated alkynyl-cubane to Cu<sub>8</sub>-alkynide cluster
 transformation.
;
_journal_issue                   94
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              18673
_journal_page_last               18676
_journal_paper_doi               10.1039/d5cc00783f
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C88 H168 Cu8 Si8'
_chemical_formula_sum            'C88 H168 Cu8 Si8'
_chemical_formula_weight         1959.25
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-10-14
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-10-16 deposited with the CCDC.	2025-10-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.9963(11)
_cell_length_b                   22.5357(16)
_cell_length_c                   30.877(2)
_cell_measurement_reflns_used    9994
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      23.76
_cell_measurement_theta_min      2.24
_cell_volume                     10434.9(13)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0482
_diffrn_reflns_av_unetI/netI     0.0601
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            66447
_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         25.250
_diffrn_reflns_theta_min         1.319
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    1.726
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6696
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.247
_exptl_crystal_description       prism
_exptl_crystal_F_000             4160
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.16
_refine_diff_density_max         2.977
_refine_diff_density_min         -1.056
_refine_diff_density_rms         0.156
_refine_ls_abs_structure_details
;
 Flack x determined using 5195 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.118(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1079
_refine_ls_number_reflns         18868
_refine_ls_number_restraints     298
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.1135
_refine_ls_R_factor_gt           0.0804
_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^)+(0.1498P)^2^+34.5707P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2178
_refine_ls_wR_factor_ref         0.2516
_reflns_Friedel_coverage         0.840
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                13930
_reflns_number_total             18868
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc00783f2.cif
_cod_data_source_block           ag_ag_193_0m_a
_cod_depositor_comments
'Adding full bibliography for 7135098--7135099.cif.'
_cod_original_cell_volume        10435.1(13)
_cod_database_code               7135099
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.770
_shelx_estimated_absorpt_t_min   0.644
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C37-C172 = C37-C173
 1.53 with sigma of 0.02
 Si6-C37
 1.89 with sigma of 0.02
 C2-C1 = C4-C3 = C9-C10 = C14A-C13A = C16-C15 = C8-C7 = C6-C5 = C21A-C12A
 1.23 with sigma of 0.02
 C21A-C12A = C6-C5 = C4-C3 = C14A-C13A = C2-C1 = C16-C15 = C8-C7 = C9-C10
 1.23 with sigma of 0.02
 Si2-C17 = Si2-C20
 1.89 with sigma of 0.02
 C29-C27
 1.53 with sigma of 0.02
 Si6-C34 = Si6-C34A
 1.89 with sigma of 0.02
 C36-C34 = C36A-C34A = Si6-C12A = C35-C34 = C35A-C34A
 1.52 with sigma of 0.02
 C172-C37 \\sim C1A-C37A
 with sigma of 0.02
 C173-C37 \\sim C38-C37A
 with sigma of 0.02
 Si6-C172 \\sim Si6-C1A
 with sigma of 0.04
 Si8-C221 \\sim Si8-C40
 with sigma of 0.02
 C173-C172 \\sim C38-C1A
 with sigma of 0.04
 Si6-C173 \\sim Si6-C38
 with sigma of 0.04
 C161-C162 \\sim C161-C163
 with sigma of 0.02
 Si6-C37 \\sim Si6-C37A
 with sigma of 0.02
 C221-C222 \\sim C40-C222
 with sigma of 0.02
 C221-C223 \\sim C40-C223
 with sigma of 0.02
 C161-C162 \\sim C14-C162
 with sigma of 0.02
 Si6-C161 \\sim Si6-C14
 with sigma of 0.02
 C61-C62 \\sim C61-C63
 with sigma of 0.02
 C161-C163 \\sim C14-C163
 with sigma of 0.02
 C62-C63 \\sim C62A-C63A
 with sigma of 0.04
 C61-C62 \\sim C61A-C62A
 with sigma of 0.02
 Si2-C62 \\sim Si2-C62A
 with sigma of 0.04
 C61-C63 \\sim C61A-C63A
 with sigma of 0.02
 Si2-C63 \\sim Si2-C63A
 with sigma of 0.04
 Si2-C61 \\sim Si2-C61A
 with sigma of 0.02
 Si6-C34 \\sim Si6-C34A
 with sigma of 0.02
 C34-C35 \\sim C34A-C35A
 with sigma of 0.02
 C34-C36 \\sim C34A-C36A
 with sigma of 0.02
 Si6-C35 \\sim Si6-C35A
 with sigma of 0.04
 Si6-C36 \\sim Si6-C36A
 with sigma of 0.04
 C35-C36 \\sim C35A-C36A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C17 \\sim C20 \\sim C18 \\sim C25 \\sim C19 \\sim C24: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C161 \\sim C14: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(C1A) \\sim Ueq, Uanis(C173) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C1A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C37A) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C37A) \\sim Ueq, Uanis(C37) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C14) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C1) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C13A) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C112) \\sim Ueq, Uanis(C113) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C62A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C21A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C62) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C61) \\sim Ueq, Uanis(C61A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C30) \\sim Ueq, Uanis(C29) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C123) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C36A) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C34) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C35A) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C172) = Uanis(C38)
Uanis(Cu7) = Uanis(Cu7A)
Uanis(C61A) = Uanis(C61)
4. Rigid body (RIGU) restrains
 C38, C1A, C37A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C173, C172, C37
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C62A, C63A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C62A, C61A, C63A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C123, C121, C122
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C34A, C35A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C62A)=Sof(H62D)=Sof(H62E)=Sof(H62F)=Sof(C63A)=Sof(H63D)=Sof(H63E)=
 Sof(H63F)=Sof(C61A)=Sof(H61A)=1-FVAR(1)
 Sof(C61)=Sof(H61)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63)=Sof(H63A)=
 Sof(H63B)=Sof(H63C)=FVAR(1)
 Sof(Cu7)=1-FVAR(2)
 Sof(Cu7A)=FVAR(2)
 Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(H16G)=Sof(H16H)=Sof(H16I)=Sof(C14)=Sof(H14)=
 1-FVAR(3)
 Sof(C161)=Sof(H161)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(H16J)=Sof(H16K)=
 Sof(H16L)=FVAR(3)
 Sof(C35A)=Sof(H35D)=Sof(H35E)=Sof(H35F)=Sof(C34A)=Sof(H34A)=Sof(C36A)=
 Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(4)
 Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=
 Sof(H36B)=Sof(H36C)=FVAR(4)
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C37A)=Sof(H37A)=Sof(C1A)=Sof(H1AA)=
 Sof(H1AB)=Sof(H1AC)=1-FVAR(5)
 Sof(C173)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C172)=Sof(H17D)=Sof(H17E)=
 Sof(H17F)=Sof(C37)=Sof(H37)=FVAR(5)
 Fixed Sof: C221(0.5) H221(0.5) H22D(0.5) H22E(0.5) H22F(0.5) H22G(0.5)
 H22H(0.5) H22I(0.5) H22J(0.5) H22K(0.5) H22L(0.5) H22M(0.5) H22N(0.5)
 H22O(0.5) C20(0.5) H20(0.5) C17(0.5) H17(0.5) C19(0.5) H19G(0.5) H19H(0.5)
 H19I(0.5) C18(0.5) H18A(0.5) H18B(0.5) H18C(0.5) C24(0.5) H24G(0.5) H24H(0.5)
 H24I(0.5) C25(0.5) H25A(0.5) H25B(0.5) H25C(0.5) C26(0.5) H26(0.5) C27(0.5)
 H27(0.5) H28A(0.5) H28B(0.5) H28C(0.5) H28D(0.5) H28E(0.5) H28F(0.5) C29(0.5)
 H29A(0.5) H29B(0.5) H29C(0.5) C30(0.5) H30A(0.5) H30B(0.5) H30C(0.5) C40(0.5)
 H40(0.5)
6.a Ternary CH refined with riding coordinates:
 C11(H11), C21(H21), C31(H31), C71(H71), C81(H81), C91(H91), C101(H101),
 C111(H111), C121(H121), C131(H131), C141(H141), C151(H151), C161(H161),
 C201(H201), C211(H211), C191(H191), C241(H241), C221(H221), C231(H231),
 C61(H61), C61A(H61A), C14(H14), C20(H20), C17(H17), C26(H26), C27(H27),
 C40(H40), C34(H34), C34A(H34A), C37(H37), C37A(H37A)
6.b Me refined with riding coordinates:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C72(H72A,H72B,H72C), C73(H73A,
 H73B,H73C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C92(H92A,H92B,H92C),
 C93(H93A,H93B,H93C), C102(H10A,H10B,H10C), C103(H10D,H10E,H10F), C112(H11A,
 H11B,H11C), C113(H11D,H11E,H11F), C122(H12D,H12E,H12F), C123(H12G,H12H,H12I),
 C132(H13D,H13E,H13F), C133(H13G,H13H,H13I), C142(H14A,H14B,H14C), C143(H14D,
 H14E,H14F), C152(H15A,H15B,H15C), C153(H15D,H15E,H15F), C163(H16J,H16K,H16L),
 C163(H16G,H16H,H16I), C202(H20A,H20B,H20C), C203(H20D,H20E,H20F), C212(H21A,
 H21B,H21C), C213(H21D,H21E,H21F), C193(H19A,H19B,H19C), C192(H19D,H19E,H19F),
 C242(H24A,H24B,H24C), C243(H24D,H24E,H24F), C222(H22D,H22E,H22F), C222(H22G,
 H22H,H22I), C223(H22J,H22K,H22L), C223(H22M,H22N,H22O), C232(H23D,H23E,H23F),
 C233(H23G,H23H,H23I), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C173(H17A,H17B,
 H17C), C172(H17D,H17E,H17F), C62A(H62D,H62E,H62F), C19(H19G,H19H,H19I),
 C18(H18A,H18B,H18C), C24(H24G,H24H,H24I), C25(H25A,H25B,H25C), C28(H28A,H28B,
 H28C), C28(H28D,H28E,H28F), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C35(H35A,
 H35B,H35C), C36(H36A,H36B,H36C), C35A(H35D,H35E,H35F), C36A(H36D,H36E,H36F),
 C38(H38A,H38B,H38C), C1A(H1AA,H1AB,H1AC)
6.c Idealised Me refined as rotating group:
 C162(H16D,H16E,H16F), C162(H16A,H16B,H16C), C63A(H63D,H63E,H63F)
;
_shelx_res_checksum              87965
_shelx_hkl_checksum              76633
_olex2_submission_special_instructions 'No special instructions were received'