A heterotrimetallic synthetic approach in versatile functionalization of nanosized {MxCu13‒xW7}3+ and {M1Cu8W6} (M = Co, Ni, Mn, Fe) metal‒cyanide magnetic clusters
Liberka, Michal; Kobylarczyk, Jedrzej; Muziol, Tadeusz M.; Ohkoshi, Shin-ichi; Chorazy, Szymon; Podgajny, Robert; Inorganic Chemistry Frontiers 6 (2019) 3104–; doi:10.1039/C9QI00898E

data_4350094
_publ_section_title
;
 A heterotrimetallic synthetic approach in versatile functionalization of
 nanosized {MxCu13--xW7}3+ and {M1Cu8W6} (M = Co, Ni, Mn, Fe)
 metal--cyanide magnetic clusters
;
_journal_issue                   11
_journal_name_full               'Inorganic Chemistry Frontiers'
_journal_page_first              3104
_journal_paper_doi               10.1039/C9QI00898E
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C172 H252 Cu11.50 N100 Ni1.50 O W8'
_chemical_formula_sum            'C172 H252 Cu11.5 N100 Ni1.5 O W8'
_chemical_formula_weight         6026.3
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      18
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_audit_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.4.3
_audit_creation_date             2019-06-06T17:30:58-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_audit_update_record
;
2019-06-30 deposited with the CCDC.	2019-09-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   32.3884(3)
_cell_length_b                   29.3119(5)
_cell_length_c                   16.0224(3)
_cell_measurement_reflns_used    74617
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.986
_cell_measurement_theta_min      1.547
_cell_measurement_wavelength     0.77538
_cell_volume                     15211.1(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.34a'
_computing_data_reduction        'CrysAlisPro 1.171.38.34a'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.972
_diffrn_measurement_device_type  synchrotron
_diffrn_measurement_method       'BESSY II, Berlin'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.77538
_diffrn_reflns_av_R_equivalents  0.0428
_diffrn_reflns_av_unetI/netI     0.0467
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            74617
_diffrn_reflns_point_group_measured_fraction_full 0.96
_diffrn_reflns_point_group_measured_fraction_max 0.96
_diffrn_reflns_theta_full        27.725
_diffrn_reflns_theta_max         28.986
_diffrn_reflns_theta_min         1.547
_diffrn_source                   synchrotron
_diffrn_standards_decay_%        0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.91
_exptl_absorpt_correction_T_max  0.897
_exptl_absorpt_correction_T_min  0.441
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.34a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            'dark violet'
_exptl_crystal_density_diffrn    1.316
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             5919
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         2.966
_refine_diff_density_min         -3.521
_refine_diff_density_rms         0.189
_refine_ls_abs_structure_details
;
 Flack x determined using 8221 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.308(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.231
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     1344
_refine_ls_number_reflns         29846
_refine_ls_number_restraints     835
_refine_ls_restrained_S_all      1.222
_refine_ls_R_factor_all          0.1058
_refine_ls_R_factor_gt           0.0949
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2964
_refine_ls_wR_factor_ref         0.308
_reflns_Friedel_coverage         0.837
_reflns_Friedel_fraction_full    0.946
_reflns_Friedel_fraction_max     0.945
_reflns_number_gt                23232
_reflns_number_total             29846
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qi00898e2.cif
_cod_data_source_block           CuNiW
_cod_original_formula_sum        'C172 H252 Cu11.50 N100 Ni1.50 O W8'
_cod_database_code               4350094
_shelx_estimated_absorpt_t_min   0.614
_shelx_estimated_absorpt_t_max   0.867
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{Cu6, Ni1}
3. Restrained distances
 N42-C42
 1.5 with sigma of 0.02
 C30-W5
 2.15 with sigma of 0.02
 C31-W5
 2.15 with sigma of 0.02
 C31-N31
 1.15 with sigma of 0.02
 C29-N29
 1.15 with sigma of 0.02
 C29-W5
 2.15 with sigma of 0.02
 C30-N30
 1.15 with sigma of 0.02
 N63-C64
 1.48 with sigma of 0.02
 C61-N61
 1.48 with sigma of 0.02
 N73-C74
 1.48 with sigma of 0.02
 N52-C53
 1.48 with sigma of 0.02
 C94-C93
 1.52 with sigma of 0.02
 N73-C79
 1.44 with sigma of 0.02
 C95-N93
 1.48 with sigma of 0.02
 N52-C52
 1.48 with sigma of 0.02
 C52-N52
 1.48 with sigma of 0.02
 C52-C53
 -2.5 with sigma of 0.02
 C4-W1
 2.15 with sigma of 0.02
 C67-N61
 1.44 with sigma of 0.02
 C55-N53
 1.5 with sigma of 0.02
 C54-N53
 1.5 with sigma of 0.02
 N53-C54
 1.48 with sigma of 0.02
 C59-N53
 1.42 with sigma of 0.02
 N52-C58
 1.42 with sigma of 0.02
 C66-N61
 1.48 with sigma of 0.02
 C51-N51
 1.48 with sigma of 0.02
 C52-C51
 1.52 with sigma of 0.02
 C32-W5
 2.15 with sigma of 0.02
 C32-N32
 1.15 with sigma of 0.02
 N72-C78
 1.44 with sigma of 0.02
 N73-C75
 1.48 with sigma of 0.02
 C72-N72
 1.48 with sigma of 0.02
 C95-C96
 1.52 with sigma of 0.02
 C91-C92
 1.52 with sigma of 0.02
 N91-C91
 1.48 with sigma of 0.02
 N92-C93
 1.48 with sigma of 0.02
 N92-C92
 1.48 with sigma of 0.02
 C96-N91
 1.48 with sigma of 0.02
 C44-N43
 1.48 with sigma of 0.02
 C43-C44
 1.52 with sigma of 0.02
 C73-C74
 1.52 with sigma of 0.02
 N72-C73
 1.48 with sigma of 0.02
 C72-C73
 -2.7 with sigma of 0.02
 N71-C71
 1.48 with sigma of 0.02
 C71-C72
 1.52 with sigma of 0.02
 C98-N92
 1.42 with sigma of 0.02
 N93-C99
 1.42 with sigma of 0.02
 C97-N91
 1.42 with sigma of 0.02
 N71-C77
 1.42 with sigma of 0.02
 N42-C48
 1.42 with sigma of 0.02
 N43-C49
 1.42 with sigma of 0.02
 N63-C65
 1.48 with sigma of 0.02
 C65-C66
 1.52 with sigma of 0.02
 N43-C45
 1.48 with sigma of 0.02
 C47-N41
 1.44 with sigma of 0.02
 C46-N41
 1.48 with sigma of 0.02
 N41-C41
 1.48 with sigma of 0.02
 C42-C41
 1.52 with sigma of 0.02
 C45-C46
 1.52 with sigma of 0.02
 C86-N81
 1.48 with sigma of 0.02
 C82-C81
 1.52 with sigma of 0.02
 H81A-H86B
 -2.1 with sigma of 0.02
 C76-N71
 1.48 with sigma of 0.02
 C76-C75
 1.52 with sigma of 0.02
 N51-C56
 1.5 with sigma of 0.02
 C56-C55
 1.5 with sigma of 0.02
 C55-C56
 1.52 with sigma of 0.02
 C85-C86
 1.52 with sigma of 0.02
 N83-C85
 1.48 with sigma of 0.02
 H84A-H85A
 -2.1 with sigma of 0.02
 H76A-H77C
 -1.9 with sigma of 0.02
 H52A-H58C
 -1.9 with sigma of 0.02
 C62-C61
 1.52 with sigma of 0.02
 N62-C62
 1.48 with sigma of 0.02
 C64-C63
 1.52 with sigma of 0.02
 C63-N62
 1.48 with sigma of 0.02
 N62-C68
 1.44 with sigma of 0.02
 H63B-H68A
 -1.9 with sigma of 0.1
 C41-C46
 2.5 with sigma of 0.01
 C86-C81
 2.4 with sigma of 0.01
 C85-C84
 2.4 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
N51 \\sim N52 \\sim C51 \\sim C52: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N52 \\sim N53 \\sim C53 \\sim C54: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N91 \\sim N92 \\sim C91 \\sim C92: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N92 \\sim N93 \\sim C93 \\sim C94: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N91 \\sim N93 \\sim C95 \\sim C96: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N92 \\sim C98: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
N71 \\sim C77: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
N72 \\sim N73 \\sim C73 \\sim C74: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N71 \\sim N72 \\sim C71 \\sim C72: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N81 \\sim N82 \\sim C81 \\sim C82: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N71 \\sim N73 \\sim C75 \\sim C76: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N51 \\sim N53 \\sim C55 \\sim C56: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N81 \\sim N83 \\sim C85 \\sim C86: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N82 \\sim N83 \\sim C83 \\sim C84: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N61 \\sim N62 \\sim C61 \\sim C62: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N62 \\sim N63 \\sim C63 \\sim C64: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02
N62 \\sim C68: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C14) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(N18)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C42) \\sim Ueq, Uanis(C45) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.2
Uanis(C16) \\sim Ueq, Uanis(C18) \\sim Ueq: with sigma of 0.0005 and sigma for
terminal atoms of 0.2
Uanis(N18) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.0005
Uanis(C13) \\sim Ueq: with sigma of 0.0005 and sigma for terminal atoms of 0.2
Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq: with sigma of 0.0005 and sigma for
terminal atoms of 0.0005
Uanis(C30) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
Uanis(N30) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.05
Uanis(C12) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.2
Uanis(C23) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.2
Uanis(C52) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.2
Uanis(C22) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
Uanis(N27) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
Uanis(C28) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.2
Uanis(C4) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.2
Uanis(C48) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.01
Uanis(C66) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.2
Uanis(C51) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C32) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C29) \\sim Ueq: with sigma of
0.02 and sigma for terminal atoms of 0.2
Uanis(C75) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.2
Uanis(C72) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.2
Uanis(C58) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.02
Uanis(C96) \\sim Ueq: with sigma of 0.03 and sigma for terminal atoms of 0.2
Uanis(C44) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
Uanis(C73) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.2
Uanis(C65) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.2
Uanis(C81) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.2
Uanis(N73) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(N71) \\sim Ueq, Uanis(C71)
\\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.2
Uanis(C56) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.2
Uanis(C19) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
Uanis(C11) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.2
Uanis(N11) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
Uanis(Cu6) = Uanis(Ni1)
5. Others
 Fixed Sof: Cu6(0.5) Ni1(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,
 H45B), C46(H46A,H46B), C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B),
 C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C61(H61A,H61B), C62(H62A,H62B),
  C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C71(H71A,
 H71B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B), C75(H75A,H75B),
 C76(H76A,H76B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B),
  C85(H85A,H85B), C86(H86A,H86B), C91(H91A,H91B), C92(H92A,H92B), C93(H93A,
 H93B), C94(H94A,H94B), C95(H95A,H95B), C96(H96A,H96B)
6.b Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C67(H67A,H67B,H67C), C68(H68A,
 H68B,H68C), C69(H69A,H69B,H69C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C),
 C79(H79A,H79B,H79C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C89(H89A,H89B,
 H89C), C97(H97A,H97B,H97C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C)
;
_shelx_res_checksum              5016
_shelx_hkl_checksum              96737