Short-bite PNP ligand-supported rare tetranuclear [Cu4I4] clusters: structural and photoluminescence studies.
Naik, Susmita; Mague, Joel T.; Balakrishna, Maravanji S.; Inorganic chemistry 53 (2014) 3864–3873; doi:10.1021/ic500240j

data_4350658
_publ_section_title
;
 Short-bite PNP ligand-supported rare tetranuclear [Cu4I4] clusters:
 structural and photoluminescence studies.
;
_journal_issue                   7
_journal_name_full               'Inorganic chemistry'
_journal_page_first              3864
_journal_page_last               3873
_journal_paper_doi               10.1021/ic500240j
_journal_volume                  53
_journal_year                    2014
_chemical_formula_moiety         'C92 H98 Br4 Cu4 N2 O16 P4'
_chemical_formula_sum            'C92 H98 Br4 Cu4 N2 O16 P4'
_chemical_formula_weight         2185.46
_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
_audit_creation_date             2014-01-21
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.268(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.6114(4)
_cell_length_b                   17.5727(4)
_cell_length_c                   32.0136(6)
_cell_measurement_temperature    150(2)
_cell_volume                     9131.6(4)
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      150.15
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.896
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0519
_diffrn_reflns_av_unetI/netI     0.1557
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.896
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            105635
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.896
_diffrn_reflns_theta_full        28.500
_diffrn_reflns_theta_max         32.778
_diffrn_reflns_theta_min         3.032
_exptl_absorpt_coefficient_mu    2.805
_exptl_crystal_density_diffrn    1.592
_exptl_crystal_F_000             4444
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.820
_refine_diff_density_min         -0.725
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.766
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1157
_refine_ls_number_reflns         30306
_refine_ls_number_restraints     230
_refine_ls_restrained_S_all      0.786
_refine_ls_R_factor_all          0.1251
_refine_ls_R_factor_gt           0.0356
_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^)+(0.0216P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0543
_refine_ls_wR_factor_ref         0.0603
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12940
_reflns_number_total             30306
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic500240j_si_001.cif
_cod_data_source_block           msb049
_cod_database_code               4350658
_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
 C5-C8 = C5-C8A = C15-C18 = C15-C18A = C61-C64 = C61-C64A
 1.523 with sigma of 0.004
 C71-C74 = C71-C74A = C81-C84 = C81-C84A
 1.523 with sigma of 0.004
 C8-C9 = C8A-C9A = C18-C19 = C18A-C19A = C64-C65 = C64A-C65A
 1.504 with sigma of 0.004
 C74-C75 = C74A-C75A = C84-C85 = C84A-C85A
 1.504 with sigma of 0.004
 C9-C10 = C9A-C10A = C19-C20 = C19A-C20A = C65-C66 = C65A-C66A
 1.308 with sigma of 0.005
 C75-C76 = C75A-C76A = C85-C86 = C85A-C86A
 1.308 with sigma of 0.005
 C5-C9 = C5-C9A = C15-C19 = C15-C19A = C61-C65 = C61-C65A
 2.513 with sigma of 0.007
 C71-C75 = C71-C75A = C81-C85 = C81-C85A
 2.513 with sigma of 0.007
 C8-C10 = C8A-C10A = C18-C20 = C18A-C20A = C64-C66 = C64A-C66A
 2.467 with sigma of 0.007
 C74-C76 = C74A-C76A = C84-C86 = C84A-C86A
 2.467 with sigma of 0.007
3. Uiso/Uaniso restraints and constraints
Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C18A) \\sim Ueq, Uanis(C19A) \\sim Ueq, Uanis(C20A) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C64A) \\sim Ueq, Uanis(C65A) \\sim Ueq, Uanis(C66A) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C74A) \\sim Ueq, Uanis(C75A) \\sim Ueq, Uanis(C76A) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C84A) \\sim Ueq, Uanis(C85A) \\sim Ueq, Uanis(C86A) \\sim Ueq: with sigma of 0.006 and sigma for terminal atoms of 0.012
Uanis(C86) = Uanis(C86A)
Uanis(C85) = Uanis(C85A)
Uanis(C84) = Uanis(C84A)
Uanis(C76) = Uanis(C76A)
Uanis(C75) = Uanis(C75A)
Uanis(C74) = Uanis(C74A)
Uanis(C66) = Uanis(C66A)
Uanis(C65) = Uanis(C65A)
Uanis(C64) = Uanis(C64A)
Uanis(C20) = Uanis(C20A)
Uanis(C19) = Uanis(C19A)
Uanis(C18) = Uanis(C18A)
Uanis(C10) = Uanis(C10A)
Uanis(C9) = Uanis(C9A)
Uanis(C8) = Uanis(C8A)
4. Others
 Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10C)=Sof(H10D)=
 1-FVAR(1)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10A)=Sof(H10B)=FVAR(1)
 Sof(C18A)=Sof(H18C)=Sof(H18D)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20C)=
 Sof(H20D)=1-FVAR(2)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 FVAR(2)
 Sof(C64A)=Sof(H64C)=Sof(H64D)=Sof(C65A)=Sof(H65A)=Sof(C66A)=Sof(H66C)=
 Sof(H66D)=1-FVAR(3)
 Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(C65)=Sof(H65)=Sof(C66)=Sof(H66A)=Sof(H66B)=
 FVAR(3)
 Sof(C74A)=Sof(H74C)=Sof(H74D)=Sof(C75A)=Sof(H75A)=Sof(C76A)=Sof(H76C)=
 Sof(H76D)=1-FVAR(4)
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76A)=Sof(H76B)=
 FVAR(4)
 Sof(C84A)=Sof(H84C)=Sof(H84D)=Sof(C85A)=Sof(H85A)=Sof(C86A)=Sof(H86C)=
 Sof(H86D)=1-FVAR(5)
 Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86A)=Sof(H86B)=
 FVAR(5)
5.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C8A(H8AA,H8AB), C18(H18A,H18B), C18A(H18C,H18D), C28(H28A,H28B),
 C38(H38A,H38B), C54(H54A,H54B), C64(H64A,H64B), C64A(H64C,H64D), C74(H74A,
 H74B), C74A(H74C,H74D), C84(H84A,H84B), C84A(H84C,H84D)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C7(H7), C9(H9), C9A(H9A), C14(H14), C16(H16), C17(H17),
 C19(H19), C19A(H19A), C24(H24), C26(H26), C27(H27), C29(H29), C34(H34),
 C36(H36), C37(H37), C39(H39), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46),
  C50(H50), C52(H52), C53(H53), C55(H55), C60(H60), C62(H62), C63(H63),
 C65(H65), C65A(H65A), C70(H70), C72(H72), C73(H73), C75(H75), C75A(H75A),
 C80(H80), C82(H82), C83(H83), C85(H85), C85A(H85A), C88(H88), C89(H89),
 C90(H90), C91(H91), C92(H92)
5.c X=CH2 refined with riding coordinates:
 C10(H10A,H10B), C10A(H10C,H10D), C20(H20A,H20B), C20A(H20C,H20D), C30(H30A,
 H30B), C40(H40A,H40B), C56(H56A,H56B), C66(H66A,H66B), C66A(H66C,H66D),
 C76(H76A,H76B), C76A(H76C,H76D), C86(H86A,H86B), C86A(H86C,H86D)
5.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C13(H13A,H13B,H13C), C23(H23A,H23B,H23C), C33(H33A,H33B,
 H33C), C49(H49A,H49B,H49C), C59(H59A,H59B,H59C), C69(H69A,H69B,H69C), C79(H79A,
 H79B,H79C)
;
_shelx_estimated_absorpt_t_max   0.662
_shelx_estimated_absorpt_t_min   0.507
_shelxl_version_number           2012-9