Triple-Stranded Cluster Helicates for the Selective Catalytic Oxidation of C-H Bonds.
Fang, Yu; Gong, Wei; Liu, Lujia; Liu, Yan; Cui, Yong; Inorganic chemistry 55 (2016) 10102–10105; doi:10.1021/acs.inorgchem.6b01828

data_4348924
_publ_section_title
;
 Triple-Stranded Cluster Helicates for the Selective Catalytic Oxidation
 of C-H Bonds.
;
_journal_issue                   20
_journal_name_full               'Inorganic chemistry'
_journal_page_first              10102
_journal_page_last               10105
_journal_paper_doi               10.1021/acs.inorgchem.6b01828
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety         'C138 H168 Cu7 N6 O14, 2(C3 N O)'
_chemical_formula_sum            'C144 H168 Cu7 N8 O16'
_chemical_formula_weight         2711.63
_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
_audit_creation_date             2016-08-17
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                97.4850(10)
_cell_angle_beta                 94.706(2)
_cell_angle_gamma                98.437(2)
_cell_formula_units_Z            2
_cell_length_a                   17.4508(6)
_cell_length_b                   18.7149(6)
_cell_length_c                   23.8379(8)
_cell_measurement_reflns_used    9974
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      58.40
_cell_measurement_theta_min      3.24
_cell_volume                     7594.6(4)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.906
_diffrn_measured_fraction_theta_max 0.906
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0365
_diffrn_reflns_av_unetI/netI     0.0568
_diffrn_reflns_Laue_measured_fraction_full 0.906
_diffrn_reflns_Laue_measured_fraction_max 0.906
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            22142
_diffrn_reflns_point_group_measured_fraction_full 0.906
_diffrn_reflns_point_group_measured_fraction_max 0.906
_diffrn_reflns_theta_full        50.000
_diffrn_reflns_theta_max         50.000
_diffrn_reflns_theta_min         2.412
_exptl_absorpt_coefficient_mu    1.517
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.186
_exptl_crystal_description       block
_exptl_crystal_F_000             2838
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.626
_refine_diff_density_min         -0.451
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1449
_refine_ls_number_reflns         14157
_refine_ls_number_restraints     219
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0822
_refine_ls_R_factor_gt           0.0690
_refine_ls_shift/su_max          0.058
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1137P)^2^+22.2426P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2000
_refine_ls_wR_factor_ref         0.2150
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11575
_reflns_number_total             14157
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b01828_si_002.cif
_cod_data_source_block           sad
_cod_database_code               4348924
_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
2. Restrained distances
 C39-C41
 1.55 with sigma of 0.02
 C60-C57
 1.5 with sigma of 0.02
 C99-C102
 1.55 with sigma of 0.02
 C14A-C12A
 2.5 with sigma of 0.02
 C12-C14
 2.5 with sigma of 0.02
 C14-C13
 2.5 with sigma of 0.02
 C12-C13
 2.5 with sigma of 0.02
 C13A-C12A
 2.5 with sigma of 0.02
 C13A-C14A
 2.5 with sigma of 0.02
 C14-C11 = C12A-C11 = C13-C11 = C13A-C11 = C14A-C11 = C12-C11
 1.51 with sigma of 0.02
 C133-C132
 2.5 with sigma of 0.02
 C1C-C1A
 2.5 with sigma of 0.02
 C133-C134
 2.5 with sigma of 0.02
 C132-C134
 2.5 with sigma of 0.02
 C1B-C1C
 2.5 with sigma of 0.02
 C1B-C1A
 2.5 with sigma of 0.02
 C4-C11
 1.51 with sigma of 0.02
 C4-C12A
 2.5 with sigma of 0.02
 N7-C139
 1.5 with sigma of 0.02
 N7-C140
 1.5 with sigma of 0.02
 N7-C140
 1.52 with sigma of 0.02
 C139-O15
 1.24 with sigma of 0.02
 O15-N7
 2.35 with sigma of 0.02
 N8-C143 = N8-C144
 1.4 with sigma of 0.02
 N8-C142
 1.4 with sigma of 0.02
 O16-C142
 1.25 with sigma of 0.02
 N8-O16
 2.23 with sigma of 0.02
 C142-C143
 2.45 with sigma of 0.02
 C142-C144
 2.45 with sigma of 0.02
 C1B-C129
 2.5 with sigma of 0.02
 C1A-C129
 2.5 with sigma of 0.02
 C1A-C1D = C133-C131 = C132-C131 = C134-C131 = C1C-C1D = C1B-C1D
 1.51 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C11 \\sim C12A: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
C11 \\sim C14A: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
C11 \\sim C13A: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
C13 \\sim C13A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C12 \\sim C13A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C133 \\sim C1C: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C132 \\sim C1A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C1C \\sim C1D: within 2A with sigma of 0.01 and sigma for terminal atoms of 1.7
C1A \\sim C1D: within 2A with sigma of 0.01 and sigma for terminal atoms of 1.7
C1B \\sim C1D: within 2A with sigma of 0.001 and sigma for terminal atoms of 1.7
C134 \\sim C1B: within 1.7A with sigma of 0.001 and sigma for terminal atoms of
0.08
C103 \\sim C96: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C103 \\sim C104: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C105 \\sim C103: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C103 \\sim C106: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C4 \\sim C11: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
N7 \\sim C141: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
N7 \\sim C140: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
N7 \\sim C139: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
O15 \\sim C139: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
N8 \\sim C143: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
N8 \\sim C144: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
N8 \\sim C142: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
O16 \\sim C142: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
O16 \\sim C142: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C142 \\sim N8: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C144 \\sim N8: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
N8 \\sim C143: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C129 \\sim C1D: within 2A with sigma of 0.01 and sigma for terminal atoms of 1.7
C131 \\sim C134: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C131 \\sim C133: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C129 \\sim C131: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C131 \\sim C132: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
Uanis(C1C) = Uanis(C133)
4. Rigid body (RIGU) restrains
 C11, C12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C14A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C13A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C12, C13A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C13, C13A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C133, C1C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.004
 C132, C1A
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.004
 C1C, C1D
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C1A, C1D
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C1B, C1D
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C134, C1B
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.004
 C103, C96
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C103, C105
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C104, C105
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C106, C105
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C4, C11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C129, C1D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C131, C134
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C129, C131
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C131, C133
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C131, C132
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=
 Sof(C1C)=Sof(H1CA)=Sof(H1CB)=Sof(H1CC)=Sof(C1D)=1-FVAR(1)
 Sof(C131)=Sof(C132)=Sof(H13M)=Sof(H13N)=Sof(H13O)=Sof(C133)=Sof(H13P)=
 Sof(H13Q)=Sof(H13R)=Sof(C134)=Sof(H13S)=Sof(H13T)=Sof(H13U)=FVAR(1)
 Sof(C12A)=Sof(H12J)=Sof(H12K)=Sof(H12L)=Sof(C13A)=Sof(H13V)=Sof(H13W)=
 Sof(H13X)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=1-FVAR(2)
 Sof(C12)=Sof(H12G)=Sof(H12H)=Sof(H12I)=Sof(C13)=Sof(H13J)=Sof(H13K)=Sof(H13L)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(2)
6.a Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C23(H23A,H23B,H23C),
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C40(H40A,H40B,H40C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,
 H46B,H46C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C),
 C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C69(H69A,H69B,
 H69C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C86(H86A,H86B,H86C), C87(H87A,
 H87B,H87C), C88(H88A,H88B,H88C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C),
 C92(H92A,H92B,H92C), C100(H10D,H10E,H10F), C101(H10G,H10H,H10I), C102(H10J,
 H10K,H10L), C104(H10M,H10N,H10O), C105(H10P,H10Q,H10R), C106(H10S,H10T,H10U),
 C115(H11D,H11E,H11F), C122(H12A,H12B,H12C), C123(H12D,H12E,H12F), C136(H13A,
 H13B,H13C), C137(H13D,H13E,H13F), C138(H13G,H13H,H13I), C132(H13M,H13N,H13O),
 C133(H13P,H13Q,H13R), C134(H13S,H13T,H13U), C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,
 H1BC), C1C(H1CA,H1CB,H1CC), C12A(H12J,H12K,H12L)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C15(H15), C21(H21), C27(H27), C32(H32), C36(H36), C38(H38),
 C49(H49), C51(H51), C61(H61), C67(H67), C73(H73), C78(H78), C82(H82), C84(H84),
  C95(H95), C97(H97), C107(H107), C113(H113), C119(H119), C124(H124),
 C128(H128), C130(H130)
6.c Fitted hexagon refined as free rotating group:
 C1(C2,C3,C4,C5,C6), C16(C17,C18,C19,C20,C21), C24(C25,C26,C27,C28,C29),
 C33(C34,C35,C36,C37,C38), C47(C48,C49,C50,C51,C52), C62(C63,C64,C65,C66,C67),
 C70(C71,C72,C73,C74,C75), C79(C80,C81,C82,C83,C84), C93(C94,C95,C96,C97,C98),
 C108(C109,C110,C111,C112,C113), C116(C117,C118,C119,C120,C121), C125(C126,C127,
 C128,C129,C130)
6.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C68(H68A,H68B,H68C), C114(H11A,H11B,H11C), C12(H12G,H12H,
 H12I), C13(H13J,H13K,H13L), C14(H14A,H14B,H14C), C13A(H13V,H13W,H13X),
 C14A(H14D,H14E,H14F)
;
_shelx_res_checksum              64501
_shelx_hkl_checksum              63073
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'