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_4348927
_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 N6 O14 Zn7, 6(C3 H7 N O), C3 N O'
_chemical_formula_sum            'C159 H210 N13 O21 Zn7'
_chemical_formula_weight         3096.98
_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             2016-08-24
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.9990(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.7405(4)
_cell_length_b                   24.2320(5)
_cell_length_c                   32.6921(5)
_cell_measurement_reflns_used    9995
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      57.67
_cell_measurement_theta_min      2.73
_cell_volume                     16270.7(5)
_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 0.936
_diffrn_measured_fraction_theta_max 0.936
_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  0.0234
_diffrn_reflns_av_unetI/netI     0.0280
_diffrn_reflns_Laue_measured_fraction_full 0.936
_diffrn_reflns_Laue_measured_fraction_max 0.936
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            22832
_diffrn_reflns_point_group_measured_fraction_full 0.936
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        54.997
_diffrn_reflns_theta_max         54.997
_diffrn_reflns_theta_min         2.730
_exptl_absorpt_coefficient_mu    1.649
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.264
_exptl_crystal_description       cubic
_exptl_crystal_F_000             6532
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.154
_refine_diff_density_min         -0.511
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     947
_refine_ls_number_reflns         9551
_refine_ls_number_restraints     349
_refine_ls_restrained_S_all      1.150
_refine_ls_R_factor_all          0.0652
_refine_ls_R_factor_gt           0.0558
_refine_ls_shift/su_max          0.015
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0860P)^2^+66.9605P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1536
_refine_ls_wR_factor_ref         0.1685
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8217
_reflns_number_total             9551
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b01828_si_003.cif
_cod_data_source_block           sad
_cod_database_code               4348927
_shelx_estimated_absorpt_t_max   0.734
_shelx_estimated_absorpt_t_min   0.734
_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
 C13-C12
 2.5 with sigma of 0.02
 C60-C58
 2.5 with sigma of 0.02
 C58-C59
 2.5 with sigma of 0.02
 C59-C60
 2.5 with sigma of 0.02
 C60-C57 = C58-C57 = C59-C57
 1.51 with sigma of 0.02
 C68-C69
 3.2 with sigma of 0.02
 C12A-C13A
 2.5 with sigma of 0.02
 C60A-C58A
 2.5 with sigma of 0.02
 C59A-C58A
 2.5 with sigma of 0.02
 C60A-C59A
 2.5 with sigma of 0.02
 C57-C50
 1.53 with sigma of 0.02
 C12A-C14A
 2.5 with sigma of 0.02
 C14A-C13A
 2.5 with sigma of 0.02
 C42A-C40A
 2.5 with sigma of 0.02
 C40-C42
 2.5 with sigma of 0.02
 C41A-C42A
 2.5 with sigma of 0.02
 C41A-C40A
 2.5 with sigma of 0.02
 C42A-C39A = C40A-C39A = C41A-C39A
 1.51 with sigma of 0.02
 C41-C40
 2.5 with sigma of 0.02
 C42-C41
 2.5 with sigma of 0.02
 C42-C39 = C40-C39 = C41-C39
 1.51 with sigma of 0.02
 C58A-C57A = C59A-C57A = C60A-C57A
 1.51 with sigma of 0.02
 C57A-C50
 1.53 with sigma of 0.02
 N7-C79
 1.49 with sigma of 0.02
 C80-C79
 2.65 with sigma of 0.02
 C80-N7
 1.45 with sigma of 0.02
 N4-C72
 1.61 with sigma of 0.02
 N4-C71
 1.55 with sigma of 0.02
 N4-C70
 1.8 with sigma of 0.02
 C79-O11
 1.25 with sigma of 0.02
 O11-N7
 2.2984 with sigma of 0.02
 O10-N6
 2.6 with sigma of 0.02
 N6-O10
 2.3 with sigma of 0.02
 C14-C13
 2.5 with sigma of 0.02
 C12-C14
 2.5 with sigma of 0.02
 C3-C11
 1.53 with sigma of 0.02
 C11-C3 = C11A-C3
 1.53 with sigma of 0.02
 C13-C11 = C12-C11 = C14-C11
 1.51 with sigma of 0.02
 C12A-C11A = C12-C11 = C13-C11 = C13A-C11A = C14-C11 = C14A-C11A
 1.51 with sigma of 0.02
 N6-C78
 1.55 with sigma of 0.02
 N6-C77
 1.55 with sigma of 0.02
 N6-C76
 1.59 with sigma of 0.02
 O10-C76
 1.25 with sigma of 0.02
 C76-C77
 2.6 with sigma of 0.02
 N5-C75
 1.59 with sigma of 0.02
 N5-C74
 1.56 with sigma of 0.02
 N5-C73
 1.7 with sigma of 0.02
3. Restrained planarity
 N7, C79, C80, O11
 with sigma of 0.1
 N6, C76, C77, C78
 with sigma of 0.1
4. Rigid bond restraints
 C75, N5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N5, C74
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C73, N5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C72, N4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C71, N4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N4, C70
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C79, O11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N6, C78
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C76, N6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O10, C76
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N6, C77
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C57 \\sim C58: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
C57 \\sim C59: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
C57 \\sim C60: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.08
C50 \\sim C57: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C3 \\sim C11A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C14A \\sim C12A \\sim C13A \\sim C11A \\sim C11A \\sim C11A: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.08
C39 \\sim C40: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C37 \\sim C39: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C39 \\sim C42: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C41A \\sim C39A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C39 \\sim C41: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C50 \\sim C57A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C60A \\sim C57A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C58A \\sim C57A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C59A \\sim C57A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
N7 \\sim C79 \\sim C80 \\sim O11: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
O8 \\sim N4 \\sim C70 \\sim C71 \\sim C72: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C11 \\sim C11 \\sim C11 \\sim C12 \\sim C13 \\sim C14: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.08
N6 \\sim C76 \\sim C77 \\sim C78 \\sim O10: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08
N5 \\sim C73 \\sim C74 \\sim C75 \\sim O9: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C14A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C14) \\sim Ueq: with sigma of 0.0001 and sigma for terminal atoms of 0.2
Uanis(C41) = Uanis(C41A)
Uanis(C42A) = Uanis(C42)
Uanis(C77) = Uanis(C78) = Uanis(C76) = Uanis(N6)
6. Rigid body (RIGU) restrains
 C57, C59
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C57, C60
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C57, C58
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C50, C57
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C12A, C11A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3, C11A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C13A, C11A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C42, C42A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39, C40
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C37, C39
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C39, C42
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C39, C41
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C41, C41A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C50, C57A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C60A, C57A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C58A, C57A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C59A, C57A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C14
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
7. Others
 Sof(C59A)=Sof(H59D)=Sof(H59E)=Sof(H59F)=Sof(C60A)=Sof(H60D)=Sof(H60E)=
 Sof(H60F)=Sof(C58A)=Sof(H58D)=Sof(H58E)=Sof(H58F)=Sof(C57A)=1-FVAR(1)
 Sof(C57)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59)=Sof(H59A)=Sof(H59B)=
 Sof(H59C)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(1)
 Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C12A)=Sof(H12D)=Sof(H12E)=
 Sof(H12F)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C11A)=1-FVAR(2)
 Sof(C11)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=
 Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(2)
 Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=Sof(C40A)=Sof(H40D)=Sof(H40E)=
 Sof(H40F)=Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(C39A)=1-FVAR(3)
 Sof(C39)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C41)=Sof(H41A)=Sof(H41B)=
 Sof(H41C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=FVAR(3)
 Fixed Sof: N7(0.5) C79(0.5) O11(0.5)
8.a Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C30(H30A,H30B,H30C),
 C31(H31A,H31B,H31C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,
 H46C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C72(H72A,
 H72B,H72C), C42(H42A,H42B,H42C), C59A(H59D,H59E,H59F), C60A(H60D,H60E,H60F),
 C58A(H58D,H58E,H58F)
8.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C15(H15), C21(H21), C27(H27), C32(H32), C36(H36), C38(H38),
 C49(H49), C51(H51), C61(H61), C67(H67), C70(H70), C73(H73), C76(H76)
8.c Fitted hexagon refined as free rotating group:
 C6(C1,C2,C3,C4,C5), 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)
8.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,
 H60B,H60C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C71(H71A,H71B,H71C),
 C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C77(H77A,H77B,H77C), C78(H78A,H78B,
 H78C), C41(H41A,H41B,H41C), C40(H40A,H40B,H40C), C14A(H14D,H14E,H14F),
 C12A(H12D,H12E,H12F), C13A(H13D,H13E,H13F), C41A(H41D,H41E,H41F), C40A(H40D,
 H40E,H40F), C42A(H42D,H42E,H42F)
;
_shelx_res_checksum              53863
_shelx_hkl_checksum              26468
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'