Organocopper(III) Spiro Complexes: Synthesis, Structural Characterization, and Redox Transformation.
Liu, Liang; Zhu, Miaomiao; Yu, Hai-Tao; Zhang, Wen-Xiong; Xi, Zhenfeng; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b08803

data_4126458
_publ_section_title
;
 Organocopper(III) Spiro Complexes: Synthesis, Structural
 Characterization, and Redox Transformation.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b08803
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H32 Cu Si2, C16 H34 Li O4'
_chemical_formula_sum            'C40 H66 Cu Li O4 Si2'
_chemical_formula_weight         737.59
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-08-08
_audit_creation_method
;
Olex2 1.2
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   17.3800(13)
_cell_length_b                   14.6516(8)
_cell_length_c                   16.6288(10)
_cell_measurement_reflns_used    3748
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      21.2180
_cell_measurement_theta_min      3.2350
_cell_volume                     4234.4(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector_area_resol_mean 10.3914
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_details
;
  1 omega   35.00  103.00   1.0000    8.5000
omega____ theta____ kappa____ phi______ frames
    -       13.4628  178.0000  -90.0000 68

  2 omega  -41.00   61.00   1.0000    8.5000
omega____ theta____ kappa____ phi______ frames
    -      -14.7128   38.0000   30.0000 102

  3 omega  -20.00   27.00   1.0000    8.5000
omega____ theta____ kappa____ phi______ frames
    -      -14.7128  -99.0000   30.0000 47

  4 omega  -41.00   61.00   1.0000    8.5000
omega____ theta____ kappa____ phi______ frames
    -      -14.7128   38.0000  -60.0000 102
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0406851000
_diffrn_orient_matrix_UB_12      0.0016922000
_diffrn_orient_matrix_UB_13      -0.0030193000
_diffrn_orient_matrix_UB_21      -0.0030688000
_diffrn_orient_matrix_UB_22      0.0066351000
_diffrn_orient_matrix_UB_23      -0.0421197000
_diffrn_orient_matrix_UB_31      -0.0009883000
_diffrn_orient_matrix_UB_32      0.0479359000
_diffrn_orient_matrix_UB_33      0.0059414000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.1329
_diffrn_reflns_av_unetI/netI     0.1168
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            26629
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_min         3.01
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.608
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45527
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.157
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1592
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.771
_refine_diff_density_min         -0.443
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     443
_refine_ls_number_reflns         6997
_refine_ls_number_restraints     143
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.1375
_refine_ls_R_factor_gt           0.0835
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1113P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1955
_refine_ls_wR_factor_ref         0.2348
_reflns_number_gt                4222
_reflns_number_total             6997
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja7b08803_si_002.cif
_cod_data_source_block           3c
_cod_database_code               4126458
_chemical_oxdiff_formula         'C1 H1 O1 Si1 Cu1'
_reflns_odcompleteness_completeness 99.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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
 O4-C39 = O4-C38 = O1-C29 = O1-C32 = O3-C36 = O3-C33 = O2-C25 = O2-C28
 1.43 with sigma of 0.02
 C36-C35 = C34-C35 = C34-C33 = C31-C32 = C30-C31 = C30-C29 = C26-C25 = C26-C27
 = C28-C27 = C37-C38 = C40-C39
 1.54 with sigma of 0.02
3. Rigid bond restraints
 O2, C28
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O4, C39
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C37, C38
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
Uanis(C35) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37)
\\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq,
Uanis(C30) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C33)
\\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C40) \\sim Ueq,
Uanis(O1) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O4) \\sim
Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq: with sigma of 0.005 and sigma
for terminal atoms of 0.01
5.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,
 H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B),
 C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C38(H38A,H38B), C39(H39A,H39B)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C13(H13), C14(H14), C15(H15), C16(H16)
5.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C37(H37A,H37B,H37C), C40(H40A,H40B,H40C)
;
_olex2_submission_special_instructions 'No special instructions were received'