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_4126457
_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_formula_moiety         '2(C32 H32 Cu), 2(C16 H32 Li O4), C4 H8 O'
_chemical_formula_sum            'C100 H136 Cu2 Li2 O9'
_chemical_formula_weight         1623.05
_chemical_name_systematic
;
 ? 
;
_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'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-03-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 129.470(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   28.2528(10)
_cell_length_b                   21.4895(7)
_cell_length_c                   19.7464(6)
_cell_measurement_reflns_used    30310
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      29.0620
_cell_measurement_theta_min      3.7780
_cell_volume                     9254.8(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      180.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -23.00  54.00   0.50    5.19    --   -1.00  38.00  30.00  154
  2  \w      6.00  54.00   0.50    5.19    --    1.40  19.00  60.00   96
  3  \w    -26.00  11.00   0.50    5.19    --   -1.00 -77.00   0.00   74
  4  \w    -12.00  26.00   0.50    5.19    --   -1.00 -82.00  60.00   76
  5  \w    -33.00  29.00   0.50    5.19    --   -1.00 -82.00 150.00  124
  6  \w    -25.00  30.00   0.50    5.19    --   -1.00 -77.00-120.00  110
  7  \w    -46.00   1.00   0.50    5.19    --   -1.00 -77.00-150.00   94
  8  \w    -87.00  31.00   0.50    5.19    --   -1.00 -19.00  60.00  236
  9  \w    -88.00  -9.00   0.50    5.19    --    1.40 -38.00  30.00  158
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0179311000
_diffrn_orient_matrix_UB_12      0.0164642000
_diffrn_orient_matrix_UB_13      0.0243520000
_diffrn_orient_matrix_UB_21      -0.0132374000
_diffrn_orient_matrix_UB_22      0.0284692000
_diffrn_orient_matrix_UB_23      -0.0122211000
_diffrn_orient_matrix_UB_31      -0.0283014000
_diffrn_orient_matrix_UB_32      -0.0028892000
_diffrn_orient_matrix_UB_33      0.0177808000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0434
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            90727
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.47
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.514
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71139
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7e (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.165
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3488
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.990
_refine_diff_density_min         -0.608
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     564
_refine_ls_number_reflns         9034
_refine_ls_number_restraints     81
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0795
_refine_ls_R_factor_gt           0.0670
_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^)+(0.1122P)^2^+18.5927P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1852
_refine_ls_wR_factor_ref         0.2046
_reflns_number_gt                7567
_reflns_number_total             9034
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja7b08803_si_002.cif
_cod_data_source_block           3b
_cod_original_cell_volume        9254.8(5)
_cod_database_code               4126457
_chemical_oxdiff_formula         'C1 H1 Li1 Cu1 O1'
_reflns_odcompleteness_completeness 99.72
_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
 C48A-C47A = C46A-C47A = C45-C46 = C48-C47 = C46A-C45A = C46-C47
 1.54 with sigma of 0.02
 O4A-C48A = O4-C45 = O4A-C45A = O4-C48
 1.43 with sigma of 0.02
 C50-C50_$1 = C49_$1-C50_$1 = C49-C50
 1.54 with sigma of 0.02
 O5-C49 = O5-C49_$1
 1.43 with sigma of 0.02
 Li1-C48
 2.98 with sigma of 0.02
 C45-Li1
 2.98 with sigma of 0.02
 C50-O5
 2.35 with sigma of 0.04
3. Rigid bond restraints
 O2, O3, C38, C39, C39, C40, C40, C43, C44, C44
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C33, C34
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(C34) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C34) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C44) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C45) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(O5)
\\sim Ueq, Uanis(C40) \\sim Ueq: with sigma of 0.001 and sigma for terminal
atoms of 0.002
5. Others
 Sof(O4A)=Sof(C45A)=Sof(H45A)=Sof(H45B)=Sof(C46A)=Sof(H46A)=Sof(H46B)=
 Sof(C47A)=Sof(H47A)=Sof(H47B)=Sof(C48A)=Sof(H48A)=Sof(H48B)=1-FVAR(1)
 Sof(O4)=Sof(C46)=Sof(H17A)=Sof(H17B)=Sof(C47)=Sof(H12A)=Sof(H12B)=Sof(C45)=
 Sof(H18A)=Sof(H18B)=Sof(C48)=Sof(H7A)=Sof(H7B)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,
 H37B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B),
 C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B), C45A(H45A,H45B), C46A(H46A,
 H46B), C47A(H47A,H47B), C48A(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B),
 C46(H17A,H17B), C47(H12A,H12B), C45(H18A,H18B), C48(H7A,H7B)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C9(H9), C12(H12), C19(H19), C22(H22), C25(H25), C28(H28)
6.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.291
_oxdiff_exptl_absorpt_empirical_full_min 0.782