Development of N-Heterocyclic Carbene‒Copper Complexes for 1,3-Halogen Migration
Schmid, Steven C.; Van Hoveln, Ryan; Rigoli, Jared W.; Schomaker, Jennifer M.; Organometallics 34 (2015) 4164–; doi:10.1021/acs.organomet.5b00629

data_4087821
_publ_section_title
;
 Development of N-Heterocyclic Carbene--Copper Complexes for 1,3-Halogen
 Migration
;
_journal_issue                   16
_journal_name_full               Organometallics
_journal_page_first              4164
_journal_paper_doi               10.1021/acs.organomet.5b00629
_journal_volume                  34
_journal_year                    2015
_chemical_absolute_configuration unk
_chemical_compound_source        'Schomaker-LabCode SCS2207'
_chemical_formula_moiety         'C35 H52 Cl Cu N2'
_chemical_formula_sum            'C35 H52 Cl Cu N2'
_chemical_formula_weight         599.77
_chemical_name_common            'carbenoid copper complex'
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_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'
_symmetry_cell_setting           monoclinic
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-12-05
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.2160(10)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   23.4669(5)
_cell_length_b                   15.9665(3)
_cell_length_c                   36.3909(8)
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.2273
_cell_measurement_theta_min      2.1685
_cell_volume                     13495.2(5)
_computing_cell_refinement       'SAINT+ Ver. 8.30C (Bruker-AXS, 2013)'
_computing_data_collection       'APEX2 Ver. 2013.2-0 (Bruker-AXS, 2013)'
_computing_data_reduction        'SAINT+ Ver. 8.30C (Bruker-AXS, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '0.60\% \w and 0.6\% \f scans'
_diffrn_radiation_collimation    '0.5 mm double-pinhole'
_diffrn_radiation_monochromator  'equatorially mounted graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0381
_diffrn_reflns_av_unetI/netI     0.0189
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            308713
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.254
_diffrn_reflns_theta_min         1.131
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'Siemens, K FFCU 2K 90'
_exptl_absorpt_coefficient_mu    0.751
_exptl_absorpt_correction_T_max  0.9186
_exptl_absorpt_correction_T_min  0.6971
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   face-indexed
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.181
_exptl_crystal_description       block
_exptl_crystal_F_000             5152
_exptl_crystal_recrystallization_method
'inert vapor diffusion of pentane into saturated THF'
_exptl_crystal_size_max          0.771
_exptl_crystal_size_mid          0.417
_exptl_crystal_size_min          0.178
_exptl_transmission_factor_max   27.2273
_exptl_transmission_factor_min   2.1685
_refine_diff_density_max         1.018
_refine_diff_density_min         -0.574
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1476
_refine_ls_number_reflns         30203
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0440
_refine_ls_R_factor_gt           0.0369
_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^)+(0.0404P)^2^+12.4569P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0935
_refine_ls_wR_factor_ref         0.0978
_reflns_Friedel_coverage         0.000
_reflns_number_gt                26636
_reflns_number_total             30203
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00629_si_004.cif
_cod_data_source_block           schomaker41
_cod_original_cell_volume        13495.1(5)
_cod_database_code               4087821
_shelx_estimated_absorpt_t_max   0.878
_shelx_estimated_absorpt_t_min   0.595
_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
 C3-C212 \\sim C3-C213 \\sim C3-C217 \\sim C3-C216
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C3 \\sim C211 \\sim C212 \\sim C213 \\sim C214 \\sim C215 \\sim C216 \\sim C217
\\sim C218: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Same fragment restrains
{C215, C216, C217, C218} sigma for 1-2: 0.02, 1-3: 0.04
as
{C211, C212, C213, C214}
5. Others
 Sof(H3B)=Sof(C215)=Sof(H21K)=Sof(H21L)=Sof(H21M)=Sof(C216)=Sof(H21N)=
 Sof(H21O)=Sof(C217)=Sof(H21P)=Sof(H21Q)=Sof(C218)=Sof(H21R)=Sof(H21S)=
 Sof(H21T)=1-FVAR(1)
 Sof(H3A)=Sof(C211)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C212)=Sof(H21D)=
 Sof(H21E)=Sof(C213)=Sof(H21F)=Sof(H21G)=Sof(C214)=Sof(H21H)=Sof(H21I)=
 Sof(H21J)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C3(H3A), C3(H3B), C12(H12), C25(H25), C30(H30), C21(H21), C46(H46), C60(H60),
 C65(H65), C73(H73), C82(H82), C96(H96), C101(H101), C108(H108), C117(H117),
 C131(H131), C136(H136)
6.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C15(H15A,H15B), C26(H26A,H26B), C28(H28A,H28B), C31(H31A,
 H31B), C33(H33A,H33B), C212(H21D,H21E), C213(H21F,H21G), C216(H21N,H21O),
 C217(H21P,H21Q), C37(H37A,H37B), C38(H38A,H38B), C47(H47A,H47B), C49(H49A,
 H49B), C61(H61A,H61B), C63(H63A,H63B), C66(H66A,H66B), C69(H69A,H69B),
 C72(H72A,H72B), C74(H74A,H74B), C83(H83A,H83B), C85(H85A,H85B), C97(H97A,H97B),
  C99(H99A,H99B), C102(H10D,H10E), C104(H10I,H10J), C107(H10Q,H10R), C109(H10S,
 H10T), C118(H11D,H11E), C120(H12A,H12B), C132(H13C,H13D), C134(H13H,H13I),
 C137(H13M,H13N), C139(H13R,H13S)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C17(H17), C18(H18), C22(H22), C23(H23), C24(H24),
 C41(H41), C42(H42), C43(H43), C51(H51), C52(H52), C56(H56), C57(H57), C58(H58),
  C77(H77), C78(H78), C79(H79), C87(H87), C88(H88), C92(H92), C93(H93),
 C94(H94), C112(H112), C113(H113), C114(H114), C122(H122), C123(H123),
 C127(H127), C128(H128), C129(H129)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C27(H27A,H27B,H27C), C29(H29A,H29B,
 H29C), C32(H32A,H32B,H32C), C35(H35A,H35B,H35C), C211(H21A,H21B,H21C),
 C214(H21H,H21I,H21J), C215(H21K,H21L,H21M), C218(H21R,H21S,H21T), C36(H36A,
 H36B,H36C), C39(H39A,H39B,H39C), C48(H48A,H48B,H48C), C50(H50A,H50B,H50C),
 C62(H62A,H62B,H62C), C64(H64A,H64B,H64C), C67(H67A,H67B,H67C), C70(H70A,H70B,
 H70C), C71(H71A,H71B,H71C), C75(H75A,H75B,H75C), C84(H84A,H84B,H84C), C86(H86A,
 H86B,H86C), C98(H98A,H98B,H98C), C100(H10A,H10B,H10C), C103(H10F,H10G,H10H),
 C105(H10K,H10L,H10M), C106(H10N,H10O,H10P), C110(H11A,H11B,H11C), C119(H11F,
 H11G,H11H), C121(H12C,H12D,H12E), C133(H13E,H13F,H13G), C135(H13J,H13K,H13L),
 C138(H13O,H13P,H13Q), C140(H14D,H14E,H14F)
;
_shelx_res_checksum              4534
_shelx_hkl_checksum              63270
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'