Zinc-Mediated Carbene Insertion to C-Cl Bonds of Chloromethanes and Isolable Zinc(II) Isocyanide Adducts.
Kulkarni, Naveen V.; Das, Animesh; Jayaratna, Naleen B.; Yousufuddin, Muhammed; Dias, H. V. Rasika; Inorganic chemistry 54 (2015) 5151–5153; doi:10.1021/acs.inorgchem.5b00929

data_4346198
_publ_section_title
;
 Zinc-Mediated Carbene Insertion to C-Cl Bonds of Chloromethanes and
 Isolable Zinc(II) Isocyanide Adducts.
;
_journal_issue                   11
_journal_name_full               'Inorganic chemistry'
_journal_page_first              5151
_journal_page_last               5153
_journal_paper_doi               10.1021/acs.inorgchem.5b00929
_journal_volume                  54
_journal_year                    2015
_chemical_formula_moiety         'C30 H31 B F18 N9 Zn, C32 H12 B F24'
_chemical_formula_sum            'C62 H43 B2 F42 N9 Zn'
_chemical_formula_weight         1799.04
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-23
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.2453(16)
_cell_length_b                   15.649(2)
_cell_length_c                   20.561(3)
_cell_measurement_reflns_used    9122
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      40.31
_cell_measurement_theta_min      2.91
_cell_volume                     7801.1(16)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      200.01
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8 Quest'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0743
_diffrn_reflns_av_unetI/netI     0.0637
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            68426
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.026
_diffrn_reflns_theta_min         2.837
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.459
_exptl_absorpt_correction_T_max  0.9823
_exptl_absorpt_correction_T_min  0.7772
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1002 before and 0.0812 after correction.
The Ratio of minimum to maximum transmission is 0.7912.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.532
_exptl_crystal_description       platy
_exptl_crystal_F_000             3584
_exptl_crystal_size_max          0.317
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.054
_refine_diff_density_max         0.850
_refine_diff_density_min         -0.413
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details
;
 Flack x determined using 3954 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.077(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1172
_refine_ls_number_reflns         13764
_refine_ls_number_restraints     249
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.0981
_refine_ls_R_factor_gt           0.0726
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1418P)^2^+0.6791P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1942
_refine_ls_wR_factor_ref         0.2125
_reflns_Friedel_coverage         0.940
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                10140
_reflns_number_total             13764
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b00929_si_002.cif
_cod_data_source_block           rad109_0m_a
_cod_original_cell_volume        7801.0(15)
_cod_database_code               4346198
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.868
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C59-F40A = C59-F41A = C59-F42A = F40A-F41A = F40A-F42A = F41A-F42A
 2.255941 with sigma of 0.005
 C62-F40A = C62-F41A = C62-F42A
 1.38147 with sigma of 0.005
 C59-F40 = C59-F41 = C59-F42 = F40-F41 = F40-F42 = F41-F42
 2.255941 with sigma of 0.005
 C62-C59 = C62-F40 = C62-F41 = C62-F42
 1.38147 with sigma of 0.005
 C41-F25A = C41-F26A = C41-F27A = F25A-F26A = F25A-F27A = F26A-F27A
 2.255941 with sigma of 0.005
 C45-C41 = C45-F25A = C45-F26A = C45-F27A
 1.38147 with sigma of 0.005
 N8-C25A = N8-C23A = N8-C24A = C25A-C24A = C25A-C23A = C23A-C24A
 2.255941 with sigma of 0.005
 N8-C22 = C22-C23A = C22-C24A = C22-C25A
 1.38147 with sigma of 0.005
 C37-C33 = C37-F19A = C37-F20A = C37-F21A
 1.38147 with sigma of 0.005
 C33-F19A = C33-F20A = C33-F21A = F19A-F20A = F19A-F21A = F20A-F21A
 2.255941 with sigma of 0.005
 C37-F19 = C37-F20 = C37-F21
 1.38147 with sigma of 0.005
 C33-F19 = C33-F20 = C33-F21 = F19-F20 = F19-F21 = F20-F21
 2.255941 with sigma of 0.005
 C45-C41 = C45-F25 = C45-F26 = C45-F27
 1.38147 with sigma of 0.005
 C41-F25 = C41-F26 = C41-F27 = F25-F26 = F25-F27 = F26-F27
 2.255941 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(F26) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(F19A) \\sim Ueq, Uanis(F20A)
\\sim Ueq, Uanis(F27A) \\sim Ueq, Uanis(F31A) \\sim Ueq, Uanis(F32A) \\sim Ueq,
Uanis(F41A) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C24A) \\sim Ueq,
Uanis(C25A) \\sim Ueq: with sigma of 0.008 and sigma for terminal atoms of 0.016
Uanis(F8) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F25)
\\sim Ueq, Uanis(F27) \\sim Ueq, Uanis(F29) \\sim Ueq, Uanis(F31) \\sim Ueq,
Uanis(F36) \\sim Ueq, Uanis(F41) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C59)
\\sim Ueq, Uanis(F21A) \\sim Ueq, Uanis(F26A) \\sim Ueq: with sigma of 0.008
and sigma for terminal atoms of 0.016
Uanis(F3) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F39) \\sim Ueq, Uanis(C25)
\\sim Ueq, Uanis(F25A) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(F21) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
4. Others
 Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=
 Sof(H24F)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(1)
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(1)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=Sof(F25A)=Sof(F26A)=Sof(F27A)=Sof(F31A)=
 Sof(F32A)=Sof(F33A)=Sof(F40A)=Sof(F41A)=Sof(F42A)=1-FVAR(2)
 Sof(F19)=Sof(F20)=Sof(F21)=Sof(F25)=Sof(F26)=Sof(F27)=Sof(F31)=Sof(F32)=
 Sof(F33)=Sof(F40)=Sof(F41)=Sof(F42)=FVAR(2)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=FVAR(3)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1.633*FVAR(4)
5.a Ternary CH refined with riding coordinates:
 B1(H1)
5.b Me refined with riding coordinates:
 C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C12(H12), C32(H32), C34(H34), C36(H36), C40(H40), C42(H42),
 C44(H44), C48(H48), C50(H50), C52(H52), C56(H56), C58(H58), C60(H60)
5.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C25(H25A,H25B,H25C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'