Direct Observation of β-Chloride Elimination from an Isolable β-Chloroalkyl Complex of Square-Planar Nickel.
Carpenter, Alex E.; McNeece, Andrew J.; Barnett, Brandon R.; Estrada, Alexander L.; Mokhtarzadeh, Charles C.; Moore, Curtis E.; Rheingold, Arnold L.; Perrin, Charles L.; Figueroa, Joshua S.; Journal of the American Chemical Society 136 (2014) 15481–15484; doi:10.1021/ja508956q

data_4122831
_publ_section_title
;
 Direct Observation of \b-Chloride Elimination from an Isolable
 \b-Chloroalkyl Complex of Square-Planar Nickel.
;
_journal_issue                   44
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15481
_journal_page_last               15484
_journal_paper_doi               10.1021/ja508956q
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety
'C50 H50 Cl2 N2 Ni, 0.375(C4 H10 O), 1.125(C6 H5 F)'
_chemical_formula_sum            'C58.25 H59.375 Cl2 F1.125 N2 Ni O0.375'
_chemical_formula_weight         944.43
_chemical_name_common            NiCl2(CNArMes2)2
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-02-06
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.01.22 svn.r2872 for OlexSys, GUI svn.r4747)
;
_cell_angle_alpha                69.508(3)
_cell_angle_beta                 70.124(3)
_cell_angle_gamma                68.086(3)
_cell_formula_units_Z            2
_cell_length_a                   12.3698(10)
_cell_length_b                   14.6490(12)
_cell_length_c                   16.2882(14)
_cell_measurement_reflns_used    7071
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.294
_cell_measurement_theta_min      2.321
_cell_volume                     2489.4(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker X8 APEX II'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0409
_diffrn_reflns_av_unetI/netI     0.0781
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            21331
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         26.440
_diffrn_reflns_theta_min         1.790
_diffrn_source                   'sealed tube'
_diffrn_source_type              fine-focus
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.542
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6891
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0412 before and 0.0354 after correction.
The Ratio of minimum to maximum transmission is 0.9245.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            Yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.260
_exptl_crystal_description       Block
_exptl_crystal_F_000             996
_exptl_crystal_size_max          0.273
_exptl_crystal_size_mid          0.255
_exptl_crystal_size_min          0.187
_refine_diff_density_max         0.321
_refine_diff_density_min         -0.366
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     619
_refine_ls_number_reflns         10070
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.004
_refine_ls_R_factor_all          0.0943
_refine_ls_R_factor_gt           0.0473
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0408P)^2^+0.5729P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0918
_refine_ls_wR_factor_ref         0.1055
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6434
_reflns_number_total             10070
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja508956q_si_002.cif
_cod_data_source_block           JFig566
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_radiation_probe' value 'X-ray' changed to 'x-ray' according
to
/home/saulius/struct/COD-crude-data--automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from
2011-04-26.

'_exptl_crystal_colour_primary' value 'Yellow' changed
to 'yellow' according to
/home/saulius/struct/COD-crude-data--automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 2827 2014-09-09 07:05:25Z andrius 

 Adding full bibliography for 4122830--4122832.cif.
;
_cod_database_code               4122831
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.866
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All F(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C10S-C9S = C8S-C7S
 1.54 with sigma of 0.02
 O1S-C8S = O1S-C9S
 1.4 with sigma of 0.02
 C13S-C11S
 2.4 with sigma of 0.02
 C13S-C11S_$1 = C13S_$1-C11S = C12S-C11S = C12S-C13S
 1.39 with sigma of 0.005
 F2S-C11S
 1.35 with sigma of 0.005
 C11S-H2SA
 0.93 with sigma of 0.001
 C12S-H2SA
 2 with sigma of 0.001
 C12S-F2S
 2.36 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(O1S) = Uanis(C8S) = Uanis(C9S) = Uanis(C11S) = Uanis(C13S) = Uanis(C7S) =
Uanis(C12S) = Uanis(C10S) = Uanis(F2S)
4. Others
 Sof(F1SB)=Sof(H1S)=1-FVAR(1)
 Sof(F1S)=Sof(H2S)=FVAR(1)
 Fixed Sof: O1S(0.375) C7S(0.375) H7SA(0.375) H7SB(0.375) H7SC(0.375)
 C8S(0.375) H8SA(0.375) H8SB(0.375) C9S(0.375) H9SA(0.375) H9SB(0.375)
 C10S(0.375) H10A(0.375) H10B(0.375) H10C(0.375) F2S(0.125) H2SA(0.125)
 C11S(0.25) C12S(0.25) H12S(0.25) C13S(0.25) H13S(0.25)
5.a Secondary CH2 refined with riding coordinates:
 C8S(H8SA,H8SB), C9S(H9SA,H9SB)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C11(H11), C13(H13), C20(H20), C22(H22), C29(H29),
 C30(H30), C31(H31), C35(H35), C37(H37), C44(H44), C46(H46), C1S(H1S), C2S(H2S),
  C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S), C12S(H12S), C13S(H13S)
5.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C39(H39A,H39B,H39C), C40(H40A,
 H40B,H40C), C41(H41A,H41B,H41C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C),
 C50(H50A,H50B,H50C), C7S(H7SA,H7SB,H7SC), C10S(H10A,H10B,H10C)
;
_shelx_res_checksum              42621
_shelx_hkl_checksum              71473