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_4122830
_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         'C52 H50 Cl6 N2 Ni, 0.5(C4 H8 O)'
_chemical_formula_sum            'C54 H54 Cl6 N2 Ni O0.5'
_chemical_formula_weight         1010.40
_chemical_name_common            NiCl(C2Cl5)(CNArMes2)2
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-02-03
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.01.22 svn.r2872 for OlexSys, GUI svn.r4747)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.9760(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.2134(5)
_cell_length_b                   22.5695(8)
_cell_length_c                   16.1066(6)
_cell_measurement_reflns_used    9927
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.32
_cell_measurement_theta_min      2.31
_cell_volume                     5138.7(3)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX CCD'
_diffrn_detector_area_resol_mean 8.0
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.934
_diffrn_measurement_device       'Siemens P4 Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker P4 APEX'
_diffrn_measurement_method       '\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  0.0402
_diffrn_reflns_av_unetI/netI     0.0455
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.934
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            44264
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         28.350
_diffrn_reflns_theta_min         1.559
_diffrn_source                   'sealed tube'
_diffrn_source_type              fine-focus
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.728
_exptl_absorpt_correction_T_max  0.7548
_exptl_absorpt_correction_T_min  0.6233
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            Orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_description       Block
_exptl_crystal_F_000             2104
_exptl_crystal_size_max          0.313
_exptl_crystal_size_mid          0.217
_exptl_crystal_size_min          0.158
_refine_diff_density_max         1.021
_refine_diff_density_min         -0.422
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     663
_refine_ls_number_reflns         12003
_refine_ls_number_restraints     131
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0555
_refine_ls_R_factor_gt           0.0404
_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^)+(0.0443P)^2^+2.6510P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1000
_refine_ls_wR_factor_ref         0.1080
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9478
_reflns_number_total             12003
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja508956q_si_002.cif
_cod_data_source_block           JFig411
_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 'Orange' changed
to 'orange' 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_original_formula_sum        'C54 H54 Cl6 N2 Ni O0.50'
_cod_database_code               4122830
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.894
_shelx_estimated_absorpt_t_min   0.804
_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
 O1S-C4S = O1S-C1S
 1.4 with sigma of 0.02
 C2S-C1S = C3S-C4S
 1.54 with sigma of 0.02
 C3S-C2S
 1.54 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C40) = Uanis(C40B)
Uanis(C39) = Uanis(C39B)
Uanis(C38B) = Uanis(C38)
Uanis(C37B) = Uanis(C37)
Uanis(C36B) = Uanis(C36)
Uanis(C35) = Uanis(C35B)
Uanis(C43B) = Uanis(C43)
Uanis(C41B) = Uanis(C41)
Uanis(C3B) = Uanis(C3)
Uanis(C4B) = Uanis(C4)
Uanis(Cl2B) = Uanis(Cl3)
Uanis(Cl3B) = Uanis(Cl5)
Uanis(Ni1B) = Uanis(Ni1)
Uanis(O1S) = Uanis(C4S) = Uanis(C1S) = Uanis(C3S) = Uanis(C2S)
4. Rigid body (RIGU) restrains
 C35, C40, C39, C38, C37, C36, C43, C42, C41
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C43B, C40B, C35B, C36B, C41B, C37B, C38B, C39B, C42B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C35B)=Sof(C36B)=Sof(C37B)=Sof(H37B)=Sof(C38B)=Sof(C39B)=Sof(H39B)=
 Sof(C40B)=Sof(C41B)=Sof(H41D)=Sof(H41E)=Sof(H41F)=Sof(C42B)=Sof(H42D)=
 Sof(H42E)=Sof(H42F)=Sof(C43B)=Sof(H43D)=Sof(H43E)=Sof(H43F)=1-FVAR(1)
 Sof(C35)=Sof(C36)=Sof(C37)=Sof(H37)=Sof(C38)=Sof(C39)=Sof(H39)=Sof(C40)=
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=FVAR(1)
 Sof(Ni1B)=Sof(Cl2B)=Sof(Cl3B)=Sof(Cl4B)=Sof(Cl5B)=Sof(Cl6B)=Sof(C3B)=Sof(C4B)=
 1-FVAR(2)
 Sof(Ni1)=Sof(Cl2)=Sof(Cl3)=Sof(Cl4)=Sof(Cl5)=Sof(Cl6)=Sof(C3)=Sof(C4)=FVAR(2)
 Fixed Sof: O1S(0.5) C1S(0.5) H1SA(0.5) H1SB(0.5) C2S(0.5) H2SA(0.5) H2SB(0.5)
 C3S(0.5) H3SA(0.5) H3SB(0.5) C4S(0.5) H4SA(0.5) H4SB(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB)
6.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C13(H13), C15(H15), C22(H22), C24(H24), C31(H31),
 C32(H32), C33(H33), C46(H46), C48(H48), C37(H37), C39(H39), C37B(H37B),
 C39B(H39B)
6.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C26(H26A,H26B,
 H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C50(H50A,H50B,H50C), C51(H51A,
 H51B,H51C), C52(H52A,H52B,H52C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C),
 C43(H43A,H43B,H43C), C41B(H41D,H41E,H41F), C42B(H42D,H42E,H42F), C43B(H43D,
 H43E,H43F)
;
_shelx_res_checksum              48655
_shelx_hkl_checksum              25264