Accessing the CpArNi(I) Synthon: Reactions with N-Heterocyclic Carbenes, TEMPO, Sulfur, and Selenium
Chakraborty, Uttam; Urban, Franziska; Mühldorf, Bernd; Rebreyend, Christophe; de Bruin, Bas; van Velzen, Niels; Harder, Sjoerd; Wolf, Robert; Organometallics 35 (2016) 1624–; doi:10.1021/acs.organomet.6b00084

data_4088444
_publ_section_title
;
 Accessing the CpArNi(I) Synthon: Reactions with N-Heterocyclic Carbenes,
 TEMPO, Sulfur, and Selenium
;
_journal_issue                   11
_journal_name_full               Organometallics
_journal_page_first              1624
_journal_paper_doi               10.1021/acs.organomet.6b00084
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety         'C90 H90 Ni2 S6, 0.5(C6 D6)'
_chemical_formula_sum            'C93 H93 D0.5 Ni2 S6'
_chemical_formula_weight         1521.46
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-11-03
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                75.613(3)
_cell_angle_beta                 87.361(3)
_cell_angle_gamma                63.023(4)
_cell_formula_units_Z            2
_cell_length_a                   14.1755(6)
_cell_length_b                   14.3510(6)
_cell_length_c                   22.4716(8)
_cell_measurement_reflns_used    8877
_cell_measurement_temperature    125(2)
_cell_measurement_theta_max      65.8810
_cell_measurement_theta_min      4.0560
_cell_volume                     3934.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      125(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2548
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.965
_diffrn_measured_fraction_theta_max 0.989
_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     -3.00  75.00   1.00   20.00    --   41.41-125.00 -60.00   78
  2  \w    -30.00  70.00   1.00   20.00    --   41.41 -57.00   0.00  100
  3  \w     17.00 109.00   1.00   20.00    --   41.41  57.00 150.00   92
  4  \w     46.00  73.00   1.00   80.00    --   93.50 -93.00 -52.50   27
  5  \w     51.00 131.00   1.00   80.00    --   93.50 -89.00 153.75   80
  6  \w     26.00  84.00   1.00   80.00    --   93.50-125.00 120.00   58
  7  \w     11.00  39.00   1.00   80.00    --   93.50 -89.00 153.75   28
  8  \w     11.00 136.00   1.00   80.00    --   93.50 -15.00 -90.00  125
  9  \w     64.00 110.00   1.00   80.00    --   93.50  61.00 -60.00   46
 10  \w    133.00 168.00   1.00   80.00    --   93.50  61.00 -60.00   35
 11  \w     10.00  77.00   1.00   80.00    --   93.50 -95.00-150.00   67
 12  \w     31.00  72.00   1.00   80.00    --   93.50 -45.00 120.00   41
 13  \w     77.00 161.00   1.00   80.00    --   93.50  30.00 -90.00   84
 14  \w     61.00 140.00   1.00   80.00    --   93.50  77.00 120.00   79
 15  \w     22.00  75.00   1.00   80.00    --   93.50 -45.00 -60.00   53
 16  \w     94.00 126.00   1.00   80.00    --   93.50 -93.00 -52.50   32
 17  \w     65.00 117.00   1.00   80.00    --   93.50 -93.00  66.62   52
 18  \w     18.00  58.00   1.00   80.00    --   93.50 -30.00  60.00   40
 19  \w     36.00  76.00   1.00   80.00    --   93.50 -45.00 -30.00   40
 20  \w     10.00  69.00   1.00   80.00    --   93.50 -92.00-131.98   59
 21  \w     73.00 133.00   1.00   80.00    --   93.50 -92.00-131.98   60
 22  \w     65.00 103.00   1.00   80.00    --   93.50  61.00 -90.00   38
 23  \w    127.00 154.00   1.00   80.00    --   93.50  61.00 -90.00   27
 24  \w     32.00  57.00   1.00   80.00    --   93.50 -61.00 -60.00   25
 25  \w     67.00 117.00   1.00   80.00    --   93.50 -61.00 -60.00   50
 26  \w     29.00  43.00   1.00   80.00    --   93.50 -93.00  66.62   14
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0600814000
_diffrn_orient_matrix_UB_12      0.0469315000
_diffrn_orient_matrix_UB_13      0.0284781000
_diffrn_orient_matrix_UB_21      0.1013672000
_diffrn_orient_matrix_UB_22      -0.0658615000
_diffrn_orient_matrix_UB_23      -0.0290781000
_diffrn_orient_matrix_UB_31      -0.0327893000
_diffrn_orient_matrix_UB_32      0.0947831000
_diffrn_orient_matrix_UB_33      -0.0581605000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0546
_diffrn_reflns_av_unetI/netI     0.0585
_diffrn_reflns_Laue_measured_fraction_full 0.965
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            35656
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         66.651
_diffrn_reflns_theta_min         3.634
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.428
_exptl_absorpt_correction_T_max  0.959
_exptl_absorpt_correction_T_min  0.933
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.284
_exptl_crystal_description       block
_exptl_crystal_F_000             1607
_exptl_crystal_size_max          0.206
_exptl_crystal_size_mid          0.149
_exptl_crystal_size_min          0.108
_refine_diff_density_max         0.674
_refine_diff_density_min         -0.471
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1040
_refine_ls_number_reflns         13733
_refine_ls_number_restraints     65
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0909
_refine_ls_R_factor_gt           0.0620
_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^)+(0.0902P)^2^+1.9860P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1545
_refine_ls_wR_factor_ref         0.1743
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9747
_reflns_number_total             13733
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            5.cif
_cod_data_source_block           uc102s_ap
_cod_original_formula_sum        'C93 H93 D0.50 Ni2 S6'
_cod_database_code               4088444
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         C45H45NiS2
_reflns_odcompleteness_completeness 97.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 S2A-S1 \\sim S2-S1
 with sigma of 0.02
 S3-S2 \\sim S3A-S2A
 with sigma of 0.02
 C34-C33 \\sim C34A-C33
 with sigma of 0.02
 C50-C49 \\sim C50A-C49
 with sigma of 0.02
 C42-C41 \\sim C42A-C41
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S2 \\sim S2A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
S3 \\sim S3A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
S4 \\sim S3A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C34A \\sim C34: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C50 \\sim C50A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C42 \\sim C42A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C73 \\sim C73A \\sim C74 \\sim C74A: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.02
S5 \\sim S5A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
4. Others
 Fixed Sof: S2(0.5) S5(0.6) H49A(0.5) H49B(0.5) H49C(0.5) H49D(0.5) H41A(0.7)
 H41B(0.7) H41C(0.3) H41D(0.3) H81A(0.5) H81B(0.5) H81C(0.5) H81D(0.5) C91(0.5)
 D91(0.5) C92(0.5) D92(0.5) C94(0.5) D94(0.5) C93(0.5) D93(0.5) C95(0.5)
 D95(0.5) C96(0.5) D96(0.5) C82A(0.6) H82A(0.6) H82B(0.6) H82C(0.6) C50(0.5)
 H50A(0.5) H50B(0.5) H50C(0.5) C42(0.7) H42A(0.7) H42B(0.7) H42C(0.7) S5A(0.4)
 S2A(0.5) C50A(0.5) H50D(0.5) H50E(0.5) H50F(0.5) H33A(0.6) H33B(0.6) H33C(0.4)
 H33D(0.4) C34A(0.6) H34A(0.6) H34B(0.6) H34C(0.6) C82(0.4) H82D(0.4) H82E(0.4)
 H82F(0.4) C34(0.4) H34D(0.4) H34E(0.4) H34F(0.4) C73A(0.4) H73A(0.4) H73B(0.4)
 C74A(0.6) H74A(0.6) H74B(0.6) H74C(0.6) S4(0.5) S3(0.5) S3A(0.5) S4A(0.5)
 C42A(0.3) H42D(0.3) H42E(0.3) H42F(0.3) C74(0.4) H74D(0.4) H74E(0.4) H74F(0.4)
 C73(0.6) H73C(0.6) H73D(0.6)
5.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C25(H25A,H25B), C49(H49A,H49B), C49(H49C,H49D), C41(H41A,
 H41B), C41(H41C,H41D), C81(H81A,H81B), C81(H81C,H81D), C65(H65A,H65B),
 C57(H57A,H57B), C89(H89A,H89B), C33(H33A,H33B), C33(H33C,H33D), C73A(H73A,
 H73B), C73(H73C,H73D)
5.b Me refined with riding coordinates:
 C82(H82D,H82E,H82F), C42A(H42D,H42E,H42F)
5.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C16(H16), C24(H24), C36(H36), C15(H15), C23(H23),
 C20(H20), C21(H21), C37(H37), C44(H44), C28(H28), C47(H47), C45(H45), C48(H48),
  C40(H40), C29(H29), C32(H32), C39(H39), C84(H84), C52(H52), C31(H31),
 C60(H60), C64(H64), C68(H68), C80(H80), C88(H88), C53(H53), C79(H79), C56(H56),
  C76(H76), C61(H61), C77(H77), C72(H72), C85(H85), C63(H63), C71(H71),
 C55(H55), C69(H69), C87(H87), C91(D91), C92(D92), C94(D94), C93(D93), C95(D95),
  C96(D96)
5.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C26(H26A,H26B,H26C), C90(H90A,H90B,H90C), C58(H58A,H58B,
 H58C), C66(H66A,H66B,H66C), C82A(H82A,H82B,H82C), C50(H50A,H50B,H50C),
 C42(H42A,H42B,H42C), C50A(H50D,H50E,H50F), C34A(H34A,H34B,H34C), C34(H34D,H34E,
 H34F), C74A(H74A,H74B,H74C), C74(H74D,H74E,H74F)
;
_shelx_res_checksum              90163
_shelx_hkl_checksum              97107
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.599
_oxdiff_exptl_absorpt_empirical_full_min 0.751