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_4088443
_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         'C54 H63 N Ni O, 0.5(C4 H10 O)'
_chemical_formula_sum            'C56 H68 N Ni O1.5'
_chemical_formula_weight         837.82
_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             2015-11-16
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                74.778(3)
_cell_angle_beta                 88.323(3)
_cell_angle_gamma                62.727(4)
_cell_formula_units_Z            4
_cell_length_a                   14.2539(5)
_cell_length_b                   14.7412(5)
_cell_length_c                   26.6743(9)
_cell_measurement_reflns_used    38036
_cell_measurement_temperature    123(1)
_cell_measurement_theta_max      66.5400
_cell_measurement_theta_min      3.6130
_cell_volume                     4779.8(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      123(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2548
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.970
_diffrn_measured_fraction_theta_max 0.984
_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     12.00 115.00   1.00    5.00    --   41.53  57.00-120.00  103
  2  \w    -32.00  71.00   1.00    5.00    --   41.53 -57.00  90.00  103
  3  \w     -3.00  96.00   1.00    5.00    --   41.53-125.00  30.00   99
  4  \w      9.00 133.00   1.00   20.00    --   93.50 -93.00 -73.93  124
  5  \w      9.00 133.00   1.00   20.00    --   93.50 -93.00 143.41  124
  6  \w      8.00 132.00   1.00   20.00    --   93.50 -91.00  69.95  124
  7  \w     19.00 124.00   1.00   20.00    --   93.50 -61.00 150.00  105
  8  \w     66.00 168.00   1.00   20.00    --   93.50  45.00 150.00  102
  9  \w     63.00 171.00   1.00   20.00    --   93.50  30.00 -90.00  108
 10  \w     79.00 172.00   1.00   20.00    --   93.50 111.00 -30.00   93
 11  \w     79.00 172.00   1.00   20.00    --   93.50 111.00-150.00   93
 12  \w      9.00  83.00   1.00   20.00    --   93.50 -94.00  60.00   74
 13  \w     19.00 124.00   1.00   20.00    --   93.50 -61.00 -90.00  105
 14  \w      9.00 133.00   1.00   20.00    --   93.50 -93.00 143.41  124
 15  \w      9.00 133.00   1.00   20.00    --   93.50 -93.00  14.47  124
 16  \w     63.00 171.00   1.00   20.00    --   93.50  30.00 120.00  108
 17  \w     35.00 135.00   1.00   20.00    --   93.50 178.00-150.00  100
 18  \w     63.00 171.00   1.00   20.00    --   93.50  30.00-150.00  108
 19  \w   -120.00  -8.00   1.00    5.00    --  -41.53 -77.00  60.00  112
 20  \w     12.00 115.00   1.00    5.00    --   41.53  57.00 150.00  103
 21  \w     12.00 115.00   1.00    5.00    --   41.53  57.00  60.00  103
 22  \w     12.00 115.00   1.00    5.00    --   41.53  57.00 -30.00  103
 23  \w     60.00 111.00   1.00   20.00    --   93.50  77.00 -60.00   51
 24  \w     63.00 171.00   1.00   20.00    --   93.50  30.00  30.00  108
;
_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      -0.0866193000
_diffrn_orient_matrix_UB_12      0.0929086000
_diffrn_orient_matrix_UB_13      -0.0418236000
_diffrn_orient_matrix_UB_21      0.0055578000
_diffrn_orient_matrix_UB_22      -0.0779472000
_diffrn_orient_matrix_UB_23      -0.0301821000
_diffrn_orient_matrix_UB_31      -0.0861433000
_diffrn_orient_matrix_UB_32      -0.0172228000
_diffrn_orient_matrix_UB_33      0.0310357000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0295
_diffrn_reflns_av_unetI/netI     0.0219
_diffrn_reflns_Laue_measured_fraction_full 0.970
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            74199
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.043
_diffrn_reflns_theta_min         3.454
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.876
_exptl_absorpt_correction_T_max  0.977
_exptl_absorpt_correction_T_min  0.949
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.164
_exptl_crystal_description       block
_exptl_crystal_F_000             1804
_exptl_crystal_size_max          0.283
_exptl_crystal_size_mid          0.248
_exptl_crystal_size_min          0.112
_refine_diff_density_max         1.102
_refine_diff_density_min         -0.738
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1159
_refine_ls_number_reflns         16764
_refine_ls_number_restraints     144
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0487
_refine_ls_R_factor_gt           0.0446
_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^)+(0.0651P)^2^+3.5469P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1203
_refine_ls_wR_factor_ref         0.1243
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15178
_reflns_number_total             16764
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            3.cif
_cod_data_source_block           uc162_abs
_cod_original_formula_sum        'C56 H68 N Ni O1.50'
_cod_database_code               4088443
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         C57H60NiNO
_reflns_odcompleteness_completeness 98.33
_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
 C1A-C1B \\sim C112-C111 \\sim C1C-C1D \\sim C110-C109
 with sigma of 0.02
 O1AA-C1B \\sim O0AA-C111 \\sim O1AA-C1C \\sim O0AA-C110
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C109 \\sim C110 \\sim C111 \\sim C112: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C37 \\sim C37A \\sim C91 \\sim C91A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
O0AA \\sim C109 \\sim C110 \\sim C111 \\sim C112 \\sim O1AA \\sim C1A \\sim C1B
\\sim C1C \\sim C1D: within 2A with sigma of 0.005 and sigma for terminal atoms
of 0.005
4. Others
 Fixed Sof: H36A(0.8) H36B(0.8) H36C(0.2) H36D(0.2) C37(0.8) H37A(0.8)
 H37B(0.8) H37C(0.8) C37A(0.2) H37D(0.2) H37E(0.2) H37F(0.2) H90A(0.6)
 H90B(0.6) H90C(0.4) H90D(0.4) C91(0.4) H91D(0.4) H91E(0.4) H91F(0.4) C91A(0.6)
 H91A(0.6) H91B(0.6) H91C(0.6) O0AA(0.60626) C109(0.60626) H10S(0.60626)
 H10T(0.60626) H10U(0.60626) C110(0.60626) H11F(0.60626) H11G(0.60626)
 C111(0.60626) H11A(0.60626) H11B(0.60626) C112(0.60626) H11C(0.60626)
 H11D(0.60626) H11E(0.60626) O1AA(0.39374) C1A(0.39374) H1AA(0.39374)
 H1AB(0.39374) H1AC(0.39374) C1B(0.39374) H1BA(0.39374) H1BB(0.39374)
 C1C(0.39374) H1CA(0.39374) H1CB(0.39374) C1D(0.39374) H1DA(0.39374)
 H1DB(0.39374) H1DC(0.39374)
5.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C20(H20A,H20B), C28(H28A,H28B), C36(H36A,H36B), C36(H36C,
 H36D), C44(H44A,H44B), C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B),
 C66(H66A,H66B), C74(H74A,H74B), C82(H82A,H82B), C90(H90A,H90B), C90(H90C,H90D),
  C98(H98A,H98B), C101(H10G,H10H), C102(H10Q,H10R), C103(H10I,H10J), C110(H11F,
 H11G), C111(H11A,H11B), C1B(H1BA,H1BB), C1C(H1CA,H1CB)
5.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11), C15(H15), C16(H16), C18(H18), C19(H19),
 C23(H23), C24(H24), C26(H26), C27(H27), C31(H31), C32(H32), C34(H34), C35(H35),
  C39(H39), C40(H40), C42(H42), C43(H43), C61(H61), C62(H62), C64(H64),
 C65(H65), C69(H69), C70(H70), C72(H72), C73(H73), C77(H77), C78(H78), C80(H80),
  C81(H81), C85(H85), C86(H86), C88(H88), C89(H89), C93(H93), C94(H94),
 C96(H96), C97(H97)
5.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C21(H21A,H21B,H21C), C29(H29A,H29B,H29C), C37(H37A,H37B,
 H37C), C37A(H37D,H37E,H37F), C45(H45A,H45B,H45C), C51(H51A,H51B,H51C),
 C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C67(H67A,H67B,
 H67C), C75(H75A,H75B,H75C), C83(H83A,H83B,H83C), C91(H91D,H91E,H91F),
 C91A(H91A,H91B,H91C), C99(H99A,H99B,H99C), C105(H10D,H10E,H10F), C106(H10N,
 H10O,H10P), C107(H10A,H10B,H10C), C108(H10K,H10L,H10M), C109(H10S,H10T,H10U),
 C112(H11C,H11D,H11E), C1A(H1AA,H1AB,H1AC), C1D(H1DA,H1DB,H1DC)
;
_shelx_res_checksum              31713
_shelx_hkl_checksum              92853
_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 1.974
_oxdiff_exptl_absorpt_empirical_full_min 0.892