Nickel(ii)-mediated cyanamide–pyrazole coupling highlights distinct reactivity of NCNR2 and NCR nitrile ligands
Zelenkov, Lev E.; Kuznetsov, Maxim L.; Andrusenko, Elena V.; Avdontceva, Margarita S.; Starova, Galina L.; Bokach, Nadezhda A.; Kukushkin, Vadim Yu.; New Journal of Chemistry 44 (2020) 6979–6991; doi:10.1039/D0NJ00704H

data_7059479
_publ_section_title
;
 Nickel(ii)-mediated cyanamide--pyrazole coupling highlights distinct
 reactivity of NCNR2 and NCR nitrile ligands
;
_journal_issue                   17
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              6979
_journal_page_last               6991
_journal_paper_doi               10.1039/D0NJ00704H
_journal_volume                  44
_journal_year                    2020
_chemical_formula_moiety         'C22 H36 N12 Ni, 2(N O3)'
_chemical_formula_sum            'C22 H36 N14 Ni O6'
_chemical_formula_weight         651.36
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-03-10 deposited with the CCDC.	2020-04-06 downloaded from the CCDC.
;
_cell_angle_alpha                78.526(6)
_cell_angle_beta                 61.114(8)
_cell_angle_gamma                71.962(7)
_cell_formula_units_Z            1
_cell_length_a                   9.5039(7)
_cell_length_b                   9.5463(7)
_cell_length_c                   9.7514(8)
_cell_measurement_reflns_used    4081
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.4480
_cell_measurement_theta_min      4.7970
_cell_volume                     735.27(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_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_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -75.00 -49.00   0.50    0.20    --  -41.35 127.00  36.00   52
  2  \w    -53.00 -20.00   0.50    0.20    --  -41.35 143.00-153.00   66
  3  \w    -48.00 -13.00   0.50    0.20    --  -41.35 127.00  36.00   70
  4  \w    -92.00 -58.00   0.50    0.20    --  -41.35 143.00-153.00   68
  5  \w     90.00 121.00   0.50    0.55    --  101.00-127.00 -39.00   62
  6  \w     64.00 116.00   0.50    0.55    --  101.00 143.00-153.00  104
  7  \w     97.00 123.00   0.50    0.55    --  101.00-143.00 150.00   52
  8  \w    115.00 140.00   0.50    0.55    --  101.00 127.00  36.00   50
  9  \w    -59.00 -28.00   0.50    0.20    --  -41.35  54.00 -60.00   62
 10  \w   -103.00 -75.00   0.50    0.20    --  -41.35 -43.00-150.00   56
 11  \w    -97.00 -46.00   0.50    0.20    --  -41.35 -54.00 120.00  102
 12  \w    -67.00 -29.00   0.50    0.20    --  -41.35 -43.00-150.00   76
 13  \w   -115.00 -66.00   0.50    0.20    --  -41.35 -11.00-120.00   98
 14  \w    -56.00 -31.00   0.50    0.20    --  -41.35  54.00-120.00   50
 15  \w    -28.00  22.00   0.50    0.20    --  -41.35  54.00-120.00  100
 16  \w    -20.00  18.00   0.50    0.20    --  -41.35  54.00 -60.00   76
 17  \w    -57.00 -22.00   0.50    0.20    --  -41.35 -11.00-120.00   70
 18  \w     56.00  99.00   0.50    0.20    --   41.35-143.00 150.00   86
 19  \w     -2.00  53.00   0.50    0.20    --   41.35 -43.00 -60.00  110
 20  \w     36.00  61.00   0.50    0.20    --   41.35  54.00 150.00   50
 21  \w     -1.00  49.00   0.50    0.20    --   41.35 -32.00 -30.00  100
 22  \w     46.00  71.00   0.50    0.20    --   41.35-127.00 -39.00   50
 23  \w     22.00  47.00   0.50    0.20    --   41.35-143.00 150.00   50
 24  \w     52.00 101.00   0.50    0.20    --   41.35  43.00-180.00   98
 25  \w     30.00  80.00   0.50    0.20    --   41.35  54.00   0.00  100
 26  \w     97.00 155.00   0.50    0.55    --  101.00  93.00  60.00  116
 27  \w     36.00 104.00   0.50    0.55    --  101.00-111.00 150.00  136
 28  \w     41.00 119.00   0.50    0.55    --  101.00 -59.00 -90.00  156
 29  \w     36.00  80.00   0.50    0.55    --  101.00 -25.00 -60.00   88
 30  \w     40.00  95.00   0.50    0.55    --  101.00 -68.00-180.00  110
 31  \w    121.00 152.00   0.50    0.55    --  101.00  93.00 -60.00   62
 32  \w     75.00 157.00   0.50    0.55    --  101.00 133.00-180.00  164
 33  \w     84.00 145.00   0.50    0.55    --  101.00 111.00 -90.00  122
 34  \w     88.00 113.00   0.50    0.55    --  101.00  93.00 -60.00   50
 35  \w     76.00 153.00   0.50    0.55    --  101.00  77.00  90.00  154
 36  \w     50.00 101.00   0.50    0.55    --  101.00 -77.00-120.00  102
 37  \w     82.00 148.00   0.50    0.55    --  101.00 111.00  30.00  132
 38  \w     49.00  75.00   0.50    0.55    --  101.00 -87.00 150.00   52
 39  \w     85.00 110.00   0.50    0.55    --  101.00-111.00-150.00   50
 40  \w    130.00 157.00   0.50    0.55    --  101.00  77.00 -30.00   54
 41  \w     59.00 123.00   0.50    0.55    --  101.00 -87.00 -60.00  128
 42  \w     75.00 106.00   0.50    0.55    --  101.00 -42.00  60.00   62
 43  \w     45.00  97.00   0.50    0.55    --  101.00 -77.00  60.00  104
 44  \w     47.00  80.00   0.50    0.55    --  101.00-111.00-150.00   66
 45  \w    102.00 144.00   0.50    0.55    --  101.00  33.00 150.00   84
 46  \w     49.00  88.00   0.50    0.55    --  101.00-111.00  60.00   78
 47  \w     86.00 136.00   0.50    0.55    --  101.00 133.00 -30.00  100
 48  \w     97.00 133.00   0.50    0.55    --  101.00 111.00-150.00   72
 49  \w     82.00 107.00   0.50    0.55    --  101.00 -87.00 150.00   50
 50  \w    116.00 155.00   0.50    0.55    --  101.00  25.00   0.00   78
 51  \w     80.00 153.00   0.50    0.55    --  101.00 111.00   0.00  146
 52  \w     78.00 109.00   0.50    0.55    --  101.00  77.00 -30.00   62
 53  \w    115.00 141.00   0.50    0.55    --  101.00 143.00-153.00   52
 54  \w    -40.00 -15.00   0.50    0.20    --    8.00 124.00 145.11   50
 55  \w    -34.00  -9.00   0.50    0.20    --   16.00 128.00  -0.59   50
 56  \w     -3.00  22.00   0.50    0.20    --   28.00  94.00 -77.81   50
 57  \w     -4.00  21.00   0.50    0.20    --   28.00  97.00 -24.41   50
 58  \w     -3.00  22.00   0.50    0.20    --   28.00  96.00-161.54   50
 59  \w     -3.00  22.00   0.50    0.20    --   28.00  95.00  71.38   50
 60  \w      4.00  29.00   0.50    0.20    --   32.00  87.00-178.37   50
 61  \w      3.00  28.00   0.50    0.20    --   32.00  89.00-105.93   50
 62  \w      3.00  28.00   0.50    0.20    --   32.00  90.00 111.34   50
 63  \w     17.00  42.00   0.50    0.20    --   40.00  79.00 -23.18   50
 64  \w     15.00  40.00   0.50    0.20    --   40.00  81.00  12.49   50
 65  \w    -76.00 -31.00   0.50    0.20    --  -41.35 138.00 120.00   90
 66  \w    -43.00 -17.00   0.50    0.20    --  -41.35 -77.00 120.00   52
 67  \w     18.00  43.00   0.50    0.20    --   44.00  82.00-110.54   50
 68  \w     19.00  44.00   0.50    0.20    --   44.00  81.00  37.72   50
 69  \w     19.00  44.00   0.50    0.20    --   44.00  78.00 -69.36   50
 70  \w     19.00  44.00   0.50    0.20    --   44.00  79.00  81.28   50
 71  \w     19.00  44.00   0.50    0.20    --   44.00  79.00  57.63   50
 72  \w     30.00  69.00   0.50    0.20    --   48.00  76.00 -47.58   78
 73  \w     26.00  52.00   0.50    0.20    --   48.00  77.00 107.78   52
 74  \w     27.00  53.00   0.50    0.20    --   48.00  75.00 140.26   52
 75  \w     29.00  63.00   0.50    0.20    --   52.00  75.00  -3.81   68
 76  \w     34.00  60.00   0.50    0.20    --   52.00  59.00-102.49   52
 77  \w     74.00 107.00   0.50    0.20    --   52.00  75.00  -3.81   66
 78  \w     32.00  58.00   0.50    0.20    --   56.00  77.00 -94.86   52
 79  \w     82.00 108.00   0.50    0.20    --   56.00  68.00 121.60   52
 80  \w     40.00  66.00   0.50    0.20    --   56.00  68.00 121.60   52
 81  \w     39.00  74.00   0.50    0.20    --   60.00  70.00-170.43   70
 82  \w     39.00  65.00   0.50    0.20    --   64.00  77.00  46.91   52
 83  \w     44.00  70.00   0.50    0.20    --   64.00  63.00  30.18   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0575355000
_diffrn_orient_matrix_UB_12      0.1695361000
_diffrn_orient_matrix_UB_13      -0.0141301000
_diffrn_orient_matrix_UB_21      0.0959877000
_diffrn_orient_matrix_UB_22      -0.0028188000
_diffrn_orient_matrix_UB_23      -0.1801165000
_diffrn_orient_matrix_UB_31      -0.1549566000
_diffrn_orient_matrix_UB_32      -0.0124908000
_diffrn_orient_matrix_UB_33      -0.0054842000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0422
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            7422
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        62.477
_diffrn_reflns_theta_max         62.477
_diffrn_reflns_theta_min         4.881
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.497
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55432
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.471
_exptl_crystal_description       prism
_exptl_crystal_F_000             342
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.689
_refine_diff_density_min         -0.552
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     198
_refine_ls_number_reflns         2327
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0586
_refine_ls_R_factor_gt           0.0551
_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^)+(0.0720P)^2^+1.2976P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1447
_refine_ls_wR_factor_ref         0.1479
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2147
_reflns_number_total             2327
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0nj00704h2.cif
_cod_data_source_block           m15
_cod_depositor_comments
;Adding full bibliography for 7059474--7059481.cif.

 Adding full bibliography for 7059474--7059481.cif.
;
_cod_database_code               7059479
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C22 N14 No O6'
_reflns_odcompleteness_completeness 98.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N6(H6), C7(H7), C8(H8), C9(H9), C6(H6A), C5(H5), C4(H4)
2.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C10(H10A,H10B,H10C)
;
_shelx_res_checksum              50340
_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 2.697
_oxdiff_exptl_absorpt_empirical_full_min 0.483