Nickel-Catalyzed Dehydrogenative Zn–Zn Coupling to a Zn(I) Dimer and Its Reactivity
Rajput, Sagrika; PADHAN, SMRUTIRANI; M T, Nithya; Mukhopadhyay, Sayantan; Nembenna, Sharanappa; Chemical Communications  (2025) –; doi:10.1039/D5CC06233K

data_7135239
_publ_section_title
;
 Nickel-Catalyzed Dehydrogenative Zn--Zn Coupling to a Zn(I) Dimer and Its
 Reactivity
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D5CC06233K
_journal_year                    2025
_chemical_formula_moiety         'C96 H118 N10 S2 Zn2, C6 H6'
_chemical_formula_sum            'C102 H124 N10 S2 Zn2'
_chemical_formula_weight         1684.96
_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     iterative
_audit_creation_date             2025-11-21
_audit_creation_method
;
Olex2 1.5-ac5-021
(compiled 2022.02.15 svn.rf212a0ae for Rigaku Oxford Diffraction, GUI svn.r6439)
;
_audit_update_record
;
2025-11-21 deposited with the CCDC.	2025-11-26 downloaded from the CCDC.
;
_cell_angle_alpha                98.6360(10)
_cell_angle_beta                 93.4970(10)
_cell_angle_gamma                109.8260(10)
_cell_formula_units_Z            1
_cell_length_a                   10.93690(10)
_cell_length_b                   13.6261(2)
_cell_length_c                   16.2574(2)
_cell_measurement_reflns_used    29635
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.2630
_cell_measurement_theta_min      4.0400
_cell_volume                     2236.97(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-021 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-021 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution
'olex2.solve 1.5-ac5-021 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.993
_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   -103.00 -53.00   0.50    0.32    --  -38.50-160.00 130.00  100
  2  \w   -107.00 -25.00   0.50    0.32    --  -38.50 160.00 161.00  164
  3  \w    -82.00   0.00   0.50    0.32    --  -38.50 118.00   9.00  164
  4  \w     22.00  93.00   0.50    0.32    --   49.06-118.00 -77.00  142
  5  \w     47.00 118.00   0.50    0.32    --   49.06-160.00 130.00  142
  6  \w     43.00 110.00   0.50    1.22    --  106.83-118.00 -77.00  134
  7  \w     47.00 136.00   0.50    1.22    --  106.83-160.00 130.00  178
  8  \w     75.00 159.00   0.50    1.22    --  106.83 160.00 161.00  168
  9  \w    101.00 171.00   0.50    1.22    --  106.83 118.00   9.00  140
 10  \w    -44.00  31.00   0.50    0.32    --  -38.50  19.00 -60.00  150
 11  \w    -44.00  31.00   0.50    0.32    --  -38.50  19.00-180.00  150
 12  \w    -20.00  55.00   0.50    0.32    --   49.06 -19.00 -90.00  150
 13  \w    102.00 171.00   0.50    1.22    --  106.83  45.00   0.00  138
 14  \w     44.00 112.00   0.50    1.22    --  106.83-125.00-120.00  136
 15  \w     42.00 111.00   0.50    1.22    --  106.83 -45.00 150.00  138
 16  \w     39.00 110.00   0.50    1.22    --  106.83 -30.00 -30.00  142
 17  \w     44.00 120.00   0.50    1.22    --  106.83 -61.00-120.00  152
 18  \w     39.00 106.00   0.50    1.22    --  106.83 -94.00 120.00  134
 19  \w    104.00 175.00   0.50    1.22    --  106.83  30.00 -30.00  142
 20  \w     39.00 115.00   0.50    1.22    --  106.83 -15.00 -30.00  152
 21  \w     44.00 112.00   0.50    1.22    --  106.83-125.00  60.00  136
 22  \w    102.00 171.00   0.50    1.22    --  106.83  45.00 -90.00  138
 23  \w     42.00 111.00   0.50    1.22    --  106.83 -45.00  60.00  138
 24  \w     42.00 111.00   0.50    1.22    --  106.83 -45.00-120.00  138
 25  \w    102.00 171.00   0.50    1.22    --  106.83  45.00 -60.00  138
 26  \w     38.00 112.00   0.50    0.32    --   49.06  57.00  90.00  148
 27  \w     38.00 112.00   0.50    0.32    --   49.06  57.00   0.00  148
 28  \w     38.00 112.00   0.50    0.32    --   49.06  57.00-150.00  148
 29  \w     38.00 112.00   0.50    0.32    --   49.06  57.00 150.00  148
 30  \w     38.00 112.00   0.50    0.32    --   49.06  57.00 -60.00  148
 31  \w     38.00 112.00   0.50    0.32    --   49.06  57.00  30.00  148
 32  \w     38.00 112.00   0.50    0.32    --   49.06  57.00 -90.00  148
 33  \w     99.00 175.00   0.50    1.22    --  106.83  15.00  90.00  152
 34  \w    104.00 175.00   0.50    1.22    --  106.83  30.00 150.00  142
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0363
_diffrn_reflns_av_unetI/netI     0.0204
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            32038
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.250
_diffrn_reflns_theta_min         3.507
_exptl_absorpt_coefficient_mu    1.498
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39733
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic light colourless'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.251
_exptl_crystal_description       block
_exptl_crystal_F_000             898
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.17
_refine_diff_density_max         2.377
_refine_diff_density_min         -1.013
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     545
_refine_ls_number_reflns         8156
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0620
_refine_ls_R_factor_gt           0.0610
_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^)+(0.0604P)^2^+4.9660P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1469
_refine_ls_wR_factor_ref         0.1477
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7982
_reflns_number_total             8156
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc06233k2.cif
_cod_data_source_block           sn-sr-c8-87_auto
_cod_database_code               7135239
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.785
_shelx_estimated_absorpt_t_min   0.754
_olex2_refinement_description
;
1. Restrained distances
 C01G_$1-C01I_$1 = C01J-C01G = C01I-C01J_$1
 1.36 with sigma of 0.02
 C015-C7
 1.55 with sigma of 0.02
 C01G_$1-C01I_$1 \\sim C01J-C01G \\sim C01I-C01J_$1
 with sigma of 0.02
2. Rigid bond restraints
 C9, C01H
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C01J, C01G, C01I
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S1, C3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C01I \\sim C01G \\sim C01J: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
S1 \\sim C3: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C3 \\sim S1: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
Uanis(C9) = Uanis(C01H)
4. Rigid body (RIGU) restrains
 C01G, C01I, C01J
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1, C3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: H01C(0.5) H01D(0.5) H01E(0.5) H01F(0.5) H01J(0.7) H01K(0.7)
 H01L(0.3) H01M(0.3) C01K(0.7) H01(0.7) HA(0.7) HB(0.7) C5(0.5) H5A(0.5)
 H5B(0.5) H5C(0.5) C7(0.5) H7A(0.5) H7B(0.5) H7C(0.5) C8(0.3) H8A(0.3) H8B(0.3)
 H8C(0.3)
6.a Secondary CH2 refined with riding coordinates:
 C00C(H00A,H00B), C00J(H00C,H00D), C00W(H00E,H00G), C012(H01A,H01B), C015(H01C,
 H01D), C015(H01E,H01F), C018(H01J,H01K), C018(H01L,H01M), C01A(H01N,H01O),
 C01H(H01Z,H)
6.b Aromatic/amide H refined with riding coordinates:
 N5(H5), N4(H4), C00F(H00F), C00K(H00K), C00L(H00L), C00N(H00N), C00P(H00P),
 C00Q(H00Q), C00R(H00R), C00S(H00S), C00V(H00V), C00X(H00X), C010(H010),
 C011(H011), C013(H013), C014(H014), C016(H016), C019(H019), C01C(H01P),
 C01G(H1), C01I(H2), C01J(H3)
6.c Idealised Me refined as rotating group:
 C017(H01G,H01H,H01I), C01D(H01Q,H01R,H01S), C01E(H01T,H01U,H01V), C01F(H01W,
 H01X,H01Y), C01K(H01,HA,HB), C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C),
  C10(H10A,H10B,H10C), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              28384
_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
;