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_7135243
_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         'C48 H59 N5 Te Zn'
_chemical_formula_sum            'C48 H59 N5 Te Zn'
_chemical_formula_weight         898.97
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-11-24
_audit_creation_method
;
Olex2 1.5-ac5-021
(compiled 2022.02.15 svn.rf212a0ae for Rigaku Oxford Diffraction, GUI svn.r6439)
;
_audit_update_record
;
2025-11-24 deposited with the CCDC.	2025-11-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.174(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.2703(6)
_cell_length_b                   27.8793(8)
_cell_length_c                   18.1885(8)
_cell_measurement_reflns_used    28522
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.8270
_cell_measurement_theta_min      3.6810
_cell_volume                     8751.2(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_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      100.00
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -17.00  35.00   0.50    6.20    --    1.32 -95.00  73.00  104
  2  \w    -18.00   7.00   0.50    6.20    --   -2.49 -95.00  73.00   50
  3  \w      1.00  71.00   0.50    6.20    --    1.32  19.00  30.00  140
  4  \w    -41.00  25.00   0.50    6.20    --    1.32 -77.00 -90.00  132
  5  \w    -65.00   5.00   0.50    6.20    --    1.32 -38.00-150.00  140
  6  \w    -65.00  -7.00   0.50    6.20    --   -2.49 -19.00  30.00  116
  7  \w    -51.00   3.00   0.50    6.20    --   -2.49 -57.00  90.00  108
  8  \w    -23.00  21.00   0.50    6.20    --   -2.49  77.00-180.00   88
  9  \w     -9.00  31.00   0.50    6.20    --   -2.49 -99.00   0.00   80
 10  \w      1.00  63.00   0.50    6.20    --   -2.49  38.00-180.00  124
;
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1271
_diffrn_reflns_av_unetI/netI     0.0712
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            132904
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         3.317
_exptl_absorpt_coefficient_mu    1.253
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.06810
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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    1.365
_exptl_crystal_description       block
_exptl_crystal_F_000             3712
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.17
_refine_diff_density_max         1.236
_refine_diff_density_min         -1.151
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1021
_refine_ls_number_reflns         15987
_refine_ls_number_restraints     208
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0693
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0318P)^2^+25.8034P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1114
_refine_ls_wR_factor_ref         0.1263
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12267
_reflns_number_total             15987
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc06233k2.cif
_cod_data_source_block           ns-sr-c9-teph-05-10
_cod_database_code               7135243
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.815
_shelx_estimated_absorpt_t_min   0.788
_olex2_refinement_description
;
1. Restrained distances
 C5-C02Y = C02X-C48
 1.3 with sigma of 0.02
 C02Y-C4
 1.4 with sigma of 0.02
 C4-C02Y
 1.5 with sigma of 0.02
 C48-C02X
 1.35 with sigma of 0.02
 C02X-C48
 1.3 with sigma of 0.02
 C02V-C6
 1.6 with sigma of 0.02
 C8-C02R
 1.55 with sigma of 0.02
 C02Y-C5
 1.35 with sigma of 0.02
 C48-C5
 1.35 with sigma of 0.02
 C5-C48
 1.33 with sigma of 0.02
 C5-C02Y
 1.33 with sigma of 0.02
 C02R-C7
 1.35 with sigma of 0.02
2. Rigid bond restraints
 C02X, C48, C5, C21, C4, C02Y
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C02H, C02X
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C02X, C02H
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C02W, C02Y
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C02Y, C02W
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C02X \\sim C48 \\sim C5 \\sim C02Y \\sim C21 \\sim C4: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C028 \\sim C02R \\sim C7 \\sim C8 \\sim C02L \\sim C021 \\sim C027 \\sim C02A
\\sim C02P: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C021 \\sim C027 \\sim C02A \\sim C02P \\sim C02L \\sim C028: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C02H \\sim C02X: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C02Y \\sim C02W: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C02X \\sim C02H: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(C4) = Uanis(C21) = Uanis(C48) = Uanis(C02X) = Uanis(C02Y)
4. Rigid body (RIGU) restrains
 C02Y, C5, C4, C21, C48, C02X
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C028, C02R, C7, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C02X, C02H
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C02Y, C02W
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C02H, C02X
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C02W, C02Y
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: H02X(0.4) H02Y(0.4) H02V(0.6) H02W(0.6) HW(0.5) HX(0.5) H2(0.5)
 HY(0.5) H19(0.5) HZ(0.5) H22(0.5) H20(0.5) C032(0.5) H03A(0.5) H03B(0.5)
 H03C(0.5) C7(0.4) H7A(0.4) H7B(0.4) H7C(0.4) C8(0.6) H8A(0.6) H8B(0.6)
 H8C(0.6) C6(0.5) H6A(0.5) H6B(0.5) H6C(0.5) C5(0.5) H5A(0.5) C4(0.5) H4A(0.5)
 C21(0.5) H21(0.5) C48(0.5) H48(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C00Z(H00A,H00B), C014(H01K,H01L), C01A(H01A,H01B), C01E(H01P,H01Q), C01F(H01D,
 H01E), C01J(H01S,H01W), C01L(H01Y,H), C01O(H01Z,HA), C01R(H6,HB), C01Y(H01I,
 H01J), C01Z(H8,HC), C020(H02A,H02B), C025(H9,HD), C02O(H02S,H02T), C02R(H02X,
 H02Y), C02R(H02V,H02W), C02V(HW,HX), C02V(H2,HY)
6.b Aromatic/amide H refined with riding coordinates:
 N5(H5), N007(H007), N00D(H00D), N4(H4), C00P(H00P), C00V(H00V), C00W(H00W),
 C016(H016), C017(H017), C018(H018), C019(H019), C01B(H01C), C01C(H01O),
 C01I(H01R), C01K(H01X), C01M(H01M), C01N(H01N), C01P(H01), C01Q(H3), C01S(H7),
 C01T(H01T), C01U(H01U), C01V(H01V), C022(H022), C023(H023), C026(H026),
 C02A(H02I), C02C(H02J), C02L(H02Q), C02M(H02R), C02P(H02U), C02S(H02Z),
 C02T(H02), C02W(H18), C02X(H19), C02X(HZ), C02Y(H22), C02Y(H20), C5(H5A),
 C4(H4A), C21(H21), C48(H48)
6.c Idealised Me refined as rotating group:
 C01W(H01F,H01G,H01H), C024(H02C,H02D,H02E), C029(H02F,H02G,H02H), C02B(H10,HE,
 HF), C02D(H11,HG,HH), C02E(H02K,H02L,H02M), C02F(H12,HI,HJ), C02G(H13,HK,HL),
 C02I(H14,HM,HN), C02J(H02N,H02O,H02P), C02K(H15,HO,HP), C02N(H16,HQ,HR),
 C02Q(H17,HS,HT), C02U(H1,HU,HV), C032(H03A,H03B,H03C), C7(H7A,H7B,H7C), C8(H8A,
 H8B,H8C), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              365
_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
;