Zinc catalyzed chemoselective hydrofunctionalization of cyanamides.
Rajput, Sagrika; Sahoo, Rajata Kumar; M T, Nithya; Nembenna, Sharanappa; Chemical communications (Cambridge, England) 60 (2024) 11148–11151; doi:10.1039/d4cc03972f

data_7133724
_publ_section_title
;
 Zinc catalyzed chemoselective hydrofunctionalization of cyanamides.
;
_journal_issue                   79
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              11148
_journal_page_last               11151
_journal_paper_doi               10.1039/d4cc03972f
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C94 H130 N14 Zn2, C6 H6'
_chemical_formula_sum            'C100 H136 N14 Zn2'
_chemical_formula_weight         1664.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-05-20
_audit_creation_method
;
Olex2 1.5-ac5-021
(compiled 2022.02.15 svn.rf212a0ae for Rigaku Oxford Diffraction, GUI svn.r6439)
;
_audit_update_record
;
2024-05-22 deposited with the CCDC.	2024-09-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.7890(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.7981(2)
_cell_length_b                   26.9412(4)
_cell_length_c                   13.2296(2)
_cell_measurement_reflns_used    23688
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.9660
_cell_measurement_theta_min      3.7180
_cell_volume                     4538.25(12)
_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      100.00(10)
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.974
_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    -63.00  27.00   0.50    0.86    --  -38.50  79.00 101.00  180
  2  \w    -16.00  74.00   0.50    0.86    --   49.31 -79.00 -22.00  180
  3  \w     36.00 125.00   0.50    2.91    --  101.05 -79.00 -22.00  178
  4  \w    103.00 166.00   0.50    2.91    --  101.05  79.00 101.00  126
  5  \w    -42.00  28.00   0.50    0.86    --  -38.50  37.00-150.00  140
  6  \w    -42.00  28.00   0.50    0.86    --  -38.50  37.00 -90.00  140
  7  \w    -42.00  28.00   0.50    0.86    --  -38.50  37.00-180.00  140
  8  \w    103.00 166.00   0.50    2.91    --  101.05  77.00-120.00  126
  9  \w     97.00 164.00   0.50    2.91    --  101.05 125.00-150.00  134
 10  \w     37.00 106.00   0.50    2.91    --  101.05 -45.00 -30.00  138
 11  \w     33.00 106.00   0.50    2.91    --  101.05 -94.00-120.00  146
 12  \w     88.00 164.00   0.50    2.91    --  101.05  61.00  90.00  152
 13  \w     97.00 166.00   0.50    2.91    --  101.05  45.00 150.00  138
 14  \w     97.00 164.00   0.50    2.91    --  101.05 125.00 -60.00  134
 15  \w     93.00 170.00   0.50    2.91    --  101.05  15.00  30.00  154
 16  \w    105.00 131.00   0.50    2.91    --  101.05 125.00 -30.00   52
 17  \w    105.00 166.00   0.50    2.91    --  101.05  77.00  30.00  122
;
_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  0.0302
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            35783
_diffrn_reflns_point_group_measured_fraction_full 0.849
_diffrn_reflns_point_group_measured_fraction_max 0.815
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.071
_diffrn_reflns_theta_min         3.358
_exptl_absorpt_coefficient_mu    1.061
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53415
_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    1.218
_exptl_crystal_description       block
_exptl_crystal_F_000             1788
_exptl_crystal_preparation       'As per reaction scheme'
_exptl_crystal_recrystallization_method 'slow evaporation'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.732
_refine_diff_density_min         -0.438
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 5287 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.472(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1041
_refine_ls_number_reflns         15258
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0501
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0718P)^2^+4.5435P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1293
_refine_ls_wR_factor_ref         0.1311
_reflns_Friedel_coverage         0.638
_reflns_Friedel_fraction_full    0.695
_reflns_Friedel_fraction_max     0.650
_reflns_number_gt                14565
_reflns_number_total             15258
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc03972f3.cif
_cod_data_source_block           sn-sr-c4-zn_auto
_cod_depositor_comments
'Adding full bibliography for 7133723--7133724.cif.'
_cod_database_code               7133724
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.840
_shelx_estimated_absorpt_t_min   0.816
_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. Rigid bond restraints
 N8, C8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N6, 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
Uanis(C02G) = Uanis(C02P) = Uanis(C014)
4. Rigid body (RIGU) restrains
 N8, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Secondary CH2 refined with riding coordinates:
 C00S(H00a,H00b), C010(H01a,H01b), C01C(H01g,H01h), C11(H6a,H6b), C01G(H01j,
 H01k), C01H(H01l,H01m), C01M(H01s,H01t), C01P(H01v,H01w), C01R(H01x,H01y),
 C01S(H01z,H), C01U(H01,Ha), C01V(H1,Hb), C024(H02a,H02b), C4(H11a,H11b),
 C02F(H02p,H02q), C02K(H02s,H02t), C02M(H02v,H02w), C02T(H10,Hk), C9(H4a,H4b),
 C6(H9a,H9b)
5.b Aromatic/amide H refined with riding coordinates:
 N4(H4), N5(H5), C3(H8), N13(H13), N14(H14), C00N(H00N), C00Y(H00Y),
 C00Z(H00Z), C013(H013), C015(H015), C018(H018), C019(H019), C01A(H01f),
 C01E(H01i), C01I(H01n), C01L(H01r), C01O(H01u), C01T(H16), C01Z(H3),
 C020(H020), C023(H023), C026(H026), C02C(H17), C02D(H02l), C02I(H02r),
 C02J(H18), C02L(H02u), C02N(H02x), C02P(H02z), C014(H014), C02G(H02), C02S(H9),
  C02Y(H19), C031(H031), C8(H3a), C038(H038)
5.c Fitted hexagon refined as free rotating group:
 C02P(C014,C02G,C01Q,C00F,C011)
5.d Idealised Me refined as rotating group:
 C016(H01c,H01d,H01e), C01K(H01o,H01p,H01q), C01X(H2,Hc,Hd), C5(H12a,H12b,
 H12c), C027(H02c,H02d,H02e), C029(H02f,H02g,H02h), C02A(H02i,H02j,H02k),
 C02E(H02m,H02n,H02o), C02O(H02y,He,Hf), C02Q(H6,Hg,Hh), C02R(H7,Hi,Hj),
 C02U(H11,Hl,Hm), C02X(H12,Hn,Ho), C02Z(H15,Hp,Hq), C12(H7a,H7b,H7c), C7(H10a,
 H10b,H10c), C033(H03a,H03b,H03c), C10(H5a,H5b,H5c), C036(H03d,H03e,H03f),
 C037(H03g,H03h,H03i)
;
_shelx_res_checksum              91345
_shelx_hkl_checksum              84841
_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 1.818
_oxdiff_exptl_absorpt_empirical_full_min 0.720