Synthesis, solution dynamics and chemical vapour deposition of heteroleptic zinc complexes via ethyl and amide zinc thioureides
Bhide, Malavika; Mears, Kristian Luke; Carmalt, Claire J.; Knapp, Caroline E.; Chemical Science  (2021) –; doi:10.1039/D1SC01846A

data_1562839
_publ_section_title
;
 Synthesis, solution dynamics and chemical vapour deposition of
 heteroleptic zinc complexes via ethyl and amide zinc thioureides
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC01846A
_journal_year                    2021
_chemical_formula_moiety
'2.5(C25.6 H57.6 N6.4 S3.2 Zn3.2), 2(C11.2 H12.8), C5.6'
_chemical_formula_sum            'C92 H169.6 N16 S8 Zn8'
_chemical_formula_weight         2279.47
_chemical_name_systematic        xstr1318
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-15
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2021-03-19 deposited with the CCDC.	2021-05-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.0722(12)
_cell_angle_gamma                90
_cell_formula_units_Z            5
_cell_length_a                   27.1708(3)
_cell_length_b                   8.98003(13)
_cell_length_c                   58.2262(7)
_cell_measurement_reflns_used    47350
_cell_measurement_temperature    150.0(4)
_cell_measurement_theta_max      72.4020
_cell_measurement_theta_min      4.3640
_cell_volume                     14204.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT n/a (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.0(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2031
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.966
_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   -112.00 -17.00   1.00    2.26    --  -43.17 -57.00 -30.00   95
  2  \w    -80.00  -6.00   1.00    2.26    --  -43.17 125.00  90.00   74
  3  \w   -113.00 -23.00   1.00    2.26    --  -43.17 -57.00  30.00   90
  4  \w   -103.00 -19.00   1.00    2.26    --  -43.17 -57.00-120.00   84
  5  \w    -74.00  -7.00   1.00    2.26    --  -43.17 125.00-150.00   67
  6  \w    -86.00 -19.00   1.00    2.26    --  -43.17 -57.00  90.00   67
  7  \w    -67.00 -18.00   1.00    2.26    --  -43.17 -57.00 150.00   49
  8  \w    -63.00  22.00   1.00    2.26    --  -43.17  57.00  60.00   85
  9  \w     11.00  41.00   1.00    2.26    --   43.17  79.00   3.97   30
 10  \w     13.00  38.00   1.00    2.26    --   43.17  78.00  72.91   25
 11  \w     11.00  66.00   1.00    2.26    --   43.17  19.00 150.00   55
 12  \w     11.00  40.00   1.00    2.26    --   43.17  79.00 -97.04   29
 13  \w     12.00  38.00   1.00    2.26    --   43.17  79.00 150.97   26
 14  \w     72.00 121.00   1.00    2.26    --   43.17  19.00 150.00   49
 15  \w    145.00 171.00   1.00    9.04    --  103.94  74.00  71.37   26
 16  \w     73.00 103.00   1.00    9.04    --  103.94  74.00  71.37   30
 17  \w     73.00 176.00   1.00    9.04    --  103.94  74.00 -26.84  103
 18  \w     75.00 101.00   1.00    9.04    --  103.94  66.00  57.35   26
 19  \w    133.00 176.00   1.00    9.04    --  103.94  72.00-144.48   43
 20  \w    116.00 174.00   1.00    9.04    --  103.94  70.00 128.63   58
 21  \w     74.00 176.00   1.00    9.04    --  103.94  71.00-109.17  102
 22  \w     74.00 100.00   1.00    9.04    --  103.94  72.00-144.48   26
 23  \w     76.00 102.00   1.00    9.04    --  103.94  61.00  30.00   26
 24  \w     76.00 103.00   1.00    9.04    --  103.94  61.00   0.00   27
 25  \w     76.00 101.00   1.00    9.04    --  103.94  61.00 120.00   25
 26  \w     46.00 105.00   1.00    9.04    --  103.94 -94.00 120.00   59
 27  \w     23.00 107.00   1.00    9.04    --  103.94 -94.00-180.00   84
 28  \w     76.00 110.00   1.00    9.04    --  103.94  61.00-120.00   34
 29  \w     77.00 102.00   1.00    9.04    --  103.94  60.00 -74.42   25
 30  \w     76.00 147.00   1.00    9.04    --  103.94  61.00 -60.00   71
 31  \w     74.00 100.00   1.00    9.04    --  103.94  70.00 128.63   26
 32  \w     23.00  85.00   1.00    9.04    --  103.94 -94.00 -30.00   62
 33  \w    114.00 141.00   1.00    9.04    --  103.94  45.00  30.00   27
 34  \w     81.00 108.00   1.00    9.04    --  103.94  45.00  30.00   27
 35  \w     75.00 143.00   1.00    9.04    --  103.94  66.00 -45.94   68
 36  \w     76.00 103.00   1.00    9.04    --  103.94  61.00 150.00   27
 37  \w     76.00 102.00   1.00    9.04    --  103.94  61.00 -30.00   26
 38  \w     30.00 107.00   1.00    9.04    --  103.94 -94.00  30.00   77
 39  \w     80.00 143.00   1.00    9.04    --  103.94  45.00 120.00   63
 40  \w     23.00 107.00   1.00    9.04    --  103.94 -94.00 -90.00   84
 41  \w     80.00 175.00   1.00    9.04    --  103.94  45.00  60.00   95
 42  \w     76.00 137.00   1.00    9.04    --  103.94  61.00-180.00   61
 43  \w     32.00  79.00   1.00    9.04    --  103.94-125.00 -90.00   47
 44  \w     77.00 103.00   1.00    9.04    --  103.94  58.00 167.61   26
 45  \w     74.00 176.00   1.00    9.04    --  103.94  73.00-170.89  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0521501000
_diffrn_orient_matrix_UB_12      -0.0216309000
_diffrn_orient_matrix_UB_13      -0.0102939000
_diffrn_orient_matrix_UB_21      0.0048287000
_diffrn_orient_matrix_UB_22      -0.1695070000
_diffrn_orient_matrix_UB_23      0.0033396000
_diffrn_orient_matrix_UB_31      -0.0217213000
_diffrn_orient_matrix_UB_32      0.0142017000
_diffrn_orient_matrix_UB_33      0.0241487000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0305
_diffrn_reflns_av_unetI/netI     0.0166
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       72
_diffrn_reflns_limit_l_min       -64
_diffrn_reflns_number            75291
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.824
_diffrn_reflns_theta_min         3.565
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.563
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74135
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.332
_exptl_crystal_description       irregular
_exptl_crystal_F_000             6008
_exptl_crystal_preparation       'ZnEt2 + HL1'
_exptl_crystal_recrystallization_method
'Crystallised out of a toluene/hexane solution'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.487
_refine_diff_density_min         -0.736
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     710
_refine_ls_number_reflns         13660
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0497
_refine_ls_R_factor_gt           0.0458
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0471P)^2^+67.3402P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1158
_refine_ls_wR_factor_ref         0.1185
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12750
_reflns_number_total             13660
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01846a2.cif
_cod_data_source_block           xstr1318
_cod_original_formula_sum        'C92 H169.60 N16 S8 Zn8'
_cod_database_code               1562839
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C448 H888 N80 S40 Zn40 '
_chemical_oxdiff_usercomment     'CEK MAB'
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: C26(0.5)
3.a Ternary CH refined with riding coordinates:
 C00P(H00P), C00U(H00U), C00Z(H00Z), C01F(H1), C01G(H7)
3.b Secondary CH2 refined with riding coordinates:
 C00R(H00A,H00B), C00V(H00K,H00L), C00X(H00I,H00J), C00Y(H00M,H00N), C01U(H10,
 HR)
3.c Aromatic/amide H refined with riding coordinates:
 C012(H012), C017(H017), C01B(H13), C01C(H14), C01D(H17), C01J(H18), C01L(H19),
  C01N(H15), C01P(H20), C01S(H21)
3.d Idealised Me refined as rotating group:
 C00S(H00C,H00D,H00E), C00W(H00F,H00G,H00H), C010(H01A,H01B,H01C), C011(H01D,
 H01E,H01F), C013(H01G,H01H,H01I), C014(H01J,H01K,H01L), C015(H01Y,H,HA),
 C016(H01Z,HB,HC), C018(H01M,H01N,H01O), C019(H01P,H01Q,H01R), C01A(H01,HD,HE),
 C01E(H01S,H01T,H01U), C01H(H2,HF,HG), C01I(H3,HH,HI), C01K(H01V,H01W,H01X),
 C01O(H4,HJ,HK), C01Q(H8,HL,HM), C01R(H9,HN,HO), C01T(H5,HP,HQ), C01V(H16,HS,
 HT), C01W(H6,HU,HV), C01X(H11,HW,HX), C01Y(H12,HY,HZ), C01Z(H22,H23,H24),
 C020(H02A,H02B,H02C), C021(H02D,H02E,H02F), C022(H02G,H02H,H02I)
;
_shelx_res_checksum              91711
_shelx_hkl_checksum              25613
_olex2_date_sample_data_collection 2021-03-05
_olex2_exptl_crystal_mounting_method 'Nylon loop'
_olex2_submission_original_sample_id xstr1318
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.472
_oxdiff_exptl_absorpt_empirical_full_min 0.680