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_1562838
_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         'C11 H24 N3 O S Zn, C3.5'
_chemical_formula_sum            'C14.5 H24 N3 O S Zn'
_chemical_formula_weight         353.80
_chemical_name_systematic        xstr1300
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-02-16
_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                 95.9940(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.86410(10)
_cell_length_b                   8.38880(10)
_cell_length_c                   18.4350(2)
_cell_measurement_reflns_used    21804
_cell_measurement_temperature    149.94(10)
_cell_measurement_theta_max      72.4010
_cell_measurement_theta_min      4.7730
_cell_volume                     1824.72(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      149.94(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2031
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_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    -74.00  30.00   1.00    1.76    --  -43.29  77.00 -60.00  104
  2  \w   -104.00 -26.00   1.00    1.76    --  -43.29 -38.00  30.00   78
  3  \w    -90.00 -17.00   1.00    1.76    --  -43.29 -57.00 -30.00   73
  4  \w   -113.00 -17.00   1.00    1.76    --  -43.29 -57.00-120.00   96
  5  \w    -68.00 -19.00   1.00    1.76    --  -43.29 -57.00  90.00   49
  6  \w    -66.00  29.00   1.00    1.76    --  -43.29  38.00-150.00   95
  7  \w    -93.00 -21.00   1.00    1.76    --  -43.29 -57.00 150.00   72
  8  \w    -86.00  -7.00   1.00    1.76    --  -43.29 125.00   0.00   79
  9  \w     12.00  39.00   1.00    1.76    --   43.29  78.00 172.94   27
 10  \w     12.00  39.00   1.00    1.76    --   43.29  76.00 101.28   27
 11  \w     11.00  42.00   1.00    1.76    --   43.29  79.00-112.91   31
 12  \w     11.00  42.00   1.00    1.76    --   43.29  79.00 -15.28   31
 13  \w     12.00  37.00   1.00    1.76    --   43.29  77.00  63.35   25
 14  \w     74.00 100.00   1.00    7.04    --  103.94  73.00  64.14   26
 15  \w    108.00 146.00   1.00    7.04    --  103.94  61.00   8.39   38
 16  \w     76.00 105.00   1.00    7.04    --  103.94  65.00 178.93   29
 17  \w     76.00 102.00   1.00    7.04    --  103.94  61.00   8.39   26
 18  \w     76.00 103.00   1.00    7.04    --  103.94  61.00-120.00   27
 19  \w     78.00 110.00   1.00    7.04    --  103.94  60.00 105.04   32
 20  \w     76.00 102.00   1.00    7.04    --  103.94  64.00-101.41   26
 21  \w     33.00 112.00   1.00    7.04    --  103.94-125.00  90.00   79
 22  \w     34.00  62.00   1.00    7.04    --  103.94 -45.00  30.00   28
 23  \w     74.00 176.00   1.00    7.04    --  103.94  72.00  34.37  102
 24  \w     28.00 108.00   1.00    7.04    --  103.94-109.00-167.87   80
 25  \w     74.00 176.00   1.00    7.04    --  103.94  72.00 -35.60  102
 26  \w     23.00 106.00   1.00    7.04    --  103.94 -94.00-120.00   83
 27  \w     79.00 107.00   1.00    7.04    --  103.94  52.00 146.50   28
 28  \w     38.00 106.00   1.00    7.04    --  103.94-125.00 150.00   68
 29  \w    113.00 174.00   1.00    7.04    --  103.94  70.00 155.96   61
 30  \w     76.00 140.00   1.00    7.04    --  103.94  66.00 -50.18   64
 31  \w     77.00 103.00   1.00    7.04    --  103.94  58.00-103.87   26
 32  \w     76.00 104.00   1.00    7.04    --  103.94  62.00 -72.25   28
 33  \w     76.00 139.00   1.00    7.04    --  103.94  61.00  30.00   63
 34  \w     76.00 148.00   1.00    7.04    --  103.94  61.00-150.00   72
 35  \w     77.00 135.00   1.00    7.04    --  103.94  61.00 -60.00   58
 36  \w     76.00 109.00   1.00    7.04    --  103.94  61.00  90.00   33
 37  \w     76.00 102.00   1.00    7.04    --  103.94  61.00   0.00   26
 38  \w     81.00 176.00   1.00    7.04    --  103.94  42.00-107.67   95
 39  \w     76.00 102.00   1.00    7.04    --  103.94  61.00  60.00   26
 40  \w     76.00 120.00   1.00    7.04    --  103.94  61.00 150.00   44
 41  \w    105.00 173.00   1.00    7.04    --  103.94  61.00 120.00   68
 42  \w     76.00 103.00   1.00    7.04    --  103.94  61.00 -90.00   27
 43  \w     76.00 104.00   1.00    7.04    --  103.94  61.00 120.00   28
 44  \w     88.00 115.00   1.00    7.04    --  103.94 -45.00  30.00   27
 45  \w    114.00 174.00   1.00    7.04    --  103.94  73.00  64.14   60
 46  \w     37.00 107.00   1.00    7.04    --  103.94 -94.00 -30.00   70
 47  \w     78.00 104.00   1.00    7.04    --  103.94  53.00-149.59   26
 48  \w     74.00 100.00   1.00    7.04    --  103.94  70.00 155.96   26
;
_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      0.0698385000
_diffrn_orient_matrix_UB_12      -0.1504385000
_diffrn_orient_matrix_UB_13      0.0219217000
_diffrn_orient_matrix_UB_21      -0.0576133000
_diffrn_orient_matrix_UB_22      -0.0115626000
_diffrn_orient_matrix_UB_23      0.0709818000
_diffrn_orient_matrix_UB_31      -0.0940050000
_diffrn_orient_matrix_UB_32      -0.1046699000
_diffrn_orient_matrix_UB_33      -0.0393322000
_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  0.0275
_diffrn_reflns_av_unetI/netI     0.0117
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            28487
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.658
_diffrn_reflns_theta_min         4.824
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.938
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87041
_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    1.288
_exptl_crystal_description       block
_exptl_crystal_F_000             744
_exptl_crystal_preparation       '[L1ZnEt] + HL4*'
_exptl_crystal_recrystallization_method 'Crystallised from a toluene solution'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.478
_refine_diff_density_min         -0.415
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     231
_refine_ls_number_reflns         3604
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0330
_refine_ls_R_factor_gt           0.0321
_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^)+(0.0525P)^2^+1.3857P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0883
_refine_ls_wR_factor_ref         0.0892
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3472
_reflns_number_total             3604
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01846a2.cif
_cod_data_source_block           xstr1300
_cod_original_formula_sum        'C14.50 H24 N3 O S Zn'
_cod_database_code               1562838
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C56 H100 N12 O8 S4 Zn4 '
_chemical_oxdiff_usercomment     'CEK MAB'
_shelx_estimated_absorpt_t_max   0.758
_shelx_estimated_absorpt_t_min   0.591
_reflns_odcompleteness_completeness 99.88
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(C2)=Sof(H2a)=Sof(H2b)=Sof(H1b)=1-FVAR(1)
 Sof(C2a)=Sof(H2aa)=Sof(H2ab)=Sof(H1a)=FVAR(1)
 Sof(C3)=Sof(H3a)=Sof(H3b)=1-FVAR(2)
 Sof(C3a)=Sof(H3aa)=Sof(H3ab)=FVAR(2)
 Fixed Sof: C16(0.5) C12(0.5) C14(0.5)
3.a Ternary CH refined with riding coordinates:
 C9(H9)
3.b Secondary CH2 refined with riding coordinates:
 C3a(H3aa,H3ab), C2a(H2aa,H2ab), C2(H2a,H2b), C3(H3a,H3b)
3.c Idealised Me refined as rotating group:
 C8(H8a,H8b,H8c), C7(H7a,H7b,H7c), C11(H11a,H11b,H11c), C5(H5a,H5b,H5c),
 C4(H4a,H4b,H4c), C10(H10a,H10b,H10c)
;
_shelx_res_checksum              33783
_shelx_hkl_checksum              59212
_olex2_date_sample_data_collection 2021-02-01
_olex2_exptl_crystal_mounting_method 'Nylon loop'
_olex2_submission_original_sample_id xstr1300
_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 1.510
_oxdiff_exptl_absorpt_empirical_full_min 0.778