Methyldisulfide groups enable the direct connection of air-stable metal bis(terpyridine) complexes to gold surfaces
Trang, Christina D. M.; Saal, Thomas; Inkpen , Michael Stephen; Dalton Transactions  (2023) –; doi:10.1039/D3DT00955F

data_7713024
_publ_section_title
;
 Methyldisulfide groups enable the direct connection of air-stable metal
 bis(terpyridine) complexes to gold surfaces
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00955F
_journal_year                    2023
_chemical_formula_moiety         'C32 H26 N6 S4 Zn, 2(F6 P)'
_chemical_formula_sum            'C32 H26 F12 N6 P2 S4 Zn'
_chemical_formula_weight         978.14
_chemical_name_common            'ZnSS, [Zn(tpySS)2](PF6)2'
_chemical_name_systematic
Zinc(II)-bis(4?-(methyldisulfide)-2,2?:6?,2??-terpyridine)
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-18
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-11-18 deposited with the CCDC.	2023-05-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.579(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.0282(2)
_cell_length_b                   9.5422(2)
_cell_length_c                   43.8494(7)
_cell_measurement_reflns_used    16333
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      79.2470
_cell_measurement_theta_min      4.0300
_cell_volume                     3765.52(13)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.936
_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   -122.00 -42.00   0.50   20.00    --  -49.65 -35.00-106.00  160
  2  \w    -39.00  23.00   0.50   20.00    --  -49.65  35.00  50.00  124
  3  \w     42.00 122.00   0.50   20.00    --   49.65  35.00  50.00  160
  4  \w    -22.00  41.00   0.50   20.00    --   49.65 -35.00-106.00  126
  5  \w   -162.00 -82.00   0.50   40.00    --  -90.00 -35.00-106.00  160
  6  \w    104.00 178.00   0.50   40.00    --  111.50  35.00  50.00  148
  7  \w    -24.00  23.00   0.50   20.00    --  -49.78  19.00-180.00   94
  8  \w   -121.00 -96.00   0.50   20.00    --  -49.78-125.00  30.00   50
  9  \w   -161.00-104.00   0.50   80.00    --  -90.00 -77.00  30.00  114
 10  \w     43.00  72.00   0.50   80.00    --  111.50 -61.00  30.00   58
 11  \w     46.00  72.00   0.50   80.00    --  111.50 -61.00 -60.00   52
 12  \w     41.00  72.00   0.50   80.00    --  111.50 -61.00 -90.00   62
 13  \w     41.00  67.00   0.50   80.00    --  111.50 -61.00-120.00   52
 14  \w     43.00  71.00   0.50   80.00    --  111.50 -61.00  90.00   56
 15  \w    106.00 137.00   0.50   80.00    --  111.50  15.00   0.00   62
 16  \w    143.00 177.00   0.50   80.00    --  111.50  15.00   0.00   68
 17  \w     41.00  69.00   0.50   80.00    --  111.50 -61.00 -30.00   56
 18  \w     43.00  69.00   0.50   80.00    --  111.50 -61.00-180.00   52
 19  \w     47.00  72.00   0.50   80.00    --  111.50 -61.00 150.00   50
 20  \w     64.00 102.00   0.50   80.00    --  111.50 -77.00  90.00   76
 21  \w     41.00  66.00   0.50   80.00    --  111.50 -61.00  60.00   50
 22  \w     46.00 111.00   0.50   80.00    --  111.50-125.00  60.00  130
 23  \w     42.00  70.00   0.50   80.00    --  111.50 -61.00 120.00   56
 24  \w    117.00 142.00   0.50   80.00    --  111.50  35.00  50.00   50
 25  \w   -121.00 -42.00   0.50   20.00    --  -49.78 -38.00-180.00  158
 26  \w   -121.00 -81.00   0.50   20.00    --  -49.78 -38.00  30.00   80
 27  \w   -121.00 -42.00   0.50   20.00    --  -49.78 -38.00 120.00  158
 28  \w    -32.00  -7.00   0.50   20.00    --  -49.78  35.00  50.00   50
 29  \w    -15.00  10.00   0.50   20.00    --   49.78 -35.00-106.00   50
 30  \w     58.00  83.00   0.50   20.00    --   49.78  35.00  50.00   50
 31  \w    -32.00  -7.00   0.50   20.00    --  -49.78  35.00  50.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0513583000
_diffrn_orient_matrix_UB_12      -0.0646509000
_diffrn_orient_matrix_UB_13      0.0295635000
_diffrn_orient_matrix_UB_21      0.1520761000
_diffrn_orient_matrix_UB_22      0.0347573000
_diffrn_orient_matrix_UB_23      0.0167926000
_diffrn_orient_matrix_UB_31      -0.0594975000
_diffrn_orient_matrix_UB_32      0.1438363000
_diffrn_orient_matrix_UB_33      0.0092621000
_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  0.0956
_diffrn_reflns_av_unetI/netI     0.0499
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.936
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       55
_diffrn_reflns_limit_l_min       -56
_diffrn_reflns_number            33496
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.165
_diffrn_reflns_theta_min         4.046
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.657
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79474
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale yellow'
_exptl_crystal_density_diffrn    1.725
_exptl_crystal_description       plate
_exptl_crystal_F_000             1968
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.683
_refine_diff_density_min         -1.064
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     609
_refine_ls_number_reflns         7704
_refine_ls_number_restraints     137
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0925
_refine_ls_R_factor_gt           0.0734
_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^)+(0.1017P)^2^+13.4453P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1888
_refine_ls_wR_factor_ref         0.2032
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5993
_reflns_number_total             7704
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00955f2.cif
_cod_data_source_block           C32H26F12N6P2S4Zn
_cod_database_code               7713024
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C32 H26 F12 N6 P2 S4 Zn1'
_shelx_estimated_absorpt_t_max   0.836
_shelx_estimated_absorpt_t_min   0.472
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C2') \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.01
Uanis(P2) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F9) \\sim
Ueq, Uanis(F10) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F12) \\sim Ueq: with
sigma of 0.04 and sigma for terminal atoms of 0.02
Uanis(P2') \\sim Ueq, Uanis(F7') \\sim Ueq, Uanis(F8') \\sim Ueq, Uanis(F9')
\\sim Ueq, Uanis(F10') \\sim Ueq, Uanis(F11') \\sim Ueq, Uanis(F12') \\sim Ueq:
with sigma of 0.04 and sigma for terminal atoms of 0.02
Uanis(S3') \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.01
3. Same fragment restrains
{P2, F7, F8, F9, F10, F11, F12} sigma for 1-2: 0.02, 1-3: 0.04
{P2', F7', F8', F9', F10', F11', F12'} sigma for 1-2: 0.02, 1-3: 0.04
as in
{P2, F7, F8, F9, F10, F12, F11}
4. Others
 Sof(S4')=Sof(S3')=Sof(C2')=Sof(H2'A)=Sof(H2'B)=Sof(H2'C)=1-FVAR(1)
 Sof(S4)=Sof(S3)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=FVAR(1)
 Sof(P2')=Sof(F7')=Sof(F8')=Sof(F9')=Sof(F10')=Sof(F11')=Sof(F12')=1-FVAR(2)
 Sof(P2)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F12)=Sof(F11)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C9(H9), C6(H6), C10(H10), C11(H11), C12(H12), C16(H16), C15(H15),
 C14(H14), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C24(H24), C26(H26),
  C29(H29), C30(H30), C31(H31), C32(H32)
5.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C2'(H2'A,H2'B,H2'C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              5302
_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 2.971
_oxdiff_exptl_absorpt_empirical_full_min 0.430