# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_lkc136
_database_code_depnum_ccdc_archive 'CCDC 1006369'
_audit_update_record             
;
2014-06-02 deposited with the CCDC.
2015-04-16 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
Bis-[2,6-di(pyrazol-1-yl)pyrid-4-yl]disulfide 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C22 H16 N10 S2'
_chemical_formula_sum            'C22 H16 N10 S2'
_chemical_formula_weight         484.57

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Triclinic
_symmetry_space_group_name_H-M   'P -1'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   8.9223(13)
_cell_length_b                   10.2903(14)
_cell_length_c                   13.341(2)
_cell_angle_alpha                90.512(6)
_cell_angle_beta                 107.862(7)
_cell_angle_gamma                100.271(6)
_cell_volume                     1144.5(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    36263
_cell_measurement_theta_min      2.02
_cell_measurement_theta_max      31.98

_exptl_crystal_description       'rectangular prism'
_exptl_crystal_colour            Colourless
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.13
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.406
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             500
_exptl_absorpt_coefficient_mu    0.266
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.728
_exptl_absorpt_correction_T_max  1.264
_exptl_absorpt_process_details   
;
Sheldrick, G. M. (2002). SADABS v. 2.03. University of 
G/ottingen, Germany.
;

_exptl_special_details           
; 
 Rotating anode power 3 kW.
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker X8 Apex diffractometer'
_diffrn_measurement_method       'Rotation images'
_diffrn_detector_area_resol_mean '120 microns'
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_decay_%        0
_diffrn_reflns_number            36263
_diffrn_reflns_av_R_equivalents  0.0521
_diffrn_reflns_av_sigmaI/netI    0.0358
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         2.02
_diffrn_reflns_theta_max         31.98
_reflns_number_total             7730
_reflns_number_gt                6262
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'APEX 2 software, Bruker Nonius 2004'
_computing_cell_refinement       'APEX 2 software, Bruker Nonius 2004'
_computing_data_reduction        'SAINT, Bruker Nonius 2004'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'X-SEED (Barbour, 2001)'
_computing_publication_material  'local program'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 

 No disorder was detected during refinement, and no restraints were applied. 
 All non-H atoms were refined anisotropically, and all H atoms were located 
 in the Fourier map and allowed to refine freely. Refined C---H distances 
 range from 0.93(2)--1.01(2) Å.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0697P)²+0.3408P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         7730
_refine_ls_number_parameters     371
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0540
_refine_ls_R_factor_gt           0.0413
_refine_ls_wR_factor_ref         0.1406
_refine_ls_wR_factor_gt          0.1242
_refine_ls_goodness_of_fit_ref   1.148
_refine_ls_restrained_S_all      1.148
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
N1 N 0.49464(14) 0.85336(12) 0.56722(9) 0.0232(2) Uani 1 1 d . . .
C2 C 0.34867(16) 0.88520(13) 0.55086(10) 0.0218(2) Uani 1 1 d . . .
C3 C 0.20712(17) 0.82653(13) 0.47014(11) 0.0233(3) Uani 1 1 d . . .
H3 H 0.104(2) 0.8588(19) 0.4624(15) 0.031(5) Uiso 1 1 d . . .
C4 C 0.22219(16) 0.72386(13) 0.40424(10) 0.0220(2) Uani 1 1 d . . .
C5 C 0.37163(17) 0.68618(14) 0.41944(11) 0.0238(3) Uani 1 1 d . . .
H5 H 0.386(2) 0.6178(18) 0.3763(14) 0.025(4) Uiso 1 1 d . . .
C6 C 0.50262(16) 0.75529(13) 0.50219(10) 0.0222(2) Uani 1 1 d . . .
N7 N 0.34502(14) 0.98519(12) 0.62485(9) 0.0237(2) Uani 1 1 d . . .
N8 N 0.20286(17) 1.02377(14) 0.62092(11) 0.0332(3) Uani 1 1 d . . .
C9 C 0.2457(2) 1.11339(17) 0.70371(13) 0.0360(4) Uani 1 1 d . . .
H9 H 0.161(3) 1.153(2) 0.7184(18) 0.046(6) Uiso 1 1 d . . .
C10 C 0.4126(2) 1.13248(15) 0.76103(12) 0.0306(3) Uani 1 1 d . . .
H10 H 0.474(3) 1.191(2) 0.8242(17) 0.040(6) Uiso 1 1 d . . .
C11 C 0.47324(18) 1.04867(15) 0.70841(12) 0.0272(3) Uani 1 1 d . . .
H11 H 0.580(3) 1.026(2) 0.7216(17) 0.040(5) Uiso 1 1 d . . .
N12 N 0.65751(15) 0.72160(13) 0.52409(10) 0.0265(2) Uani 1 1 d . . .
N13 N 0.67915(17) 0.62044(14) 0.46387(11) 0.0321(3) Uani 1 1 d . . .
C14 C 0.8344(2) 0.61297(19) 0.50785(14) 0.0363(4) Uani 1 1 d . . .
H14 H 0.878(3) 0.547(2) 0.4788(18) 0.045(6) Uiso 1 1 d . . .
C15 C 0.9135(2) 0.7071(2) 0.59561(15) 0.0381(4) Uani 1 1 d . . .
H15 H 1.026(3) 0.718(2) 0.6418(19) 0.053(7) Uiso 1 1 d . . .
C16 C 0.79685(19) 0.77566(18) 0.60403(13) 0.0327(3) Uani 1 1 d . . .
H16 H 0.798(3) 0.849(2) 0.652(2) 0.054(7) Uiso 1 1 d . . .
S17 S 0.03901(4) 0.64319(3) 0.30600(3) 0.02441(9) Uani 1 1 d . . .
S18 S 0.11242(4) 0.53246(3) 0.20716(3) 0.02479(9) Uani 1 1 d . . .
N19 N 0.26184(15) 0.81197(11) -0.02914(9) 0.0249(2) Uani 1 1 d . . .
C20 C 0.21157(17) 0.85903(13) 0.04747(11) 0.0235(3) Uani 1 1 d . . .
C21 C 0.16031(17) 0.78273(13) 0.12240(11) 0.0235(3) Uani 1 1 d . . .
H21 H 0.122(2) 0.8227(19) 0.1734(16) 0.034(5) Uiso 1 1 d . . .
C22 C 0.16681(16) 0.64720(13) 0.11721(10) 0.0221(2) Uani 1 1 d . . .
C23 C 0.21999(17) 0.59343(13) 0.03914(11) 0.0239(3) Uani 1 1 d . . .
H23 H 0.228(3) 0.501(2) 0.0366(17) 0.042(6) Uiso 1 1 d . . .
C24 C 0.26429(17) 0.68107(13) -0.03217(10) 0.0228(2) Uani 1 1 d . . .
N25 N 0.21589(16) 0.99817(12) 0.05013(10) 0.0270(2) Uani 1 1 d . . .
N26 N 0.17615(18) 1.06122(13) 0.12788(11) 0.0325(3) Uani 1 1 d . . .
C27 C 0.1972(2) 1.18900(16) 0.10555(15) 0.0372(4) Uani 1 1 d . . .
H27 H 0.177(3) 1.253(2) 0.1541(17) 0.041(6) Uiso 1 1 d . . .
C28 C 0.2500(3) 1.20969(17) 0.01522(15) 0.0396(4) Uani 1 1 d . . .
H28 H 0.271(3) 1.289(2) -0.0149(19) 0.052(6) Uiso 1 1 d . . .
C29 C 0.2603(2) 1.08510(15) -0.01848(14) 0.0361(4) Uani 1 1 d . . .
H29 H 0.294(3) 1.053(2) -0.075(2) 0.055(7) Uiso 1 1 d . . .
N30 N 0.31543(15) 0.63466(11) -0.11529(9) 0.0241(2) Uani 1 1 d . . .
N31 N 0.32822(17) 0.50386(12) -0.12505(10) 0.0292(3) Uani 1 1 d . . .
C32 C 0.3755(2) 0.49589(16) -0.21146(12) 0.0305(3) Uani 1 1 d . . .
H32 H 0.389(2) 0.411(2) -0.2347(16) 0.033(5) Uiso 1 1 d . . .
C33 C 0.3927(2) 0.61902(17) -0.25788(13) 0.0361(4) Uani 1 1 d . . .
H33 H 0.418(3) 0.638(2) -0.3210(19) 0.051(6) Uiso 1 1 d . . .
C34 C 0.3540(2) 0.70662(16) -0.19431(13) 0.0339(3) Uani 1 1 d . . .
H34 H 0.348(3) 0.802(3) -0.197(2) 0.062(7) Uiso 1 1 d . . .


_geom_special_details            
; 
 All esds (except the esd in the dihedral angle between two l.s. planes) 
 are estimated using the full covariance matrix.  The cell esds are taken 
 into account individually in the estimation of esds in distances, angles 
 and torsion angles; correlations between esds in cell parameters are only 
 used when they are defined by crystal symmetry.  An approximate (isotropic) 
 treatment of cell esds is used for estimating esds involving l.s. planes. 
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
N1 C6 1.3506(17) . ?
N1 C2 1.3529(18) . ?
C2 C3 1.415(2) . ?
C2 N7 1.4309(17) . ?
C3 C4 1.4191(18) . ?
C3 H3 1.01(2) . ?
C4 C5 1.4104(19) . ?
C4 S17 1.8057(14) . ?
C5 C6 1.410(2) . ?
C5 H5 0.956(18) . ?
C6 N12 1.4284(18) . ?
N7 N8 1.3815(18) . ?
N7 C11 1.3843(19) . ?
N8 C9 1.347(2) . ?
C9 C10 1.426(2) . ?
C9 H9 0.99(2) . ?
C10 C11 1.385(2) . ?
C10 H10 0.98(2) . ?
C11 H11 0.98(2) . ?
N12 N13 1.3850(18) . ?
N12 C16 1.386(2) . ?
N13 C14 1.345(2) . ?
C14 C15 1.427(3) . ?
C14 H14 0.97(2) . ?
C15 C16 1.388(2) . ?
C15 H15 0.99(2) . ?
C16 H16 0.98(2) . ?
S17 S18 2.0579(5) . ?
S18 C22 1.8022(14) . ?
N19 C24 1.3514(18) . ?
N19 C20 1.3527(18) . ?
C20 C21 1.4111(19) . ?
C20 N25 1.4253(17) . ?
C21 C22 1.4081(18) . ?
C21 H21 0.97(2) . ?
C22 C23 1.4151(18) . ?
C23 C24 1.4119(19) . ?
C23 H23 0.97(2) . ?
C24 N30 1.4300(17) . ?
N25 C29 1.380(2) . ?
N25 N26 1.3851(17) . ?
N26 C27 1.344(2) . ?
C27 C28 1.427(3) . ?
C27 H27 1.00(2) . ?
C28 C29 1.382(2) . ?
C28 H28 0.93(2) . ?
C29 H29 0.96(2) . ?
N30 N31 1.3793(17) . ?
N30 C34 1.3868(18) . ?
N31 C32 1.3500(18) . ?
C32 C33 1.420(2) . ?
C32 H32 0.96(2) . ?
C33 C34 1.389(2) . ?
C33 H33 0.95(2) . ?
C34 H34 1.00(3) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C6 N1 C2 116.45(12) . . ?
N1 C2 C3 125.18(12) . . ?
N1 C2 N7 114.29(12) . . ?
C3 C2 N7 120.52(12) . . ?
C2 C3 C4 116.01(13) . . ?
C2 C3 H3 119.7(11) . . ?
C4 C3 H3 124.3(11) . . ?
C5 C4 C3 120.68(12) . . ?
C5 C4 S17 123.46(10) . . ?
C3 C4 S17 115.82(10) . . ?
C6 C5 C4 116.79(12) . . ?
C6 C5 H5 120.3(11) . . ?
C4 C5 H5 122.9(11) . . ?
N1 C6 C5 124.86(13) . . ?
N1 C6 N12 114.80(12) . . ?
C5 C6 N12 120.33(12) . . ?
N8 N7 C11 112.60(11) . . ?
N8 N7 C2 120.85(11) . . ?
C11 N7 C2 126.49(12) . . ?
C9 N8 N7 103.58(13) . . ?
N8 C9 C10 112.50(14) . . ?
N8 C9 H9 118.1(13) . . ?
C10 C9 H9 129.4(13) . . ?
C11 C10 C9 104.97(13) . . ?
C11 C10 H10 126.2(13) . . ?
C9 C10 H10 128.8(13) . . ?
N7 C11 C10 106.35(14) . . ?
N7 C11 H11 120.1(12) . . ?
C10 C11 H11 133.5(13) . . ?
N13 N12 C16 112.26(13) . . ?
N13 N12 C6 119.85(12) . . ?
C16 N12 C6 127.85(13) . . ?
C14 N13 N12 103.90(14) . . ?
N13 C14 C15 112.40(15) . . ?
N13 C14 H14 119.2(14) . . ?
C15 C14 H14 128.4(14) . . ?
C16 C15 C14 105.00(15) . . ?
C16 C15 H15 127.8(14) . . ?
C14 C15 H15 127.1(14) . . ?
N12 C16 C15 106.45(15) . . ?
N12 C16 H16 120.6(14) . . ?
C15 C16 H16 132.9(14) . . ?
C4 S17 S18 104.77(5) . . ?
C22 S18 S17 104.91(5) . . ?
C24 N19 C20 116.40(12) . . ?
N19 C20 C21 125.44(12) . . ?
N19 C20 N25 114.62(12) . . ?
C21 C20 N25 119.93(12) . . ?
C22 C21 C20 116.23(12) . . ?
C22 C21 H21 122.9(12) . . ?
C20 C21 H21 120.9(12) . . ?
C21 C22 C23 120.47(12) . . ?
C21 C22 S18 123.74(10) . . ?
C23 C22 S18 115.79(10) . . ?
C24 C23 C22 117.10(12) . . ?
C24 C23 H23 121.9(13) . . ?
C22 C23 H23 121.0(13) . . ?
N19 C24 C23 124.34(12) . . ?
N19 C24 N30 114.75(12) . . ?
C23 C24 N30 120.91(12) . . ?
C29 N25 N26 112.36(12) . . ?
C29 N25 C20 126.65(12) . . ?
N26 N25 C20 120.99(12) . . ?
C27 N26 N25 103.56(13) . . ?
N26 C27 C28 112.60(14) . . ?
N26 C27 H27 116.6(12) . . ?
C28 C27 H27 130.8(12) . . ?
C29 C28 C27 104.75(15) . . ?
C29 C28 H28 127.7(15) . . ?
C27 C28 H28 127.6(15) . . ?
N25 C29 C28 106.74(14) . . ?
N25 C29 H29 119.9(14) . . ?
C28 C29 H29 133.3(14) . . ?
N31 N30 C34 111.92(11) . . ?
N31 N30 C24 120.52(11) . . ?
C34 N30 C24 127.55(12) . . ?
C32 N31 N30 104.14(12) . . ?
N31 C32 C33 112.34(13) . . ?
N31 C32 H32 118.5(12) . . ?
C33 C32 H32 129.1(12) . . ?
C34 C33 C32 104.91(13) . . ?
C34 C33 H33 126.6(14) . . ?
C32 C33 H33 128.4(14) . . ?
N30 C34 C33 106.69(14) . . ?
N30 C34 H34 119.6(15) . . ?
C33 C34 H34 133.7(15) . . ?

_diffrn_measured_fraction_theta_max 0.976
_diffrn_reflns_theta_full        31.98
_diffrn_measured_fraction_theta_full 0.976
_refine_diff_density_max         0.471
_refine_diff_density_min         -0.767
_refine_diff_density_rms         0.073
