# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2023

####################################################################### 
# 
# 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. 
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data_jhl-thiann2
_database_code_depnum_ccdc_archive 'CCDC 2181543'
loop_
_audit_author_name
_audit_author_address
'Vince Lynch'
;The University of Texas at Austin
United States of America
;
_audit_update_record             
;
2022-06-23 deposited with the CCDC.	2023-02-23 downloaded from the CCDC.
;
_audit_creation_date             2019-08-14
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        thianth-py2
_chemical_formula_moiety         'C22 H14 N2 S2, C H2 Cl2'
_chemical_formula_sum            'C23 H16 Cl2 N2 S2'
_chemical_formula_weight         455.40
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   7.5739(2)
_cell_length_b                   11.5905(3)
_cell_length_c                   11.9375(3)
_cell_angle_alpha                77.276(2)
_cell_angle_beta                 88.191(2)
_cell_angle_gamma                83.065(2)
_cell_volume                     1014.72(5)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    6090
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.5
_cell_measurement_theta_min      3.76
_shelx_estimated_absorpt_T_max   0.508
_shelx_estimated_absorpt_T_min   0.251
_exptl_absorpt_coefficient_mu    4.897
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_correction_T_min  0.676
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;

_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.490
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       prism
_exptl_crystal_F_000             468
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.16
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0259
_diffrn_reflns_av_unetI/netI     0.0290
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            7859
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.633
_diffrn_reflns_theta_min         3.796
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.962
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            AtlasS2
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3935
_reflns_number_total             4062
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       ?
_computing_data_collection       ?
_computing_data_reduction        ?
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    ?
_refine_diff_density_max         0.835
_refine_diff_density_min         -0.836
_refine_diff_density_rms         0.097
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         4062
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0496
_refine_ls_R_factor_gt           0.0486
_refine_ls_restrained_S_all      1.046
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0883P)²+1.2750P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1384
_refine_ls_wR_factor_ref         0.1396
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C23-Cl2 \\sim C23-Cl2A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Cl2) = Uanis(Cl2A)
4. Others
 Sof(H23C)=Sof(H23D)=Sof(Cl2A)=1-FVAR(1)
 Sof(H23A)=Sof(H23B)=Sof(Cl2)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C23(H23C,H23D)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C14(H14), C15(H15),
 C16(H16), C17(H17), C19(H19), C20(H20), C21(H21), C22(H22)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.4588(3) 0.36342(18) 0.17925(18) 0.0120(4) Uani 1 1 d . . . . .
C2 C 0.5925(3) 0.28929(18) 0.13609(18) 0.0125(4) Uani 1 1 d . . . . .
C3 C 0.5807(3) 0.2797(2) 0.02173(19) 0.0163(4) Uani 1 1 d . . . . .
H3 H 0.671867 0.232277 -0.009620 0.020 Uiso 1 1 calc R . . . .
C4 C 0.4381(3) 0.3384(2) -0.04674(19) 0.0183(5) Uani 1 1 d . . . . .
H4 H 0.432728 0.330494 -0.124070 0.022 Uiso 1 1 calc R . . . .
C5 C 0.3037(3) 0.4083(2) -0.00282(19) 0.0167(4) Uani 1 1 d . . . . .
H5 H 0.203977 0.445910 -0.048697 0.020 Uiso 1 1 calc R . . . .
C6 C 0.3166(3) 0.42278(19) 0.10964(19) 0.0139(4) Uani 1 1 d . . . . .
C7 C 0.1134(3) 0.44063(19) 0.29918(18) 0.0137(4) Uani 1 1 d . . . . .
C8 C -0.0610(3) 0.4352(2) 0.3387(2) 0.0163(4) Uani 1 1 d . . . . .
H8 H -0.157417 0.475256 0.290863 0.020 Uiso 1 1 calc R . . . .
C9 C -0.0929(3) 0.3713(2) 0.4480(2) 0.0199(5) Uani 1 1 d . . . . .
H9 H -0.211651 0.368109 0.475609 0.024 Uiso 1 1 calc R . . . .
C10 C 0.0480(3) 0.3114(2) 0.5179(2) 0.0186(5) Uani 1 1 d . . . . .
H10 H 0.024161 0.266988 0.592593 0.022 Uiso 1 1 calc R . . . .
C11 C 0.2232(3) 0.31558(19) 0.47981(18) 0.0133(4) Uani 1 1 d . . . . .
C12 C 0.2552(3) 0.38156(19) 0.36952(18) 0.0125(4) Uani 1 1 d . . . . .
C13 C 0.7458(3) 0.22257(18) 0.20698(19) 0.0135(4) Uani 1 1 d . . . . .
C14 C 0.7179(3) 0.1446(2) 0.3118(2) 0.0180(5) Uani 1 1 d . . . . .
H14 H 0.598460 0.136340 0.335976 0.022 Uiso 1 1 calc R . . . .
C15 C 1.0153(3) 0.0942(2) 0.3451(2) 0.0247(5) Uani 1 1 d . . . . .
H15 H 1.109535 0.052148 0.393793 0.030 Uiso 1 1 calc R . . . .
C16 C 1.0577(3) 0.1660(2) 0.2414(2) 0.0236(5) Uani 1 1 d . . . . .
H16 H 1.178375 0.170368 0.218495 0.028 Uiso 1 1 calc R . . . .
C17 C 0.9206(3) 0.2319(2) 0.1710(2) 0.0180(5) Uani 1 1 d . . . . .
H17 H 0.946460 0.282301 0.099618 0.022 Uiso 1 1 calc R . . . .
C18 C 0.3740(3) 0.2546(2) 0.55632(18) 0.0132(4) Uani 1 1 d . . . . .
C19 C 0.4248(3) 0.1326(2) 0.5712(2) 0.0235(5) Uani 1 1 d . . . . .
H19 H 0.359378 0.088698 0.532168 0.028 Uiso 1 1 calc R . . . .
C20 C 0.6512(3) 0.1373(2) 0.6919(2) 0.0225(5) Uani 1 1 d . . . . .
H20 H 0.748387 0.096938 0.738945 0.027 Uiso 1 1 calc R . . . .
C21 C 0.6110(3) 0.2582(2) 0.6833(2) 0.0201(5) Uani 1 1 d . . . . .
H21 H 0.678304 0.299684 0.723815 0.024 Uiso 1 1 calc R . . . .
C22 C 0.4702(3) 0.3180(2) 0.6141(2) 0.0183(5) Uani 1 1 d . . . . .
H22 H 0.439814 0.401290 0.606340 0.022 Uiso 1 1 calc R . . . .
C23 C -0.2065(6) 0.9289(3) 0.1283(3) 0.0489(9) Uani 1 1 d D . . . .
H23A H -0.149508 0.991695 0.152920 0.059 Uiso 0.910(3) 1 calc R . P A 1
H23B H -0.318431 0.918436 0.172457 0.059 Uiso 0.910(3) 1 calc R . P A 1
H23C H -0.280584 0.929463 0.198041 0.059 Uiso 0.090(3) 1 calc R . P A 2
H23D H -0.129540 0.993230 0.122632 0.059 Uiso 0.090(3) 1 calc R . P A 2
N1 N 0.8472(3) 0.08114(19) 0.38029(19) 0.0238(4) Uani 1 1 d . . . . .
N2 N 0.5607(3) 0.0738(2) 0.6376(2) 0.0297(5) Uani 1 1 d . . . . .
S1 S 0.47679(6) 0.39027(4) 0.31859(4) 0.01234(16) Uani 1 1 d . . . . .
S2 S 0.15437(7) 0.52292(5) 0.15942(4) 0.01513(16) Uani 1 1 d . . . . .
Cl1 Cl -0.06385(11) 0.79456(6) 0.15748(6) 0.0374(2) Uani 1 1 d . . . . .
Cl2 Cl -0.25453(14) 0.97331(7) -0.01951(8) 0.0428(3) Uani 0.910(3) 1 d D . P A
1
Cl2A Cl -0.3381(16) 0.9696(8) 0.0231(9) 0.0428(3) Uani 0.090(3) 1 d D . P A 2


_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
C1 C2 1.408(3) . ?
C1 C6 1.396(3) . ?
C1 S1 1.771(2) . ?
C2 C3 1.400(3) . ?
C2 C13 1.489(3) . ?
C3 H3 0.9500 . ?
C3 C4 1.389(3) . ?
C4 H4 0.9500 . ?
C4 C5 1.386(3) . ?
C5 H5 0.9500 . ?
C5 C6 1.397(3) . ?
C6 S2 1.767(2) . ?
C7 C8 1.393(3) . ?
C7 C12 1.397(3) . ?
C7 S2 1.768(2) . ?
C8 H8 0.9500 . ?
C8 C9 1.381(3) . ?
C9 H9 0.9500 . ?
C9 C10 1.393(3) . ?
C10 H10 0.9500 . ?
C10 C11 1.393(3) . ?
C11 C12 1.399(3) . ?
C11 C18 1.492(3) . ?
C12 S1 1.774(2) . ?
C13 C14 1.400(3) . ?
C13 C17 1.388(3) . ?
C14 H14 0.9500 . ?
C14 N1 1.335(3) . ?
C15 H15 0.9500 . ?
C15 C16 1.383(4) . ?
C15 N1 1.343(4) . ?
C16 H16 0.9500 . ?
C16 C17 1.397(3) . ?
C17 H17 0.9500 . ?
C18 C19 1.392(3) . ?
C18 C22 1.389(3) . ?
C19 H19 0.9500 . ?
C19 N2 1.340(3) . ?
C20 H20 0.9500 . ?
C20 C21 1.379(4) . ?
C20 N2 1.339(3) . ?
C21 H21 0.9500 . ?
C21 C22 1.387(3) . ?
C22 H22 0.9500 . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?
C23 H23C 0.9900 . ?
C23 H23D 0.9900 . ?
C23 Cl1 1.758(4) . ?
C23 Cl2 1.763(4) . ?
C23 Cl2A 1.580(9) . ?

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
C2 C1 S1 120.39(16) . . ?
C6 C1 C2 120.2(2) . . ?
C6 C1 S1 119.30(16) . . ?
C1 C2 C13 122.45(19) . . ?
C3 C2 C1 118.22(19) . . ?
C3 C2 C13 119.32(19) . . ?
C2 C3 H3 119.4 . . ?
C4 C3 C2 121.3(2) . . ?
C4 C3 H3 119.4 . . ?
C3 C4 H4 119.8 . . ?
C5 C4 C3 120.3(2) . . ?
C5 C4 H4 119.8 . . ?
C4 C5 H5 120.4 . . ?
C4 C5 C6 119.3(2) . . ?
C6 C5 H5 120.4 . . ?
C1 C6 C5 120.7(2) . . ?
C1 C6 S2 120.83(17) . . ?
C5 C6 S2 118.46(17) . . ?
C8 C7 C12 120.2(2) . . ?
C8 C7 S2 119.56(17) . . ?
C12 C7 S2 120.21(16) . . ?
C7 C8 H8 120.2 . . ?
C9 C8 C7 119.6(2) . . ?
C9 C8 H8 120.2 . . ?
C8 C9 H9 119.8 . . ?
C8 C9 C10 120.4(2) . . ?
C10 C9 H9 119.8 . . ?
C9 C10 H10 119.5 . . ?
C11 C10 C9 120.9(2) . . ?
C11 C10 H10 119.5 . . ?
C10 C11 C12 118.6(2) . . ?
C10 C11 C18 120.8(2) . . ?
C12 C11 C18 120.64(19) . . ?
C7 C12 C11 120.36(19) . . ?
C7 C12 S1 119.78(16) . . ?
C11 C12 S1 119.86(16) . . ?
C14 C13 C2 120.70(19) . . ?
C17 C13 C2 121.9(2) . . ?
C17 C13 C14 117.3(2) . . ?
C13 C14 H14 117.7 . . ?
N1 C14 C13 124.6(2) . . ?
N1 C14 H14 117.7 . . ?
C16 C15 H15 118.4 . . ?
N1 C15 H15 118.4 . . ?
N1 C15 C16 123.2(2) . . ?
C15 C16 H16 120.5 . . ?
C15 C16 C17 119.1(2) . . ?
C17 C16 H16 120.5 . . ?
C13 C17 C16 118.8(2) . . ?
C13 C17 H17 120.6 . . ?
C16 C17 H17 120.6 . . ?
C19 C18 C11 121.29(19) . . ?
C22 C18 C11 121.0(2) . . ?
C22 C18 C19 117.7(2) . . ?
C18 C19 H19 118.2 . . ?
N2 C19 C18 123.7(2) . . ?
N2 C19 H19 118.2 . . ?
C21 C20 H20 118.2 . . ?
N2 C20 H20 118.2 . . ?
N2 C20 C21 123.5(2) . . ?
C20 C21 H21 120.7 . . ?
C20 C21 C22 118.6(2) . . ?
C22 C21 H21 120.7 . . ?
C18 C22 H22 120.4 . . ?
C21 C22 C18 119.2(2) . . ?
C21 C22 H22 120.4 . . ?
H23A C23 H23B 108.1 . . ?
H23C C23 H23D 106.3 . . ?
Cl1 C23 H23A 109.5 . . ?
Cl1 C23 H23B 109.5 . . ?
Cl1 C23 H23C 106.1 . . ?
Cl1 C23 H23D 106.1 . . ?
Cl1 C23 Cl2 110.65(18) . . ?
Cl2 C23 H23A 109.5 . . ?
Cl2 C23 H23B 109.5 . . ?
Cl2A C23 H23C 106.1 . . ?
Cl2A C23 H23D 106.1 . . ?
Cl2A C23 Cl1 124.8(4) . . ?
C14 N1 C15 116.9(2) . . ?
C20 N2 C19 117.2(2) . . ?
C1 S1 C12 101.11(10) . . ?
C6 S2 C7 100.97(10) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C1 C2 C3 C4 -2.1(3) . . . . ?
C1 C2 C13 C14 55.9(3) . . . . ?
C1 C2 C13 C17 -126.1(2) . . . . ?
C1 C6 S2 C7 -44.96(19) . . . . ?
C2 C1 C6 C5 0.9(3) . . . . ?
C2 C1 C6 S2 -176.29(16) . . . . ?
C2 C1 S1 C12 -138.32(17) . . . . ?
C2 C3 C4 C5 0.1(3) . . . . ?
C2 C13 C14 N1 179.7(2) . . . . ?
C2 C13 C17 C16 -179.5(2) . . . . ?
C3 C2 C13 C14 -124.9(2) . . . . ?
C3 C2 C13 C17 53.1(3) . . . . ?
C3 C4 C5 C6 2.4(3) . . . . ?
C4 C5 C6 C1 -2.9(3) . . . . ?
C4 C5 C6 S2 174.32(17) . . . . ?
C5 C6 S2 C7 137.79(17) . . . . ?
C6 C1 C2 C3 1.6(3) . . . . ?
C6 C1 C2 C13 -179.16(18) . . . . ?
C6 C1 S1 C12 45.95(18) . . . . ?
C7 C8 C9 C10 -0.7(4) . . . . ?
C7 C12 S1 C1 -46.03(19) . . . . ?
C8 C7 C12 C11 0.6(3) . . . . ?
C8 C7 C12 S1 -179.44(16) . . . . ?
C8 C7 S2 C6 -135.28(18) . . . . ?
C8 C9 C10 C11 0.6(4) . . . . ?
C9 C10 C11 C12 0.1(3) . . . . ?
C9 C10 C11 C18 178.0(2) . . . . ?
C10 C11 C12 C7 -0.7(3) . . . . ?
C10 C11 C12 S1 179.36(17) . . . . ?
C10 C11 C18 C19 80.5(3) . . . . ?
C10 C11 C18 C22 -100.3(3) . . . . ?
C11 C12 S1 C1 133.93(17) . . . . ?
C11 C18 C19 N2 179.0(2) . . . . ?
C11 C18 C22 C21 -179.2(2) . . . . ?
C12 C7 C8 C9 0.1(3) . . . . ?
C12 C7 S2 C6 44.81(19) . . . . ?
C12 C11 C18 C19 -101.6(3) . . . . ?
C12 C11 C18 C22 77.6(3) . . . . ?
C13 C2 C3 C4 178.6(2) . . . . ?
C13 C14 N1 C15 0.2(4) . . . . ?
C14 C13 C17 C16 -1.4(3) . . . . ?
C15 C16 C17 C13 -0.5(3) . . . . ?
C16 C15 N1 C14 -2.3(4) . . . . ?
C17 C13 C14 N1 1.6(3) . . . . ?
C18 C11 C12 C7 -178.62(19) . . . . ?
C18 C11 C12 S1 1.4(3) . . . . ?
C18 C19 N2 C20 0.0(4) . . . . ?
C19 C18 C22 C21 0.1(3) . . . . ?
C20 C21 C22 C18 0.2(3) . . . . ?
C21 C20 N2 C19 0.4(4) . . . . ?
C22 C18 C19 N2 -0.2(4) . . . . ?
N1 C15 C16 C17 2.4(4) . . . . ?
N2 C20 C21 C22 -0.5(4) . . . . ?
S1 C1 C2 C3 -174.07(15) . . . . ?
S1 C1 C2 C13 5.1(3) . . . . ?
S1 C1 C6 C5 176.63(16) . . . . ?
S1 C1 C6 S2 -0.6(2) . . . . ?
S2 C7 C8 C9 -179.80(18) . . . . ?
S2 C7 C12 C11 -179.49(16) . . . . ?
S2 C7 C12 S1 0.5(3) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_exptl_crystal_recrystallization_method 'Vapor diffusion'
####################################################################### 
# 
# 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_thian_mnn2
_database_code_depnum_ccdc_archive 'CCDC 2181544'
loop_
_audit_author_name
_audit_author_address
'Vince Lynch'
;The University of Texas at Austin
United States of America
;
_audit_update_record             
;
2022-06-23 deposited with the CCDC.	2023-02-23 downloaded from the CCDC.
;
_audit_creation_date             2021-12-18
_audit_creation_method           
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        (thianth-py2)Mn(CO)3Br
_chemical_formula_moiety         'C25 H14 Br Mn N2 O3 S2, C4 H8 O'
_chemical_formula_sum            'C29 H22 Br Mn N2 O4 S2'
_chemical_formula_weight         661.45
_chemical_melting_point          ?
_chemical_oxdiff_formula         C18H20N2S2O4MnBr
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'
O O 0.0106 0.0060 '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'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   8.7988(2)
_cell_length_b                   9.5552(3)
_cell_length_c                   17.5608(4)
_cell_angle_alpha                74.444(2)
_cell_angle_beta                 80.984(2)
_cell_angle_gamma                76.153(2)
_cell_volume                     1374.22(6)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    9511
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      27.5140
_cell_measurement_theta_min      2.2290
_shelx_estimated_absorpt_T_max   0.920
_shelx_estimated_absorpt_T_min   0.785
_exptl_absorpt_coefficient_mu    2.125
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87408
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.599
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             668
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0723
_diffrn_reflns_av_unetI/netI     0.0785
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            25797
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         2.262
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω   -110.00  24.00   0.50   45.00    --  -20.00 -60.00 240.00  268
  2  ω   -110.00  24.00   0.50   45.00    --  -20.00 -60.00 120.00  268
  3  ω   -110.00  70.00   0.50   45.00    --  -20.00   0.00   0.00  360
  4  ω    -50.00  70.00   0.50   45.00    --  -20.00  60.00  60.00  240
  5  ω    -50.00  70.00   0.50   45.00    --  -20.00  60.00 180.00  240
  6  ω    -50.00  62.50   0.50   45.00    --  -20.00  60.00 360.00  225
;
_diffrn_measurement_device       'Rigaku AFC-12 with a Satrun S2 CCD'
_diffrn_measurement_device_type  
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0758104000
_diffrn_orient_matrix_UB_12      -0.0013769000
_diffrn_orient_matrix_UB_13      0.0207245000
_diffrn_orient_matrix_UB_21      0.0286864000
_diffrn_orient_matrix_UB_22      -0.0724449000
_diffrn_orient_matrix_UB_23      0.0228589000
_diffrn_orient_matrix_UB_31      0.0197834000
_diffrn_orient_matrix_UB_32      0.0308868000
_diffrn_orient_matrix_UB_33      0.0286918000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4687
_reflns_number_total             6305
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         1.028
_refine_diff_density_min         -0.708
_refine_diff_density_rms         0.111
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     407
_refine_ls_number_reflns         6305
_refine_ls_number_restraints     430
_refine_ls_R_factor_all          0.1048
_refine_ls_R_factor_gt           0.0716
_refine_ls_restrained_S_all      1.109
_refine_ls_shift/su_max          0.035
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0221P)²+5.9643P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1257
_refine_ls_wR_factor_ref         0.1357
_refine_special_details          
'A molecule of THF was disordered over two orientations.  The Br ion and one of the CO groups were also disordered.  These disorders were modeled using features found in OLEX2.'
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C25-O3 = C25A-O3A
 1.15 with sigma of 0.01
 Mn1-Br1 = Mn1-Br1A
 2.5 with sigma of 0.01
 Mn1-O3 = Mn1-O3A
 2.95 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O4 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim O4A \\sim C26A \\sim C27A
\\sim C28A \\sim C29A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.01 and sigma
for terminal atoms of 0.02
4. Same fragment restrains
{O4, C26, C27, C28, C29} sigma for 1-2: 0.01, 1-3: 0.04
as in
{O4A, C26A, C27A, C28A, C29A}
5. Others
 Fixed Sof: O4(0.63) C26(0.63) H26A(0.63) H26B(0.63) C27(0.63) H27A(0.63)
 H27B(0.63) C28(0.63) H28A(0.63) H28B(0.63) C29(0.63) H29A(0.63) H29B(0.63)
 O4A(0.37) C26A(0.37) H26C(0.37) H26D(0.37) C27A(0.37) H27C(0.37) H27D(0.37)
 C28A(0.37) H28C(0.37) H28D(0.37) C29A(0.37) H29C(0.37) H29D(0.37) Br1(0.87)
 O3(0.87) C25(0.87) Br1A(0.13) O3A(0.13) C25A(0.13)
 Fixed Uiso: O3A(0.025) C25A(0.025)
6.a Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B), C26A(H26C,
 H26D), C27A(H27C,H27D), C28A(H28C,H28D), C29A(H29C,H29D)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C14(H14), C15(H15),
 C16(H16), C19(H19), C20(H20), C21(H21), C22(H22)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.5775(6) 0.1736(5) 0.7530(3) 0.0200(11) Uani 1 1 d . U . . .
H1 H 0.647466 0.117631 0.791580 0.024 Uiso 1 1 calc R U . . .
C2 C 0.4188(6) 0.2139(6) 0.7792(3) 0.0212(11) Uani 1 1 d . U . . .
C3 C 0.3169(6) 0.2900(7) 0.7232(3) 0.0310(13) Uani 1 1 d . U . . .
H3 H 0.207819 0.318781 0.738644 0.037 Uiso 1 1 calc R U . . .
C4 C 0.3745(7) 0.3246(7) 0.6438(3) 0.0372(15) Uani 1 1 d . U . . .
H4 H 0.305191 0.376694 0.604349 0.045 Uiso 1 1 calc R U . . .
C5 C 0.5348(6) 0.2821(6) 0.6225(3) 0.0292(13) Uani 1 1 d . U . . .
H5 H 0.573117 0.305481 0.567921 0.035 Uiso 1 1 calc R U . . .
C6 C 0.4203(6) 0.2400(5) 0.9183(3) 0.0217(11) Uani 1 1 d . U . . .
C7 C 0.3675(6) 0.1769(5) 0.8662(3) 0.0212(11) Uani 1 1 d . U . . .
C8 C 0.2638(6) 0.0812(6) 0.8969(3) 0.0242(12) Uani 1 1 d . U . . .
H8 H 0.222417 0.042282 0.862020 0.029 Uiso 1 1 calc R U . . .
C9 C 0.2203(6) 0.0422(6) 0.9782(3) 0.0261(12) Uani 1 1 d . U . . .
H9 H 0.148541 -0.022253 0.998470 0.031 Uiso 1 1 calc R U . . .
C10 C 0.2809(6) 0.0967(6) 1.0292(3) 0.0265(12) Uani 1 1 d . U . . .
H10 H 0.255618 0.065247 1.084885 0.032 Uiso 1 1 calc R U . . .
C11 C 0.3795(6) 0.1978(6) 0.9996(3) 0.0226(11) Uani 1 1 d . U . . .
C12 C 0.6696(6) 0.3443(5) 0.9440(3) 0.0199(11) Uani 1 1 d . U . . .
C13 C 0.8219(6) 0.3664(5) 0.9138(3) 0.0194(10) Uani 1 1 d . U . . .
C14 C 0.9297(6) 0.3562(6) 0.9665(3) 0.0244(12) Uani 1 1 d . U . . .
H14 H 1.030649 0.377275 0.946547 0.029 Uiso 1 1 calc R U . . .
C15 C 0.8899(7) 0.3154(6) 1.0480(3) 0.0282(12) Uani 1 1 d . U . . .
H15 H 0.964672 0.306195 1.083561 0.034 Uiso 1 1 calc R U . . .
C16 C 0.7410(7) 0.2881(6) 1.0775(3) 0.0285(12) Uani 1 1 d . U . . .
H16 H 0.714894 0.257991 1.133149 0.034 Uiso 1 1 calc R U . . .
C17 C 0.6302(6) 0.3047(6) 1.0254(3) 0.0234(11) Uani 1 1 d . U . . .
C18 C 0.8658(6) 0.4045(5) 0.8265(3) 0.0192(10) Uani 1 1 d . U . . .
C19 C 0.8698(5) 0.3002(6) 0.7833(3) 0.0195(11) Uani 1 1 d . U . . .
H19 H 0.850504 0.205703 0.812289 0.023 Uiso 1 1 calc R U . . .
C20 C 0.9309(6) 0.4584(6) 0.6650(3) 0.0249(12) Uani 1 1 d . U . . .
H20 H 0.951953 0.478974 0.608773 0.030 Uiso 1 1 calc R U . . .
C21 C 0.9346(6) 0.5662(6) 0.7025(3) 0.0282(12) Uani 1 1 d . U . . .
H21 H 0.960815 0.657596 0.672760 0.034 Uiso 1 1 calc R U . . .
C22 C 0.8998(6) 0.5408(6) 0.7842(3) 0.0270(12) Uani 1 1 d . U . . .
H22 H 0.899274 0.615280 0.810932 0.032 Uiso 1 1 calc R U . . .
C23 C 1.0940(7) 0.1284(6) 0.6142(3) 0.0273(12) Uani 1 1 d . U . . .
C24 C 0.8669(6) 0.0272(7) 0.5923(3) 0.0286(13) Uani 1 1 d . U . . .
O4 O 0.5730(11) 0.3044(11) 0.4279(6) 0.078(2) Uani 0.63 1 d D U P A 1
C26 C 0.6834(16) 0.2717(17) 0.3692(8) 0.073(3) Uani 0.63 1 d D U P A 1
H26A H 0.761445 0.181881 0.391158 0.088 Uiso 0.63 1 calc R U P A 1
H26B H 0.739072 0.354734 0.347722 0.088 Uiso 0.63 1 calc R U P A 1
C27 C 0.6124(18) 0.245(2) 0.3031(9) 0.080(3) Uani 0.63 1 d D U P A 1
H27A H 0.681049 0.164867 0.280202 0.096 Uiso 0.63 1 calc R U P A 1
H27B H 0.587593 0.336301 0.260464 0.096 Uiso 0.63 1 calc R U P A 1
C28 C 0.464(2) 0.1982(19) 0.3501(10) 0.083(3) Uani 0.63 1 d D U P A 1
H28A H 0.377812 0.223850 0.315545 0.100 Uiso 0.63 1 calc R U P A 1
H28B H 0.484404 0.089908 0.374011 0.100 Uiso 0.63 1 calc R U P A 1
C29 C 0.4234(18) 0.283(2) 0.4128(9) 0.086(3) Uani 0.63 1 d D U P A 1
H29A H 0.351872 0.379424 0.394167 0.103 Uiso 0.63 1 calc R U P A 1
H29B H 0.371785 0.225885 0.461523 0.103 Uiso 0.63 1 calc R U P A 1
O4A O 0.471(2) 0.152(2) 0.3160(11) 0.086(3) Uani 0.37 1 d D U P B 2
C26A C 0.572(3) 0.226(3) 0.2652(13) 0.080(3) Uani 0.37 1 d D U P B 2
H26C H 0.513777 0.298710 0.222376 0.096 Uiso 0.37 1 calc R U P B 2
H26D H 0.652156 0.155101 0.240471 0.096 Uiso 0.37 1 calc R U P B 2
C27A C 0.654(3) 0.307(3) 0.3026(13) 0.071(3) Uani 0.37 1 d D U P B 2
H27C H 0.672355 0.401657 0.266554 0.086 Uiso 0.37 1 calc R U P B 2
H27D H 0.754040 0.245083 0.322004 0.086 Uiso 0.37 1 calc R U P B 2
C28A C 0.528(3) 0.331(3) 0.3701(14) 0.081(3) Uani 0.37 1 d D U P B 2
H28C H 0.573070 0.342524 0.415454 0.097 Uiso 0.37 1 calc R U P B 2
H28D H 0.444935 0.419484 0.352356 0.097 Uiso 0.37 1 calc R U P B 2
C29A C 0.462(3) 0.192(3) 0.3923(13) 0.081(3) Uani 0.37 1 d D U P B 2
H29C H 0.525930 0.112225 0.430188 0.097 Uiso 0.37 1 calc R U P B 2
H29D H 0.351982 0.211388 0.416388 0.097 Uiso 0.37 1 calc R U P B 2
N1 N 0.6383(5) 0.2088(5) 0.6767(2) 0.0215(9) Uani 1 1 d . U . . .
N2 N 0.8986(5) 0.3231(5) 0.7041(2) 0.0189(9) Uani 1 1 d . U . . .
O1 O 1.2251(5) 0.1051(5) 0.5947(3) 0.0425(11) Uani 1 1 d . U . . .
O2 O 0.8605(5) -0.0629(5) 0.5610(2) 0.0433(11) Uani 1 1 d . U . . .
S1 S 0.52585(15) 0.38471(14) 0.87686(7) 0.0206(3) Uani 1 1 d . U . . .
S2 S 0.43852(17) 0.27913(16) 1.06724(8) 0.0285(3) Uani 1 1 d . U . . .
Mn1 Mn 0.88290(9) 0.16501(9) 0.64175(4) 0.01971(19) Uani 1 1 d D U . . .
Br1 Br 0.94261(9) -0.05148(7) 0.76195(4) 0.02541(17) Uani 0.87 1 d D U P C 1
O3 O 0.8598(9) 0.3837(8) 0.4900(4) 0.044(2) Uani 0.87 1 d D U P C 1
C25 C 0.8665(8) 0.3011(8) 0.5489(4) 0.0341(17) Uani 0.87 1 d D U P C 1
Br1A Br 0.8518(10) 0.3532(8) 0.5108(4) 0.0251(14) Uiso 0.13 1 d D . P C 2
O3A O 0.934(5) -0.100(3) 0.7747(17) 0.025 Uiso 0.13 1 d D U P C 2
C25A C 0.902(5) 0.010(3) 0.7262(19) 0.025 Uiso 0.13 1 d D U P C 2


_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
C1 H1 0.9500 . ?
C1 C2 1.395(7) . ?
C1 N1 1.347(6) . ?
C2 C3 1.372(7) . ?
C2 C7 1.494(7) . ?
C3 H3 0.9500 . ?
C3 C4 1.385(8) . ?
C4 H4 0.9500 . ?
C4 C5 1.392(8) . ?
C5 H5 0.9500 . ?
C5 N1 1.354(7) . ?
C6 C7 1.406(7) . ?
C6 C11 1.389(7) . ?
C6 S1 1.780(5) . ?
C7 C8 1.393(7) . ?
C8 H8 0.9500 . ?
C8 C9 1.391(7) . ?
C9 H9 0.9500 . ?
C9 C10 1.376(8) . ?
C10 H10 0.9500 . ?
C10 C11 1.395(7) . ?
C11 S2 1.780(6) . ?
C12 C13 1.404(7) . ?
C12 C17 1.388(7) . ?
C12 S1 1.769(5) . ?
C13 C14 1.395(7) . ?
C13 C18 1.489(7) . ?
C14 H14 0.9500 . ?
C14 C15 1.390(7) . ?
C15 H15 0.9500 . ?
C15 C16 1.390(8) . ?
C16 H16 0.9500 . ?
C16 C17 1.392(7) . ?
C17 S2 1.776(5) . ?
C18 C19 1.396(7) . ?
C18 C22 1.391(7) . ?
C19 H19 0.9500 . ?
C19 N2 1.341(6) . ?
C20 H20 0.9500 . ?
C20 C21 1.374(8) . ?
C20 N2 1.364(6) . ?
C21 H21 0.9500 . ?
C21 C22 1.386(7) . ?
C22 H22 0.9500 . ?
C23 O1 1.137(6) . ?
C23 Mn1 1.817(6) . ?
C24 O2 1.154(7) . ?
C24 Mn1 1.803(6) . ?
O4 C26 1.348(14) . ?
O4 C29 1.454(15) . ?
C26 H26A 0.9900 . ?
C26 H26B 0.9900 . ?
C26 C27 1.506(18) . ?
C27 H27A 0.9900 . ?
C27 H27B 0.9900 . ?
C27 C28 1.526(17) . ?
C28 H28A 0.9900 . ?
C28 H28B 0.9900 . ?
C28 C29 1.486(16) . ?
C29 H29A 0.9900 . ?
C29 H29B 0.9900 . ?
O4A C26A 1.342(15) . ?
O4A C29A 1.476(17) . ?
C26A H26C 0.9900 . ?
C26A H26D 0.9900 . ?
C26A C27A 1.493(19) . ?
C27A H27C 0.9900 . ?
C27A H27D 0.9900 . ?
C27A C28A 1.516(18) . ?
C28A H28C 0.9900 . ?
C28A H28D 0.9900 . ?
C28A C29A 1.501(17) . ?
C29A H29C 0.9900 . ?
C29A H29D 0.9900 . ?
N1 Mn1 2.116(4) . ?
N2 Mn1 2.130(4) . ?
Mn1 Br1 2.5488(10) . ?
Mn1 C25 1.794(7) . ?
Mn1 Br1A 2.518(7) . ?
Mn1 C25A 1.792(16) . ?
O3 C25 1.120(7) . ?
O3A C25A 1.166(10) . ?

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
C2 C1 H1 117.8 . . ?
N1 C1 H1 117.8 . . ?
N1 C1 C2 124.4(5) . . ?
C1 C2 C7 119.3(4) . . ?
C3 C2 C1 117.8(5) . . ?
C3 C2 C7 122.8(5) . . ?
C2 C3 H3 120.3 . . ?
C2 C3 C4 119.4(5) . . ?
C4 C3 H3 120.3 . . ?
C3 C4 H4 120.3 . . ?
C3 C4 C5 119.4(5) . . ?
C5 C4 H4 120.3 . . ?
C4 C5 H5 118.8 . . ?
N1 C5 C4 122.4(5) . . ?
N1 C5 H5 118.8 . . ?
C7 C6 S1 118.3(4) . . ?
C11 C6 C7 120.2(5) . . ?
C11 C6 S1 121.2(4) . . ?
C6 C7 C2 120.8(4) . . ?
C8 C7 C2 120.4(5) . . ?
C8 C7 C6 118.8(5) . . ?
C7 C8 H8 119.7 . . ?
C9 C8 C7 120.5(5) . . ?
C9 C8 H8 119.7 . . ?
C8 C9 H9 119.9 . . ?
C10 C9 C8 120.1(5) . . ?
C10 C9 H9 119.9 . . ?
C9 C10 H10 119.8 . . ?
C9 C10 C11 120.3(5) . . ?
C11 C10 H10 119.8 . . ?
C6 C11 C10 119.7(5) . . ?
C6 C11 S2 121.7(4) . . ?
C10 C11 S2 118.5(4) . . ?
C13 C12 S1 118.7(4) . . ?
C17 C12 C13 120.1(5) . . ?
C17 C12 S1 120.9(4) . . ?
C12 C13 C18 120.2(4) . . ?
C14 C13 C12 119.3(5) . . ?
C14 C13 C18 120.5(5) . . ?
C13 C14 H14 119.9 . . ?
C15 C14 C13 120.3(5) . . ?
C15 C14 H14 119.9 . . ?
C14 C15 H15 119.9 . . ?
C14 C15 C16 120.1(5) . . ?
C16 C15 H15 119.9 . . ?
C15 C16 H16 120.0 . . ?
C15 C16 C17 120.1(5) . . ?
C17 C16 H16 120.0 . . ?
C12 C17 C16 120.1(5) . . ?
C12 C17 S2 122.2(4) . . ?
C16 C17 S2 117.7(4) . . ?
C19 C18 C13 118.9(4) . . ?
C22 C18 C13 123.7(5) . . ?
C22 C18 C19 117.4(5) . . ?
C18 C19 H19 117.5 . . ?
N2 C19 C18 125.0(5) . . ?
N2 C19 H19 117.5 . . ?
C21 C20 H20 118.3 . . ?
N2 C20 H20 118.3 . . ?
N2 C20 C21 123.4(5) . . ?
C20 C21 H21 120.2 . . ?
C20 C21 C22 119.5(5) . . ?
C22 C21 H21 120.2 . . ?
C18 C22 H22 120.5 . . ?
C21 C22 C18 118.9(5) . . ?
C21 C22 H22 120.5 . . ?
O1 C23 Mn1 177.8(5) . . ?
O2 C24 Mn1 178.2(5) . . ?
C26 O4 C29 109.0(10) . . ?
O4 C26 H26A 109.3 . . ?
O4 C26 H26B 109.3 . . ?
O4 C26 C27 111.7(11) . . ?
H26A C26 H26B 107.9 . . ?
C27 C26 H26A 109.3 . . ?
C27 C26 H26B 109.3 . . ?
C26 C27 H27A 112.0 . . ?
C26 C27 H27B 112.0 . . ?
C26 C27 C28 98.9(12) . . ?
H27A C27 H27B 109.7 . . ?
C28 C27 H27A 112.0 . . ?
C28 C27 H27B 112.0 . . ?
C27 C28 H28A 110.8 . . ?
C27 C28 H28B 110.8 . . ?
H28A C28 H28B 108.9 . . ?
C29 C28 C27 104.7(13) . . ?
C29 C28 H28A 110.8 . . ?
C29 C28 H28B 110.8 . . ?
O4 C29 C28 104.9(12) . . ?
O4 C29 H29A 110.8 . . ?
O4 C29 H29B 110.8 . . ?
C28 C29 H29A 110.8 . . ?
C28 C29 H29B 110.8 . . ?
H29A C29 H29B 108.8 . . ?
C26A O4A C29A 106.5(14) . . ?
O4A C26A H26C 108.8 . . ?
O4A C26A H26D 108.7 . . ?
O4A C26A C27A 114.1(16) . . ?
H26C C26A H26D 107.6 . . ?
C27A C26A H26C 108.8 . . ?
C27A C26A H26D 108.7 . . ?
C26A C27A H27C 112.2 . . ?
C26A C27A H27D 112.3 . . ?
C26A C27A C28A 97.4(15) . . ?
H27C C27A H27D 109.9 . . ?
C28A C27A H27C 112.3 . . ?
C28A C27A H27D 112.3 . . ?
C27A C28A H28C 111.0 . . ?
C27A C28A H28D 111.0 . . ?
H28C C28A H28D 109.0 . . ?
C29A C28A C27A 104.0(16) . . ?
C29A C28A H28C 111.0 . . ?
C29A C28A H28D 111.0 . . ?
O4A C29A C28A 103.8(15) . . ?
O4A C29A H29C 111.0 . . ?
O4A C29A H29D 111.0 . . ?
C28A C29A H29C 111.0 . . ?
C28A C29A H29D 111.0 . . ?
H29C C29A H29D 109.0 . . ?
C1 N1 C5 116.5(4) . . ?
C1 N1 Mn1 122.8(3) . . ?
C5 N1 Mn1 120.6(3) . . ?
C19 N2 C20 115.7(4) . . ?
C19 N2 Mn1 122.7(3) . . ?
C20 N2 Mn1 121.5(3) . . ?
C12 S1 C6 102.0(2) . . ?
C17 S2 C11 103.1(2) . . ?
C23 Mn1 N1 178.5(2) . . ?
C23 Mn1 N2 92.0(2) . . ?
C23 Mn1 Br1 85.56(17) . . ?
C23 Mn1 Br1A 88.3(3) . . ?
C24 Mn1 C23 89.0(2) . . ?
C24 Mn1 N1 92.3(2) . . ?
C24 Mn1 N2 177.9(2) . . ?
C24 Mn1 Br1 85.77(17) . . ?
C24 Mn1 Br1A 87.8(3) . . ?
N1 Mn1 N2 86.71(16) . . ?
N1 Mn1 Br1 93.70(12) . . ?
N1 Mn1 Br1A 92.5(2) . . ?
N2 Mn1 Br1 92.48(11) . . ?
N2 Mn1 Br1A 94.1(2) . . ?
C25 Mn1 C23 86.9(3) . . ?
C25 Mn1 C24 89.0(3) . . ?
C25 Mn1 N1 94.0(2) . . ?
C25 Mn1 N2 92.9(3) . . ?
C25 Mn1 Br1 170.9(2) . . ?
C25A Mn1 C23 91.5(13) . . ?
C25A Mn1 C24 82.8(14) . . ?
C25A Mn1 N1 87.8(13) . . ?
C25A Mn1 N2 95.4(14) . . ?
C25A Mn1 Br1A 170.6(14) . . ?
O3 C25 Mn1 178.1(7) . . ?
O3A C25A Mn1 170(4) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C1 C2 C3 C4 -0.4(8) . . . . ?
C1 C2 C7 C6 63.9(7) . . . . ?
C1 C2 C7 C8 -117.3(6) . . . . ?
C2 C1 N1 C5 -3.2(8) . . . . ?
C2 C1 N1 Mn1 173.3(4) . . . . ?
C2 C3 C4 C5 -0.4(9) . . . . ?
C2 C7 C8 C9 177.6(5) . . . . ?
C3 C2 C7 C6 -114.2(6) . . . . ?
C3 C2 C7 C8 64.6(7) . . . . ?
C3 C4 C5 N1 -0.6(9) . . . . ?
C4 C5 N1 C1 2.3(8) . . . . ?
C4 C5 N1 Mn1 -174.3(5) . . . . ?
C6 C7 C8 C9 -3.6(7) . . . . ?
C6 C11 S2 C17 -36.8(5) . . . . ?
C7 C2 C3 C4 177.8(5) . . . . ?
C7 C6 C11 C10 -2.4(7) . . . . ?
C7 C6 C11 S2 -178.0(4) . . . . ?
C7 C6 S1 C12 -142.1(4) . . . . ?
C7 C8 C9 C10 -0.7(8) . . . . ?
C8 C9 C10 C11 3.6(7) . . . . ?
C9 C10 C11 C6 -2.0(7) . . . . ?
C9 C10 C11 S2 173.7(4) . . . . ?
C10 C11 S2 C17 147.6(4) . . . . ?
C11 C6 C7 C2 -176.0(4) . . . . ?
C11 C6 C7 C8 5.2(7) . . . . ?
C11 C6 S1 C12 43.0(5) . . . . ?
C12 C13 C14 C15 4.0(7) . . . . ?
C12 C13 C18 C19 -65.3(6) . . . . ?
C12 C13 C18 C22 113.0(6) . . . . ?
C12 C17 S2 C11 36.2(5) . . . . ?
C13 C12 C17 C16 0.5(7) . . . . ?
C13 C12 C17 S2 178.6(4) . . . . ?
C13 C12 S1 C6 142.2(4) . . . . ?
C13 C14 C15 C16 -1.6(8) . . . . ?
C13 C18 C19 N2 176.1(4) . . . . ?
C13 C18 C22 C21 -178.0(5) . . . . ?
C14 C13 C18 C19 116.5(5) . . . . ?
C14 C13 C18 C22 -65.3(7) . . . . ?
C14 C15 C16 C17 -1.4(8) . . . . ?
C15 C16 C17 C12 1.9(8) . . . . ?
C15 C16 C17 S2 -176.2(4) . . . . ?
C16 C17 S2 C11 -145.7(4) . . . . ?
C17 C12 C13 C14 -3.5(7) . . . . ?
C17 C12 C13 C18 178.2(5) . . . . ?
C17 C12 S1 C6 -43.7(5) . . . . ?
C18 C13 C14 C15 -177.7(5) . . . . ?
C18 C19 N2 C20 2.1(7) . . . . ?
C18 C19 N2 Mn1 -174.5(4) . . . . ?
C19 C18 C22 C21 0.3(7) . . . . ?
C20 C21 C22 C18 1.6(8) . . . . ?
C21 C20 N2 C19 0.0(7) . . . . ?
C21 C20 N2 Mn1 176.7(4) . . . . ?
C22 C18 C19 N2 -2.4(7) . . . . ?
O4 C26 C27 C28 -24.9(17) . . . . ?
C26 O4 C29 C28 13.7(17) . . . . ?
C26 C27 C28 C29 31.7(17) . . . . ?
C27 C28 C29 O4 -29.1(18) . . . . ?
C29 O4 C26 C27 7.8(18) . . . . ?
O4A C26A C27A C28A -27(3) . . . . ?
C26A O4A C29A C28A 17(3) . . . . ?
C26A C27A C28A C29A 36(3) . . . . ?
C27A C28A C29A O4A -34(3) . . . . ?
C29A O4A C26A C27A 7(3) . . . . ?
N1 C1 C2 C3 2.4(8) . . . . ?
N1 C1 C2 C7 -175.9(5) . . . . ?
N2 C20 C21 C22 -1.9(8) . . . . ?
S1 C6 C7 C2 9.0(6) . . . . ?
S1 C6 C7 C8 -169.8(4) . . . . ?
S1 C6 C11 C10 172.4(4) . . . . ?
S1 C6 C11 S2 -3.2(6) . . . . ?
S1 C12 C13 C14 170.6(4) . . . . ?
S1 C12 C13 C18 -7.7(6) . . . . ?
S1 C12 C17 C16 -173.5(4) . . . . ?
S1 C12 C17 S2 4.6(6) . . . . ?

_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 1.334
_oxdiff_exptl_absorpt_empirical_full_min 0.815
_exptl_crystal_recrystallization_method 'vapor diffusion'
