# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2021

####################################################################### 
# 
# 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_mntpzp-mn
_database_code_depnum_ccdc_archive 'CCDC 2087767'
loop_
_audit_author_name
_audit_author_address
'Long-Zhang Dong'
;Nanjing Normal University
China
;
_audit_update_record             
;
2021-06-03 deposited with the CCDC.	2021-08-09 downloaded from the CCDC.
;
_audit_creation_date             2021-06-02
_audit_creation_method           
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_shelx_SHELXL_version_number     2016/6
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C32 H20 Cl Mn2 N12 O8 S2, 0.5(C4 H16 N2)'
_chemical_formula_sum            'C34 H28 Cl Mn2 N13 O8 S2'
_chemical_formula_weight         956.14
_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 0.0033 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'
Cl Cl 0.1484 0.1585 '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'
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'

_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      orthorhombic
_space_group_IT_number           53
_space_group_name_H-M_alt        'P m n a'
_space_group_name_Hall           '-P 2ac 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x+1/2, y, -z+1/2'
'x, -y, -z'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x-1/2, -y, z-1/2'
'-x, y, z'

_cell_length_a                   21.678(6)
_cell_length_b                   13.712(4)
_cell_length_c                   15.918(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4732(2)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    7336
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      25.43
_cell_measurement_theta_min      2.55
_shelx_estimated_absorpt_T_max   0.941
_shelx_estimated_absorpt_T_min   0.657
_exptl_absorpt_coefficient_mu    0.736
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6755
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0716 before and 0.0584 after correction.
The Ratio of minimum to maximum transmission is 0.9065.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'metallic greenish violet'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1944
_exptl_crystal_size_max          0.623
_exptl_crystal_size_mid          0.152
_exptl_crystal_size_min          0.083
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0334
_diffrn_reflns_av_unetI/netI     0.0373
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            13419
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        23.256
_diffrn_reflns_theta_max         23.256
_diffrn_reflns_theta_min         1.587
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'sealed tube'
_diffrn_source_current           0.0
_diffrn_source_power             0.0
_diffrn_source_voltage           0.0
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                2600
_reflns_number_total             3395
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_refine_diff_density_max         0.977
_refine_diff_density_min         -1.823
_refine_diff_density_rms         0.124
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     293
_refine_ls_number_reflns         3395
_refine_ls_number_restraints     7
_refine_ls_R_factor_all          0.1537
_refine_ls_R_factor_gt           0.1289
_refine_ls_restrained_S_all      1.066
_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)+(0.0338P)²+91.4041P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2663
_refine_ls_wR_factor_ref         0.2821
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C14-N4
 2.1 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O4B \\sim O4A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
4. Others
 Sof(O4A)=1-FVAR(1)
 Sof(O4B)=FVAR(1)
 Fixed Sof: H8A(0.5) H8B(0.5) H18A(0.5) H18B(0.5) H18C(0.5) H17A(0.5)
 H17B(0.5) H17C(0.5)
5.a Riding coordinates:
 C18(H18A,H18B,H18C)
5.b Secondary CH2 refined with riding coordinates:
 N8(H8A,H8B)
5.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N4(H4), C13(H13), C4(H4A), C14(H14), C3(H3), C9(H9), C1(H1), C8(H8),
 C16(H16)
5.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C)
;
_atom_sites_solution_hydrogens   mixed
_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
Mn2 Mn 0.500000 0.13156(15) 0.62936(17) 0.0464(7) Uani 1 2 d S T P . .
Mn1 Mn 0.250000 0.63170(16) 0.750000 0.0874(13) Uani 1 2 d S T P . .
Cl1 Cl 0.500000 0.1244(4) 0.7788(4) 0.109(2) Uani 1 2 d S T P . .
S1 S 0.36726(16) 0.6402(3) 0.8879(4) 0.1057(19) Uani 1 1 d . . . . .
O1 O 0.3344(5) 0.6329(8) 0.8092(9) 0.111(4) Uani 1 1 d . . . . .
O2 O 0.3679(5) 0.7422(10) 0.9047(10) 0.142(5) Uani 1 1 d . . . . .
O3 O 0.4285(5) 0.6145(11) 0.8873(14) 0.216(10) Uani 1 1 d . . . . .
O4B O 0.3246(17) 0.627(6) 0.961(3) 0.14(2) Uani 0.50(9) 1 d . U P A 2
N5 N 0.500000 0.2765(7) 0.6166(9) 0.050(4) Uani 1 2 d S T P . .
N7 N 0.500000 -0.0127(8) 0.6099(9) 0.044(3) Uani 1 2 d S T P . .
N6 N 0.4078(4) 0.1313(5) 0.6153(6) 0.047(2) Uani 1 1 d . . . . .
N2 N 0.2590(5) 0.4697(7) 0.6051(9) 0.090(4) Uani 1 1 d . . . . .
H2 H 0.224296 0.489613 0.585149 0.109 Uiso 1 1 calc R U . . .
N1 N 0.2876(4) 0.5126(7) 0.6653(10) 0.094(5) Uani 1 1 d . . . . .
N4 N 0.2567(5) -0.2029(8) 0.6072(10) 0.104(5) Uani 1 1 d D . . . .
H4 H 0.220929 -0.220178 0.589176 0.124 Uiso 1 1 calc R U . . .
N3 N 0.2885(5) -0.2503(6) 0.6661(8) 0.067(3) Uani 1 1 d . . . . .
C5 C 0.4495(4) 0.3363(6) 0.6102(7) 0.044(3) Uani 1 1 d . . . . .
C11 C 0.3885(5) -0.0447(7) 0.6146(8) 0.052(3) Uani 1 1 d . . . . .
C13 C 0.4698(4) -0.1684(6) 0.5804(7) 0.042(3) Uani 1 1 d . . . . .
H13 H 0.444753 -0.221984 0.569669 0.051 Uiso 1 1 calc R U . . .
C4 C 0.4687(5) 0.4336(7) 0.5956(8) 0.057(3) Uani 1 1 d . . . . .
H4A H 0.443225 0.487304 0.587537 0.069 Uiso 1 1 calc R U . . .
C10 C 0.3703(5) 0.0508(7) 0.6253(8) 0.055(3) Uani 1 1 d . . . . .
C14 C 0.3390(5) -0.1997(7) 0.6739(8) 0.059(3) Uani 1 1 d D . . . .
H14 H 0.370131 -0.215070 0.711908 0.071 Uiso 1 1 calc R U . . .
C7 C 0.3708(4) 0.2098(7) 0.6244(9) 0.057(4) Uani 1 1 d . . . . .
C15 C 0.3416(5) -0.1186(7) 0.6185(8) 0.053(3) Uani 1 1 d . . . . .
C6 C 0.3894(5) 0.3080(7) 0.6170(8) 0.054(3) Uani 1 1 d . . . . .
C2 C 0.3401(5) 0.3858(7) 0.6215(9) 0.063(4) Uani 1 1 d . . . . .
C3 C 0.2881(6) 0.3926(9) 0.5772(11) 0.086(5) Uani 1 1 d . . . . .
H3 H 0.275026 0.350739 0.534841 0.103 Uiso 1 1 calc R U . . .
C9 C 0.3114(6) 0.0820(8) 0.6448(10) 0.080(5) Uani 1 1 d . . . . .
H9 H 0.277918 0.041730 0.656435 0.097 Uiso 1 1 calc R U . . .
C1 C 0.3390(5) 0.4616(8) 0.6772(12) 0.092(6) Uani 1 1 d . . . . .
H1 H 0.369306 0.475326 0.716917 0.111 Uiso 1 1 calc R U . . .
C8 C 0.3103(5) 0.1796(8) 0.6441(12) 0.099(6) Uani 1 1 d . . . . .
H8 H 0.276501 0.219460 0.654498 0.119 Uiso 1 1 calc R U . . .
C16 C 0.2877(6) -0.1254(10) 0.5799(13) 0.107(6) Uani 1 1 d . . . . .
H16 H 0.273418 -0.082039 0.539339 0.129 Uiso 1 1 calc R U . . .
C12 C 0.4490(4) -0.0719(6) 0.5996(7) 0.042(3) Uani 1 1 d . . . . .
N8 N 0.500000 0.8070(18) 0.8876(15) 0.135(8) Uani 1 2 d S T P . .
H8A H 0.532854 0.768381 0.891607 0.162 Uiso 0.5 1 calc R U P . .
H8B H 0.467146 0.768381 0.891607 0.162 Uiso 0.5 1 calc R U P . .
C18 C 0.500000 0.867(3) 0.963(2) 0.200(19) Uani 1 2 d S T P . .
H18A H 0.463670 0.906796 0.963373 0.300 Uiso 0.5 1 d R U P B -1
H18B H 0.535990 0.907556 0.962913 0.300 Uiso 0.5 1 d R U P B -1
H18C H 0.500340 0.825706 1.011613 0.300 Uiso 0.5 1 d R U P B -1
C17 C 0.500000 0.843(3) 0.804(2) 0.185(16) Uani 1 2 d S T P . .
H17A H 0.488126 0.792165 0.766501 0.278 Uiso 0.5 1 calc R U P C -1
H17B H 0.540602 0.865818 0.790307 0.278 Uiso 0.5 1 calc R U P C -1
H17C H 0.471272 0.896260 0.800147 0.278 Uiso 0.5 1 calc R U P C -1
O4A O 0.343(2) 0.560(6) 0.940(4) 0.18(2) Uani 0.50(9) 1 d . U P A 1


_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
Mn2 Cl1 2.381(8) . ?
Mn2 N5 1.997(10) . ?
Mn2 N7 2.002(11) . ?
Mn2 N6 2.011(8) . ?
Mn2 N6 2.011(8) 8_655 ?
Mn1 O1 2.058(13) 3_556 ?
Mn1 O1 2.058(13) . ?
Mn1 N1 2.269(12) . ?
Mn1 N1 2.269(12) 3_556 ?
Mn1 N3 2.258(10) 3_566 ?
Mn1 N3 2.258(10) 1_565 ?
S1 O1 1.445(13) . ?
S1 O2 1.424(14) . ?
S1 O3 1.373(11) . ?
S1 O4B 1.49(3) . ?
S1 O4A 1.48(4) . ?
N5 C5 1.372(11) . ?
N5 C5 1.372(11) 8_655 ?
N7 C12 1.382(11) 8_655 ?
N7 C12 1.382(11) . ?
N6 C10 1.380(12) . ?
N6 C7 1.351(12) . ?
N2 H2 0.8600 . ?
N2 N1 1.284(17) . ?
N2 C3 1.309(15) . ?
N1 C1 1.331(16) . ?
N4 H4 0.8600 . ?
N4 N3 1.334(16) . ?
N4 C16 1.330(16) . ?
N3 C14 1.302(13) . ?
C5 C4 1.417(13) . ?
C5 C6 1.364(14) . ?
C11 C10 1.378(14) . ?
C11 C15 1.437(13) . ?
C11 C12 1.383(14) . ?
C13 C13 1.308(18) 8_655 ?
C13 H13 0.9300 . ?
C13 C12 1.432(13) . ?
C4 C4 1.36(2) 8_655 ?
C4 H4A 0.9300 . ?
C10 C9 1.383(16) . ?
C14 H14 0.9300 . ?
C14 C15 1.422(15) . ?
C7 C6 1.411(14) . ?
C7 C8 1.409(14) . ?
C15 C16 1.324(17) . ?
C6 C2 1.511(14) . ?
C2 C3 1.332(18) . ?
C2 C1 1.368(18) . ?
C3 H3 0.9300 . ?
C9 H9 0.9300 . ?
C9 C8 1.338(16) . ?
C1 H1 0.9300 . ?
C8 H8 0.9300 . ?
C16 H16 0.9300 . ?
N8 H8A 0.8900 . ?
N8 H8B 0.8900 . ?
N8 C18 1.45(3) . ?
N8 C17 1.41(3) . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C17 H17A 0.9600 . ?
C17 H17B 0.9600 . ?
C17 H17C 0.9600 . ?

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
N5 Mn2 Cl1 98.2(5) . . ?
N5 Mn2 N7 165.3(6) . . ?
N5 Mn2 N6 89.4(2) . 8_655 ?
N5 Mn2 N6 89.4(2) . . ?
N7 Mn2 Cl1 96.5(4) . . ?
N7 Mn2 N6 88.9(2) . 8_655 ?
N7 Mn2 N6 88.9(2) . . ?
N6 Mn2 Cl1 96.4(3) 8_655 . ?
N6 Mn2 Cl1 96.4(3) . . ?
N6 Mn2 N6 167.2(6) . 8_655 ?
O1 Mn1 O1 179.1(6) 3_556 . ?
O1 Mn1 N1 87.6(5) 3_556 3_556 ?
O1 Mn1 N1 93.0(5) . 3_556 ?
O1 Mn1 N1 87.6(5) . . ?
O1 Mn1 N1 93.0(5) 3_556 . ?
O1 Mn1 N3 86.4(4) 3_556 3_566 ?
O1 Mn1 N3 93.0(4) 3_556 1_565 ?
O1 Mn1 N3 93.0(4) . 3_566 ?
O1 Mn1 N3 86.4(4) . 1_565 ?
N1 Mn1 N1 87.9(6) 3_556 . ?
N3 Mn1 N1 179.3(4) 3_566 . ?
N3 Mn1 N1 91.8(4) 1_565 . ?
N3 Mn1 N1 91.8(4) 3_566 3_556 ?
N3 Mn1 N1 179.3(4) 1_565 3_556 ?
N3 Mn1 N3 88.5(5) 3_566 1_565 ?
O1 S1 O4B 111.0(16) . . ?
O1 S1 O4A 105(2) . . ?
O2 S1 O1 103.7(7) . . ?
O2 S1 O4B 89(4) . . ?
O2 S1 O4A 129(4) . . ?
O3 S1 O1 116.9(12) . . ?
O3 S1 O2 104.1(9) . . ?
O3 S1 O4B 125(2) . . ?
O3 S1 O4A 99(3) . . ?
S1 O1 Mn1 146.7(7) . . ?
C5 N5 Mn2 127.0(5) . . ?
C5 N5 Mn2 127.0(5) 8_655 . ?
C5 N5 C5 105.9(10) . 8_655 ?
C12 N7 Mn2 126.8(5) 8_655 . ?
C12 N7 Mn2 126.8(5) . . ?
C12 N7 C12 106.4(10) . 8_655 ?
C10 N6 Mn2 125.0(7) . . ?
C7 N6 Mn2 125.3(7) . . ?
C7 N6 C10 105.9(8) . . ?
N1 N2 H2 123.5 . . ?
N1 N2 C3 112.9(12) . . ?
C3 N2 H2 123.5 . . ?
N2 N1 Mn1 126.9(8) . . ?
N2 N1 C1 105.7(11) . . ?
C1 N1 Mn1 126.5(13) . . ?
N3 N4 H4 124.5 . . ?
C16 N4 H4 124.5 . . ?
C16 N4 N3 111.0(11) . . ?
N4 N3 Mn1 125.0(8) . 1_545 ?
C14 N3 Mn1 129.5(10) . 1_545 ?
C14 N3 N4 104.0(9) . . ?
N5 C5 C4 109.9(9) . . ?
C6 C5 N5 125.9(8) . . ?
C6 C5 C4 124.2(9) . . ?
C10 C11 C15 117.5(9) . . ?
C10 C11 C12 123.3(9) . . ?
C12 C11 C15 119.2(9) . . ?
C13 C13 H13 125.8 8_655 . ?
C13 C13 C12 108.4(5) 8_655 . ?
C12 C13 H13 125.8 . . ?
C5 C4 H4A 126.4 . . ?
C4 C4 C5 107.1(6) 8_655 . ?
C4 C4 H4A 126.4 8_655 . ?
N6 C10 C9 108.8(9) . . ?
C11 C10 N6 125.3(10) . . ?
C11 C10 C9 125.9(10) . . ?
N3 C14 H14 123.5 . . ?
N3 C14 C15 113.0(11) . . ?
C15 C14 H14 123.5 . . ?
N6 C7 C6 125.5(9) . . ?
N6 C7 C8 110.0(9) . . ?
C8 C7 C6 124.4(10) . . ?
C14 C15 C11 127.3(11) . . ?
C16 C15 C11 130.9(12) . . ?
C16 C15 C14 101.4(11) . . ?
C5 C6 C7 123.4(9) . . ?
C5 C6 C2 118.6(9) . . ?
C7 C6 C2 117.9(9) . . ?
C3 C2 C6 128.5(12) . . ?
C3 C2 C1 106.0(11) . . ?
C1 C2 C6 125.4(13) . . ?
N2 C3 C2 106.6(14) . . ?
N2 C3 H3 126.7 . . ?
C2 C3 H3 126.7 . . ?
C10 C9 H9 125.6 . . ?
C8 C9 C10 108.8(11) . . ?
C8 C9 H9 125.6 . . ?
N1 C1 C2 108.7(14) . . ?
N1 C1 H1 125.7 . . ?
C2 C1 H1 125.7 . . ?
C7 C8 H8 126.9 . . ?
C9 C8 C7 106.3(11) . . ?
C9 C8 H8 126.9 . . ?
N4 C16 H16 124.7 . . ?
C15 C16 N4 110.5(15) . . ?
C15 C16 H16 124.7 . . ?
N7 C12 C11 125.4(9) . . ?
N7 C12 C13 108.4(8) . . ?
C11 C12 C13 125.8(8) . . ?
H8A N8 H8B 106.3 . . ?
C18 N8 H8A 106.1 . . ?
C18 N8 H8B 106.1 . . ?
C17 N8 H8A 106.1 . . ?
C17 N8 H8B 106.1 . . ?
C17 N8 C18 125(3) . . ?
N8 C18 H18A 109.3 . . ?
N8 C18 H18B 109.3 . . ?
N8 C18 H18C 109.7 . . ?
H18A C18 H18B 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
N8 C17 H17A 109.5 . . ?
N8 C17 H17B 109.5 . . ?
N8 C17 H17C 109.5 . . ?
H17A C17 H17B 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?

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
Mn2 N5 C5 C4 -175.6(10) . . . . ?
Mn2 N5 C5 C6 5(2) . . . . ?
Mn2 N7 C12 C11 -11(2) . . . . ?
Mn2 N7 C12 C13 175.2(9) . . . . ?
Mn2 N6 C10 C11 -26.2(18) . . . . ?
Mn2 N6 C10 C9 155.9(10) . . . . ?
Mn2 N6 C7 C6 22.8(19) . . . . ?
Mn2 N6 C7 C8 -156.2(11) . . . . ?
Mn1 N1 C1 C2 169.2(9) . . . . ?
Mn1 N3 C14 C15 -167.8(8) 1_545 . . . ?
O2 S1 O1 Mn1 -79.7(15) . . . . ?
O3 S1 O1 Mn1 166.4(13) . . . . ?
O4B S1 O1 Mn1 15(4) . . . . ?
N5 C5 C4 C4 -1.7(12) . . . 8_655 ?
N5 C5 C6 C7 -6(2) . . . . ?
N5 C5 C6 C2 170.7(13) . . . . ?
N6 C10 C9 C8 2.3(19) . . . . ?
N6 C7 C6 C5 -9(2) . . . . ?
N6 C7 C6 C2 174.5(13) . . . . ?
N6 C7 C8 C9 -1(2) . . . . ?
N2 N1 C1 C2 -0.2(17) . . . . ?
N1 N2 C3 C2 -1.2(18) . . . . ?
N4 N3 C14 C15 -1.2(14) . . . . ?
N3 N4 C16 C15 1(2) . . . . ?
N3 C14 C15 C11 175.6(11) . . . . ?
N3 C14 C15 C16 1.6(15) . . . . ?
C5 N5 C5 C4 2.8(18) 8_655 . . . ?
C5 N5 C5 C6 -176.9(8) 8_655 . . . ?
C5 C6 C2 C3 130.7(15) . . . . ?
C5 C6 C2 C1 -53.4(19) . . . . ?
C11 C10 C9 C8 -175.6(15) . . . . ?
C11 C15 C16 N4 -175.1(13) . . . . ?
C13 C13 C12 N7 1.0(11) 8_655 . . . ?
C13 C13 C12 C11 -172.4(11) 8_655 . . . ?
C4 C5 C6 C7 174.4(13) . . . . ?
C4 C5 C6 C2 -9(2) . . . . ?
C10 N6 C7 C6 -178.3(14) . . . . ?
C10 N6 C7 C8 2.7(16) . . . . ?
C10 C11 C15 C14 -122.2(13) . . . . ?
C10 C11 C15 C16 50(2) . . . . ?
C10 C11 C12 N7 14(2) . . . . ?
C10 C11 C12 C13 -173.8(12) . . . . ?
C10 C9 C8 C7 -1(2) . . . . ?
C14 C15 C16 N4 -1.4(18) . . . . ?
C7 N6 C10 C11 174.9(14) . . . . ?
C7 N6 C10 C9 -3.1(15) . . . . ?
C7 C6 C2 C3 -52(2) . . . . ?
C7 C6 C2 C1 123.4(15) . . . . ?
C15 C11 C10 N6 -173.2(12) . . . . ?
C15 C11 C10 C9 4(2) . . . . ?
C15 C11 C12 N7 -166.9(12) . . . . ?
C15 C11 C12 C13 5(2) . . . . ?
C6 C5 C4 C4 178.0(11) . . . 8_655 ?
C6 C7 C8 C9 179.7(15) . . . . ?
C6 C2 C3 N2 177.6(12) . . . . ?
C6 C2 C1 N1 -177.2(12) . . . . ?
C3 N2 N1 Mn1 -168.5(10) . . . . ?
C3 N2 N1 C1 0.9(18) . . . . ?
C3 C2 C1 N1 -0.6(17) . . . . ?
C1 C2 C3 N2 1.0(17) . . . . ?
C8 C7 C6 C5 170.0(15) . . . . ?
C8 C7 C6 C2 -7(2) . . . . ?
C16 N4 N3 Mn1 167.6(11) . . . 1_545 ?
C16 N4 N3 C14 0.2(17) . . . . ?
C12 N7 C12 C11 171.8(8) 8_655 . . . ?
C12 N7 C12 C13 -1.6(17) 8_655 . . . ?
C12 C11 C10 N6 6(2) . . . . ?
C12 C11 C10 C9 -176.4(14) . . . . ?
C12 C11 C15 C14 58.5(18) . . . . ?
C12 C11 C15 C16 -129.3(17) . . . . ?
O4A S1 O1 Mn1 57(4) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
####################################################################### 
# 
# 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_cotpzp-co
_database_code_depnum_ccdc_archive 'CCDC 2087768'
loop_
_audit_author_name
_audit_author_address
'Long-Zhang Dong'
;Nanjing Normal University
China
;
_audit_update_record             
;
2021-06-03 deposited with the CCDC.	2021-08-09 downloaded from the CCDC.
;
_audit_creation_date             2021-06-02
_audit_creation_method           
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C32 H22 Co2 N12 O9 S2, 0.5(C4 H16 N2)'
_chemical_formula_sum            'C34 H30 Co2 N13 O9 S2'
_chemical_formula_weight         946.69
_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 0.0033 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'
Co Co 0.3494 0.9721 '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'

_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      orthorhombic
_space_group_IT_number           53
_space_group_name_H-M_alt        'P m n a'
_space_group_name_Hall           '-P 2ac 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x+1/2, y, -z+1/2'
'x, -y, -z'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x-1/2, -y, z-1/2'
'-x, y, z'

_cell_length_a                   22.1875(12)
_cell_length_b                   13.4774(7)
_cell_length_c                   15.9045(9)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4755.9(4)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    6594
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      26.172
_cell_measurement_theta_min      2.561
_shelx_estimated_absorpt_T_max   0.897
_shelx_estimated_absorpt_T_min   0.815
_exptl_absorpt_coefficient_mu    0.845
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6927
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0535 before and 0.0405 after correction.
The Ratio of minimum to maximum transmission is 0.9293.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'metallic dark blue'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.322
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1932
_exptl_crystal_size_max          0.252
_exptl_crystal_size_mid          0.142
_exptl_crystal_size_min          0.132
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0275
_diffrn_reflns_av_unetI/netI     0.0317
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            20722
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.431
_diffrn_reflns_theta_min         2.183
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3311
_reflns_number_total             4919
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_refine_diff_density_max         0.618
_refine_diff_density_min         -0.774
_refine_diff_density_rms         0.075
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     310
_refine_ls_number_reflns         4919
_refine_ls_number_restraints     72
_refine_ls_R_factor_all          0.0886
_refine_ls_R_factor_gt           0.0602
_refine_ls_restrained_S_all      1.065
_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)+(0.0889P)²+7.3056P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1626
_refine_ls_wR_factor_ref         0.1829
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
S1 \\sim O2A \\sim O3A \\sim O4A \\sim O4B \\sim O3B \\sim O2B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
3. Others
 Sof(O4B)=Sof(O3B)=Sof(O2B)=1-FVAR(1)
 Sof(O2A)=Sof(O3A)=Sof(O4A)=FVAR(1)
 Fixed Sof: H18A(0.5) H18B(0.5) H18C(0.5) H17A(0.5) H17B(0.5) H17C(0.5)
 H8A(0.5) H8B(0.5)
4.a Riding coordinates:
 O5(H5A,H5B), C18(H18A,H18B,H18C), C17(H17A,H17B,H17C)
4.b Secondary CH2 refined with riding coordinates:
 N8(H8A,H8B)
4.c Aromatic/amide H refined with riding coordinates:
 C13(H13), N2(H2), C4(H4), N4(H4A), C1(H1), C14(H14), C8(H8), C9(H9), C3(H3),
 C16(H16)
;
_atom_sites_solution_hydrogens   mixed
_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
Co1 Co 0.250000 0.64250(5) 0.250000 0.0487(3) Uani 1 2 d S T P . .
S1 S 0.35855(6) 0.64483(12) 0.39489(13) 0.0848(5) Uani 1 1 d . U . . .
N7 N 0.500000 -0.0062(3) 0.1069(3) 0.0339(10) Uani 1 2 d S T P . .
N5 N 0.500000 0.2842(3) 0.1218(3) 0.0366(10) Uani 1 2 d S T P . .
N6 N 0.41137(13) 0.13812(19) 0.1254(2) 0.0365(7) Uani 1 1 d . . . . .
N3 N 0.28909(14) -0.2446(2) 0.1710(3) 0.0498(9) Uani 1 1 d . . . . .
O1 O 0.33089(15) 0.6405(3) 0.3219(3) 0.0806(11) Uani 1 1 d . . . . .
N1 N 0.28913(16) 0.5264(2) 0.1737(3) 0.0585(11) Uani 1 1 d . . . . .
C12 C 0.45076(16) -0.0674(2) 0.0960(2) 0.0354(8) Uani 1 1 d . . . . .
C5 C 0.45059(18) 0.3460(2) 0.1158(3) 0.0402(9) Uani 1 1 d . . . . .
C11 C 0.39173(16) -0.0403(3) 0.1149(2) 0.0378(9) Uani 1 1 d . . . . .
C6 C 0.39080(17) 0.3176(3) 0.1274(3) 0.0427(9) Uani 1 1 d . . . . .
C10 C 0.37480(16) 0.0566(3) 0.1329(3) 0.0406(9) Uani 1 1 d . . . . .
C13 C 0.46965(17) -0.1641(3) 0.0710(3) 0.0435(9) Uani 1 1 d . . . . .
H13 H 0.444748 -0.217159 0.057241 0.052 Uiso 1 1 calc R U . . .
C15 C 0.34525(17) -0.1196(3) 0.1201(3) 0.0433(9) Uani 1 1 d . . . . .
C7 C 0.37434(16) 0.2192(3) 0.1377(3) 0.0427(9) Uani 1 1 d . . . . .
N2 N 0.2614(2) 0.4801(3) 0.1102(3) 0.0809(14) Uani 1 1 d . . . . .
H2 H 0.227542 0.498755 0.089072 0.097 Uiso 1 1 calc R U . . .
C4 C 0.46954(18) 0.4467(3) 0.1018(3) 0.0484(10) Uani 1 1 d . . . . .
H4 H 0.444601 0.501479 0.094221 0.058 Uiso 1 1 calc R U . . .
C2 C 0.34368(18) 0.3954(3) 0.1317(3) 0.0503(11) Uani 1 1 d . . . . .
N4 N 0.2677(2) -0.2145(4) 0.0980(3) 0.0931(17) Uani 1 1 d . . . . .
H4A H 0.237067 -0.240292 0.073094 0.112 Uiso 1 1 calc R U . . .
C1 C 0.33862(18) 0.4750(3) 0.1863(3) 0.0590(13) Uani 1 1 d . . . . .
H1 H 0.367049 0.490319 0.227295 0.071 Uiso 1 1 calc R U . . .
C14 C 0.33623(19) -0.1875(3) 0.1842(3) 0.0620(13) Uani 1 1 d . . . . .
H14 H 0.360793 -0.192134 0.231384 0.074 Uiso 1 1 calc R U . . .
C8 C 0.31538(18) 0.1861(3) 0.1593(3) 0.0585(12) Uani 1 1 d . . . . .
H8 H 0.282710 0.226385 0.172633 0.070 Uiso 1 1 calc R U . . .
C9 C 0.31535(18) 0.0871(3) 0.1568(3) 0.0560(12) Uani 1 1 d . . . . .
H9 H 0.282871 0.045716 0.168493 0.067 Uiso 1 1 calc R U . . .
C3 C 0.2925(3) 0.4016(4) 0.0837(4) 0.0873(19) Uani 1 1 d . . . . .
H3 H 0.281485 0.358811 0.040416 0.105 Uiso 1 1 calc R U . . .
C16 C 0.2999(3) -0.1382(5) 0.0677(4) 0.110(3) Uani 1 1 d . . . . .
H16 H 0.291895 -0.103937 0.018211 0.132 Uiso 1 1 calc R U . . .
O2A O 0.3224(5) 0.6088(10) 0.4594(8) 0.141(4) Uani 0.620(7) 1 d . U P A 1
O5 O 0.500000 0.1282(6) 0.2764(6) 0.165(4) Uani 1 2 d S T P . .
H5A H 0.500000 0.175334 0.311877 0.248 Uiso 1 2 d R U P . .
H5B H 0.500000 0.075804 0.306147 0.248 Uiso 1 2 d R U P . .
C18 C 0.500000 0.6621(13) 0.2456(11) 0.208(9) Uani 1 2 d S T P . .
H18A H 0.462930 0.625518 0.247859 0.312 Uiso 0.5 1 d R U P B -1
H18B H 0.533280 0.617788 0.254279 0.312 Uiso 0.5 1 d R U P B -1
H18C H 0.503800 0.693288 0.191579 0.312 Uiso 0.5 1 d R U P B -1
C17 C 0.500000 0.8459(11) 0.2974(10) 0.164(6) Uani 1 2 d S T P . .
H17A H 0.468880 0.859763 0.257178 0.246 Uiso 0.5 1 d R U P C -1
H17B H 0.538400 0.864223 0.274348 0.246 Uiso 0.5 1 d R U P C -1
H17C H 0.492720 0.883283 0.347798 0.246 Uiso 0.5 1 d R U P C -1
O3A O 0.3709(4) 0.7540(7) 0.3998(6) 0.129(3) Uani 0.620(7) 1 d . U P A 1
O4A O 0.4163(4) 0.6007(7) 0.3964(7) 0.127(3) Uani 0.620(7) 1 d . U P A 1
N8 N 0.500000 0.7415(12) 0.3197(8) 0.165(5) Uani 1 2 d S T P . .
H8A H 0.467726 0.730178 0.351559 0.198 Uiso 0.5 1 calc R U P . .
H8B H 0.532274 0.730179 0.351560 0.198 Uiso 0.5 1 calc R U P . .
O4B O 0.3681(7) 0.5314(9) 0.4034(10) 0.120(4) Uani 0.380(7) 1 d . U P A 2
O3B O 0.4127(6) 0.6820(14) 0.4227(11) 0.133(4) Uani 0.380(7) 1 d . U P A 2
O2B O 0.3174(6) 0.6691(11) 0.4688(11) 0.097(4) Uani 0.380(7) 1 d . U P A 2
Co2 Co 0.500000 0.13887(4) 0.12114(5) 0.0337(2) Uani 1 2 d S T P . .


_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
Co1 N3 2.156(3) 3_565 ?
Co1 N3 2.156(3) 1_565 ?
Co1 O1 2.128(4) 3 ?
Co1 O1 2.128(4) . ?
Co1 N1 2.162(4) . ?
Co1 N1 2.162(4) 3 ?
S1 O1 1.314(5) . ?
S1 O2A 1.389(11) . ?
S1 O3A 1.499(9) . ?
S1 O4A 1.413(7) . ?
S1 O4B 1.550(12) . ?
S1 O3B 1.376(12) . ?
S1 O2B 1.524(15) . ?
N7 C12 1.380(4) . ?
N7 C12 1.380(4) 8_655 ?
N7 Co2 1.968(4) . ?
N5 C5 1.380(4) 8_655 ?
N5 C5 1.380(4) . ?
N5 Co2 1.959(4) . ?
N6 C10 1.371(4) . ?
N6 C7 1.381(4) . ?
N6 Co2 1.968(3) . ?
N3 N4 1.318(6) . ?
N3 C14 1.316(5) . ?
N1 N2 1.338(6) . ?
N1 C1 1.314(5) . ?
C12 C11 1.392(5) . ?
C12 C13 1.426(5) . ?
C5 C6 1.393(5) . ?
C5 C4 1.438(5) . ?
C11 C10 1.390(5) . ?
C11 C15 1.487(5) . ?
C6 C7 1.386(5) . ?
C6 C2 1.482(5) . ?
C10 C9 1.433(5) . ?
C13 C13 1.347(8) 8_655 ?
C13 H13 0.9300 . ?
C15 C14 1.384(6) . ?
C15 C16 1.329(7) . ?
C7 C8 1.423(5) . ?
N2 H2 0.8600 . ?
N2 C3 1.332(6) . ?
C4 C4 1.352(8) 8_655 ?
C4 H4 0.9300 . ?
C2 C1 1.385(6) . ?
C2 C3 1.372(7) . ?
N4 H4A 0.8600 . ?
N4 C16 1.342(6) . ?
C1 H1 0.9300 . ?
C14 H14 0.9300 . ?
C8 H8 0.9300 . ?
C8 C9 1.335(6) . ?
C9 H9 0.9300 . ?
C3 H3 0.9300 . ?
C16 H16 0.9300 . ?
O5 H5A 0.8501 . ?
O5 H5B 0.8500 . ?
O5 Co2 2.473(9) . ?
C18 H18A 0.9599 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C18 N8 1.592(18) . ?
C17 H17A 0.9599 . ?
C17 H17B 0.9600 . ?
C17 H17C 0.9600 . ?
C17 N8 1.451(15) . ?
N8 H8A 0.8900 . ?
N8 H8B 0.8900 . ?

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
N3 Co1 N3 90.20(18) 3_565 1_565 ?
N3 Co1 N1 178.39(15) 1_565 3 ?
N3 Co1 N1 91.27(13) 1_565 . ?
N3 Co1 N1 91.26(13) 3_565 3 ?
N3 Co1 N1 178.39(15) 3_565 . ?
O1 Co1 N3 89.01(14) 3 3_565 ?
O1 Co1 N3 92.01(14) . 3_565 ?
O1 Co1 N3 92.01(14) 3 1_565 ?
O1 Co1 N3 89.01(15) . 1_565 ?
O1 Co1 O1 178.6(2) 3 . ?
O1 Co1 N1 91.61(16) 3 . ?
O1 Co1 N1 87.35(15) 3 3 ?
O1 Co1 N1 87.35(15) . . ?
O1 Co1 N1 91.61(16) . 3 ?
N1 Co1 N1 87.28(19) 3 . ?
O1 S1 O2A 111.5(5) . . ?
O1 S1 O3A 100.0(4) . . ?
O1 S1 O4A 114.8(5) . . ?
O1 S1 O4B 95.6(6) . . ?
O1 S1 O3B 135.1(8) . . ?
O1 S1 O2B 114.2(6) . . ?
O2A S1 O3A 114.2(7) . . ?
O2A S1 O4A 111.3(7) . . ?
O4A S1 O3A 104.3(5) . . ?
O3B S1 O4B 102.2(10) . . ?
O3B S1 O2B 101.4(10) . . ?
O2B S1 O4B 103.1(8) . . ?
C12 N7 C12 104.7(4) 8_655 . ?
C12 N7 Co2 127.47(19) 8_655 . ?
C12 N7 Co2 127.47(19) . . ?
C5 N5 C5 105.2(4) 8_655 . ?
C5 N5 Co2 127.1(2) . . ?
C5 N5 Co2 127.1(2) 8_655 . ?
C10 N6 C7 105.6(3) . . ?
C10 N6 Co2 126.8(2) . . ?
C7 N6 Co2 126.6(2) . . ?
N4 N3 Co1 125.9(3) . 1_545 ?
C14 N3 Co1 129.8(3) . 1_545 ?
C14 N3 N4 104.3(4) . . ?
S1 O1 Co1 150.2(2) . . ?
N2 N1 Co1 125.2(3) . . ?
C1 N1 Co1 129.2(4) . . ?
C1 N1 N2 104.7(4) . . ?
N7 C12 C11 124.1(3) . . ?
N7 C12 C13 110.4(3) . . ?
C11 C12 C13 125.2(3) . . ?
N5 C5 C6 125.6(3) . . ?
N5 C5 C4 110.4(3) . . ?
C6 C5 C4 123.9(3) . . ?
C12 C11 C15 118.4(3) . . ?
C10 C11 C12 123.0(3) . . ?
C10 C11 C15 118.5(3) . . ?
C5 C6 C2 118.9(3) . . ?
C7 C6 C5 122.0(3) . . ?
C7 C6 C2 119.0(3) . . ?
N6 C10 C11 125.2(3) . . ?
N6 C10 C9 109.8(3) . . ?
C11 C10 C9 125.0(3) . . ?
C12 C13 H13 126.5 . . ?
C13 C13 C12 107.1(2) 8_655 . ?
C13 C13 H13 126.5 8_655 . ?
C14 C15 C11 128.0(4) . . ?
C16 C15 C11 128.7(4) . . ?
C16 C15 C14 103.2(4) . . ?
N6 C7 C6 125.7(3) . . ?
N6 C7 C8 109.5(3) . . ?
C6 C7 C8 124.7(3) . . ?
N1 N2 H2 124.1 . . ?
C3 N2 N1 111.8(4) . . ?
C3 N2 H2 124.1 . . ?
C5 C4 H4 126.5 . . ?
C4 C4 C5 107.0(2) 8_655 . ?
C4 C4 H4 126.5 8_655 . ?
C1 C2 C6 129.4(4) . . ?
C3 C2 C6 127.0(4) . . ?
C3 C2 C1 103.6(4) . . ?
N3 N4 H4A 124.5 . . ?
N3 N4 C16 111.1(4) . . ?
C16 N4 H4A 124.5 . . ?
N1 C1 C2 112.4(5) . . ?
N1 C1 H1 123.8 . . ?
C2 C1 H1 123.8 . . ?
N3 C14 C15 112.6(4) . . ?
N3 C14 H14 123.7 . . ?
C15 C14 H14 123.7 . . ?
C7 C8 H8 126.1 . . ?
C9 C8 C7 107.8(3) . . ?
C9 C8 H8 126.1 . . ?
C10 C9 H9 126.5 . . ?
C8 C9 C10 107.1(4) . . ?
C8 C9 H9 126.5 . . ?
N2 C3 C2 107.5(5) . . ?
N2 C3 H3 126.2 . . ?
C2 C3 H3 126.2 . . ?
C15 C16 N4 108.8(5) . . ?
C15 C16 H16 125.6 . . ?
N4 C16 H16 125.6 . . ?
H5A O5 H5B 104.5 . . ?
Co2 O5 H5A 128.3 . . ?
Co2 O5 H5B 127.2 . . ?
H18A C18 H18B 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
N8 C18 H18A 108.5 . . ?
N8 C18 H18B 108.2 . . ?
N8 C18 H18C 111.7 . . ?
H17A C17 H17B 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
N8 C17 H17A 110.6 . . ?
N8 C17 H17B 110.1 . . ?
N8 C17 H17C 107.7 . . ?
C18 N8 H8A 107.8 . . ?
C18 N8 H8B 107.8 . . ?
C17 N8 C18 118.1(12) . . ?
C17 N8 H8A 107.8 . . ?
C17 N8 H8B 107.8 . . ?
H8A N8 H8B 107.1 . . ?
N7 Co2 N6 89.93(8) . 8_655 ?
N7 Co2 N6 89.93(8) . . ?
N7 Co2 O5 93.2(2) . . ?
N5 Co2 N7 173.73(19) . . ?
N5 Co2 N6 90.29(8) . . ?
N5 Co2 N6 90.28(8) . 8_655 ?
N5 Co2 O5 93.0(2) . . ?
N6 Co2 N6 175.99(19) . 8_655 ?
N6 Co2 O5 88.00(10) 8_655 . ?
N6 Co2 O5 88.00(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
Co1 N3 N4 C16 175.4(5) 1_545 . . . ?
Co1 N3 C14 C15 -176.5(3) 1_545 . . . ?
Co1 N1 N2 C3 -169.8(4) . . . . ?
Co1 N1 C1 C2 169.4(3) . . . . ?
N7 C12 C11 C10 11.6(6) . . . . ?
N7 C12 C11 C15 -165.4(4) . . . . ?
N7 C12 C13 C13 3.3(4) . . . 8_655 ?
N5 C5 C6 C7 -7.0(7) . . . . ?
N5 C5 C6 C2 170.7(4) . . . . ?
N5 C5 C4 C4 -1.8(4) . . . 8_655 ?
N6 C10 C9 C8 3.3(6) . . . . ?
N6 C7 C8 C9 -2.5(6) . . . . ?
N3 N4 C16 C15 2.5(8) . . . . ?
N1 N2 C3 C2 -0.2(7) . . . . ?
C12 N7 C12 C11 169.1(2) 8_655 . . . ?
C12 N7 C12 C13 -5.2(6) 8_655 . . . ?
C12 C11 C10 N6 7.6(7) . . . . ?
C12 C11 C10 C9 -176.6(4) . . . . ?
C12 C11 C15 C14 75.7(6) . . . . ?
C12 C11 C15 C16 -109.6(7) . . . . ?
C5 N5 C5 C6 -173.0(3) 8_655 . . . ?
C5 N5 C5 C4 2.9(6) 8_655 . . . ?
C5 C6 C7 N6 -10.5(7) . . . . ?
C5 C6 C7 C8 172.5(5) . . . . ?
C5 C6 C2 C1 -57.8(7) . . . . ?
C5 C6 C2 C3 125.6(6) . . . . ?
C11 C12 C13 C13 -170.9(3) . . . 8_655 ?
C11 C10 C9 C8 -173.1(4) . . . . ?
C11 C15 C14 N3 176.8(4) . . . . ?
C11 C15 C16 N4 -177.7(5) . . . . ?
C6 C5 C4 C4 174.1(3) . . . 8_655 ?
C6 C7 C8 C9 174.9(5) . . . . ?
C6 C2 C1 N1 -177.3(4) . . . . ?
C6 C2 C3 N2 177.4(5) . . . . ?
C10 N6 C7 C6 -173.0(4) . . . . ?
C10 N6 C7 C8 4.4(5) . . . . ?
C10 C11 C15 C14 -101.4(5) . . . . ?
C10 C11 C15 C16 73.3(7) . . . . ?
C13 C12 C11 C10 -175.0(4) . . . . ?
C13 C12 C11 C15 8.1(6) . . . . ?
C15 C11 C10 N6 -175.5(4) . . . . ?
C15 C11 C10 C9 0.4(6) . . . . ?
C7 N6 C10 C11 171.6(4) . . . . ?
C7 N6 C10 C9 -4.7(5) . . . . ?
C7 C6 C2 C1 120.0(5) . . . . ?
C7 C6 C2 C3 -56.5(7) . . . . ?
C7 C8 C9 C10 -0.5(6) . . . . ?
N2 N1 C1 C2 0.0(5) . . . . ?
C4 C5 C6 C7 177.7(4) . . . . ?
C4 C5 C6 C2 -4.6(7) . . . . ?
C2 C6 C7 N6 171.7(4) . . . . ?
C2 C6 C7 C8 -5.3(7) . . . . ?
N4 N3 C14 C15 0.4(6) . . . . ?
C1 N1 N2 C3 0.1(6) . . . . ?
C1 C2 C3 N2 0.2(6) . . . . ?
C14 N3 N4 C16 -1.7(7) . . . . ?
C14 C15 C16 N4 -2.0(7) . . . . ?
C3 C2 C1 N1 -0.1(6) . . . . ?
C16 C15 C14 N3 1.0(6) . . . . ?
O2A S1 O1 Co1 29.0(9) . . . . ?
O3A S1 O1 Co1 -92.1(6) . . . . ?
O4A S1 O1 Co1 156.9(6) . . . . ?
O4B S1 O1 Co1 100.5(8) . . . . ?
O3B S1 O1 Co1 -146.0(12) . . . . ?
O2B S1 O1 Co1 -6.6(9) . . . . ?
Co2 N7 C12 C11 -17.6(6) . . . . ?
Co2 N7 C12 C13 168.1(3) . . . . ?
Co2 N5 C5 C6 15.6(7) . . . . ?
Co2 N5 C5 C4 -168.6(3) . . . . ?
Co2 N6 C10 C11 -19.5(6) . . . . ?
Co2 N6 C10 C9 164.1(3) . . . . ?
Co2 N6 C7 C6 18.1(6) . . . . ?
Co2 N6 C7 C8 -164.5(3) . . . . ?

_platon_squeeze_details          ?
_platon_squeeze_special_details  ?
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 0.000 -0.001 0.000 621 132 ' '
2 0.500 0.004 0.500 621 132 ' '
3 0.127 0.357 0.563 9 0 ' '
4 0.873 0.357 0.563 9 0 ' '
5 0.373 0.357 0.937 9 0 ' '
6 0.627 0.357 0.937 9 0 ' '
7 0.373 0.643 0.063 9 0 ' '
8 0.627 0.643 0.063 9 0 ' '
9 0.127 0.642 0.437 9 0 ' '
10 0.873 0.643 0.437 9 0 ' '

_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'
####################################################################### 
# 
# 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_cotpzp-mn
_database_code_depnum_ccdc_archive 'CCDC 2087766'
loop_
_audit_author_name
_audit_author_address
'Long-Zhang Dong'
;Nanjing Normal University
China
;
_audit_update_record             
;
2021-08-02 deposited with the CCDC.	2021-08-09 downloaded from the CCDC.
;
_audit_creation_date             2021-08-02
_audit_creation_method           
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C32 H22 Co Mn N12 O9 S2, 0.5(C4 H16 N2)'
_chemical_formula_sum            'C34 H30 Co Mn N13 O9 S2'
_chemical_formula_weight         942.70
_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 0.0033 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'
Co Co 0.3494 0.9721 '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'
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'

_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      orthorhombic
_space_group_IT_number           53
_space_group_name_H-M_alt        'P m n a'
_space_group_name_Hall           '-P 2ac 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x+1/2, y, -z+1/2'
'x, -y, -z'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x-1/2, -y, z-1/2'
'-x, y, z'

_cell_length_a                   22.29(2)
_cell_length_b                   13.477(12)
_cell_length_c                   15.919(16)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4782(8)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    296
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      23.14
_cell_measurement_theta_min      3.02
_shelx_estimated_absorpt_T_max   0.962
_shelx_estimated_absorpt_T_min   0.938
_exptl_absorpt_coefficient_mu    0.757
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5836
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0969 before and 0.0600 after correction.
The Ratio of minimum to maximum transmission is 0.7831.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'metallic dark violet'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.309
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1924
_exptl_crystal_size_max          0.085
_exptl_crystal_size_mid          0.052
_exptl_crystal_size_min          0.051
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0604
_diffrn_reflns_av_unetI/netI     0.0789
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            10598
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        23.255
_diffrn_reflns_theta_max         23.255
_diffrn_reflns_theta_min         1.827
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'sealed tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                2140
_reflns_number_total             3499
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_refine_diff_density_max         1.127
_refine_diff_density_min         -0.638
_refine_diff_density_rms         0.104
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     310
_refine_ls_number_reflns         3499
_refine_ls_number_restraints     84
_refine_ls_R_factor_all          0.1198
_refine_ls_R_factor_gt           0.0778
_refine_ls_restrained_S_all      1.026
_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)+(0.1371P)²+11.3409P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2087
_refine_ls_wR_factor_ref         0.2480
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
O2B \\sim O2A \\sim O4A \\sim O4B \\sim O3A \\sim S1 \\sim O3B: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
Uanis(O3A) \\sim Ueq, Uanis(O2A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3. Others
 Sof(O4A)=Sof(O2A)=Sof(O3A)=1-FVAR(1)
 Sof(O2B)=Sof(O4B)=Sof(O3B)=FVAR(1)
 Fixed Sof: H9A(0.5) H9B(0.5) H17A(0.5) H17B(0.5) H17C(0.5) H18A(0.5)
 H18B(0.5) H18C(0.5)
4.a Riding coordinates:
 O5(H5A,H5B), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
4.b Secondary CH2 refined with riding coordinates:
 N9(H9A,H9B)
4.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C13(H13), N2(H2), C16(H16), C9(H9), C3(H3), C8(H8), N4(H4A), C14(H14),
  C1(H1)
;
_atom_sites_solution_hydrogens   mixed
_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
Mn2 Mn 0.500000 0.63954(8) 0.37866(9) 0.0309(4) Uani 1 2 d S T P . .
Co1 Co 0.750000 1.14342(9) 0.250000 0.0533(5) Uani 1 2 d S T P . .
S1 S 0.64153(11) 1.1458(2) 0.1051(2) 0.0893(9) Uani 1 1 d . U . . .
N7 N 0.500000 0.4951(5) 0.3925(5) 0.0401(19) Uani 1 2 d S T P . .
N5 N 0.500000 0.7842(5) 0.3778(5) 0.0399(19) Uani 1 2 d S T P . .
N6 N 0.5886(2) 0.6390(4) 0.3746(4) 0.0426(14) Uani 1 1 d . . . . .
N3 N 0.7110(3) 0.2557(4) 0.3288(5) 0.0533(17) Uani 1 1 d . . . . .
O1 O 0.6697(3) 1.1422(5) 0.1799(4) 0.0841(19) Uani 1 1 d . . . . .
N1 N 0.7112(3) 1.0276(4) 0.3257(5) 0.0613(19) Uani 1 1 d . . . . .
C5 C 0.5493(3) 0.4329(5) 0.4035(4) 0.0428(17) Uani 1 1 d . . . . .
C7 C 0.6250(3) 0.5579(5) 0.3673(5) 0.0456(18) Uani 1 1 d . . . . .
C4 C 0.5305(3) 0.3376(4) 0.4292(5) 0.0482(18) Uani 1 1 d . . . . .
H4 H 0.555284 0.284714 0.443543 0.058 Uiso 1 1 calc R U . . .
C2 C 0.6544(3) 0.3810(5) 0.3798(5) 0.0481(19) Uani 1 1 d . . . . .
C15 C 0.6564(3) 0.8954(5) 0.3687(5) 0.053(2) Uani 1 1 d . . . . .
C6 C 0.6087(3) 0.4604(5) 0.3844(5) 0.0460(18) Uani 1 1 d . . . . .
C12 C 0.5494(3) 0.8465(5) 0.3841(4) 0.0449(17) Uani 1 1 d . . . . .
C11 C 0.6094(3) 0.8184(5) 0.3725(5) 0.0483(18) Uani 1 1 d . . . . .
C10 C 0.6255(3) 0.7198(5) 0.3623(5) 0.0483(19) Uani 1 1 d . . . . .
C13 C 0.5307(3) 0.9465(5) 0.3979(5) 0.055(2) Uani 1 1 d . . . . .
H13 H 0.555569 1.001266 0.405371 0.065 Uiso 1 1 calc R U . . .
N2 N 0.7389(4) 0.9815(6) 0.3897(5) 0.090(3) Uani 1 1 d . . . . .
H2 H 0.772506 0.999711 0.411387 0.108 Uiso 1 1 calc R U . . .
C16 C 0.6617(3) 0.9754(5) 0.3133(6) 0.062(2) Uani 1 1 d . . . . .
H16 H 0.633510 0.990329 0.272195 0.075 Uiso 1 1 calc R U . . .
C9 C 0.6843(3) 0.6857(6) 0.3403(6) 0.064(2) Uani 1 1 d . . . . .
H9 H 0.716884 0.725572 0.326470 0.076 Uiso 1 1 calc R U . . .
C3 C 0.6639(3) 0.3128(6) 0.3163(6) 0.070(3) Uani 1 1 d . . . . .
H3 H 0.639355 0.307785 0.269265 0.084 Uiso 1 1 calc R U . . .
C8 C 0.6842(3) 0.5883(5) 0.3430(6) 0.062(2) Uani 1 1 d . . . . .
H8 H 0.716450 0.546759 0.331331 0.074 Uiso 1 1 calc R U . . .
N4 N 0.7319(4) 0.2853(6) 0.4018(5) 0.099(3) Uani 1 1 d . . . . .
H4A H 0.762648 0.259947 0.426310 0.119 Uiso 1 1 calc R U . . .
O5 O 0.500000 0.6283(10) 0.2235(9) 0.184(7) Uani 1 2 d S T P . .
H5A H 0.500000 0.575774 0.193932 0.276 Uiso 1 2 d R U P . .
H5B H 0.500000 0.675254 0.187882 0.276 Uiso 1 2 d R U P . .
O2B O 0.6802(9) 1.1131(17) 0.0395(14) 0.151(7) Uani 0.625(12) 1 d . U P A 2
C14 C 0.7064(5) 0.9026(7) 0.4150(7) 0.094(3) Uani 1 1 d . . . . .
H14 H 0.717018 0.859587 0.458213 0.113 Uiso 1 1 calc R U . . .
C1 C 0.6989(6) 0.3605(8) 0.4335(7) 0.120(5) Uani 1 1 d . . . . .
H1 H 0.705978 0.392691 0.484254 0.144 Uiso 1 1 calc R U . . .
N9 N 0.500000 1.239(2) 0.1794(15) 0.198(12) Uani 1 2 d S T P . .
H9A H 0.532149 1.227357 0.147712 0.238 Uiso 0.5 1 calc R U P . .
H9B H 0.467851 1.227357 0.147712 0.238 Uiso 0.5 1 calc R U P . .
C17 C 0.500000 1.3422(17) 0.2019(15) 0.164(9) Uani 1 2 d S T P . .
H17A H 0.501290 1.384199 0.153249 0.246 Uiso 0.5 1 d R U P B -1
H17B H 0.534510 1.354849 0.236419 0.246 Uiso 0.5 1 d R U P B -1
H17C H 0.464200 1.355909 0.233419 0.246 Uiso 0.5 1 d R U P B -1
O4B O 0.5844(6) 1.0994(13) 0.1036(11) 0.135(5) Uani 0.625(12) 1 d . U P A 2
O3B O 0.6300(6) 1.2556(11) 0.0997(10) 0.139(6) Uani 0.625(12) 1 d . U P A 2
O4A O 0.6330(12) 1.0328(16) 0.0938(17) 0.131(8) Uani 0.375(12) 1 d . U P A 1
O2A O 0.6819(12) 1.1711(18) 0.0297(18) 0.095(7) Uani 0.375(12) 1 d . U P A 1
O3A O 0.5872(9) 1.184(2) 0.0807(16) 0.118(7) Uani 0.375(12) 1 d . U P A 1
C18 C 0.500000 1.160(2) 0.2545(16) 0.25(2) Uani 1 2 d S T P . .
H18A H 0.484860 1.191043 0.304434 0.369 Uiso 0.5 1 d R U P C -1
H18B H 0.540200 1.137082 0.264334 0.369 Uiso 0.5 1 d R U P C -1
H18C H 0.474940 1.104502 0.240104 0.369 Uiso 0.5 1 d R U P C -1


_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
Mn2 N7 1.959(8) . ?
Mn2 N5 1.949(7) . ?
Mn2 N6 1.976(6) 8_655 ?
Mn2 N6 1.976(6) . ?
Mn2 O5 2.475(14) . ?
Co1 N3 2.150(6) 3_665 ?
Co1 N3 2.150(6) 1_565 ?
Co1 O1 2.110(7) . ?
Co1 O1 2.110(7) 3_655 ?
Co1 N1 2.153(6) 3_655 ?
Co1 N1 2.153(6) . ?
S1 O1 1.346(7) . ?
S1 O2B 1.42(2) . ?
S1 O4B 1.419(12) . ?
S1 O3B 1.505(15) . ?
S1 O4A 1.55(2) . ?
S1 O2A 1.54(3) . ?
S1 O3A 1.376(17) . ?
N7 C5 1.394(8) . ?
N7 C5 1.394(8) 8_655 ?
N5 C12 1.388(8) . ?
N5 C12 1.388(8) 8_655 ?
N6 C7 1.367(8) . ?
N6 C10 1.378(8) . ?
N3 C3 1.316(9) . ?
N3 N4 1.315(9) . ?
N1 N2 1.345(10) . ?
N1 C16 1.322(9) . ?
C5 C4 1.411(9) . ?
C5 C6 1.408(10) . ?
C7 C6 1.390(9) . ?
C7 C8 1.434(10) . ?
C4 C4 1.361(14) 8_655 ?
C4 H4 0.9300 . ?
C2 C6 1.479(9) . ?
C2 C3 1.383(10) . ?
C2 C1 1.338(12) . ?
C15 C11 1.476(9) . ?
C15 C16 1.398(10) . ?
C15 C14 1.340(12) . ?
C12 C11 1.402(10) . ?
C12 C13 1.428(9) . ?
C11 C10 1.385(9) . ?
C10 C9 1.433(10) . ?
C13 C13 1.370(14) 8_655 ?
C13 H13 0.9300 . ?
N2 H2 0.8600 . ?
N2 C14 1.350(10) . ?
C16 H16 0.9300 . ?
C9 H9 0.9300 . ?
C9 C8 1.314(10) . ?
C3 H3 0.9300 . ?
C8 H8 0.9300 . ?
N4 H4A 0.8600 . ?
N4 C1 1.349(10) . ?
O5 H5A 0.8498 . ?
O5 H5B 0.8499 . ?
C14 H14 0.9300 . ?
C1 H1 0.9300 . ?
N9 H9A 0.8900 . ?
N9 H9B 0.8900 . ?
N9 C17 1.44(2) . ?
N9 C18 1.60(3) . ?
C17 H17A 0.9600 . ?
C17 H17B 0.9600 . ?
C17 H17C 0.9600 . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?

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
N7 Mn2 N6 90.02(14) . . ?
N7 Mn2 N6 90.02(14) . 8_655 ?
N7 Mn2 O5 93.0(4) . . ?
N5 Mn2 N7 173.9(3) . . ?
N5 Mn2 N6 90.18(14) . 8_655 ?
N5 Mn2 N6 90.18(14) . . ?
N5 Mn2 O5 93.1(4) . . ?
N6 Mn2 N6 176.2(3) . 8_655 ?
N6 Mn2 O5 88.12(17) . . ?
N6 Mn2 O5 88.12(17) 8_655 . ?
N3 Co1 N3 90.5(3) 1_565 3_665 ?
N3 Co1 N1 91.2(2) 1_565 . ?
N3 Co1 N1 91.2(2) 3_665 3_655 ?
N3 Co1 N1 178.2(2) 1_565 3_655 ?
N3 Co1 N1 178.2(2) 3_665 . ?
O1 Co1 N3 88.3(3) . 1_565 ?
O1 Co1 N3 88.3(3) 3_655 3_665 ?
O1 Co1 N3 92.3(3) 3_655 1_565 ?
O1 Co1 N3 92.3(3) . 3_665 ?
O1 Co1 O1 179.1(3) . 3_655 ?
O1 Co1 N1 92.2(3) . 3_655 ?
O1 Co1 N1 92.2(3) 3_655 . ?
O1 Co1 N1 87.1(3) 3_655 3_655 ?
O1 Co1 N1 87.1(3) . . ?
N1 Co1 N1 87.1(3) 3_655 . ?
O1 S1 O2B 110.8(9) . . ?
O1 S1 O4B 114.7(8) . . ?
O1 S1 O3B 99.6(7) . . ?
O1 S1 O4A 97.2(9) . . ?
O1 S1 O2A 115.2(10) . . ?
O1 S1 O3A 132.4(11) . . ?
O2B S1 O3B 111.4(12) . . ?
O4B S1 O2B 113.2(12) . . ?
O4B S1 O3B 106.2(8) . . ?
O2A S1 O4A 101.5(14) . . ?
O3A S1 O4A 103.4(15) . . ?
O3A S1 O2A 102.1(16) . . ?
C5 N7 Mn2 127.8(4) . . ?
C5 N7 Mn2 127.8(4) 8_655 . ?
C5 N7 C5 104.1(7) . 8_655 ?
C12 N5 Mn2 127.2(4) 8_655 . ?
C12 N5 Mn2 127.2(4) . . ?
C12 N5 C12 104.9(7) 8_655 . ?
C7 N6 Mn2 126.8(4) . . ?
C7 N6 C10 105.4(5) . . ?
C10 N6 Mn2 126.7(4) . . ?
C3 N3 Co1 130.3(6) . 1_545 ?
N4 N3 Co1 125.9(5) . 1_545 ?
N4 N3 C3 103.8(7) . . ?
S1 O1 Co1 149.7(4) . . ?
N2 N1 Co1 125.1(5) . . ?
C16 N1 Co1 129.6(7) . . ?
C16 N1 N2 104.5(7) . . ?
N7 C5 C4 110.5(6) . . ?
N7 C5 C6 123.7(6) . . ?
C6 C5 C4 125.5(6) . . ?
N6 C7 C6 125.7(6) . . ?
N6 C7 C8 109.9(6) . . ?
C6 C7 C8 124.3(6) . . ?
C5 C4 H4 126.4 . . ?
C4 C4 C5 107.2(4) 8_655 . ?
C4 C4 H4 126.4 8_655 . ?
C3 C2 C6 128.4(7) . . ?
C1 C2 C6 129.0(7) . . ?
C1 C2 C3 102.5(7) . . ?
C16 C15 C11 129.0(7) . . ?
C14 C15 C11 128.2(7) . . ?
C14 C15 C16 102.7(7) . . ?
C5 C6 C2 117.9(6) . . ?
C7 C6 C5 122.5(6) . . ?
C7 C6 C2 119.6(6) . . ?
N5 C12 C11 125.7(6) . . ?
N5 C12 C13 110.6(6) . . ?
C11 C12 C13 123.6(6) . . ?
C12 C11 C15 119.5(6) . . ?
C10 C11 C15 119.1(6) . . ?
C10 C11 C12 121.4(6) . . ?
N6 C10 C11 125.9(6) . . ?
N6 C10 C9 109.1(6) . . ?
C11 C10 C9 125.0(6) . . ?
C12 C13 H13 126.5 . . ?
C13 C13 C12 106.9(4) 8_655 . ?
C13 C13 H13 126.5 8_655 . ?
N1 N2 H2 125.0 . . ?
N1 N2 C14 110.1(8) . . ?
C14 N2 H2 125.0 . . ?
N1 C16 C15 112.9(8) . . ?
N1 C16 H16 123.6 . . ?
C15 C16 H16 123.6 . . ?
C10 C9 H9 125.9 . . ?
C8 C9 C10 108.1(7) . . ?
C8 C9 H9 125.9 . . ?
N3 C3 C2 113.6(8) . . ?
N3 C3 H3 123.2 . . ?
C2 C3 H3 123.2 . . ?
C7 C8 H8 126.4 . . ?
C9 C8 C7 107.2(7) . . ?
C9 C8 H8 126.4 . . ?
N3 N4 H4A 124.3 . . ?
N3 N4 C1 111.5(7) . . ?
C1 N4 H4A 124.3 . . ?
Mn2 O5 H5A 127.1 . . ?
Mn2 O5 H5B 128.3 . . ?
H5A O5 H5B 104.5 . . ?
C15 C14 N2 109.9(9) . . ?
C15 C14 H14 125.1 . . ?
N2 C14 H14 125.1 . . ?
C2 C1 N4 108.6(8) . . ?
C2 C1 H1 125.7 . . ?
N4 C1 H1 125.7 . . ?
H9A N9 H9B 107.2 . . ?
C17 N9 H9A 108.0 . . ?
C17 N9 H9B 108.0 . . ?
C17 N9 C18 117(2) . . ?
C18 N9 H9A 108.0 . . ?
C18 N9 H9B 108.0 . . ?
N9 C17 H17A 111.7 . . ?
N9 C17 H17B 108.3 . . ?
N9 C17 H17C 108.4 . . ?
H17A C17 H17B 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
N9 C18 H18A 109.1 . . ?
N9 C18 H18B 109.5 . . ?
N9 C18 H18C 109.8 . . ?
H18A C18 H18B 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?

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
Mn2 N7 C5 C4 167.2(6) . . . . ?
Mn2 N7 C5 C6 -17.6(11) . . . . ?
Mn2 N5 C12 C11 16.0(12) . . . . ?
Mn2 N5 C12 C13 -168.5(6) . . . . ?
Mn2 N6 C7 C6 -19.0(10) . . . . ?
Mn2 N6 C7 C8 163.8(5) . . . . ?
Mn2 N6 C10 C11 18.2(11) . . . . ?
Mn2 N6 C10 C9 -164.0(6) . . . . ?
Co1 N3 C3 C2 -176.4(5) 1_545 . . . ?
Co1 N3 N4 C1 176.8(8) 1_545 . . . ?
Co1 N1 N2 C14 -170.1(7) . . . . ?
Co1 N1 C16 C15 169.8(5) . . . . ?
N7 C5 C4 C4 3.9(6) . . . 8_655 ?
N7 C5 C6 C7 12.0(12) . . . . ?
N7 C5 C6 C2 -165.9(7) . . . . ?
N5 C12 C11 C15 170.9(7) . . . . ?
N5 C12 C11 C10 -7.4(12) . . . . ?
N5 C12 C13 C13 -1.6(6) . . . 8_655 ?
N6 C7 C6 C5 6.8(12) . . . . ?
N6 C7 C6 C2 -175.3(7) . . . . ?
N6 C7 C8 C9 3.3(10) . . . . ?
N6 C10 C9 C8 -2.9(10) . . . . ?
N3 N4 C1 C2 0.4(14) . . . . ?
N1 N2 C14 C15 -0.4(13) . . . . ?
C5 N7 C5 C4 -6.1(10) 8_655 . . . ?
C5 N7 C5 C6 169.1(4) 8_655 . . . ?
C7 N6 C10 C11 -172.9(8) . . . . ?
C7 N6 C10 C9 4.8(8) . . . . ?
C4 C5 C6 C7 -173.6(7) . . . . ?
C4 C5 C6 C2 8.5(11) . . . . ?
C15 C11 C10 N6 171.3(7) . . . . ?
C15 C11 C10 C9 -6.1(12) . . . . ?
C6 C5 C4 C4 -171.1(6) . . . 8_655 ?
C6 C7 C8 C9 -173.9(8) . . . . ?
C6 C2 C3 N3 175.8(7) . . . . ?
C6 C2 C1 N4 -176.4(8) . . . . ?
C12 N5 C12 C11 -173.0(5) 8_655 . . . ?
C12 N5 C12 C13 2.5(10) 8_655 . . . ?
C12 C11 C10 N6 -10.4(12) . . . . ?
C12 C11 C10 C9 172.2(8) . . . . ?
C11 C15 C16 N1 -177.2(7) . . . . ?
C11 C15 C14 N2 177.3(8) . . . . ?
C11 C12 C13 C13 174.0(6) . . . 8_655 ?
C11 C10 C9 C8 174.9(8) . . . . ?
C10 N6 C7 C6 172.2(7) . . . . ?
C10 N6 C7 C8 -5.0(8) . . . . ?
C10 C9 C8 C7 -0.2(10) . . . . ?
C13 C12 C11 C15 -4.0(11) . . . . ?
C13 C12 C11 C10 177.7(7) . . . . ?
N2 N1 C16 C15 0.2(9) . . . . ?
C16 N1 N2 C14 0.2(11) . . . . ?
C16 C15 C11 C12 -58.5(11) . . . . ?
C16 C15 C11 C10 119.8(9) . . . . ?
C16 C15 C14 N2 0.5(11) . . . . ?
C3 N3 N4 C1 -1.0(12) . . . . ?
C3 C2 C6 C5 76.3(11) . . . . ?
C3 C2 C6 C7 -101.7(10) . . . . ?
C3 C2 C1 N4 0.3(12) . . . . ?
C8 C7 C6 C5 -176.4(8) . . . . ?
C8 C7 C6 C2 1.5(12) . . . . ?
N4 N3 C3 C2 1.2(10) . . . . ?
O2B S1 O1 Co1 24.6(15) . . . . ?
C14 C15 C11 C12 125.5(10) . . . . ?
C14 C15 C11 C10 -56.2(13) . . . . ?
C14 C15 C16 N1 -0.4(10) . . . . ?
C1 C2 C6 C5 -107.8(12) . . . . ?
C1 C2 C6 C7 74.2(13) . . . . ?
C1 C2 C3 N3 -1.0(11) . . . . ?
O4B S1 O1 Co1 154.3(10) . . . . ?
O3B S1 O1 Co1 -92.8(10) . . . . ?
O4A S1 O1 Co1 97.6(14) . . . . ?
O2A S1 O1 Co1 -8.7(15) . . . . ?
O3A S1 O1 Co1 -146.8(18) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
