# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_5
_database_code_depnum_ccdc_archive 'CCDC 1522230'
_audit_update_record             
;
2016-12-12 deposited with the CCDC.
2017-05-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C4 H9 Cl3 Mn N2 O'
_chemical_formula_weight         262.42

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'
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'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P21/c

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   8.9890(18)
_cell_length_b                   14.612(3)
_cell_length_c                   7.2748(15)
_cell_angle_alpha                90.00
_cell_angle_beta                 93.86(3)
_cell_angle_gamma                90.00
_cell_volume                     953.4(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2179
_cell_measurement_theta_min      3.13
_cell_measurement_theta_max      27.48

_exptl_crystal_description       block
_exptl_crystal_colour            pink
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.828
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             524
_exptl_absorpt_coefficient_mu    2.172
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.0000
_exptl_absorpt_correction_T_max  0.0000
_exptl_absorpt_process_details   'CrystalClear (Rigaku, 2005)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Rigaku, SCXmini'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            6483
_diffrn_reflns_av_R_equivalents  0.0464
_diffrn_reflns_av_sigmaI/netI    0.0480
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_theta_min         3.13
_diffrn_reflns_theta_max         27.48
_reflns_number_total             2179
_reflns_number_gt                1850
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'CrystalClear (Rigaku, 2005)'
_computing_cell_refinement       'CrystalClear (Rigaku, 2005)'
_computing_data_reduction        'CrystalClear (Rigaku, 2005)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'DIAMOND (Brandenburg & Putz, 2005)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 2008)'

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

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.1359P)²+43.7981P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2179
_refine_ls_number_parameters     100
_refine_ls_number_restraints     218
_refine_ls_R_factor_all          0.1148
_refine_ls_R_factor_gt           0.0944
_refine_ls_wR_factor_ref         0.3455
_refine_ls_wR_factor_gt          0.3399
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_restrained_S_all      1.016
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Mn1 Mn -0.07841(19) -0.73872(11) 0.1840(2) 0.0211(5) Uani 1 1 d U . .
Cl1 Cl -0.2798(3) -0.75698(19) 0.4186(4) 0.0253(7) Uani 1 1 d U . .
Cl2 Cl 0.1113(3) -0.7378(2) -0.0529(4) 0.0281(7) Uani 1 1 d U . .
Cl3 Cl -0.0918(3) -0.56793(19) 0.2185(4) 0.0285(7) Uani 1 1 d U . .
O1W O -0.0906(10) -0.8907(6) 0.1508(13) 0.0306(18) Uani 1 1 d U . .
H1WA H -0.0297 -0.9076 0.0731 0.046 Uiso 1 1 d R . .
H1WB H -0.0679 -0.9161 0.2540 0.046 Uiso 1 1 d R . .
N1 N -0.373(5) -0.967(3) 0.271(8) 0.0318(18) Uani 0.50 1 d PDU A 1
H1A H -0.3254 -0.9157 0.2669 0.038 Uiso 0.50 1 calc PR A 1
N2 N -0.564(4) -1.042(2) 0.273(6) 0.0318(18) Uani 0.50 1 d PU A 1
H2A H -0.6562 -1.0569 0.2725 0.038 Uiso 0.50 1 calc PR A 1
C1 C -0.307(3) -1.0490(19) 0.316(6) 0.0318(18) Uani 0.50 1 d PDU A 1
H1B H -0.2061 -1.0617 0.3338 0.038 Uiso 0.50 1 calc PR A 1
C2 C -0.424(3) -1.108(2) 0.327(6) 0.0318(18) Uani 0.50 1 d PDU A 1
H2B H -0.4224 -1.1701 0.3573 0.038 Uiso 0.50 1 calc PR A 1
C3 C -0.519(5) -0.975(3) 0.236(8) 0.0318(18) Uani 0.50 1 d PU A 1
C4 C -0.618(3) -0.897(2) 0.177(5) 0.0318(18) Uani 0.50 1 d PU A 1
H4A H -0.7190 -0.9185 0.1596 0.048 Uiso 0.50 1 d PR A 1
H4B H -0.6125 -0.8504 0.2704 0.048 Uiso 0.50 1 d PR A 1
H4C H -0.5876 -0.8722 0.0637 0.048 Uiso 0.50 1 d PR A 1
N1' N -0.355(5) -0.978(3) 0.258(7) 0.032(5) Uani 0.50 1 d PU B 2
H1'A H -0.2868 -0.9392 0.2350 0.038 Uiso 0.50 1 calc PR B 2
N2' N -0.552(4) -1.060(2) 0.270(6) 0.0318(18) Uani 0.50 1 d PU B 2
H2'A H -0.6418 -1.0781 0.2449 0.038 Uiso 0.50 1 calc PR B 2
C1' C -0.332(3) -1.065(2) 0.326(6) 0.0318(18) Uani 0.50 1 d PU B 2
H1'B H -0.2395 -1.0908 0.3592 0.038 Uiso 0.50 1 calc PR B 2
C2' C -0.462(3) -1.105(2) 0.335(6) 0.035(5) Uani 0.50 1 d PU B 2
H2'B H -0.4766 -1.1624 0.3861 0.042 Uiso 0.50 1 calc PR B 2
C3' C -0.502(5) -0.963(3) 0.233(8) 0.0318(18) Uani 0.50 1 d PU B 2
C4' C -0.581(3) -0.881(2) 0.174(5) 0.0318(18) Uani 0.50 1 d PU B 2
H4'A H -0.5103 -0.8323 0.1658 0.048 Uiso 0.50 1 d PR B 2
H4'B H -0.6315 -0.8911 0.0554 0.048 Uiso 0.50 1 d PR B 2
H4'C H -0.6521 -0.8650 0.2612 0.048 Uiso 0.50 1 d PR B 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
Mn1 O1W 2.235(8) . ?
Mn1 Cl2 2.500(3) 4_546 ?
Mn1 Cl2 2.505(3) . ?
Mn1 Cl3 2.512(3) . ?
Mn1 Cl1 2.558(3) 4_545 ?
Mn1 Cl1 2.584(3) . ?
Cl1 Mn1 2.558(3) 4_546 ?
Cl2 Mn1 2.500(3) 4_545 ?
O1W H1WA 0.8500 . ?
O1W H1WB 0.8500 . ?
N1 C3 1.33(5) . ?
N1 C1 1.371(18) . ?
N1 H1A 0.8600 . ?
N2 C3 1.10(6) . ?
N2 C2 1.61(5) . ?
N2 H2A 0.8600 . ?
C1 C2 1.364(17) . ?
C1 H1B 0.9300 . ?
C2 H2B 0.9300 . ?
C3 C4 1.48(5) . ?
C4 H4A 0.9600 . ?
C4 H4B 0.9600 . ?
C4 H4C 0.9600 . ?
C4 H4'B 0.8911 . ?
C4 H4'C 0.8430 . ?
N1' C3' 1.34(5) . ?
N1' C1' 1.37(4) . ?
N1' H1'A 0.8600 . ?
N2' C2' 1.13(5) . ?
N2' C3' 1.50(6) . ?
N2' H2'A 0.8600 . ?
C1' C2' 1.31(4) . ?
C1' H1'B 0.9300 . ?
C2' H2'B 0.9300 . ?
C3' C4' 1.44(5) . ?
C4' H4B 0.8944 . ?
C4' H4C 0.8125 . ?
C4' H4'A 0.9600 . ?
C4' H4'B 0.9600 . ?
C4' H4'C 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
O1W Mn1 Cl2 88.4(2) . 4_546 ?
O1W Mn1 Cl2 87.8(2) . . ?
Cl2 Mn1 Cl2 93.81(11) 4_546 . ?
O1W Mn1 Cl3 174.5(2) . . ?
Cl2 Mn1 Cl3 95.45(11) 4_546 . ?
Cl2 Mn1 Cl3 95.89(11) . . ?
O1W Mn1 Cl1 82.4(2) . 4_545 ?
Cl2 Mn1 Cl1 170.56(12) 4_546 4_545 ?
Cl2 Mn1 Cl1 87.76(10) . 4_545 ?
Cl3 Mn1 Cl1 93.64(11) . 4_545 ?
O1W Mn1 Cl1 86.4(2) . . ?
Cl2 Mn1 Cl1 87.28(10) 4_546 . ?
Cl2 Mn1 Cl1 174.10(12) . . ?
Cl3 Mn1 Cl1 89.78(11) . . ?
Cl1 Mn1 Cl1 90.24(10) 4_545 . ?
Mn1 Cl1 Mn1 90.53(10) 4_546 . ?
Mn1 Cl2 Mn1 93.72(11) 4_545 . ?
Mn1 O1W H1WA 109.4 . . ?
Mn1 O1W H1WB 109.4 . . ?
H1WA O1W H1WB 109.5 . . ?
C3 N1 C1 112(5) . . ?
C3 N1 H1A 124.0 . . ?
C1 N1 H1A 124.0 . . ?
C3 N2 C2 108(3) . . ?
C3 N2 H2A 126.1 . . ?
C2 N2 H2A 126.1 . . ?
C2 C1 N1 105(4) . . ?
C2 C1 H1B 127.7 . . ?
N1 C1 H1B 127.7 . . ?
C1 C2 N2 101(3) . . ?
C1 C2 H2B 129.5 . . ?
N2 C2 H2B 129.5 . . ?
N2 C3 N1 114(5) . . ?
N2 C3 C4 122(3) . . ?
N1 C3 C4 124(4) . . ?
C3 C4 H4A 109.4 . . ?
C3 C4 H4B 109.7 . . ?
H4A C4 H4B 109.3 . . ?
C3 C4 H4C 109.6 . . ?
H4A C4 H4C 109.3 . . ?
H4B C4 H4C 109.5 . . ?
C3 C4 H4'A 97.7 . . ?
H4A C4 H4'A 152.7 . . ?
H4B C4 H4'A 62.9 . . ?
H4C C4 H4'A 55.8 . . ?
C3 C4 H4'B 113.5 . . ?
H4A C4 H4'B 80.5 . . ?
H4B C4 H4'B 129.0 . . ?
H4C C4 H4'B 29.9 . . ?
H4'A C4 H4'B 85.4 . . ?
C3 C4 H4'C 117.1 . . ?
H4A C4 H4'C 83.9 . . ?
H4B C4 H4'C 25.7 . . ?
H4C C4 H4'C 123.4 . . ?
H4'A C4 H4'C 87.2 . . ?
H4'B C4 H4'C 129.4 . . ?
C3' N1' C1' 109(5) . . ?
C3' N1' H1'A 125.7 . . ?
C1' N1' H1'A 125.7 . . ?
C2' N2' C3' 114(3) . . ?
C2' N2' H2'A 122.8 . . ?
C3' N2' H2'A 122.8 . . ?
C2' C1' N1' 109(4) . . ?
C2' C1' H1'B 125.7 . . ?
N1' C1' H1'B 125.7 . . ?
N2' C2' C1' 109(4) . . ?
N2' C2' H2'B 125.3 . . ?
C1' C2' H2'B 125.3 . . ?
N1' C3' C4' 129(3) . . ?
N1' C3' N2' 98(4) . . ?
C4' C3' N2' 133(3) . . ?
C3' C4' H4A 96.6 . . ?
C3' C4' H4B 111.1 . . ?
H4A C4' H4B 85.7 . . ?
C3' C4' H4C 115.6 . . ?
H4A C4' H4C 88.9 . . ?
H4B C4' H4C 133.4 . . ?
C3' C4' H4'A 109.1 . . ?
H4A C4' H4'A 154.3 . . ?
H4B C4' H4'A 85.5 . . ?
H4C C4' H4'A 79.8 . . ?
C3' C4' H4'B 109.6 . . ?
H4A C4' H4'B 59.5 . . ?
H4B C4' H4'B 128.6 . . ?
H4C C4' H4'B 30.1 . . ?
H4'A C4' H4'B 109.3 . . ?
C3' C4' H4'C 110.0 . . ?
H4A C4' H4'C 60.1 . . ?
H4B C4' H4'C 25.6 . . ?
H4C C4' H4'C 127.1 . . ?
H4'A C4' H4'C 109.3 . . ?
H4'B C4' H4'C 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
O1W Mn1 Cl1 Mn1 94.9(2) . . . 4_546 ?
Cl2 Mn1 Cl1 Mn1 6.31(10) 4_546 . . 4_546 ?
Cl2 Mn1 Cl1 Mn1 107.1(11) . . . 4_546 ?
Cl3 Mn1 Cl1 Mn1 -89.16(11) . . . 4_546 ?
Cl1 Mn1 Cl1 Mn1 177.20(15) 4_545 . . 4_546 ?
O1W Mn1 Cl2 Mn1 75.9(2) . . . 4_545 ?
Cl2 Mn1 Cl2 Mn1 164.16(16) 4_546 . . 4_545 ?
Cl3 Mn1 Cl2 Mn1 -99.95(12) . . . 4_545 ?
Cl1 Mn1 Cl2 Mn1 -6.52(10) 4_545 . . 4_545 ?
Cl1 Mn1 Cl2 Mn1 63.7(11) . . . 4_545 ?
C3 N1 C1 C2 -7(6) . . . . ?
N1 C1 C2 N2 2(5) . . . . ?
C3 N2 C2 C1 4(6) . . . . ?
C2 N2 C3 N1 -9(7) . . . . ?
C2 N2 C3 C4 180(4) . . . . ?
C1 N1 C3 N2 11(8) . . . . ?
C1 N1 C3 C4 -178(5) . . . . ?
C3' N1' C1' C2' 3(5) . . . . ?
C3' N2' C2' C1' -12(6) . . . . ?
N1' C1' C2' N2' 6(5) . . . . ?
C1' N1' C3' C4' 176(5) . . . . ?
C1' N1' C3' N2' -8(5) . . . . ?
C2' N2' C3' N1' 13(6) . . . . ?
C2' N2' C3' C4' -172(5) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O1W H1WA Cl3 0.85 2.63 3.202(10) 126.1 4_545
O1W H1WB Cl3 0.85 2.64 3.176(9) 122.0 2_545
N2 H2A Cl3 0.86 2.28 3.13(4) 169.4 2_445
N2' H2'A Cl3 0.86 2.43 3.21(4) 150.9 2_445
N2' H2'A Cl1 0.86 2.94 3.50(4) 124.4 2_445
N1 H1A O1W 0.86 2.35 2.96(5) 127.5 .
N1 H1A Cl1 0.86 2.59 3.33(5) 145.4 .
N1' H1'A O1W 0.86 2.03 2.85(5) 159.0 .
N1' H1'A Cl1 0.86 2.98 3.48(5) 119.7 .

_diffrn_measured_fraction_theta_max 0.994
_diffrn_reflns_theta_full        27.48
_diffrn_measured_fraction_theta_full 0.994
_refine_diff_density_max         1.832
_refine_diff_density_min         -1.799
_refine_diff_density_rms         0.312
####################################################################### 
# 
# 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_3
_database_code_depnum_ccdc_archive 'CCDC 1522231'
_audit_update_record             
;
2016-12-12 deposited with the CCDC.
2017-05-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C4 H9 Cl3 Mn N2 O'
_chemical_formula_weight         262.42

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'
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'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P21/c

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   26.896(3)
_cell_length_b                   14.523(3)
_cell_length_c                   7.2525(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 93.862(7)
_cell_angle_gamma                90.00
_cell_volume                     2826.4(7)
_cell_formula_units_Z            12
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    6337
_cell_measurement_theta_min      1.5
_cell_measurement_theta_max      27.5

_exptl_crystal_description       block
_exptl_crystal_colour            pink
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.850
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1572
_exptl_absorpt_coefficient_mu    2.198
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.7582
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   'CrystalClear (Rigaku, 2005)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Rigaku, SCXmini'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            18039
_diffrn_reflns_av_R_equivalents  0.0500
_diffrn_reflns_av_sigmaI/netI    0.0830
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -6
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         1.52
_diffrn_reflns_theta_max         27.46
_reflns_number_total             3337
_reflns_number_gt                2204
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'CrystalClear (Rigaku, 2005)'
_computing_cell_refinement       'CrystalClear (Rigaku, 2005)'
_computing_data_reduction        'CrystalClear (Rigaku, 2005)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'DIAMOND (Brandenburg & Putz, 2005)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 2008)'

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

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0773P)²+352.2365P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         6337
_refine_ls_number_parameters     268
_refine_ls_number_restraints     177
_refine_ls_R_factor_all          0.1315
_refine_ls_R_factor_gt           0.1015
_refine_ls_wR_factor_ref         0.3425
_refine_ls_wR_factor_gt          0.3216
_refine_ls_goodness_of_fit_ref   1.278
_refine_ls_restrained_S_all      1.260
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Mn1 Mn 0.14037(5) 0.23860(9) 0.18275(17) 0.0134(3) Uani 1 1 d U . .
Mn3 Mn 0.19295(5) 0.73929(9) 0.32634(16) 0.0123(3) Uani 1 1 d U . .
Cl9 Cl 0.26002(7) 0.75692(15) 0.0919(3) 0.0141(4) Uani 1 1 d U . .
Cl3 Cl 0.07339(7) 0.25784(15) 0.4161(3) 0.0155(5) Uani 1 1 d U . .
Cl7 Cl 0.12916(7) 0.76237(15) 0.0627(3) 0.0148(5) Uani 1 1 d U . .
Cl2 Cl 0.20397(8) 0.26344(15) 0.4447(3) 0.0161(5) Uani 1 1 d U . .
Cl8 Cl 0.19808(8) 0.56709(15) 0.2858(3) 0.0193(5) Uani 1 1 d U . .
Cl1 Cl 0.13633(7) 0.06679(14) 0.2152(3) 0.0144(5) Uani 1 1 d U . .
Mn2 Mn 0.47391(4) 0.23890(8) 0.17900(17) 0.0083(3) Uani 1 1 d U . .
Cl5 Cl 0.40649(7) 0.25731(14) 0.4139(3) 0.0114(4) Uani 1 1 d U . .
Cl6 Cl 0.53752(7) 0.23808(15) -0.0587(3) 0.0145(5) Uani 1 1 d U . .
Cl4 Cl 0.46964(7) 0.06579(13) 0.2141(3) 0.0138(5) Uani 1 1 d U . .
O2 O 0.4704(2) 0.3916(4) 0.1431(9) 0.0173(6) Uani 1 1 d U . .
H2C H 0.4908 0.4083 0.0650 0.026 Uiso 1 1 d R . .
H2D H 0.4779 0.4175 0.2463 0.026 Uiso 1 1 d R . .
O1 O 0.1376(2) 0.3910(4) 0.1455(8) 0.0163(14) Uani 1 1 d U . .
H1C H 0.1582 0.4068 0.0673 0.024 Uiso 1 1 d R . .
H1D H 0.1454 0.4171 0.2484 0.024 Uiso 1 1 d R . .
O3 O 0.1989(2) 0.8921(4) 0.3573(9) 0.0173(6) Uani 1 1 d U . .
H3B H 0.1788 0.9103 0.4353 0.026 Uiso 1 1 d R . .
H3C H 0.1915 0.9176 0.2535 0.026 Uiso 1 1 d R . .
N2 N 0.3140(3) 0.5554(6) 0.2776(11) 0.0226(15) Uani 1 1 d U . .
H2B H 0.2829 0.5744 0.2648 0.027 Uiso 1 1 calc R . .
C2 C 0.3545(4) 0.6033(7) 0.3394(14) 0.0262(19) Uani 1 1 d U . .
H2A H 0.3533 0.6638 0.3886 0.031 Uiso 1 1 calc R . .
C3 C 0.3322(4) 0.4716(7) 0.2400(12) 0.0200(16) Uani 1 1 d U . .
C1 C 0.3952(4) 0.5580(7) 0.3245(12) 0.0226(18) Uani 1 1 d U . .
H1A H 0.4286 0.5789 0.3444 0.027 Uiso 1 1 calc R . .
C6 C 0.2716(3) 0.0596(6) 0.1743(13) 0.0173(6) Uani 1 1 d U . .
H6A H 0.2384 0.0797 0.1443 0.021 Uiso 1 1 calc R . .
C8 C 0.3645(4) -0.1069(7) 0.3332(14) 0.023(2) Uani 1 1 d U . .
H8A H 0.4003 -0.0940 0.3383 0.035 Uiso 1 1 calc R . .
H8B H 0.3570 -0.1595 0.2515 0.035 Uiso 1 1 calc R . .
H8C H 0.3546 -0.1212 0.4575 0.035 Uiso 1 1 calc R . .
N4 N 0.3529(3) 0.0530(6) 0.2354(13) 0.0260(18) Uani 1 1 d U . .
H4D H 0.3839 0.0707 0.2604 0.031 Uiso 1 1 calc R . .
C7 C 0.3371(3) -0.0265(6) 0.2621(13) 0.0173(6) Uani 1 1 d U . .
N1 N 0.3782(3) 0.4717(6) 0.2724(11) 0.0253(17) Uani 1 1 d U . .
H1B H 0.3974 0.4230 0.2632 0.030 Uiso 1 1 calc R . .
N3 N 0.2860(3) -0.0234(5) 0.2386(11) 0.0177(16) Uani 1 1 d U . .
H3A H 0.2659 -0.0690 0.2623 0.021 Uiso 1 1 calc R . .
C4 C 0.2997(5) 0.3896(9) 0.1671(16) 0.039(2) Uani 1 1 d U . .
H4A H 0.3210 0.3359 0.1509 0.059 Uiso 1 1 calc R . .
H4B H 0.2826 0.4061 0.0482 0.059 Uiso 1 1 calc R . .
H4C H 0.2750 0.3749 0.2561 0.059 Uiso 1 1 calc R . .
C5 C 0.3150(3) 0.1101(7) 0.1607(13) 0.0209(18) Uani 1 1 d U . .
H5A H 0.3182 0.1702 0.1113 0.025 Uiso 1 1 calc R . .
N5 N 1.0195(3) 0.0496(5) 0.2031(11) 0.0173(6) Uani 1 1 d U . .
H5B H 1.0507 0.0614 0.1825 0.021 Uiso 1 1 calc R . .
C10 C 0.9805(4) 0.1091(6) 0.1680(13) 0.0204(18) Uani 1 1 d U . .
H10A H 0.9829 0.1732 0.1442 0.024 Uiso 1 1 calc R . .
C11 C 1.0024(3) -0.0319(6) 0.2762(13) 0.0186(17) Uani 1 1 d U . .
N6 N 0.9526(3) -0.0262(5) 0.2403(11) 0.0173(6) Uani 1 1 d U . .
H6B H 0.9314 -0.0712 0.2566 0.021 Uiso 1 1 calc R . .
C12 C 1.0323(4) -0.1094(7) 0.3279(14) 0.025(2) Uani 1 1 d U . .
H12A H 1.0113 -0.1577 0.3764 0.037 Uiso 1 1 calc R . .
H12B H 1.0579 -0.0913 0.4233 0.037 Uiso 1 1 calc R . .
H12C H 1.0482 -0.1327 0.2196 0.037 Uiso 1 1 calc R . .
C9 C 0.9394(3) 0.0621(7) 0.1731(13) 0.0224(19) Uani 1 1 d U . .
H9A H 0.9067 0.0833 0.1381 0.027 Uiso 1 1 calc R . .


_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
Mn1 O1 2.230(6) . ?
Mn1 Cl2 2.496(2) . ?
Mn1 Cl1 2.509(2) . ?
Mn1 Cl2 2.511(2) 4_565 ?
Mn1 Cl3 2.553(2) 4_565 ?
Mn1 Cl3 2.569(2) . ?
Mn3 O3 2.236(6) . ?
Mn3 Cl7 2.504(2) . ?
Mn3 Cl7 2.506(2) 4_576 ?
Mn3 Cl8 2.523(3) . ?
Mn3 Cl9 2.549(2) 4_576 ?
Mn3 Cl9 2.574(2) . ?
Cl9 Mn3 2.549(2) 4_575 ?
Cl3 Mn1 2.553(2) 4_566 ?
Cl7 Mn3 2.506(2) 4_575 ?
Cl2 Mn1 2.511(2) 4_566 ?
Mn2 O2 2.235(6) . ?
Mn2 Cl6 2.494(2) 4_566 ?
Mn2 Cl6 2.509(2) . ?
Mn2 Cl4 2.530(2) . ?
Mn2 Cl5 2.553(2) 4_565 ?
Mn2 Cl5 2.584(2) . ?
Cl5 Mn2 2.553(2) 4_566 ?
Cl6 Mn2 2.494(2) 4_565 ?
N2 C3 1.345(13) . ?
N2 C2 1.344(13) . ?
C2 C1 1.288(15) . ?
C3 N1 1.246(13) . ?
C3 C4 1.548(15) . ?
C1 N1 1.378(13) . ?
C6 N3 1.340(12) . ?
C6 C5 1.388(12) . ?
C8 C7 1.456(13) . ?
N4 C7 1.250(12) . ?
N4 C5 1.395(12) . ?
C7 N3 1.373(11) . ?
N5 C10 1.369(12) . ?
N5 C11 1.388(12) . ?
C10 C9 1.302(13) . ?
C11 N6 1.350(11) . ?
C11 C12 1.419(13) . ?
N6 C9 1.408(12) . ?

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
O1 Mn1 Cl2 87.95(17) . . ?
O1 Mn1 Cl1 175.43(18) . . ?
Cl2 Mn1 Cl1 95.98(8) . . ?
O1 Mn1 Cl2 86.97(18) . 4_565 ?
Cl2 Mn1 Cl2 93.51(8) . 4_565 ?
Cl1 Mn1 Cl2 95.08(8) . 4_565 ?
O1 Mn1 Cl3 82.65(17) . 4_565 ?
Cl2 Mn1 Cl3 170.47(9) . 4_565 ?
Cl1 Mn1 Cl3 93.34(8) . 4_565 ?
Cl2 Mn1 Cl3 87.60(8) 4_565 4_565 ?
O1 Mn1 Cl3 87.28(18) . . ?
Cl2 Mn1 Cl3 87.59(8) . . ?
Cl1 Mn1 Cl3 90.56(8) . . ?
Cl2 Mn1 Cl3 174.11(9) 4_565 . ?
Cl3 Mn1 Cl3 90.37(8) 4_565 . ?
O3 Mn3 Cl7 89.10(17) . . ?
O3 Mn3 Cl7 89.31(18) . 4_576 ?
Cl7 Mn3 Cl7 93.33(8) . 4_576 ?
O3 Mn3 Cl8 172.67(17) . . ?
Cl7 Mn3 Cl8 94.81(8) . . ?
Cl7 Mn3 Cl8 96.64(9) 4_576 . ?
O3 Mn3 Cl9 81.99(17) . 4_576 ?
Cl7 Mn3 Cl9 170.98(9) . 4_576 ?
Cl7 Mn3 Cl9 88.03(7) 4_576 4_576 ?
Cl8 Mn3 Cl9 93.90(8) . 4_576 ?
O3 Mn3 Cl9 85.38(18) . . ?
Cl7 Mn3 Cl9 87.53(7) . . ?
Cl7 Mn3 Cl9 174.61(9) 4_576 . ?
Cl8 Mn3 Cl9 88.59(8) . . ?
Cl9 Mn3 Cl9 90.30(7) 4_576 . ?
Mn3 Cl9 Mn3 90.54(7) 4_575 . ?
Mn1 Cl3 Mn1 90.62(8) 4_566 . ?
Mn3 Cl7 Mn3 93.19(8) . 4_575 ?
Mn1 Cl2 Mn1 93.32(8) . 4_566 ?
O2 Mn2 Cl6 88.71(17) . 4_566 ?
O2 Mn2 Cl6 87.16(18) . . ?
Cl6 Mn2 Cl6 93.45(7) 4_566 . ?
O2 Mn2 Cl4 174.93(16) . . ?
Cl6 Mn2 Cl4 95.16(8) 4_566 . ?
Cl6 Mn2 Cl4 95.86(8) . . ?
O2 Mn2 Cl5 82.43(17) . 4_565 ?
Cl6 Mn2 Cl5 170.95(9) 4_566 4_565 ?
Cl6 Mn2 Cl5 88.01(7) . 4_565 ?
Cl4 Mn2 Cl5 93.58(7) . 4_565 ?
O2 Mn2 Cl5 87.01(17) . . ?
Cl6 Mn2 Cl5 87.65(7) 4_566 . ?
Cl6 Mn2 Cl5 174.04(8) . . ?
Cl4 Mn2 Cl5 89.88(7) . . ?
Cl5 Mn2 Cl5 90.00(7) 4_565 . ?
Mn2 Cl5 Mn2 90.25(7) 4_566 . ?
Mn2 Cl6 Mn2 93.38(7) 4_565 . ?
C3 N2 C2 103.8(8) . . ?
C1 C2 N2 112.4(9) . . ?
N1 C3 N2 109.3(9) . . ?
N1 C3 C4 126.5(10) . . ?
N2 C3 C4 124.1(9) . . ?
C2 C1 N1 102.8(9) . . ?
N3 C6 C5 105.9(8) . . ?
C7 N4 C5 111.2(8) . . ?
N4 C7 N3 107.3(8) . . ?
N4 C7 C8 128.8(8) . . ?
N3 C7 C8 123.2(8) . . ?
C3 N1 C1 111.0(9) . . ?
C6 N3 C7 109.7(7) . . ?
C6 C5 N4 104.7(8) . . ?
C10 N5 C11 109.9(7) . . ?
C9 C10 N5 107.8(8) . . ?
N6 C11 N5 102.9(7) . . ?
N6 C11 C12 129.6(9) . . ?
N5 C11 C12 125.5(8) . . ?
C11 N6 C9 110.3(8) . . ?
C10 C9 N6 107.0(8) . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O2 H2C Cl4 0.85 2.60 3.170(7) 125.8 4_565
O2 H2D Cl4 0.85 2.58 3.137(6) 124.4 2_655
O1 H1C Cl1 0.85 2.61 3.181(6) 125.4 4_565
O3 H3B Cl8 0.85 2.58 3.164(7) 126.9 4_576
O3 H3C Cl1 0.85 2.63 3.179(6) 123.3 1_565
N3 H3A O3 0.88 2.05 2.832(10) 147.0 1_545
N3 H3A Cl9 0.88 2.81 3.421(8) 127.5 1_545
N5 H5B Cl1 0.88 2.30 3.146(7) 161.9 1_655
N6 H6B O1 0.88 2.10 2.874(10) 146.4 2_645
N6 H6B Cl3 0.88 2.78 3.392(8) 127.7 2_645
O1 H1D Cl8 0.85 2.60 3.161(6) 124.3 .
N2 H2B Cl8 0.88 2.30 3.126(9) 156.8 .
N2 H2B Cl9 0.88 2.98 3.495(8) 119.4 .
N4 H4D Cl4 0.88 2.35 3.163(8) 152.8 .
N4 H4D Cl5 0.88 2.98 3.512(9) 120.5 .
N1 H1B O2 0.88 2.25 2.950(11) 136.4 .
N1 H1B Cl5 0.88 2.65 3.349(9) 137.5 .

_diffrn_measured_fraction_theta_max 0.980
_diffrn_reflns_theta_full        27.46
_diffrn_measured_fraction_theta_full 0.980
_refine_diff_density_max         2.495
_refine_diff_density_min         -1.389
_refine_diff_density_rms         0.304
