# Electronic Supplementary Material (ESI) for CrystEngComm.
# This journal is © The Royal Society of Chemistry 2014

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_c:\cz207\cz207

_audit_creation_method           SHELXL-97
_chemical_name_common            
(dimethylammonium)(manganese(II)-(benezenetetrasulfonate))(dimethylfornamide)
_chemical_formula_moiety         'C12 H16 Mn N2 O14 S4, 2(C2 H8 N)'
_chemical_formula_sum            'C16 H32 Mn N4 O14 S4'
_chemical_formula_weight         687.64

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0033 0.0016 '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'
S S 0.1246 0.1234 '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'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'P 21/c'
_symmetry_space_group_name_Hall  '-P 2ybc'

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                   9.4202(5)
_cell_length_b                   16.8486(6)
_cell_length_c                   9.1845(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 97.746(6)
_cell_angle_gamma                90.00
_cell_volume                     1444.44(12)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       blocks
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.14
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.581
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             714
_exptl_absorpt_coefficient_mu    0.815
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.8739
_exptl_absorpt_correction_T_max  0.8945
_exptl_absorpt_process_details   'X-RED 1.22 (Stoe & Cie 2001)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(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  'IPDS-I, Stoe & Cie'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            22160
_diffrn_reflns_av_R_equivalents  0.0668
_diffrn_reflns_av_sigmaI/netI    0.0514
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         3.15
_diffrn_reflns_theta_max         28.25
_reflns_number_total             3560
_reflns_number_gt                2330
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'IPDS I (Stoe & Cie)'
_computing_cell_refinement       'IPDS I (Stoe & Cie)'
_computing_data_reduction        'X-RED 1.22 (Stoe & Cie 2001)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Diamond 3.2e (Brandenburg 2010)'
_computing_publication_material  'SHELX-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)+(0.0485P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3560
_refine_ls_number_parameters     194
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0643
_refine_ls_R_factor_gt           0.0357
_refine_ls_wR_factor_ref         0.0837
_refine_ls_wR_factor_gt          0.0771
_refine_ls_goodness_of_fit_ref   0.870
_refine_ls_restrained_S_all      0.870
_refine_ls_shift/su_max          0.001
_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 0.5000 0.0000 0.0000 0.03834(14) Uani 1 2 d S . .
S1 S 0.24060(5) -0.13395(3) 0.01233(6) 0.03024(13) Uani 1 1 d . . .
O11 O 0.35589(15) -0.09845(11) -0.05772(19) 0.0419(4) Uani 1 1 d . . .
O12 O 0.2831(2) -0.15655(11) 0.16239(18) 0.0478(4) Uani 1 1 d . . .
O13 O 0.17105(16) -0.19665(10) -0.07879(18) 0.0393(4) Uani 1 1 d . . .
S2 S 0.26749(5) 0.03110(3) 0.25076(6) 0.03220(14) Uani 1 1 d . . .
O14 O 0.40072(15) 0.00920(11) 0.19730(18) 0.0426(4) Uani 1 1 d . . .
O15 O 0.25629(18) 0.11430(11) 0.2777(2) 0.0527(5) Uani 1 1 d . . .
O16 O 0.2422(2) -0.01724(12) 0.37439(18) 0.0487(5) Uani 1 1 d . . .
C1 C 0.1092(2) -0.05686(12) 0.0125(2) 0.0263(4) Uani 1 1 d . . .
C2 C 0.12239(19) 0.00926(12) 0.1063(2) 0.0259(4) Uani 1 1 d . . .
C3 C 0.0121(2) 0.06475(13) 0.0909(2) 0.0268(4) Uani 1 1 d . . .
H31 H 0.0197 0.1089 0.1523 0.032 Uiso 1 1 calc R . .
O1 O 0.34271(19) 0.08203(13) -0.1093(2) 0.0593(5) Uani 1 1 d . . .
C11 C 0.2596(3) 0.07830(18) -0.2229(4) 0.0522(7) Uani 1 1 d . . .
H111 H 0.270(4) 0.032(2) -0.297(4) 0.083(11) Uiso 1 1 d . . .
N1 N 0.1603(2) 0.13131(14) -0.2661(3) 0.0495(5) Uani 1 1 d . . .
C12 C 0.0654(4) 0.1208(3) -0.4050(4) 0.0903(12) Uani 1 1 d . . .
H121 H 0.0727 0.1663 -0.4666 0.108 Uiso 1 1 calc R . .
H122 H -0.0316 0.1153 -0.3854 0.108 Uiso 1 1 calc R . .
H123 H 0.0931 0.0741 -0.4538 0.108 Uiso 1 1 calc R . .
C13 C 0.1372(4) 0.2001(2) -0.1802(5) 0.0852(11) Uani 1 1 d . . .
H131 H 0.0364 0.2068 -0.1774 0.102 Uiso 1 1 calc R . .
H132 H 0.1742 0.2462 -0.2238 0.102 Uiso 1 1 calc R . .
H133 H 0.1854 0.1935 -0.0821 0.102 Uiso 1 1 calc R . .
N2 N 0.3616(3) -0.16656(16) 0.4634(2) 0.0464(5) Uani 1 1 d . . .
H21 H 0.297(3) -0.206(2) 0.428(4) 0.066(9) Uiso 1 1 d . . .
H22 H 0.338(4) -0.116(3) 0.410(4) 0.093(12) Uiso 1 1 d . . .
C21 C 0.5067(3) -0.1935(3) 0.4448(4) 0.0795(11) Uani 1 1 d . . .
H211 H 0.5129 -0.2007 0.3422 0.095 Uiso 1 1 calc R . .
H212 H 0.5264 -0.2429 0.4955 0.095 Uiso 1 1 calc R . .
H213 H 0.5754 -0.1544 0.4846 0.095 Uiso 1 1 calc R . .
C22 C 0.3457(4) -0.14814(19) 0.6172(3) 0.0636(8) Uani 1 1 d . . .
H221 H 0.2474 -0.1355 0.6240 0.076 Uiso 1 1 calc R . .
H222 H 0.4052 -0.1036 0.6499 0.076 Uiso 1 1 calc R . .
H223 H 0.3740 -0.1933 0.6779 0.076 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 O14 2.1539(16) . ?
Mn1 O14 2.1539(16) 3_655 ?
Mn1 O11 2.1636(16) . ?
Mn1 O11 2.1636(16) 3_655 ?
Mn1 O1 2.1707(19) . ?
Mn1 O1 2.1708(19) 3_655 ?
S1 O12 1.4339(17) . ?
S1 O13 1.4484(16) . ?
S1 O11 1.4628(17) . ?
S1 C1 1.794(2) . ?
S2 O15 1.4298(19) . ?
S2 O16 1.4430(19) . ?
S2 O14 1.4556(16) . ?
S2 C2 1.810(2) . ?
C1 C3 1.390(3) 3 ?
C1 C2 1.403(3) . ?
C2 C3 1.391(3) . ?
C3 C1 1.390(3) 3 ?
C3 H31 0.9300 . ?
O1 C11 1.219(4) . ?
C11 N1 1.315(3) . ?
C11 H111 1.04(4) . ?
N1 C13 1.436(4) . ?
N1 C12 1.466(4) . ?
C12 H121 0.9600 . ?
C12 H122 0.9600 . ?
C12 H123 0.9600 . ?
C13 H131 0.9600 . ?
C13 H132 0.9600 . ?
C13 H133 0.9600 . ?
N2 C21 1.471(4) . ?
N2 C22 1.474(3) . ?
N2 H21 0.93(4) . ?
N2 H22 1.00(4) . ?
C21 H211 0.9600 . ?
C21 H212 0.9600 . ?
C21 H213 0.9600 . ?
C22 H221 0.9600 . ?
C22 H222 0.9600 . ?
C22 H223 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
O14 Mn1 O14 180.0 . 3_655 ?
O14 Mn1 O11 86.11(6) . . ?
O14 Mn1 O11 93.89(6) 3_655 . ?
O14 Mn1 O11 93.89(6) . 3_655 ?
O14 Mn1 O11 86.11(6) 3_655 3_655 ?
O11 Mn1 O11 180.0 . 3_655 ?
O14 Mn1 O1 89.79(7) . . ?
O14 Mn1 O1 90.21(7) 3_655 . ?
O11 Mn1 O1 90.47(7) . . ?
O11 Mn1 O1 89.53(7) 3_655 . ?
O14 Mn1 O1 90.21(7) . 3_655 ?
O14 Mn1 O1 89.79(7) 3_655 3_655 ?
O11 Mn1 O1 89.53(7) . 3_655 ?
O11 Mn1 O1 90.47(7) 3_655 3_655 ?
O1 Mn1 O1 180.0 . 3_655 ?
O12 S1 O13 114.06(11) . . ?
O12 S1 O11 113.81(11) . . ?
O13 S1 O11 110.42(10) . . ?
O12 S1 C1 107.14(10) . . ?
O13 S1 C1 105.67(9) . . ?
O11 S1 C1 104.93(10) . . ?
S1 O11 Mn1 133.17(10) . . ?
O15 S2 O16 113.17(12) . . ?
O15 S2 O14 113.20(11) . . ?
O16 S2 O14 111.33(11) . . ?
O15 S2 C2 105.07(10) . . ?
O16 S2 C2 105.89(10) . . ?
O14 S2 C2 107.54(9) . . ?
S2 O14 Mn1 142.56(11) . . ?
C3 C1 C2 119.47(18) 3 . ?
C3 C1 S1 115.69(15) 3 . ?
C2 C1 S1 124.84(15) . . ?
C3 C2 C1 117.93(17) . . ?
C3 C2 S2 114.69(15) . . ?
C1 C2 S2 127.37(15) . . ?
C1 C3 C2 122.60(19) 3 . ?
C1 C3 H31 118.7 3 . ?
C2 C3 H31 118.7 . . ?
C11 O1 Mn1 133.0(2) . . ?
O1 C11 N1 124.9(3) . . ?
O1 C11 H111 120(2) . . ?
N1 C11 H111 115(2) . . ?
C11 N1 C13 122.5(3) . . ?
C11 N1 C12 120.4(3) . . ?
C13 N1 C12 117.1(3) . . ?
N1 C12 H121 109.5 . . ?
N1 C12 H122 109.5 . . ?
H121 C12 H122 109.5 . . ?
N1 C12 H123 109.5 . . ?
H121 C12 H123 109.5 . . ?
H122 C12 H123 109.5 . . ?
N1 C13 H131 109.5 . . ?
N1 C13 H132 109.5 . . ?
H131 C13 H132 109.5 . . ?
N1 C13 H133 109.5 . . ?
H131 C13 H133 109.5 . . ?
H132 C13 H133 109.5 . . ?
C21 N2 C22 113.1(3) . . ?
C21 N2 H21 108(2) . . ?
C22 N2 H21 110(2) . . ?
C21 N2 H22 111(2) . . ?
C22 N2 H22 105(2) . . ?
H21 N2 H22 110(3) . . ?
N2 C21 H211 109.5 . . ?
N2 C21 H212 109.5 . . ?
H211 C21 H212 109.5 . . ?
N2 C21 H213 109.5 . . ?
H211 C21 H213 109.5 . . ?
H212 C21 H213 109.5 . . ?
N2 C22 H221 109.5 . . ?
N2 C22 H222 109.5 . . ?
H221 C22 H222 109.5 . . ?
N2 C22 H223 109.5 . . ?
H221 C22 H223 109.5 . . ?
H222 C22 H223 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
O12 S1 O11 Mn1 -53.93(18) . . . . ?
O13 S1 O11 Mn1 176.30(12) . . . . ?
C1 S1 O11 Mn1 62.87(15) . . . . ?
O14 Mn1 O11 S1 3.14(15) . . . . ?
O14 Mn1 O11 S1 -176.87(15) 3_655 . . . ?
O1 Mn1 O11 S1 -86.63(15) . . . . ?
O1 Mn1 O11 S1 93.37(15) 3_655 . . . ?
O15 S2 O14 Mn1 -85.25(19) . . . . ?
O16 S2 O14 Mn1 145.93(17) . . . . ?
C2 S2 O14 Mn1 30.4(2) . . . . ?
O11 Mn1 O14 S2 -69.73(19) . . . . ?
O11 Mn1 O14 S2 110.27(19) 3_655 . . . ?
O1 Mn1 O14 S2 20.75(19) . . . . ?
O1 Mn1 O14 S2 -159.24(19) 3_655 . . . ?
O12 S1 C1 C3 -134.26(17) . . . 3 ?
O13 S1 C1 C3 -12.28(18) . . . 3 ?
O11 S1 C1 C3 104.45(16) . . . 3 ?
O12 S1 C1 C2 46.8(2) . . . . ?
O13 S1 C1 C2 168.73(18) . . . . ?
O11 S1 C1 C2 -74.53(19) . . . . ?
C3 C1 C2 C3 -0.1(3) 3 . . . ?
S1 C1 C2 C3 178.81(15) . . . . ?
C3 C1 C2 S2 178.64(15) 3 . . . ?
S1 C1 C2 S2 -2.4(3) . . . . ?
O15 S2 C2 C3 -20.52(19) . . . . ?
O16 S2 C2 C3 99.51(17) . . . . ?
O14 S2 C2 C3 -141.38(16) . . . . ?
O15 S2 C2 C1 160.67(19) . . . . ?
O16 S2 C2 C1 -79.3(2) . . . . ?
O14 S2 C2 C1 39.8(2) . . . . ?
C1 C2 C3 C1 0.1(3) . . . 3 ?
S2 C2 C3 C1 -178.79(16) . . . 3 ?
O14 Mn1 O1 C11 -125.5(3) . . . . ?
O14 Mn1 O1 C11 54.5(3) 3_655 . . . ?
O11 Mn1 O1 C11 -39.4(3) . . . . ?
O11 Mn1 O1 C11 140.6(3) 3_655 . . . ?
Mn1 O1 C11 N1 172.87(19) . . . . ?
O1 C11 N1 C13 -1.3(4) . . . . ?
O1 C11 N1 C12 -179.8(3) . . . . ?

_diffrn_measured_fraction_theta_max 0.994
_diffrn_reflns_theta_full        28.25
_diffrn_measured_fraction_theta_full 0.994
_refine_diff_density_max         0.624
_refine_diff_density_min         -0.261
_refine_diff_density_rms         0.067
_database_code_depnum_ccdc_archive 'CCDC 951310'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_c:\cz211a\cz211a

_audit_creation_method           SHELXL-97
_chemical_name_common            
(hydroxymethyldihydropyrrolium)(manganese(II)-(benezenetetrasulfonate))(N-methylpyrrolidone)
_chemical_formula_sum            'C26 H40 Mn N4 O16 S4'
_chemical_formula_weight         847.80

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'
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      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   9.3170(7)
_cell_length_b                   10.4919(7)
_cell_length_c                   19.4487(12)
_cell_angle_alpha                90
_cell_angle_beta                 113.529(3)
_cell_angle_gamma                90
_cell_volume                     1743.1(2)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    ?
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      ?
_cell_measurement_theta_min      ?
_exptl_absorpt_coefficient_mu    0.697
_exptl_absorpt_correction_T_max  0.935
_exptl_absorpt_correction_T_min  0.863
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.615
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needles
_exptl_crystal_F_000             882
_exptl_crystal_size_max          0.218
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.098
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_unetI/netI     0.0384
_diffrn_reflns_Laue_measured_fraction_full 0.970
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            77638
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.875
_diffrn_reflns_theta_min         2.252
_diffrn_ambient_temperature      120.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.970
_diffrn_measured_fraction_theta_max 0.962
_diffrn_measurement_device_type  ?
_diffrn_measurement_method       ?
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4016
_reflns_number_total             5757
_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       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_refine_diff_density_max         1.104
_refine_diff_density_min         -0.465
_refine_diff_density_rms         0.084
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     320
_refine_ls_number_reflns         5757
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0818
_refine_ls_R_factor_gt           0.0501
_refine_ls_restrained_S_all      1.029
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0781P)²+0.9186P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1310
_refine_ls_wR_factor_ref         0.1484
_refine_special_details          
;
 ?
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O2-H2
 0.85 with sigma of 0.001
 C22A-C23A
 1.5 with sigma of 0.001
3. Others
 Fixed Sof: O11(0.6) O12(0.6) O13(0.6) O14(0.6) O15(0.6) O16(0.6) O11A(0.4)
 O12A(0.4) O13A(0.4) O14A(0.4) O15A(0.4) O16A(0.4) O2(0.7) H2(0.7) C21(0.7)
 C22(0.7) H22a(0.7) H22b(0.7) C23(0.7) H23a(0.7) H23b(0.7) C24(0.7) H24a(0.7)
 H24b(0.7) N2(0.7) C25(0.7) H25a(0.7) H25b(0.7) H25c(0.7) O2A(0.3) C21A(0.3)
 C22A(0.3) C23A(0.3) C24A(0.3) N2A(0.3) C25A(0.3)
4.a Secondary CH2 refined with riding coordinates:
 C12(H12a,H12b), C13(H13a,H13b), C14(H14a,H14b), C22(H22a,H22b), C23(H23a,
 H23b), C24(H24a,H24b)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3)
4.c Idealised Me refined as rotating group:
 C15(H15a,H15b,H15c), C25(H25a,H25b,H25c)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_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
Mn1 Mn -0.5000 -0.5000 -0.5000 0.03169(14) Uani 1 2 d S T P A .
S1 S -0.20067(7) -0.71239(5) -0.45955(3) 0.02803(14) Uani 1 1 d . . . A .
S2 S -0.34043(6) -0.54191(5) -0.62995(3) 0.02593(13) Uani 1 1 d . . . A .
C1 C -0.0957(2) -0.59116(18) -0.48621(11) 0.0202(4) Uani 1 1 d . . . A .
C2 C -0.1511(2) -0.52547(18) -0.55482(11) 0.0202(4) Uani 1 1 d . . . A .
C3 C -0.0530(2) -0.43617(18) -0.56686(11) 0.0207(4) Uani 1 1 d . . . A .
H3 H -0.0894 -0.3921 -0.6134 0.025 Uiso 1 1 calc R . . A .
O11 O -0.3212(5) -0.6444(4) -0.44421(19) 0.0315(8) Uani 0.6 1 d . . . B 1
O12 O -0.2639(5) -0.7990(4) -0.5219(2) 0.0369(8) Uani 0.6 1 d . . . C 1
O13 O -0.0855(5) -0.7686(4) -0.3927(3) 0.0356(9) Uani 0.6 1 d . . . D 1
O14 O -0.4531(3) -0.5498(3) -0.59794(15) 0.0303(6) Uani 0.6 1 d . . . E 1
O15 O -0.3330(4) -0.6632(3) -0.66860(17) 0.0304(6) Uani 0.6 1 d . . . F 1
O16 O -0.3577(5) -0.4358(3) -0.6788(2) 0.0319(8) Uani 0.6 1 d . . . G 1
O11A O -0.3576(7) -0.6622(7) -0.4780(4) 0.0432(15) Uani 0.4 1 d . . . A 2
O12A O -0.1977(8) -0.8234(6) -0.5019(5) 0.0479(17) Uani 0.4 1 d . . . A 2
O13A O -0.1176(9) -0.7229(7) -0.3796(5) 0.0502(18) Uani 0.4 1 d . . . A 2
O14A O -0.4476(6) -0.4711(5) -0.6007(3) 0.0426(12) Uani 0.4 1 d . . . A 2
O15A O -0.3859(8) -0.6712(5) -0.6385(4) 0.0623(18) Uani 0.4 1 d . . . A 2
O16A O -0.3301(8) -0.4785(5) -0.6917(4) 0.0365(14) Uani 0.4 1 d . . . A 2
O1 O -0.3198(2) -0.3560(2) -0.46676(12) 0.0458(5) Uani 1 1 d . . . . .
C11 C -0.2125(3) -0.3320(3) -0.40559(16) 0.0441(7) Uani 1 1 d . . . . .
C12 C -0.1772(4) -0.4061(4) -0.33248(18) 0.0612(10) Uani 1 1 d . . . . .
H12A H -0.2529 -0.3838 -0.3104 0.073 Uiso 1 1 calc R . . . .
H12B H -0.1817 -0.4992 -0.3416 0.073 Uiso 1 1 calc R . . . .
C13 C -0.0143(4) -0.3655(5) -0.2818(2) 0.0775(13) Uani 1 1 d . . . . .
H13A H 0.0648 -0.4258 -0.2848 0.093 Uiso 1 1 calc R . . . .
H13B H -0.0028 -0.3596 -0.2291 0.093 Uiso 1 1 calc R . . . .
C14 C 0.0019(5) -0.2320(5) -0.3131(3) 0.0866(16) Uani 1 1 d . . . . .
H14A H -0.0276 -0.1629 -0.2866 0.104 Uiso 1 1 calc R . . . .
H14B H 0.1098 -0.2172 -0.3092 0.104 Uiso 1 1 calc R . . . .
N1 N -0.1080(3) -0.2416(3) -0.39049(19) 0.0633(9) Uani 1 1 d . . . . .
C15 C -0.1094(5) -0.1478(4) -0.4487(3) 0.0776(13) Uani 1 1 d . . . . .
H15A H -0.0148 -0.1587 -0.4585 0.116 Uiso 1 1 calc GR . . . .
H15B H -0.1123 -0.0610 -0.4306 0.116 Uiso 1 1 calc GR . . . .
H15C H -0.2021 -0.1623 -0.4950 0.116 Uiso 1 1 calc GR . . . .
O2 O 0.6720(3) -0.6052(2) -0.16779(15) 0.0324(5) Uani 0.7 1 d D . . H 1
H2 H 0.649(5) -0.6812(16) -0.161(3) 0.061(15) Uiso 0.7 1 d D . . I 1
C21 C 0.5764(6) -0.5344(4) -0.1538(2) 0.0240(8) Uani 0.7 1 d . . . H 1
C22 C 0.4374(4) -0.5773(3) -0.1381(2) 0.0339(7) Uani 0.7 1 d . . . H 1
H22A H 0.4683 -0.6427 -0.0981 0.041 Uiso 0.7 1 calc R . . H 1
H22B H 0.3537 -0.6124 -0.1838 0.041 Uiso 0.7 1 calc R . . H 1
C23 C 0.3839(10) -0.4547(7) -0.1129(4) 0.0593(18) Uani 0.7 1 d . . . H 1
H23A H 0.2682 -0.4493 -0.1339 0.071 Uiso 0.7 1 calc R . . H 1
H23B H 0.4240 -0.4506 -0.0575 0.071 Uiso 0.7 1 calc R . . H 1
C24 C 0.4523(8) -0.3487(4) -0.1430(3) 0.0585(15) Uani 0.7 1 d . . . H 1
H24A H 0.3744 -0.3152 -0.1910 0.070 Uiso 0.7 1 calc R . . H 1
H24B H 0.4910 -0.2780 -0.1065 0.070 Uiso 0.7 1 calc R . . H 1
N2 N 0.5830(4) -0.4139(3) -0.15395(16) 0.0312(6) Uani 0.7 1 d . . . H 1
C25 C 0.6994(9) -0.3466(5) -0.1717(4) 0.068(2) Uani 0.7 1 d . . . H 1
H25A H 0.7728 -0.3037 -0.1266 0.101 Uiso 0.7 1 calc GR . . H 1
H25B H 0.6477 -0.2832 -0.2108 0.101 Uiso 0.7 1 calc GR . . H 1
H25C H 0.7565 -0.4073 -0.1896 0.101 Uiso 0.7 1 calc GR . . H 1
O2A O 0.4788(14) -0.6484(11) -0.1460(6) 0.085(3) Uiso 0.3 1 d . . . J 2
C21A C 0.5390(15) -0.5428(12) -0.1494(8) 0.031(3) Uiso 0.3 1 d . . . J 2
C22A C 0.6795(19) -0.5192(12) -0.1661(8) 0.069(3) Uiso 0.3 1 d D . . J 2
C23A C 0.673(3) -0.3763(12) -0.1677(16) 0.098(8) Uiso 0.3 1 d D . . J 2
C24A C 0.537(2) -0.3317(18) -0.1490(10) 0.082(5) Uiso 0.3 1 d . . . J 2
N2A N 0.4697(19) -0.4386(15) -0.1404(9) 0.090(4) Uiso 0.3 1 d . . . J 2
C25A C 0.336(4) -0.447(4) -0.1254(19) 0.121(12) Uiso 0.3 1 d . . . J 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 O11A 2.095(7) 3_444 ?
Mn1 O11A 2.095(7) . ?
Mn1 O14A 2.220(6) . ?
Mn1 O14A 2.221(6) 3_444 ?
Mn1 O1 2.156(2) . ?
Mn1 O1 2.156(2) 3_444 ?
S1 C1 1.802(2) . ?
S1 O11A 1.458(7) . ?
S1 O12A 1.433(8) . ?
S1 O13A 1.438(9) . ?
S2 C2 1.794(2) . ?
S2 O14A 1.525(6) . ?
S2 O15A 1.412(5) . ?
S2 O16A 1.410(7) . ?
C1 C2 1.404(3) . ?
C1 C3 1.388(3) 3_544 ?
C2 C3 1.393(3) . ?
C3 C1 1.388(3) 3_544 ?
C3 H3 0.9500 . ?
O1 C11 1.237(3) . ?
C11 C12 1.537(5) . ?
C11 N1 1.307(4) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C12 C13 1.504(5) . ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?
C13 C14 1.559(7) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C14 N1 1.447(5) . ?
N1 C15 1.495(6) . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?
O2 H2 0.8500(10) . ?
O2 C21 1.270(5) . ?
C21 C22 1.512(6) . ?
C21 N2 1.267(5) . ?
C22 H22A 0.9900 . ?
C22 H22B 0.9900 . ?
C22 C23 1.530(7) . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?
C23 C24 1.511(10) . ?
C24 H24A 0.9900 . ?
C24 H24B 0.9900 . ?
C24 N2 1.484(6) . ?
N2 C25 1.446(7) . ?
C25 H25A 0.9800 . ?
C25 H25B 0.9800 . ?
C25 H25C 0.9800 . ?
O2A C21A 1.255(16) . ?
C21A C22A 1.490(19) . ?
C21A N2A 1.32(2) . ?
C22A C23A 1.5003(10) . ?
C23A C24A 1.52(3) . ?
C24A N2A 1.33(2) . ?
N2A C25A 1.39(4) . ?

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
O11A Mn1 O11A 180.0 3_444 . ?
O11A Mn1 O14A 93.0(2) . 3_444 ?
O11A Mn1 O14A 87.0(2) . . ?
O11A Mn1 O14A 87.0(2) 3_444 3_444 ?
O11A Mn1 O14A 93.0(2) 3_444 . ?
O11A Mn1 O1 98.86(19) 3_444 3_444 ?
O11A Mn1 O1 98.87(19) . . ?
O11A Mn1 O1 81.14(19) . 3_444 ?
O11A Mn1 O1 81.14(19) 3_444 . ?
O14A Mn1 O14A 180.0 . 3_444 ?
O1 Mn1 O14A 104.48(16) 3_444 . ?
O1 Mn1 O14A 104.48(16) . 3_444 ?
O1 Mn1 O14A 75.52(16) 3_444 3_444 ?
O1 Mn1 O14A 75.52(16) . . ?
O1 Mn1 O1 180.0 3_444 . ?
O11A S1 C1 106.3(3) . . ?
O12A S1 C1 105.7(3) . . ?
O12A S1 O11A 113.6(4) . . ?
O12A S1 O13A 115.7(4) . . ?
O13A S1 C1 104.2(3) . . ?
O13A S1 O11A 110.3(4) . . ?
O14A S2 C2 103.1(2) . . ?
O15A S2 C2 109.9(3) . . ?
O15A S2 O14A 107.6(4) . . ?
O16A S2 C2 105.6(3) . . ?
O16A S2 O14A 111.4(3) . . ?
O16A S2 O15A 118.2(4) . . ?
C2 C1 S1 125.73(15) . . ?
C3 C1 S1 115.28(14) 3_544 . ?
C3 C1 C2 118.99(18) 3_544 . ?
C1 C2 S2 126.57(15) . . ?
C3 C2 S2 115.21(14) . . ?
C3 C2 C1 118.22(18) . . ?
C1 C3 C2 122.79(18) 3_544 . ?
C1 C3 H3 118.6 3_544 . ?
C2 C3 H3 118.6 . . ?
S1 O11A Mn1 146.6(4) . . ?
S2 O14A Mn1 132.0(3) . . ?
C11 O1 Mn1 131.7(2) . . ?
O1 C11 C12 125.4(3) . . ?
O1 C11 N1 127.5(3) . . ?
N1 C11 C12 107.1(3) . . ?
C11 C12 H12A 110.9 . . ?
C11 C12 H12B 110.9 . . ?
H12A C12 H12B 108.9 . . ?
C13 C12 C11 104.5(3) . . ?
C13 C12 H12A 110.9 . . ?
C13 C12 H12B 110.9 . . ?
C12 C13 H13A 111.1 . . ?
C12 C13 H13B 111.1 . . ?
C12 C13 C14 103.2(3) . . ?
H13A C13 H13B 109.1 . . ?
C14 C13 H13A 111.1 . . ?
C14 C13 H13B 111.1 . . ?
C13 C14 H14A 111.4 . . ?
C13 C14 H14B 111.4 . . ?
H14A C14 H14B 109.3 . . ?
N1 C14 C13 101.9(3) . . ?
N1 C14 H14A 111.4 . . ?
N1 C14 H14B 111.4 . . ?
C11 N1 C14 116.0(4) . . ?
C11 N1 C15 121.8(3) . . ?
C14 N1 C15 122.0(3) . . ?
N1 C15 H15A 109.5 . . ?
N1 C15 H15B 109.5 . . ?
N1 C15 H15C 109.5 . . ?
H15A C15 H15B 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
C21 O2 H2 106(3) . . ?
O2 C21 C22 126.9(4) . . ?
N2 C21 O2 123.0(4) . . ?
N2 C21 C22 110.1(4) . . ?
C21 C22 H22A 111.1 . . ?
C21 C22 H22B 111.1 . . ?
C21 C22 C23 103.3(4) . . ?
H22A C22 H22B 109.1 . . ?
C23 C22 H22A 111.1 . . ?
C23 C22 H22B 111.1 . . ?
C22 C23 H23A 110.8 . . ?
C22 C23 H23B 110.8 . . ?
H23A C23 H23B 108.9 . . ?
C24 C23 C22 104.6(4) . . ?
C24 C23 H23A 110.8 . . ?
C24 C23 H23B 110.8 . . ?
C23 C24 H24A 111.3 . . ?
C23 C24 H24B 111.3 . . ?
H24A C24 H24B 109.2 . . ?
N2 C24 C23 102.4(3) . . ?
N2 C24 H24A 111.3 . . ?
N2 C24 H24B 111.3 . . ?
C21 N2 C24 114.6(4) . . ?
C21 N2 C25 122.0(4) . . ?
C25 N2 C24 123.1(4) . . ?
N2 C25 H25A 109.5 . . ?
N2 C25 H25B 109.5 . . ?
N2 C25 H25C 109.5 . . ?
H25A C25 H25B 109.5 . . ?
H25A C25 H25C 109.5 . . ?
H25B C25 H25C 109.5 . . ?
O2A C21A C22A 127.4(13) . . ?
O2A C21A N2A 118.3(13) . . ?
N2A C21A C22A 114.3(12) . . ?
C21A C22A C23A 97.9(15) . . ?
C22A C23A C24A 109.5(19) . . ?
N2A C24A C23A 104.3(17) . . ?
C21A N2A C24A 114.0(17) . . ?
C21A N2A C25A 120(2) . . ?
C24A N2A C25A 126(2) . . ?

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
Mn1 O1 C11 C12 0.9(4) . . . . ?
Mn1 O1 C11 N1 -179.8(2) . . . . ?
S1 C1 C2 S2 2.6(3) . . . . ?
S1 C1 C2 C3 -178.67(15) . . . . ?
S2 C2 C3 C1 178.17(16) . . . 3_544 ?
C1 S1 O11A Mn1 -20.5(8) . . . . ?
C1 C2 C3 C1 -0.7(3) . . . 3_544 ?
C2 S2 O14A Mn1 -59.6(4) . . . . ?
C3 C1 C2 S2 -178.04(15) 3_544 . . . ?
C3 C1 C2 C3 0.7(3) 3_544 . . . ?
O11A S1 C1 C2 -47.5(3) . . . . ?
O11A S1 C1 C3 133.2(3) . . . 3_544 ?
O12A S1 C1 C2 73.5(3) . . . . ?
O12A S1 C1 C3 -105.8(3) . . . 3_544 ?
O12A S1 O11A Mn1 -136.3(8) . . . . ?
O13A S1 C1 C2 -164.1(3) . . . . ?
O13A S1 C1 C3 16.6(3) . . . 3_544 ?
O13A S1 O11A Mn1 91.9(8) . . . . ?
O14A S2 C2 C1 74.9(3) . . . . ?
O14A S2 C2 C3 -103.8(3) . . . . ?
O15A S2 C2 C1 -39.5(4) . . . . ?
O15A S2 C2 C3 141.8(4) . . . . ?
O15A S2 O14A Mn1 56.5(5) . . . . ?
O16A S2 C2 C1 -168.0(3) . . . . ?
O16A S2 C2 C3 13.2(3) . . . . ?
O16A S2 O14A Mn1 -172.4(4) . . . . ?
O1 C11 C12 C13 164.4(3) . . . . ?
O1 C11 N1 C14 177.9(3) . . . . ?
O1 C11 N1 C15 2.2(5) . . . . ?
C11 C12 C13 C14 24.9(4) . . . . ?
C12 C11 N1 C14 -2.6(4) . . . . ?
C12 C11 N1 C15 -178.3(3) . . . . ?
C12 C13 C14 N1 -25.8(4) . . . . ?
C13 C14 N1 C11 18.4(4) . . . . ?
C13 C14 N1 C15 -166.0(3) . . . . ?
N1 C11 C12 C13 -15.1(4) . . . . ?
O2 C21 C22 C23 171.0(4) . . . . ?
O2 C21 N2 C24 174.7(4) . . . . ?
O2 C21 N2 C25 1.1(7) . . . . ?
C21 C22 C23 C24 20.5(6) . . . . ?
C22 C21 N2 C24 -2.9(5) . . . . ?
C22 C21 N2 C25 -176.5(4) . . . . ?
C22 C23 C24 N2 -21.6(6) . . . . ?
C23 C24 N2 C21 16.1(5) . . . . ?
C23 C24 N2 C25 -170.4(5) . . . . ?
N2 C21 C22 C23 -11.5(5) . . . . ?
O2A C21A C22A C23A 175.0(17) . . . . ?
O2A C21A N2A C24A -176.4(15) . . . . ?
O2A C21A N2A C25A 2(3) . . . . ?
C21A C22A C23A C24A 2(2) . . . . ?
C22A C21A N2A C24A 1(2) . . . . ?
C22A C21A N2A C25A 179(2) . . . . ?
C22A C23A C24A N2A -2(2) . . . . ?
C23A C24A N2A C21A 1(2) . . . . ?
C23A C24A N2A C25A -178(2) . . . . ?
N2A C21A C22A C23A -2.0(19) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_database_code_depnum_ccdc_archive 'CCDC 959360'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_c:\cz316\cz316

_audit_creation_method           SHELXL-97
_chemical_name_common            
'(manganese(II)-benzenedisulfonoc acid)(dimethylformamide)'
_chemical_formula_moiety         'C12 H18 Mn N2 O8 S2'
_chemical_formula_sum            'C12 H18 Mn N2 O8 S2'
_chemical_formula_weight         437.34

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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'

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   P-1
_symmetry_space_group_name_Hall  '-P 1'

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

_cell_length_a                   5.1430(7)
_cell_length_b                   9.2620(12)
_cell_length_c                   9.4020(13)
_cell_angle_alpha                93.552(8)
_cell_angle_beta                 99.993(7)
_cell_angle_gamma                99.237(7)
_cell_volume                     433.48(10)
_cell_formula_units_Z            1
_cell_measurement_temperature    120(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       plates
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.06
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.675
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             225
_exptl_absorpt_coefficient_mu    1.046
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.8972
_exptl_absorpt_correction_T_max  0.9447
_exptl_absorpt_process_details   'Bruker SAINT'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      120(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  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            9686
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_sigmaI/netI    0.0520
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         2.21
_diffrn_reflns_theta_max         33.78
_reflns_number_total             3443
_reflns_number_gt                2587
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.0317P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3443
_refine_ls_number_parameters     155
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0462
_refine_ls_R_factor_gt           0.0290
_refine_ls_wR_factor_ref         0.0670
_refine_ls_wR_factor_gt          0.0637
_refine_ls_goodness_of_fit_ref   0.956
_refine_ls_restrained_S_all      0.956
_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 0.0000 0.5000 0.5000 0.00983(7) Uani 1 2 d S . .
S1 S 0.58756(6) 0.71419(3) 0.65128(3) 0.01166(7) Uani 1 1 d . . .
O11 O 0.32232(17) 0.63366(9) 0.65915(9) 0.01331(18) Uani 1 1 d . . .
O12 O 0.72421(19) 0.63365(10) 0.55880(11) 0.0189(2) Uani 1 1 d . . .
O13 O 0.7448(2) 0.76489(11) 0.79317(10) 0.0220(2) Uani 1 1 d . . .
C1 C 0.5339(2) 0.87272(13) 0.56292(13) 0.0108(2) Uani 1 1 d . . .
C2 C 0.6781(3) 0.91501(14) 0.45652(15) 0.0159(2) Uani 1 1 d . . .
H21 H 0.7983 0.8564 0.4270 0.019 Uiso 1 1 calc R . .
C3 C 0.3554(3) 0.95570(14) 0.60660(15) 0.0165(3) Uani 1 1 d . . .
H31 H 0.2567 0.9245 0.6791 0.020 Uiso 1 1 calc R . .
O1 O 0.06537(19) 0.64632(10) 0.33579(10) 0.01669(19) Uani 1 1 d . . .
C11 C 0.2098(8) 0.6510(4) 0.2465(5) 0.0183(7) Uani 0.50 1 d P A 1
H111 H 0.3364 0.5863 0.2520 0.022 Uiso 0.50 1 calc PR A 1
N1 N 0.2030(11) 0.7402(4) 0.1418(5) 0.0176(8) Uani 0.50 1 d P A 1
C13 C 0.3827(7) 0.7418(4) 0.0382(4) 0.0362(8) Uani 0.50 1 d P A 1
H131 H 0.4898 0.8403 0.0438 0.043 Uiso 0.50 1 calc PR A 1
H132 H 0.2775 0.7157 -0.0600 0.043 Uiso 0.50 1 calc PR A 1
H133 H 0.5021 0.6706 0.0610 0.043 Uiso 0.50 1 calc PR A 1
C12 C 0.0244(8) 0.8467(4) 0.1322(4) 0.0252(8) Uani 0.50 1 d P A 1
H121 H -0.1096 0.8217 0.1933 0.038 Uiso 0.50 1 calc PR A 1
H123 H -0.0662 0.8455 0.0314 0.038 Uiso 0.50 1 calc PR A 1
H122 H 0.1280 0.9449 0.1656 0.038 Uiso 0.50 1 calc PR A 1
C11A C 0.1348(7) 0.6079(4) 0.2175(4) 0.0149(7) Uani 0.50 1 d P A 2
H114 H 0.1596 0.5091 0.2022 0.018 Uiso 0.50 1 calc PR A 2
N1A N 0.1745(10) 0.6944(4) 0.1154(5) 0.0161(7) Uani 0.50 1 d P A 2
C13A C 0.2500(6) 0.6412(4) -0.0189(3) 0.0256(6) Uani 0.50 1 d P A 2
H134 H 0.1207 0.6601 -0.1022 0.031 Uiso 0.50 1 calc PR A 2
H135 H 0.2504 0.5353 -0.0196 0.031 Uiso 0.50 1 calc PR A 2
H136 H 0.4295 0.6924 -0.0247 0.031 Uiso 0.50 1 calc PR A 2
C12A C 0.1510(8) 0.8490(4) 0.1297(4) 0.0233(8) Uani 0.50 1 d P A 2
H124 H 0.0136 0.8686 0.0507 0.028 Uiso 0.50 1 calc PR A 2
H125 H 0.3235 0.9097 0.1252 0.028 Uiso 0.50 1 calc PR A 2
H126 H 0.1001 0.8729 0.2230 0.028 Uiso 0.50 1 calc PR 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
Mn1 O12 2.1449(9) 2_666 ?
Mn1 O12 2.1449(9) 1_455 ?
Mn1 O1 2.1509(9) . ?
Mn1 O1 2.1509(9) 2_566 ?
Mn1 O11 2.1841(9) . ?
Mn1 O11 2.1841(9) 2_566 ?
S1 O13 1.4424(10) . ?
S1 O12 1.4514(10) . ?
S1 O11 1.4621(9) . ?
S1 C1 1.7675(12) . ?
O12 Mn1 2.1450(9) 1_655 ?
C1 C2 1.3843(18) . ?
C1 C3 1.3858(18) . ?
C2 C3 1.3909(18) 2_676 ?
C2 H21 0.9500 . ?
C3 C2 1.3908(18) 2_676 ?
C3 H31 0.9500 . ?
O1 C11 1.212(5) . ?
O1 C11A 1.272(4) . ?
C11 N1 1.324(7) . ?
C11 H111 0.9500 . ?
N1 C12 1.448(6) . ?
N1 C13 1.453(6) . ?
C13 H131 0.9800 . ?
C13 H132 0.9800 . ?
C13 H133 0.9800 . ?
C12 H121 0.9800 . ?
C12 H123 0.9800 . ?
C12 H122 0.9800 . ?
C11A N1A 1.310(7) . ?
C11A H114 0.9500 . ?
N1A C12A 1.457(5) . ?
N1A C13A 1.464(5) . ?
C13A H134 0.9800 . ?
C13A H135 0.9800 . ?
C13A H136 0.9800 . ?
C12A H124 0.9800 . ?
C12A H125 0.9800 . ?
C12A H126 0.9800 . ?

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
O12 Mn1 O12 180.0 2_666 1_455 ?
O12 Mn1 O1 93.09(4) 2_666 . ?
O12 Mn1 O1 86.91(4) 1_455 . ?
O12 Mn1 O1 86.91(4) 2_666 2_566 ?
O12 Mn1 O1 93.09(4) 1_455 2_566 ?
O1 Mn1 O1 180.00(5) . 2_566 ?
O12 Mn1 O11 90.16(4) 2_666 . ?
O12 Mn1 O11 89.84(4) 1_455 . ?
O1 Mn1 O11 91.86(4) . . ?
O1 Mn1 O11 88.14(4) 2_566 . ?
O12 Mn1 O11 89.84(4) 2_666 2_566 ?
O12 Mn1 O11 90.16(4) 1_455 2_566 ?
O1 Mn1 O11 88.14(3) . 2_566 ?
O1 Mn1 O11 91.86(4) 2_566 2_566 ?
O11 Mn1 O11 179.999(1) . 2_566 ?
O13 S1 O12 114.01(6) . . ?
O13 S1 O11 112.01(6) . . ?
O12 S1 O11 112.07(5) . . ?
O13 S1 C1 106.61(6) . . ?
O12 S1 C1 105.02(6) . . ?
O11 S1 C1 106.41(6) . . ?
S1 O11 Mn1 133.74(5) . . ?
S1 O12 Mn1 158.66(7) . 1_655 ?
C2 C1 C3 121.37(11) . . ?
C2 C1 S1 119.76(9) . . ?
C3 C1 S1 118.81(10) . . ?
C1 C2 C3 119.17(12) . 2_676 ?
C1 C2 H21 120.4 . . ?
C3 C2 H21 120.4 2_676 . ?
C1 C3 C2 119.46(12) . 2_676 ?
C1 C3 H31 120.3 . . ?
C2 C3 H31 120.3 2_676 . ?
C11 O1 Mn1 132.6(2) . . ?
C11A O1 Mn1 123.63(19) . . ?
O1 C11 N1 124.4(4) . . ?
O1 C11 H111 117.8 . . ?
N1 C11 H111 117.8 . . ?
C11 N1 C12 120.4(4) . . ?
C11 N1 C13 122.0(4) . . ?
C12 N1 C13 117.5(4) . . ?
O1 C11A N1A 124.9(4) . . ?
O1 C11A H114 117.5 . . ?
N1A C11A H114 117.5 . . ?
C11A N1A C12A 122.1(4) . . ?
C11A N1A C13A 121.7(3) . . ?
C12A N1A C13A 116.2(4) . . ?
N1A C13A H134 109.5 . . ?
N1A C13A H135 109.5 . . ?
H134 C13A H135 109.5 . . ?
N1A C13A H136 109.5 . . ?
H134 C13A H136 109.5 . . ?
H135 C13A H136 109.5 . . ?
N1A C12A H124 109.5 . . ?
N1A C12A H125 109.5 . . ?
H124 C12A H125 109.5 . . ?
N1A C12A H126 109.5 . . ?
H124 C12A H126 109.5 . . ?
H125 C12A H126 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
O13 S1 O11 Mn1 -169.80(7) . . . . ?
O12 S1 O11 Mn1 -40.20(9) . . . . ?
C1 S1 O11 Mn1 74.07(8) . . . . ?
O12 Mn1 O11 S1 54.09(8) 2_666 . . . ?
O12 Mn1 O11 S1 -125.91(8) 1_455 . . . ?
O1 Mn1 O11 S1 -39.00(8) . . . . ?
O1 Mn1 O11 S1 141.00(8) 2_566 . . . ?
O13 S1 O12 Mn1 26.28(19) . . . 1_655 ?
O11 S1 O12 Mn1 -102.28(17) . . . 1_655 ?
C1 S1 O12 Mn1 142.61(16) . . . 1_655 ?
O13 S1 C1 C2 104.26(11) . . . . ?
O12 S1 C1 C2 -17.05(12) . . . . ?
O11 S1 C1 C2 -136.04(10) . . . . ?
O13 S1 C1 C3 -73.01(11) . . . . ?
O12 S1 C1 C3 165.68(10) . . . . ?
O11 S1 C1 C3 46.69(11) . . . . ?
C3 C1 C2 C3 0.7(2) . . . 2_676 ?
S1 C1 C2 C3 -176.54(10) . . . 2_676 ?
C2 C1 C3 C2 -0.7(2) . . . 2_676 ?
S1 C1 C3 C2 176.56(10) . . . 2_676 ?
O12 Mn1 O1 C11 -1.3(2) 2_666 . . . ?
O12 Mn1 O1 C11 178.7(2) 1_455 . . . ?
O11 Mn1 O1 C11 88.9(2) . . . . ?
O11 Mn1 O1 C11 -91.1(2) 2_566 . . . ?
O12 Mn1 O1 C11A 27.9(2) 2_666 . . . ?
O12 Mn1 O1 C11A -152.1(2) 1_455 . . . ?
O11 Mn1 O1 C11A 118.2(2) . . . . ?
O11 Mn1 O1 C11A -61.8(2) 2_566 . . . ?
C11A O1 C11 N1 93.6(9) . . . . ?
Mn1 O1 C11 N1 172.0(2) . . . . ?
O1 C11 N1 C12 3.3(6) . . . . ?
O1 C11 N1 C13 179.5(3) . . . . ?
C11 O1 C11A N1A -60.5(8) . . . . ?
Mn1 O1 C11A N1A 179.6(3) . . . . ?
O1 C11A N1A C12A 2.1(7) . . . . ?
O1 C11A N1A C13A -179.0(3) . . . . ?

_diffrn_measured_fraction_theta_max 0.992
_diffrn_reflns_theta_full        33.78
_diffrn_measured_fraction_theta_full 0.992
_refine_diff_density_max         0.456
_refine_diff_density_min         -0.399
_refine_diff_density_rms         0.082
_database_code_depnum_ccdc_archive 'CCDC 951313'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_c:\cz318a\cz318

_audit_creation_method           SHELXL-97
_chemical_name_common            
manganese(II)-benzenedisulfonate-dimethylacetamide
_chemical_formula_moiety         'C14 H22 Mn N2 O8 S2'
_chemical_formula_sum            'C14 H22 Mn N2 O8 S2'
_chemical_formula_weight         465.40
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'
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      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                   9.3600(4)
_cell_length_b                   9.8494(4)
_cell_length_c                   10.3475(5)
_cell_angle_alpha                81.606(2)
_cell_angle_beta                 88.941(2)
_cell_angle_gamma                82.364(2)
_cell_volume                     935.35(7)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    ?
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      ?
_cell_measurement_theta_min      ?
_exptl_absorpt_coefficient_mu    0.975
_exptl_absorpt_correction_T_max  0.965
_exptl_absorpt_correction_T_min  0.406
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   'Bruker SAINT'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.652
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plates
_exptl_crystal_F_000             482
_exptl_crystal_size_max          1.128
_exptl_crystal_size_mid          0.231
_exptl_crystal_size_min          0.037
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0726
_diffrn_reflns_av_unetI/netI     0.0502
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            25447
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         35.067
_diffrn_reflns_theta_min         2.108
_diffrn_ambient_temperature      120.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  ?
_diffrn_measurement_method       ?
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6324
_reflns_number_total             8169
_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       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS-97 (Sheldrick, 2008)'
_refine_diff_density_max         1.091
_refine_diff_density_min         -0.588
_refine_diff_density_rms         0.091
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         8169
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0504
_refine_ls_R_factor_gt           0.0348
_refine_ls_restrained_S_all      1.019
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0555P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0939
_refine_ls_wR_factor_ref         0.1002
_refine_special_details          
;
 ?
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: O2(0.75) C21(0.75) C22(0.75) H22A(0.75) H22B(0.75) H22C(0.75)
 N2(0.75) C23(0.75) H23A(0.75) H23B(0.75) H23C(0.75) C24(0.75) H24A(0.75)
 H24B(0.75) H24C(0.75) N2A(0.25) C21A(0.25) C22A(0.25) C24A(0.25) O2A(0.25)
 C23A(0.25)
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6)
3.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C)
;
_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
Mn1 Mn 0.51949(2) -0.00192(2) 0.74766(2) 0.01177(5) Uani 1 1 d . . . . .
S1 S 0.61997(3) 0.19284(3) 0.46050(3) 0.01212(6) Uani 1 1 d . . . . .
O11 O 0.63569(10) 0.11465(10) 0.59192(9) 0.01729(18) Uani 1 1 d . . . . .
O12 O 0.50757(10) 0.15033(10) 0.38520(10) 0.01776(18) Uani 1 1 d . . . . .
O13 O 0.75617(10) 0.19946(10) 0.39368(10) 0.01985(19) Uani 1 1 d . . . . .
S2 S 0.63003(3) 0.19230(3) 0.97519(3) 0.01254(6) Uani 1 1 d . . . . .
O14 O 0.55031(13) 0.15407(11) 0.86995(11) 0.0261(2) Uani 1 1 d . . . . .
O15 O 0.60791(12) 0.11089(10) 1.10066(10) 0.0234(2) Uani 1 1 d . . . . .
O16 O 0.78048(11) 0.19821(12) 0.94626(12) 0.0274(2) Uani 1 1 d . . . . .
C1 C 0.55306(13) 0.36576(12) 0.48182(12) 0.0127(2) Uani 1 1 d . . . . .
C2 C 0.40917(14) 0.39778(13) 0.51549(14) 0.0170(2) Uani 1 1 d . . . . .
H2 H 0.3473 0.3279 0.5257 0.020 Uiso 1 1 calc R . . . .
C3 C 0.64373(14) 0.46783(13) 0.46589(13) 0.0167(2) Uani 1 1 d . . . . .
H3 H 0.7417 0.4458 0.4423 0.020 Uiso 1 1 calc R . . . .
C4 C 0.55400(13) 0.36455(12) 0.98923(12) 0.0129(2) Uani 1 1 d . . . . .
C5 C 0.57330(14) 0.41607(13) 1.10501(12) 0.0148(2) Uani 1 1 d . . . . .
H5 H 0.6232 0.3585 1.1762 0.018 Uiso 1 1 calc R . . . .
C6 C 0.48099(14) 0.44745(13) 0.88416(12) 0.0149(2) Uani 1 1 d . . . . .
H6 H 0.4683 0.4112 0.8056 0.018 Uiso 1 1 calc R . . . .
O1 O 0.31876(10) 0.11318(10) 0.68085(9) 0.01808(18) Uani 1 1 d . . . . .
C11 C 0.20348(14) 0.17216(13) 0.72032(12) 0.0154(2) Uani 1 1 d . . . . .
C12 C 0.10535(17) 0.17795(19) 0.50458(15) 0.0282(3) Uani 1 1 d . . . . .
H12A H 0.1112 0.2629 0.4433 0.042 Uiso 1 1 calc GR . . . .
H12B H 0.0208 0.1363 0.4837 0.042 Uiso 1 1 calc GR . . . .
H12C H 0.1927 0.1125 0.4974 0.042 Uiso 1 1 calc GR . . . .
N1 N 0.09257(12) 0.21097(13) 0.63747(12) 0.0191(2) Uani 1 1 d . . . . .
C13 C -0.04368(16) 0.29002(19) 0.66876(17) 0.0303(3) Uani 1 1 d . . . . .
H13A H -0.0503 0.2899 0.7634 0.045 Uiso 1 1 calc GR . . . .
H13B H -0.1240 0.2477 0.6393 0.045 Uiso 1 1 calc GR . . . .
H13C H -0.0482 0.3855 0.6246 0.045 Uiso 1 1 calc GR . . . .
C14 C 0.18735(17) 0.20175(17) 0.85851(14) 0.0257(3) Uani 1 1 d . . . . .
H14A H 0.2671 0.1485 0.9115 0.039 Uiso 1 1 calc GR . . . .
H14B H 0.0957 0.1752 0.8942 0.039 Uiso 1 1 calc GR . . . .
H14C H 0.1887 0.3008 0.8600 0.039 Uiso 1 1 calc GR . . . .
O2 O 0.7071(4) -0.1357(4) 0.8159(4) 0.0208(5) Uani 0.75 1 d . . P A 1
C21 C 0.84296(18) -0.16883(18) 0.81559(15) 0.0111(3) Uani 0.75 1 d . . P A 1
C22 C 0.9429(3) -0.0639(3) 0.8043(3) 0.0243(5) Uani 0.75 1 d . . P A 1
H22A H 0.8876 0.0287 0.7958 0.036 Uiso 0.75 1 calc GR . P A 1
H22B H 1.0039 -0.0717 0.7271 0.036 Uiso 0.75 1 calc GR . P A 1
H22C H 1.0036 -0.0789 0.8826 0.036 Uiso 0.75 1 calc GR . P A 1
N2 N 0.89344(14) -0.30555(14) 0.82749(14) 0.0115(2) Uani 0.75 1 d . . P A 1
C23 C 1.0476(7) -0.3554(8) 0.8331(9) 0.0257(15) Uani 0.75 1 d . . P A 1
H23A H 1.0806 -0.3772 0.7471 0.039 Uiso 0.75 1 calc GR . P A 1
H23B H 1.0654 -0.4388 0.8979 0.039 Uiso 0.75 1 calc GR . P A 1
H23C H 1.1002 -0.2835 0.8579 0.039 Uiso 0.75 1 calc GR . P A 1
C24 C 0.7935(2) -0.4066(2) 0.8346(2) 0.0235(4) Uani 0.75 1 d . . P A 1
H24A H 0.7187 -0.3870 0.8994 0.035 Uiso 0.75 1 calc GR . P A 1
H24B H 0.8455 -0.4995 0.8604 0.035 Uiso 0.75 1 calc GR . P A 1
H24C H 0.7487 -0.4017 0.7489 0.035 Uiso 0.75 1 calc GR . P A 1
N2A N 0.9280(14) -0.2379(13) 0.8308(12) 0.082(3) Uiso 0.25 1 d . . P A 2
C21A C 0.8094(12) -0.2142(11) 0.8116(10) 0.049(2) Uiso 0.25 1 d . . P A 2
C22A C 0.7567(10) -0.3700(10) 0.8122(9) 0.034(2) Uiso 0.25 1 d . . P A 2
C24A C 0.9864(9) -0.0815(10) 0.8166(10) 0.030(2) Uiso 0.25 1 d . . P A 2
O2A O 0.7241(14) -0.1206(15) 0.8036(13) 0.027(3) Uiso 0.25 1 d . . P A 2
C23A C 1.044(3) -0.356(3) 0.842(3) 0.038(7) Uiso 0.25 1 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
Mn1 O11 2.1965(10) . ?
Mn1 O12 2.1884(9) 2_656 ?
Mn1 O14 2.1780(10) . ?
Mn1 O15 2.1946(11) 2_657 ?
Mn1 O1 2.1322(9) . ?
Mn1 O2 2.117(3) . ?
Mn1 O2A 2.149(14) . ?
S1 O11 1.4614(10) . ?
S1 O12 1.4601(10) . ?
S1 O13 1.4435(10) . ?
S1 C1 1.7784(12) . ?
O12 Mn1 2.1883(9) 2_656 ?
S2 O14 1.4522(10) . ?
S2 O15 1.4498(10) . ?
S2 O16 1.4412(11) . ?
S2 C4 1.7757(12) . ?
O15 Mn1 2.1946(11) 2_657 ?
C1 C2 1.3916(17) . ?
C1 C3 1.3897(17) . ?
C2 H2 0.9500 . ?
C2 C3 1.3898(18) 2_666 ?
C3 C2 1.3897(18) 2_666 ?
C3 H3 0.9500 . ?
C4 C5 1.3912(17) . ?
C4 C6 1.3914(17) . ?
C5 H5 0.9500 . ?
C5 C6 1.3921(17) 2_667 ?
C6 C5 1.3921(17) 2_667 ?
C6 H6 0.9500 . ?
O1 C11 1.2470(15) . ?
C11 N1 1.3381(17) . ?
C11 C14 1.5014(19) . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
C12 N1 1.4577(19) . ?
N1 C13 1.4601(18) . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
O2 C21 1.270(4) . ?
C21 C22 1.475(3) . ?
C21 N2 1.355(2) . ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?
N2 C23 1.460(6) . ?
N2 C24 1.447(2) . ?
C23 H23A 0.9800 . ?
C23 H23B 0.9800 . ?
C23 H23C 0.9800 . ?
C24 H24A 0.9800 . ?
C24 H24B 0.9800 . ?
C24 H24C 0.9800 . ?
N2A C21A 1.119(15) . ?
N2A C24A 1.687(16) . ?
N2A C23A 1.48(3) . ?
C21A C22A 1.672(14) . ?
C21A O2A 1.131(16) . ?

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
O12 Mn1 O11 88.75(4) 2_656 . ?
O12 Mn1 O15 91.38(4) 2_656 2_657 ?
O14 Mn1 O11 87.94(4) . . ?
O14 Mn1 O12 176.59(4) . 2_656 ?
O14 Mn1 O15 91.89(4) . 2_657 ?
O15 Mn1 O11 176.75(4) 2_657 . ?
O1 Mn1 O11 91.12(4) . . ?
O1 Mn1 O12 89.18(4) . 2_656 ?
O1 Mn1 O14 90.10(4) . . ?
O1 Mn1 O15 85.64(4) . 2_657 ?
O1 Mn1 O2A 176.6(4) . . ?
O2 Mn1 O11 93.37(12) . . ?
O2 Mn1 O12 86.55(11) . 2_656 ?
O2 Mn1 O14 94.43(11) . . ?
O2 Mn1 O15 89.87(12) . 2_657 ?
O2 Mn1 O1 173.73(12) . . ?
O2A Mn1 O11 86.9(3) . . ?
O2A Mn1 O12 88.1(4) . 2_656 ?
O2A Mn1 O14 92.5(4) . . ?
O2A Mn1 O15 96.4(3) . 2_657 ?
O11 S1 C1 105.82(6) . . ?
O12 S1 O11 112.50(6) . . ?
O12 S1 C1 104.08(6) . . ?
O13 S1 O11 112.62(6) . . ?
O13 S1 O12 114.67(6) . . ?
O13 S1 C1 106.13(6) . . ?
S1 O11 Mn1 143.26(6) . . ?
S1 O12 Mn1 140.03(6) . 2_656 ?
O14 S2 C4 104.92(6) . . ?
O15 S2 O14 113.08(7) . . ?
O15 S2 C4 105.97(6) . . ?
O16 S2 O14 113.66(7) . . ?
O16 S2 O15 112.44(7) . . ?
O16 S2 C4 105.87(6) . . ?
S2 O14 Mn1 147.77(7) . . ?
S2 O15 Mn1 154.85(8) . 2_657 ?
C2 C1 S1 119.37(9) . . ?
C3 C1 S1 120.37(9) . . ?
C3 C1 C2 120.26(11) . . ?
C1 C2 H2 120.1 . . ?
C3 C2 C1 119.83(12) 2_666 . ?
C3 C2 H2 120.1 2_666 . ?
C1 C3 H3 120.0 . . ?
C2 C3 C1 119.90(12) 2_666 . ?
C2 C3 H3 120.0 2_666 . ?
C5 C4 S2 118.84(9) . . ?
C5 C4 C6 120.92(11) . . ?
C6 C4 S2 120.21(9) . . ?
C4 C5 H5 120.2 . . ?
C4 C5 C6 119.55(11) . 2_667 ?
C6 C5 H5 120.2 2_667 . ?
C4 C6 C5 119.53(11) . 2_667 ?
C4 C6 H6 120.2 . . ?
C5 C6 H6 120.2 2_667 . ?
C11 O1 Mn1 142.33(9) . . ?
O1 C11 N1 119.30(12) . . ?
O1 C11 C14 121.27(12) . . ?
N1 C11 C14 119.43(12) . . ?
H12A C12 H12B 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
N1 C12 H12A 109.5 . . ?
N1 C12 H12B 109.5 . . ?
N1 C12 H12C 109.5 . . ?
C11 N1 C12 119.81(12) . . ?
C11 N1 C13 124.49(12) . . ?
C12 N1 C13 115.67(12) . . ?
N1 C13 H13A 109.5 . . ?
N1 C13 H13B 109.5 . . ?
N1 C13 H13C 109.5 . . ?
H13A C13 H13B 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C11 C14 H14A 109.5 . . ?
C11 C14 H14B 109.5 . . ?
C11 C14 H14C 109.5 . . ?
H14A C14 H14B 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C21 O2 Mn1 150.7(3) . . ?
O2 C21 C22 121.9(3) . . ?
O2 C21 N2 117.3(3) . . ?
N2 C21 C22 120.83(17) . . ?
C21 C22 H22A 109.5 . . ?
C21 C22 H22B 109.5 . . ?
C21 C22 H22C 109.5 . . ?
H22A C22 H22B 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
C21 N2 C23 121.9(3) . . ?
C21 N2 C24 119.94(15) . . ?
C24 N2 C23 118.2(3) . . ?
N2 C23 H23A 109.5 . . ?
N2 C23 H23B 109.5 . . ?
N2 C23 H23C 109.5 . . ?
H23A C23 H23B 109.5 . . ?
H23A C23 H23C 109.5 . . ?
H23B C23 H23C 109.5 . . ?
N2 C24 H24A 109.5 . . ?
N2 C24 H24B 109.5 . . ?
N2 C24 H24C 109.5 . . ?
H24A C24 H24B 109.5 . . ?
H24A C24 H24C 109.5 . . ?
H24B C24 H24C 109.5 . . ?
C21A N2A C24A 104.6(11) . . ?
C21A N2A C23A 139.9(18) . . ?
C23A N2A C24A 114.4(15) . . ?
N2A C21A C22A 103.7(11) . . ?
N2A C21A O2A 137.5(15) . . ?
O2A C21A C22A 118.4(11) . . ?
C21A O2A Mn1 155.7(13) . . ?

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
Mn1 O1 C11 N1 -167.09(10) . . . . ?
Mn1 O1 C11 C14 13.6(2) . . . . ?
Mn1 O2 C21 C22 37.7(7) . . . . ?
Mn1 O2 C21 N2 -143.0(5) . . . . ?
S1 C1 C2 C3 179.13(10) . . . 2_666 ?
S1 C1 C3 C2 -179.13(10) . . . 2_666 ?
O11 S1 O12 Mn1 -89.75(10) . . . 2_656 ?
O11 S1 C1 C2 -75.07(11) . . . . ?
O11 S1 C1 C3 104.49(11) . . . . ?
O12 S1 O11 Mn1 -26.19(12) . . . . ?
O12 S1 C1 C2 43.68(12) . . . . ?
O12 S1 C1 C3 -136.75(11) . . . . ?
O13 S1 O11 Mn1 -157.65(9) . . . . ?
O13 S1 O12 Mn1 40.67(12) . . . 2_656 ?
O13 S1 C1 C2 165.05(11) . . . . ?
O13 S1 C1 C3 -15.38(12) . . . . ?
S2 C4 C5 C6 177.62(10) . . . 2_667 ?
S2 C4 C6 C5 -177.59(10) . . . 2_667 ?
O14 S2 O15 Mn1 -39.00(18) . . . 2_657 ?
O14 S2 C4 C5 159.88(11) . . . . ?
O14 S2 C4 C6 -22.39(12) . . . . ?
O15 S2 O14 Mn1 -66.26(16) . . . . ?
O15 S2 C4 C5 39.99(12) . . . . ?
O15 S2 C4 C6 -142.27(11) . . . . ?
O16 S2 O14 Mn1 63.51(16) . . . . ?
O16 S2 O15 Mn1 -169.38(14) . . . 2_657 ?
O16 S2 C4 C5 -79.62(12) . . . . ?
O16 S2 C4 C6 98.12(11) . . . . ?
C1 S1 O11 Mn1 86.83(11) . . . . ?
C1 S1 O12 Mn1 156.17(9) . . . 2_656 ?
C2 C1 C3 C2 0.4(2) . . . 2_666 ?
C3 C1 C2 C3 -0.4(2) . . . 2_666 ?
C4 S2 O14 Mn1 178.71(13) . . . . ?
C4 S2 O15 Mn1 75.41(16) . . . 2_657 ?
C5 C4 C6 C5 0.1(2) . . . 2_667 ?
C6 C4 C5 C6 -0.1(2) . . . 2_667 ?
O1 C11 N1 C12 3.0(2) . . . . ?
O1 C11 N1 C13 -175.04(14) . . . . ?
C14 C11 N1 C12 -177.64(13) . . . . ?
C14 C11 N1 C13 4.3(2) . . . . ?
O2 C21 N2 C23 -177.7(5) . . . . ?
O2 C21 N2 C24 2.5(3) . . . . ?
C22 C21 N2 C23 1.6(5) . . . . ?
C22 C21 N2 C24 -178.23(19) . . . . ?
N2A C21A O2A Mn1 161.2(19) . . . . ?
C22A C21A O2A Mn1 -27(3) . . . . ?
C24A N2A C21A C22A 174.8(7) . . . . ?
C24A N2A C21A O2A -13(2) . . . . ?
C23A N2A C21A C22A 8(3) . . . . ?
C23A N2A C21A O2A -180(2) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_database_code_depnum_ccdc_archive 'CCDC 951315'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_c:\cz322\cz322

_audit_creation_method           SHELXL-97
_chemical_name_common            
(manganese(II)-benzenedisulfonate)(N-methylpyrrolidone)
_chemical_formula_moiety         'C16 H22 Mn N2 O8 S2'
_chemical_formula_sum            'C16 H22 Mn N2 O8 S2'
_chemical_formula_weight         489.42

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'
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'

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   P-1
_symmetry_space_group_name_Hall  '-P 1'

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

_cell_length_a                   9.6297(3)
_cell_length_b                   9.7676(3)
_cell_length_c                   10.3423(3)
_cell_angle_alpha                89.3710(10)
_cell_angle_beta                 78.8390(10)
_cell_angle_gamma                87.604(2)
_cell_volume                     953.55(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       plates
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.17
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.705
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             506
_exptl_absorpt_coefficient_mu    0.961
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.7158
_exptl_absorpt_correction_T_max  0.8529
_exptl_absorpt_process_details   'Bruker SAINT'

_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  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            46913
_diffrn_reflns_av_R_equivalents  0.0315
_diffrn_reflns_av_sigmaI/netI    0.0237
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.01
_diffrn_reflns_theta_max         40.29
_reflns_number_total             11970
_reflns_number_gt                9790
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.0384P)²+0.0750P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         11970
_refine_ls_number_parameters     264
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0315
_refine_ls_R_factor_gt           0.0244
_refine_ls_wR_factor_ref         0.0750
_refine_ls_wR_factor_gt          0.0732
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_restrained_S_all      1.066
_refine_ls_shift/su_max          0.004
_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
Mn2 Mn 0.496343(9) 0.003189(9) 0.750387(7) 0.00785(2) Uani 1 1 d . . .
S1 S 0.295982(15) -0.128985(15) 1.035531(13) 0.00820(3) Uani 1 1 d . . .
O11 O 0.38781(5) -0.13139(5) 0.90520(4) 0.01204(8) Uani 1 1 d . . .
O12 O 0.26401(5) -0.26514(5) 1.08594(5) 0.01457(8) Uani 1 1 d . . .
O13 O 0.34611(5) -0.04031(5) 1.12826(5) 0.01411(8) Uani 1 1 d . . .
S2 S 0.702282(15) 0.131071(15) 0.468058(13) 0.00921(3) Uani 1 1 d . . .
O14 O 0.61256(5) 0.13368(5) 0.59920(4) 0.01331(8) Uani 1 1 d . . .
O15 O 0.65275(5) 0.03926(6) 0.37785(5) 0.01688(9) Uani 1 1 d . . .
O16 O 0.73078(6) 0.26718(6) 0.41701(6) 0.02011(10) Uani 1 1 d . . .
C1 C 0.13206(6) -0.05194(6) 1.01404(5) 0.00872(8) Uani 1 1 d . . .
C2 C 0.08506(6) -0.07489(6) 0.89692(5) 0.01017(9) Uani 1 1 d . . .
H21 H 0.1418 -0.1247 0.8290 0.012 Uiso 1 1 calc R . .
C3 C 0.04807(6) 0.02212(6) 1.11695(5) 0.01045(9) Uani 1 1 d . . .
H31 H 0.0807 0.0363 1.1945 0.013 Uiso 1 1 calc R . .
C4 C 0.86890(6) 0.05609(6) 0.48672(5) 0.00993(9) Uani 1 1 d . . .
C5 C 0.90918(8) -0.07514(7) 0.44163(8) 0.01942(13) Uani 1 1 d . . .
H51 H 0.8485 -0.1254 0.4026 0.023 Uiso 1 1 calc R . .
C6 C 0.95902(8) 0.13180(8) 0.54506(8) 0.02137(14) Uani 1 1 d . . .
H61 H 0.9315 0.2200 0.5752 0.026 Uiso 1 1 calc R . .
O1 O 0.61777(5) -0.17312(5) 0.66778(5) 0.01428(8) Uani 1 1 d . . .
C11 C 0.34696(6) 0.29854(6) 0.81596(5) 0.01026(9) Uani 1 1 d . . .
C12 C 0.46761(7) 0.39371(7) 0.78036(7) 0.01466(10) Uani 1 1 d . . .
H121 H 0.5100 0.3865 0.6875 0.018 Uiso 1 1 calc R . .
H122 H 0.5400 0.3731 0.8319 0.018 Uiso 1 1 calc R . .
C13 C 0.39967(8) 0.53665(8) 0.81272(9) 0.02159(13) Uani 1 1 d . . .
H131 H 0.4340 0.6008 0.7427 0.026 Uiso 1 1 calc R . .
H132 H 0.4210 0.5698 0.8945 0.026 Uiso 1 1 calc R . .
C14 C 0.24016(7) 0.51993(6) 0.82576(6) 0.01301(10) Uani 1 1 d . . .
H141 H 0.1874 0.5686 0.9021 0.016 Uiso 1 1 calc R . .
H142 H 0.2077 0.5535 0.7477 0.016 Uiso 1 1 calc R . .
N1 N 0.74744(7) -0.37207(6) 0.62476(5) 0.01599(10) Uani 1 1 d . . .
C15 C 0.08755(7) 0.31162(7) 0.86658(7) 0.01569(11) Uani 1 1 d . . .
H151 H 0.0396 0.3327 0.7952 0.024 Uiso 1 1 calc R . .
H152 H 0.0323 0.3479 0.9471 0.024 Uiso 1 1 calc R . .
H153 H 0.0998 0.2140 0.8744 0.024 Uiso 1 1 calc R . .
O2 O 0.35417(5) 0.17116(5) 0.82176(5) 0.01430(8) Uani 1 1 d . . .
C21 C 0.68989(6) -0.26906(6) 0.70373(6) 0.01106(9) Uani 1 1 d . . .
C22 C 0.72327(7) -0.29357(7) 0.83880(6) 0.01493(11) Uani 1 1 d . . .
H221 H 0.6416 -0.3265 0.8995 0.018 Uiso 1 1 calc R . .
H222 H 0.7532 -0.2104 0.8739 0.018 Uiso 1 1 calc R . .
C23 C 0.84365(10) -0.40259(9) 0.81514(8) 0.02683(17) Uani 1 1 d . . .
H231 H 0.8340 -0.4678 0.8874 0.032 Uiso 1 1 calc R . .
H232 H 0.9348 -0.3610 0.8059 0.032 Uiso 1 1 calc R . .
C24 C 0.82941(8) -0.47297(8) 0.68671(7) 0.01950(13) Uani 1 1 d . . .
H241 H 0.9215 -0.4926 0.6316 0.023 Uiso 1 1 calc R . .
H242 H 0.7798 -0.5576 0.7045 0.023 Uiso 1 1 calc R . .
N2 N 0.22453(6) 0.37226(5) 0.84097(5) 0.01096(8) Uani 1 1 d . . .
C25 C 0.72062(10) -0.39084(9) 0.49339(7) 0.02414(15) Uani 1 1 d . . .
H251 H 0.8077 -0.3853 0.4305 0.036 Uiso 1 1 calc R . .
H252 H 0.6544 -0.3206 0.4750 0.036 Uiso 1 1 calc R . .
H253 H 0.6819 -0.4791 0.4875 0.036 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
Mn2 O1 2.1307(5) . ?
Mn2 O2 2.1351(5) . ?
Mn2 O14 2.1725(5) . ?
Mn2 O15 2.1888(5) 2_656 ?
Mn2 O13 2.1912(4) 2_657 ?
Mn2 O11 2.1920(5) . ?
S1 O12 1.4464(5) . ?
S1 O13 1.4613(5) . ?
S1 O11 1.4618(5) . ?
S1 C1 1.7720(6) . ?
O13 Mn2 2.1912(4) 2_657 ?
S2 O16 1.4424(6) . ?
S2 O15 1.4589(5) . ?
S2 O14 1.4601(5) . ?
S2 C4 1.7795(6) . ?
O15 Mn2 2.1889(5) 2_656 ?
C1 C3 1.3947(8) . ?
C1 C2 1.3961(7) . ?
C2 C3 1.3943(8) 2_557 ?
C2 H21 0.9300 . ?
C3 C2 1.3943(8) 2_557 ?
C3 H31 0.9300 . ?
C4 C5 1.3829(9) . ?
C4 C6 1.3893(9) . ?
C5 C6 1.3941(9) 2_756 ?
C5 H51 0.9300 . ?
C6 C5 1.3940(9) 2_756 ?
C6 H61 0.9300 . ?
O1 C21 1.2396(7) . ?
C11 O2 1.2446(8) . ?
C11 N2 1.3381(8) . ?
C11 C12 1.5056(9) . ?
C12 C13 1.5292(10) . ?
C12 H121 0.9700 . ?
C12 H122 0.9700 . ?
C13 C14 1.5313(10) . ?
C13 H131 0.9700 . ?
C13 H132 0.9700 . ?
C14 N2 1.4601(8) . ?
C14 H141 0.9700 . ?
C14 H142 0.9700 . ?
N1 C21 1.3352(8) . ?
N1 C25 1.4462(9) . ?
N1 C24 1.4567(9) . ?
C15 N2 1.4449(9) . ?
C15 H151 0.9600 . ?
C15 H152 0.9600 . ?
C15 H153 0.9600 . ?
C21 C22 1.5073(8) . ?
C22 C23 1.5266(10) . ?
C22 H221 0.9700 . ?
C22 H222 0.9700 . ?
C23 C24 1.5343(11) . ?
C23 H231 0.9700 . ?
C23 H232 0.9700 . ?
C24 H241 0.9700 . ?
C24 H242 0.9700 . ?
C25 H251 0.9600 . ?
C25 H252 0.9600 . ?
C25 H253 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
O1 Mn2 O2 172.860(19) . . ?
O1 Mn2 O14 91.115(19) . . ?
O2 Mn2 O14 90.431(19) . . ?
O1 Mn2 O15 87.327(19) . 2_656 ?
O2 Mn2 O15 85.70(2) . 2_656 ?
O14 Mn2 O15 90.26(2) . 2_656 ?
O1 Mn2 O13 90.099(19) . 2_657 ?
O2 Mn2 O13 96.909(19) . 2_657 ?
O14 Mn2 O13 88.561(19) . 2_657 ?
O15 Mn2 O13 177.147(17) 2_656 2_657 ?
O1 Mn2 O11 87.521(19) . . ?
O2 Mn2 O11 91.174(19) . . ?
O14 Mn2 O11 177.524(16) . . ?
O15 Mn2 O11 91.74(2) 2_656 . ?
O13 Mn2 O11 89.374(19) 2_657 . ?
O12 S1 O13 113.89(3) . . ?
O12 S1 O11 112.33(3) . . ?
O13 S1 O11 112.85(3) . . ?
O12 S1 C1 105.64(3) . . ?
O13 S1 C1 105.07(3) . . ?
O11 S1 C1 106.18(3) . . ?
S1 O11 Mn2 142.24(3) . . ?
S1 O13 Mn2 148.39(3) . 2_657 ?
O16 S2 O15 114.62(3) . . ?
O16 S2 O14 111.94(3) . . ?
O15 S2 O14 112.85(3) . . ?
O16 S2 C4 105.85(3) . . ?
O15 S2 C4 104.18(3) . . ?
O14 S2 C4 106.48(3) . . ?
S2 O14 Mn2 142.78(3) . . ?
S2 O15 Mn2 149.63(3) . 2_656 ?
C3 C1 C2 121.15(5) . . ?
C3 C1 S1 119.79(4) . . ?
C2 C1 S1 118.90(4) . . ?
C3 C2 C1 119.13(5) 2_557 . ?
C3 C2 H21 120.4 2_557 . ?
C1 C2 H21 120.4 . . ?
C2 C3 C1 119.72(5) 2_557 . ?
C2 C3 H31 120.1 2_557 . ?
C1 C3 H31 120.1 . . ?
C5 C4 C6 120.41(6) . . ?
C5 C4 S2 120.36(5) . . ?
C6 C4 S2 119.22(5) . . ?
C4 C5 C6 119.77(6) . 2_756 ?
C4 C5 H51 120.1 . . ?
C6 C5 H51 120.1 2_756 . ?
C4 C6 C5 119.83(6) . 2_756 ?
C4 C6 H61 120.1 . . ?
C5 C6 H61 120.1 2_756 . ?
C21 O1 Mn2 138.67(4) . . ?
O2 C11 N2 123.21(6) . . ?
O2 C11 C12 127.53(6) . . ?
N2 C11 C12 109.26(5) . . ?
C11 C12 C13 104.51(5) . . ?
C11 C12 H121 110.9 . . ?
C13 C12 H121 110.9 . . ?
C11 C12 H122 110.9 . . ?
C13 C12 H122 110.9 . . ?
H121 C12 H122 108.9 . . ?
C12 C13 C14 105.40(6) . . ?
C12 C13 H131 110.7 . . ?
C14 C13 H131 110.7 . . ?
C12 C13 H132 110.7 . . ?
C14 C13 H132 110.7 . . ?
H131 C13 H132 108.8 . . ?
N2 C14 C13 103.67(5) . . ?
N2 C14 H141 111.0 . . ?
C13 C14 H141 111.0 . . ?
N2 C14 H142 111.0 . . ?
C13 C14 H142 111.0 . . ?
H141 C14 H142 109.0 . . ?
C21 N1 C25 123.63(6) . . ?
C21 N1 C24 114.14(5) . . ?
C25 N1 C24 121.96(6) . . ?
N2 C15 H151 109.5 . . ?
N2 C15 H152 109.5 . . ?
H151 C15 H152 109.5 . . ?
N2 C15 H153 109.5 . . ?
H151 C15 H153 109.5 . . ?
H152 C15 H153 109.5 . . ?
C11 O2 Mn2 139.84(4) . . ?
O1 C21 N1 123.25(5) . . ?
O1 C21 C22 127.71(6) . . ?
N1 C21 C22 109.00(5) . . ?
C21 C22 C23 103.63(5) . . ?
C21 C22 H221 111.0 . . ?
C23 C22 H221 111.0 . . ?
C21 C22 H222 111.0 . . ?
C23 C22 H222 111.0 . . ?
H221 C22 H222 109.0 . . ?
C22 C23 C24 104.76(6) . . ?
C22 C23 H231 110.8 . . ?
C24 C23 H231 110.8 . . ?
C22 C23 H232 110.8 . . ?
C24 C23 H232 110.8 . . ?
H231 C23 H232 108.9 . . ?
N1 C24 C23 103.17(6) . . ?
N1 C24 H241 111.1 . . ?
C23 C24 H241 111.1 . . ?
N1 C24 H242 111.1 . . ?
C23 C24 H242 111.1 . . ?
H241 C24 H242 109.1 . . ?
C11 N2 C15 123.27(5) . . ?
C11 N2 C14 114.18(5) . . ?
C15 N2 C14 122.22(5) . . ?
N1 C25 H251 109.5 . . ?
N1 C25 H252 109.5 . . ?
H251 C25 H252 109.5 . . ?
N1 C25 H253 109.5 . . ?
H251 C25 H253 109.5 . . ?
H252 C25 H253 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
O12 S1 O11 Mn2 -178.88(4) . . . . ?
O13 S1 O11 Mn2 -48.47(5) . . . . ?
C1 S1 O11 Mn2 66.11(5) . . . . ?
O1 Mn2 O11 S1 165.18(5) . . . . ?
O2 Mn2 O11 S1 -21.84(5) . . . . ?
O15 Mn2 O11 S1 -107.57(5) 2_656 . . . ?
O13 Mn2 O11 S1 75.06(5) 2_657 . . . ?
O12 S1 O13 Mn2 59.49(7) . . . 2_657 ?
O11 S1 O13 Mn2 -70.13(7) . . . 2_657 ?
C1 S1 O13 Mn2 174.62(6) . . . 2_657 ?
O16 S2 O14 Mn2 172.69(4) . . . . ?
O15 S2 O14 Mn2 41.62(6) . . . . ?
C4 S2 O14 Mn2 -72.08(5) . . . . ?
O1 Mn2 O14 S2 19.48(5) . . . . ?
O2 Mn2 O14 S2 -153.55(5) . . . . ?
O15 Mn2 O14 S2 -67.85(5) 2_656 . . . ?
O13 Mn2 O14 S2 109.55(5) 2_657 . . . ?
O16 S2 O15 Mn2 -53.45(8) . . . 2_656 ?
O14 S2 O15 Mn2 76.27(8) . . . 2_656 ?
C4 S2 O15 Mn2 -168.64(7) . . . 2_656 ?
O12 S1 C1 C3 90.30(5) . . . . ?
O13 S1 C1 C3 -30.43(6) . . . . ?
O11 S1 C1 C3 -150.22(5) . . . . ?
O12 S1 C1 C2 -85.28(5) . . . . ?
O13 S1 C1 C2 153.99(5) . . . . ?
O11 S1 C1 C2 34.20(6) . . . . ?
C3 C1 C2 C3 0.24(10) . . . 2_557 ?
S1 C1 C2 C3 175.76(5) . . . 2_557 ?
C2 C1 C3 C2 -0.24(10) . . . 2_557 ?
S1 C1 C3 C2 -175.72(5) . . . 2_557 ?
O16 S2 C4 C5 -133.18(6) . . . . ?
O15 S2 C4 C5 -11.96(7) . . . . ?
O14 S2 C4 C5 107.54(6) . . . . ?
O16 S2 C4 C6 45.73(7) . . . . ?
O15 S2 C4 C6 166.95(6) . . . . ?
O14 S2 C4 C6 -73.55(6) . . . . ?
C6 C4 C5 C6 0.05(13) . . . 2_756 ?
S2 C4 C5 C6 178.95(6) . . . 2_756 ?
C5 C4 C6 C5 -0.05(13) . . . 2_756 ?
S2 C4 C6 C5 -178.96(6) . . . 2_756 ?
O14 Mn2 O1 C21 127.18(7) . . . . ?
O15 Mn2 O1 C21 -142.61(7) 2_656 . . . ?
O13 Mn2 O1 C21 38.61(7) 2_657 . . . ?
O11 Mn2 O1 C21 -50.76(7) . . . . ?
O2 C11 C12 C13 -170.38(6) . . . . ?
N2 C11 C12 C13 10.07(7) . . . . ?
C11 C12 C13 C14 -16.30(7) . . . . ?
C12 C13 C14 N2 16.57(7) . . . . ?
N2 C11 O2 Mn2 159.31(5) . . . . ?
C12 C11 O2 Mn2 -20.18(10) . . . . ?
O14 Mn2 O2 C11 -18.06(7) . . . . ?
O15 Mn2 O2 C11 -108.29(7) 2_656 . . . ?
O13 Mn2 O2 C11 70.54(7) 2_657 . . . ?
O11 Mn2 O2 C11 160.05(6) . . . . ?
Mn2 O1 C21 N1 175.55(5) . . . . ?
Mn2 O1 C21 C22 -2.08(12) . . . . ?
C25 N1 C21 O1 -6.49(11) . . . . ?
C24 N1 C21 O1 179.32(7) . . . . ?
C25 N1 C21 C22 171.53(7) . . . . ?
C24 N1 C21 C22 -2.67(8) . . . . ?
O1 C21 C22 C23 -165.99(7) . . . . ?
N1 C21 C22 C23 16.10(8) . . . . ?
C21 C22 C23 C24 -22.46(8) . . . . ?
C21 N1 C24 C23 -11.87(9) . . . . ?
C25 N1 C24 C23 173.83(8) . . . . ?
C22 C23 C24 N1 20.94(9) . . . . ?
O2 C11 N2 C15 -5.31(9) . . . . ?
C12 C11 N2 C15 174.27(5) . . . . ?
O2 C11 N2 C14 -178.79(5) . . . . ?
C12 C11 N2 C14 0.79(7) . . . . ?
C13 C14 N2 C11 -11.24(7) . . . . ?
C13 C14 N2 C15 175.20(6) . . . . ?

_diffrn_measured_fraction_theta_max 0.995
_diffrn_reflns_theta_full        40.29
_diffrn_measured_fraction_theta_full 0.995
_refine_diff_density_max         0.584
_refine_diff_density_min         -0.468
_refine_diff_density_rms         0.075
_database_code_depnum_ccdc_archive 'CCDC 951316'
