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

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

data_2
_database_code_depnum_ccdc_archive 'CCDC 1016514'
_audit_update_record             
;
2015-08-07 deposited with the CCDC.
2015-08-12 downloaded from the CCDC.
;
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_formula_moiety         'C42 H36 Mn2 N2 O8 Si2'
_chemical_formula_sum            'C42 H36 Mn2 N2 O8 Si2'
_chemical_formula_iupac          ?
_chemical_formula_weight         862.79

_chemical_melting_point          ?

_space_group_crystal_system      triclinic
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   8.6185(17)
_cell_length_b                   10.683(2)
_cell_length_c                   11.709(2)
_cell_angle_alpha                73.176(3)
_cell_angle_beta                 81.737(3)
_cell_angle_gamma                86.247(3)
_cell_volume                     1020.9(3)
_cell_formula_units_Z            1
_cell_measurement_reflns_used    2189
_cell_measurement_theta_min      2.3901
_cell_measurement_theta_max      21.1802
_cell_measurement_temperature    296.(2)

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.08
_exptl_crystal_density_diffrn    1.397
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             444

_exptl_absorpt_coefficient_mu    0.731
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS V2012/1 (Bruker AXS Inc.)'
_exptl_absorpt_correction_T_min  0.6141
_exptl_absorpt_correction_T_max  0.7452

_exptl_special_details           
;
;

_diffrn_ambient_temperature      296.(2)

_diffrn_source                   'sealed tube'
_diffrn_source_type              'fine focus'

_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_monochromator  graphite

_diffrn_measurement_device_type  'Bruker Kappa APEX II'
_diffrn_measurement_method       'phi and omega scans'


_diffrn_detector_area_resol_mean 8.3333


_diffrn_reflns_number            5838
_diffrn_reflns_av_R_equivalents  0.0845
_diffrn_reflns_av_unetI/netI     0.1464
_diffrn_reflns_theta_min         1.83
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_max 0.953
_diffrn_measured_fraction_theta_full 0.953
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       13

_refine_special_details          
;
;

_reflns_number_total             3421
_reflns_number_gt                2145
_reflns_threshold_expression     'I > 2σ(I)'

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_R_factor_all          0.1167
_refine_ls_R_factor_gt           0.0733
_refine_ls_wR_factor_gt          0.1745
_refine_ls_wR_factor_ref         0.2009
_refine_ls_goodness_of_fit_ref   0.987
_refine_ls_restrained_S_all      0.987
_refine_ls_number_reflns         3421
_refine_ls_number_parameters     255
_refine_ls_number_restraints     0
_refine_ls_hydrogen_treatment    constr
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
w=1/[σ²(Fo²)+(0.0800P)²]
where P=(Fo²+2Fc²)/3
;

_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?

_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_diff_density_max         0.440
_refine_diff_density_min         -0.607
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?

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'
Si Si 0.0817 0.0704 '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'

_computing_data_collection       'APEX2 (Bruker)'
_computing_cell_refinement       'SAINT V8.30C (Bruker AXS Inc., 2013)'
_computing_data_reduction        'SAINT V8.30C (Bruker AXS Inc., 2013)'
_computing_structure_solution    'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'SHELXTL (Bruker AXS)'
_computing_publication_material  'SHELXTL (Bruker AXS)'

loop_
_atom_site_type_symbol
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Mn Mn1 0.62087(10) 0.56930(8) 0.53804(8) 0.0315(3) Uani d . 1 . .
Si Si2 -0.2465(2) 0.75336(16) 0.99944(16) 0.0363(5) Uani d . 1 . .
O O1 0.4229(5) 0.6124(4) 0.6518(4) 0.0502(12) Uani d . 1 . .
O O2 0.5014(6) 0.6822(5) 0.3917(4) 0.0600(14) Uani d . 1 . .
O O3 0.7542(5) 0.4886(4) 0.4094(4) 0.0476(12) Uani d . 1 . .
O O4 0.6842(6) 0.4003(5) 0.6741(4) 0.0574(14) Uani d . 1 . .
N N1 0.7711(6) 0.7271(5) 0.5269(5) 0.0421(13) Uani d . 1 . .
C C1 -0.0840(7) 0.6953(6) 0.9006(6) 0.0377(15) Uani d . 1 . .
C C2 0.2850(8) 0.5787(6) 0.6551(6) 0.0401(16) Uani d . 1 . .
C C3 0.1579(7) 0.6168(6) 0.7416(6) 0.0359(15) Uani d . 1 . .
C C4 0.0094(8) 0.5718(6) 0.7576(6) 0.0422(16) Uani d . 1 . .
H H4 -0.0135 0.5159 0.7147 0.051 Uiso calc R 1 . .
C C5 -0.1080(7) 0.6083(6) 0.8372(6) 0.0420(16) Uani d . 1 . .
H H5 -0.2067 0.573 0.8484 0.05 Uiso calc R 1 . .
C C6 0.0678(8) 0.7410(7) 0.8820(7) 0.056(2) Uani d . 1 . .
H H6 0.0905 0.7994 0.9224 0.067 Uiso calc R 1 . .
C C7 0.1864(8) 0.7019(7) 0.8052(7) 0.0522(19) Uani d . 1 . .
H H7 0.2868 0.7334 0.7963 0.063 Uiso calc R 1 . .
C C8 -0.1747(8) 0.7661(6) 1.1373(6) 0.0468(17) Uani d . 1 . .
H H8A -0.1174 0.6874 1.172 0.07 Uiso calc R 1 . .
H H8B -0.2622 0.7781 1.1941 0.07 Uiso calc R 1 . .
H H8C -0.1071 0.8394 1.117 0.07 Uiso calc R 1 . .
C C9 -0.4144(8) 0.6415(7) 1.0342(6) 0.0544(19) Uani d . 1 . .
H H9A -0.446 0.636 0.9605 0.082 Uiso calc R 1 . .
H H9B -0.5006 0.6748 1.0796 0.082 Uiso calc R 1 . .
H H9C -0.3833 0.5561 1.0805 0.082 Uiso calc R 1 . .
C C10 -0.3047(7) 0.9233(6) 0.9093(6) 0.0391(16) Uani d . 1 . .
C C11 -0.4272(8) 0.9463(7) 0.8393(6) 0.0502(18) Uani d . 1 . .
H H11 -0.4894 0.8773 0.842 0.06 Uiso calc R 1 . .
C C12 -0.2187(8) 1.0307(6) 0.9032(6) 0.0489(18) Uani d . 1 . .
H H12 -0.1372 1.0193 0.9497 0.059 Uiso calc R 1 . .
C C13 0.6028(8) 0.3084(7) 0.6743(6) 0.0451(18) Uani d . 1 . .
C C14 0.6316(7) 0.1746(6) 0.7576(5) 0.0367(15) Uani d . 1 . .
C C15 0.5421(8) 0.0702(7) 0.7657(6) 0.0486(18) Uani d . 1 . .
H H15 0.4588 0.0828 0.7208 0.058 Uiso calc R 1 . .
C C16 0.7497(8) 0.1549(6) 0.8301(7) 0.0506(19) Uani d . 1 . .
H H16 0.8082 0.2251 0.8298 0.061 Uiso calc R 1 . .
C C17 0.9174(8) 0.7358(7) 0.4754(8) 0.063(2) Uani d . 1 . .
H H17 0.9612 0.6679 0.4455 0.075 Uiso calc R 1 . .
C C18 1.0088(8) 0.8409(8) 0.4638(8) 0.068(3) Uani d . 1 . .
H H18 1.1119 0.842 0.4268 0.081 Uiso calc R 1 . .
C C19 0.9511(8) 0.9425(7) 0.5052(7) 0.0487(18) Uani d . 1 . .
C C20 0.8019(11) 0.9323(10) 0.5610(12) 0.135(6) Uani d . 1 . .
H H20 0.7552 0.9988 0.5917 0.162 Uiso calc R 1 . .
C C21 0.7193(10) 0.8209(9) 0.5718(11) 0.122(5) Uani d . 1 . .
H H21 0.6191 0.8137 0.6146 0.147 Uiso calc R 1 . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
Mn1 O3 . 2.111(4) ?
Mn1 O1 . 2.121(4) ?
Mn1 O4 . 2.134(4) ?
Mn1 O2 . 2.145(5) ?
Mn1 N1 . 2.155(5) ?
Mn1 Mn1 2_666 3.0046(18) ?
Si2 C8 . 1.852(7) ?
Si2 C9 . 1.861(7) ?
Si2 C1 . 1.877(6) ?
Si2 C10 . 1.894(6) ?
O1 C2 . 1.256(8) ?
O2 C13 2_666 1.248(8) ?
O3 C2 2_666 1.273(8) ?
O4 C13 . 1.242(9) ?
N1 C21 . 1.288(9) ?
N1 C17 . 1.314(8) ?
C1 C5 . 1.388(8) ?
C1 C6 . 1.392(9) ?
C2 O3 2_666 1.273(8) ?
C2 C3 . 1.501(8) ?
C3 C4 . 1.365(9) ?
C3 C7 . 1.384(9) ?
C4 C5 . 1.390(8) ?
C4 H4 . 0.93 ?
C5 H5 . 0.93 ?
C6 C7 . 1.388(9) ?
C6 H6 . 0.93 ?
C7 H7 . 0.93 ?
C8 H8A . 0.96 ?
C8 H8B . 0.96 ?
C8 H8C . 0.96 ?
C9 H9A . 0.96 ?
C9 H9B . 0.96 ?
C9 H9C . 0.96 ?
C10 C12 . 1.386(9) ?
C10 C11 . 1.395(9) ?
C11 C15 1_465 1.387(9) ?
C11 H11 . 0.93 ?
C12 C16 1_465 1.389(9) ?
C12 H12 . 0.93 ?
C13 O2 2_666 1.248(8) ?
C13 C14 . 1.507(9) ?
C14 C15 . 1.370(9) ?
C14 C16 . 1.385(9) ?
C15 C11 1_645 1.387(9) ?
C15 H15 . 0.93 ?
C16 C12 1_645 1.389(9) ?
C16 H16 . 0.93 ?
C17 C18 . 1.378(10) ?
C17 H17 . 0.93 ?
C18 C19 . 1.351(9) ?
C18 H18 . 0.93 ?
C19 C20 . 1.352(10) ?
C19 C19 2_776 1.501(12) ?
C20 C21 . 1.392(11) ?
C20 H20 . 0.93 ?
C21 H21 . 0.93 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
O3 Mn1 O1 . . 158.89(18) ?
O3 Mn1 O4 . . 88.06(18) ?
O1 Mn1 O4 . . 92.45(18) ?
O3 Mn1 O2 . . 85.59(18) ?
O1 Mn1 O2 . . 85.90(18) ?
O4 Mn1 O2 . . 157.4(2) ?
O3 Mn1 N1 . . 99.11(19) ?
O1 Mn1 N1 . . 100.65(19) ?
O4 Mn1 N1 . . 109.1(2) ?
O2 Mn1 N1 . . 93.3(2) ?
O3 Mn1 Mn1 . 2_666 77.22(13) ?
O1 Mn1 Mn1 . 2_666 81.69(13) ?
O4 Mn1 Mn1 . 2_666 94.06(15) ?
O2 Mn1 Mn1 . 2_666 63.37(15) ?
N1 Mn1 Mn1 . 2_666 156.49(15) ?
C8 Si2 C9 . . 112.2(3) ?
C8 Si2 C1 . . 110.4(3) ?
C9 Si2 C1 . . 109.4(3) ?
C8 Si2 C10 . . 108.3(3) ?
C9 Si2 C10 . . 110.6(3) ?
C1 Si2 C10 . . 105.8(3) ?
C2 O1 Mn1 . . 125.5(4) ?
C13 O2 Mn1 2_666 . 149.6(5) ?
C2 O3 Mn1 2_666 . 131.6(4) ?
C13 O4 Mn1 . . 108.2(5) ?
C21 N1 C17 . . 115.7(6) ?
C21 N1 Mn1 . . 120.4(5) ?
C17 N1 Mn1 . . 123.9(5) ?
C5 C1 C6 . . 115.4(6) ?
C5 C1 Si2 . . 122.5(5) ?
C6 C1 Si2 . . 122.1(5) ?
O1 C2 O3 . 2_666 123.9(6) ?
O1 C2 C3 . . 118.8(6) ?
O3 C2 C3 2_666 . 117.2(6) ?
C4 C3 C7 . . 117.8(6) ?
C4 C3 C2 . . 121.2(6) ?
C7 C3 C2 . . 121.0(6) ?
C3 C4 C5 . . 120.9(6) ?
C3 C4 H4 . . 119.6 ?
C5 C4 H4 . . 119.6 ?
C1 C5 C4 . . 122.8(6) ?
C1 C5 H5 . . 118.6 ?
C4 C5 H5 . . 118.6 ?
C7 C6 C1 . . 122.0(6) ?
C7 C6 H6 . . 119.0 ?
C1 C6 H6 . . 119.0 ?
C3 C7 C6 . . 121.2(6) ?
C3 C7 H7 . . 119.4 ?
C6 C7 H7 . . 119.4 ?
Si2 C8 H8A . . 109.5 ?
Si2 C8 H8B . . 109.5 ?
H8A C8 H8B . . 109.5 ?
Si2 C8 H8C . . 109.5 ?
H8A C8 H8C . . 109.5 ?
H8B C8 H8C . . 109.5 ?
Si2 C9 H9A . . 109.5 ?
Si2 C9 H9B . . 109.5 ?
H9A C9 H9B . . 109.5 ?
Si2 C9 H9C . . 109.5 ?
H9A C9 H9C . . 109.5 ?
H9B C9 H9C . . 109.5 ?
C12 C10 C11 . . 116.6(6) ?
C12 C10 Si2 . . 120.8(5) ?
C11 C10 Si2 . . 122.5(5) ?
C15 C11 C10 1_465 . 121.2(6) ?
C15 C11 H11 1_465 . 119.4 ?
C10 C11 H11 . . 119.4 ?
C10 C12 C16 . 1_465 122.2(6) ?
C10 C12 H12 . . 118.9 ?
C16 C12 H12 1_465 . 118.9 ?
O4 C13 O2 . 2_666 124.6(7) ?
O4 C13 C14 . . 118.9(7) ?
O2 C13 C14 2_666 . 116.5(7) ?
C15 C14 C16 . . 118.1(6) ?
C15 C14 C13 . . 121.9(6) ?
C16 C14 C13 . . 120.0(6) ?
C14 C15 C11 . 1_645 121.6(6) ?
C14 C15 H15 . . 119.2 ?
C11 C15 H15 1_645 . 119.2 ?
C14 C16 C12 . 1_645 120.3(6) ?
C14 C16 H16 . . 119.8 ?
C12 C16 H16 1_645 . 119.8 ?
N1 C17 C18 . . 122.9(6) ?
N1 C17 H17 . . 118.5 ?
C18 C17 H17 . . 118.5 ?
C19 C18 C17 . . 121.0(6) ?
C19 C18 H18 . . 119.5 ?
C17 C18 H18 . . 119.5 ?
C18 C19 C20 . . 116.1(7) ?
C18 C19 C19 . 2_776 122.0(7) ?
C20 C19 C19 . 2_776 121.8(8) ?
C19 C20 C21 . . 119.1(8) ?
C19 C20 H20 . . 120.5 ?
C21 C20 H20 . . 120.5 ?
N1 C21 C20 . . 124.9(7) ?
N1 C21 H21 . . 117.5 ?
C20 C21 H21 . . 117.5 ?

#
_vrf_THETM01_1                   
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.575
RESPONSE: Despite numerous attempts, the best crystal failed to diffract 
beyond 2-theta = 47.48 degree; however the value of sine(theta_max)/wavelength 
for this measurement, 0.5664, is very close to 0.575 for which this alert 
is present.
;
_vrf_PLAT242_1                   
;
PROBLEM: Low Ueq as Compared to Neighbors for ..... C19 Check
RESPONSE: We did not find it to be disordered over two positions; 
the residual electron density is less than 1 e/A3. Further explanantion 
is provided in the experimental section.
;
_vrf_PLAT341_1                   
;
PROBLEM: Low Bond Precision on C-C Bonds
RESPONSE: As mentioned above, the quality of the crystal could not be 
improved after repeated tries.
;
_vrf_PLAT020_1                   
;
PROBLEM: The value of Rint is greater than 0.12
RESPONSE: As mentioned above, the quality of the crystal could not be 
improved after repeated tries.
;
_vrf_PLAT084_1                   
;
PROBLEM: High wR2 Value (i.e. > 0.25)
RESPONSE: As mentioned above, the quality of the crystal could not be 
improved after repeated tries.
;
_vrf_PLAT029_2                   
;
PROBLEM: _diffrn_measured_fraction_theta_full Low ...0.953 Note
RESPONSE: We could not recollect the data.
;
_vrf_PLAT242_2                   
;
PROBLEM: Low Ueq as Compared to Neighbors for ..... C19
RESPONSE: We did not find it to be disordered over two positions; 
the residual electron density is less than 1 e/A3. Further explanantion 
is provided in the experimental section.
;
#
#===END

####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1407952'
_audit_update_record             
;
2015-08-07 deposited with the CCDC.
2015-08-12 downloaded from the CCDC.
;
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_formula_moiety         'C42 H36 Mn2 N2 O8 Si2'
_chemical_formula_sum            'C42 H36 Mn2 N2 O8 Si2'
_chemical_formula_iupac          ?
_chemical_formula_weight         862.79

_chemical_melting_point          ?

_space_group_crystal_system      triclinic
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   8.532(12)
_cell_length_b                   10.794(15)
_cell_length_c                   11.375(16)
_cell_angle_alpha                73.267(16)
_cell_angle_beta                 82.708(16)
_cell_angle_gamma                87.105(18)
_cell_volume                     995.(2)
_cell_formula_units_Z            1
_cell_measurement_reflns_used    785
_cell_measurement_theta_min      2.3062
_cell_measurement_theta_max      16.0021
_cell_measurement_temperature    100.(2)

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_exptl_crystal_density_diffrn    1.440
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             444

_exptl_absorpt_coefficient_mu    0.750
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS V2012/1 (Bruker AXS Inc.)'
_exptl_absorpt_correction_T_min  0.5364
_exptl_absorpt_correction_T_max  0.7449

_exptl_special_details           
;
;

_diffrn_ambient_temperature      100.(2)

_diffrn_source                   'Sealed tube'
_diffrn_source_type              'Fine Focus'

_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_monochromator  Graphite

_diffrn_measurement_device_type  'Bruker Kappa APEX II'
_diffrn_measurement_method       'phi and omega scan'

_diffrn_detector_area_resol_mean 8.3333

_diffrn_reflns_number            10571
_diffrn_reflns_av_R_equivalents  0.1440
_diffrn_reflns_av_unetI/netI     0.1604
_diffrn_reflns_theta_min         1.88
_diffrn_reflns_theta_max         23.74
_diffrn_reflns_theta_full        23.74
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measured_fraction_theta_full 0.982
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12

_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.
;

_reflns_number_total             2970
_reflns_number_gt                1595
_reflns_threshold_expression     >2sigma(I)

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_R_factor_all          0.1679
_refine_ls_R_factor_gt           0.0903
_refine_ls_wR_factor_gt          0.2182
_refine_ls_wR_factor_ref         0.2625
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_restrained_S_all      1.023
_refine_ls_number_reflns         2970
_refine_ls_number_parameters     255
_refine_ls_number_restraints     0
_refine_ls_hydrogen_treatment    mixed
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.1000P)²+0.0000P] where P=(Fo²+2Fc²)/3'

_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap

_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_diff_density_max         0.708
_refine_diff_density_min         -0.975
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?

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'
Si Si 0.0817 0.0704 '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'

_computing_data_collection       'APEX2 V2012.12-0 (Bruker AXS)'
_computing_cell_refinement       'SAINT V8.27B (Bruker AXS Inc., 2012)'
_computing_data_reduction        'SAINT V8.27B (Bruker AXS Inc., 2012)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'SHELXTL (Bruker AXS)'
_computing_publication_material  'SHELXTL (Bruker AXS)'

loop_
_atom_site_type_symbol
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Mn Mn1 0.62245(17) 0.56601(14) 0.54244(13) 0.0346(6) Uani d . 1 . .
Si Si1 0.7486(3) -0.2477(3) 1.0017(3) 0.0366(8) Uani d . 1 . .
O O1 0.5027(8) 0.3221(7) 0.6065(6) 0.0449(18) Uani d . 1 . .
O O2 0.7567(8) 0.4892(6) 0.4098(6) 0.0421(18) Uani d . 1 . .
O O3 0.4269(8) 0.6052(6) 0.6604(6) 0.0438(18) Uani d . 1 . .
O O4 0.6932(8) 0.3988(7) 0.6812(6) 0.0435(18) Uani d . 1 . .
N N1 0.7721(10) 0.7267(7) 0.5286(7) 0.036(2) Uani d . 1 . .
C C1 0.2867(12) 0.5748(9) 0.6593(8) 0.033(2) Uani d . 1 . .
C C2 0.1614(12) 0.6129(9) 0.7481(9) 0.034(2) Uani d . 1 . .
C C3 0.1872(12) 0.6968(10) 0.8126(9) 0.045(3) Uani d . 1 . .
H H4 0.2883 0.7291 0.8042 0.054 Uiso calc R 1 . .
C C4 0.0684(12) 0.7364(10) 0.8909(9) 0.044(3) Uani d . 1 . .
H H3 0.0916 0.7931 0.934 0.053 Uiso calc R 1 . .
C C5 -0.0878(12) 0.6901(9) 0.9047(9) 0.037(2) Uani d . 1 . .
C C6 -0.1140(12) 0.6046(9) 0.8413(9) 0.038(3) Uani d . 1 . .
H H2 -0.2147 0.5716 0.8499 0.046 Uiso calc R 1 . .
C C7 0.0070(14) 0.5653(10) 0.7634(10) 0.048(3) Uani d . 1 . .
H H1 -0.015 0.5072 0.7214 0.058 Uiso calc R 1 . .
C C8 0.6106(12) 0.3073(10) 0.6747(9) 0.038(3) Uani d . 1 . .
C C9 0.6369(11) 0.1743(9) 0.7584(9) 0.034(2) Uani d . 1 . .
C C10 0.7600(12) 0.1490(10) 0.8324(10) 0.053(3) Uani d . 1 . .
H H14 0.8248 0.216 0.8319 0.064 Uiso calc R 1 . .
C C11 0.7866(12) 0.0265(10) 0.9060(10) 0.050(3) Uani d . 1 . .
H H13 0.8678 0.0139 0.9557 0.06 Uiso calc R 1 . .
C C12 0.6989(11) -0.0795(9) 0.9100(9) 0.037(2) Uani d . 1 . .
C C13 0.8181(12) -0.2347(10) 1.1481(9) 0.041(3) Uani d . 1 . .
H H5 0.7319 -0.2065 1.1975 0.061 Uiso calc R 1 . .
H H6 0.9019 -0.1733 1.1279 0.061 Uiso calc R 1 . .
H H7 0.8561 -0.3177 1.1935 0.061 Uiso calc R 1 . .
C C14 0.5763(12) -0.3572(9) 1.0303(9) 0.039(3) Uani d . 1 . .
H H9 0.4857 -0.32 1.0676 0.059 Uiso calc R 1 . .
H H8 0.6011 -0.4399 1.0848 0.059 Uiso calc R 1 . .
H H10 0.5536 -0.3678 0.9533 0.059 Uiso calc R 1 . .
C C15 0.5733(13) -0.0520(10) 0.8371(11) 0.056(3) Uani d . 1 . .
H H12 0.5074 -0.1183 0.838 0.068 Uiso calc R 1 . .
C C16 0.5460(14) 0.0726(10) 0.7638(10) 0.052(3) Uani d . 1 . .
H H11 0.462 0.0869 0.7166 0.062 Uiso calc R 1 . .
C C17 0.7159(16) 0.8237(14) 0.5676(19) 0.128(8) Uani d . 1 . .
H H18 0.6132 0.819 0.6071 0.153 Uiso calc R 1 . .
C C18 0.8006(17) 0.9326(15) 0.5532(19) 0.133(9) Uani d . 1 . .
H H15 0.7508 1.0019 0.5766 0.16 Uiso calc R 1 . .
C C19 0.9512(13) 0.9420(11) 0.5071(10) 0.046(3) Uani d . 1 . .
C C20 1.0135(14) 0.8401(11) 0.4693(12) 0.065(4) Uani d . 1 . .
H H16 1.119 0.8406 0.4363 0.078 Uiso calc R 1 . .
C C21 0.9204(16) 0.7352(10) 0.4796(11) 0.062(4) Uani d . 1 . .
H H17 0.9649 0.6676 0.4505 0.074 Uiso calc R 1 . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
Mn1 O3 . 2.110(7) ?
Mn1 O2 . 2.113(7) ?
Mn1 O4 . 2.145(6) ?
Mn1 O1 2_666 2.149(7) ?
Mn1 N1 . 2.163(8) ?
Mn1 Mn1 2_666 2.989(4) ?
Si1 C14 . 1.870(10) ?
Si1 C12 . 1.873(10) ?
Si1 C13 . 1.881(10) ?
Si1 C5 1_645 1.886(11) ?
O1 C8 . 1.254(12) ?
O1 Mn1 2_666 2.149(7) ?
O2 C1 2_666 1.282(11) ?
O3 C1 . 1.259(11) ?
O4 C8 . 1.266(12) ?
N1 C17 . 1.298(14) ?
N1 C21 . 1.312(13) ?
C1 O2 2_666 1.282(11) ?
C1 C2 . 1.501(14) ?
C2 C3 . 1.360(14) ?
C2 C7 . 1.410(14) ?
C3 C4 . 1.396(14) ?
C3 H4 . 0.93 ?
C4 C5 . 1.421(13) ?
C4 H3 . 0.93 ?
C5 C6 . 1.366(13) ?
C5 Si1 1_465 1.886(11) ?
C6 C7 . 1.403(14) ?
C6 H2 . 0.93 ?
C7 H1 . 0.93 ?
C8 C9 . 1.501(13) ?
C9 C16 . 1.359(14) ?
C9 C10 . 1.396(14) ?
C10 C11 . 1.371(14) ?
C10 H14 . 0.93 ?
C11 C12 . 1.385(14) ?
C11 H13 . 0.93 ?
C12 C15 . 1.406(14) ?
C13 H5 . 0.96 ?
C13 H6 . 0.96 ?
C13 H7 . 0.96 ?
C14 H9 . 0.96 ?
C14 H8 . 0.96 ?
C14 H10 . 0.96 ?
C15 C16 . 1.389(14) ?
C15 H12 . 0.93 ?
C16 H11 . 0.93 ?
C17 C18 . 1.370(17) ?
C17 H18 . 0.93 ?
C18 C19 . 1.322(16) ?
C18 H15 . 0.93 ?
C19 C20 . 1.354(15) ?
C19 C19 2_776 1.50(2) ?
C20 C21 . 1.385(15) ?
C20 H16 . 0.93 ?
C21 H17 . 0.93 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
O3 Mn1 O2 . . 159.8(3) ?
O3 Mn1 O4 . . 92.8(3) ?
O2 Mn1 O4 . . 87.5(3) ?
O3 Mn1 O1 . 2_666 85.8(3) ?
O2 Mn1 O1 . 2_666 86.4(3) ?
O4 Mn1 O1 . 2_666 158.1(3) ?
O3 Mn1 N1 . . 100.4(3) ?
O2 Mn1 N1 . . 98.5(3) ?
O4 Mn1 N1 . . 109.6(3) ?
O1 Mn1 N1 2_666 . 92.1(3) ?
O3 Mn1 Mn1 . 2_666 82.3(2) ?
O2 Mn1 Mn1 . 2_666 77.6(2) ?
O4 Mn1 Mn1 . 2_666 96.3(2) ?
O1 Mn1 Mn1 2_666 2_666 61.8(2) ?
N1 Mn1 Mn1 . 2_666 153.7(2) ?
C14 Si1 C12 . . 111.2(5) ?
C14 Si1 C13 . . 113.1(5) ?
C12 Si1 C13 . . 106.9(5) ?
C14 Si1 C5 . 1_645 107.8(5) ?
C12 Si1 C5 . 1_645 106.7(4) ?
C13 Si1 C5 . 1_645 110.9(5) ?
C8 O1 Mn1 . 2_666 152.1(7) ?
C1 O2 Mn1 2_666 . 130.4(6) ?
C1 O3 Mn1 . . 124.7(6) ?
C8 O4 Mn1 . . 105.3(6) ?
C17 N1 C21 . . 115.9(10) ?
C17 N1 Mn1 . . 120.2(8) ?
C21 N1 Mn1 . . 123.8(7) ?
O3 C1 O2 . 2_666 125.0(9) ?
O3 C1 C2 . . 117.6(9) ?
O2 C1 C2 2_666 . 117.5(9) ?
C3 C2 C7 . . 117.1(10) ?
C3 C2 C1 . . 123.1(9) ?
C7 C2 C1 . . 119.8(9) ?
C2 C3 C4 . . 122.8(10) ?
C2 C3 H4 . . 118.6 ?
C4 C3 H4 . . 118.6 ?
C3 C4 C5 . . 120.1(10) ?
C3 C4 H3 . . 120.0 ?
C5 C4 H3 . . 120.0 ?
C6 C5 C4 . . 117.4(9) ?
C6 C5 Si1 . 1_465 122.4(8) ?
C4 C5 Si1 . 1_465 120.1(8) ?
C5 C6 C7 . . 121.8(10) ?
C5 C6 H2 . . 119.1 ?
C7 C6 H2 . . 119.1 ?
C6 C7 C2 . . 120.8(10) ?
C6 C7 H1 . . 119.6 ?
C2 C7 H1 . . 119.6 ?
O1 C8 O4 . . 123.8(9) ?
O1 C8 C9 . . 117.7(10) ?
O4 C8 C9 . . 118.3(9) ?
C16 C9 C10 . . 116.8(9) ?
C16 C9 C8 . . 122.2(9) ?
C10 C9 C8 . . 121.0(10) ?
C11 C10 C9 . . 120.8(10) ?
C11 C10 H14 . . 119.6 ?
C9 C10 H14 . . 119.6 ?
C10 C11 C12 . . 123.5(10) ?
C10 C11 H13 . . 118.3 ?
C12 C11 H13 . . 118.3 ?
C11 C12 C15 . . 115.0(9) ?
C11 C12 Si1 . . 122.4(7) ?
C15 C12 Si1 . . 122.6(8) ?
Si1 C13 H5 . . 109.5 ?
Si1 C13 H6 . . 109.5 ?
H5 C13 H6 . . 109.5 ?
Si1 C13 H7 . . 109.5 ?
H5 C13 H7 . . 109.5 ?
H6 C13 H7 . . 109.5 ?
Si1 C14 H9 . . 109.5 ?
Si1 C14 H8 . . 109.5 ?
H9 C14 H8 . . 109.5 ?
Si1 C14 H10 . . 109.5 ?
H9 C14 H10 . . 109.5 ?
H8 C14 H10 . . 109.5 ?
C16 C15 C12 . . 121.2(10) ?
C16 C15 H12 . . 119.4 ?
C12 C15 H12 . . 119.4 ?
C9 C16 C15 . . 122.7(10) ?
C9 C16 H11 . . 118.7 ?
C15 C16 H11 . . 118.7 ?
N1 C17 C18 . . 123.2(12) ?
N1 C17 H18 . . 118.4 ?
C18 C17 H18 . . 118.4 ?
C19 C18 C17 . . 121.9(12) ?
C19 C18 H15 . . 119.1 ?
C17 C18 H15 . . 119.1 ?
C18 C19 C20 . . 115.7(11) ?
C18 C19 C19 . 2_776 123.5(14) ?
C20 C19 C19 . 2_776 120.8(13) ?
C19 C20 C21 . . 120.2(11) ?
C19 C20 H16 . . 119.9 ?
C21 C20 H16 . . 119.9 ?
N1 C21 C20 . . 123.0(11) ?
N1 C21 H17 . . 118.5 ?
C20 C21 H17 . . 118.5 ?
