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

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

data_compound1
_database_code_depnum_ccdc_archive 'CCDC 1529646'
_audit_update_record             
;
2017-01-25 deposited with the CCDC.
2017-02-28 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        compound1
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         {[Mn3(bipy)3(H2O)4][Mn(CN)6]2.2(bipy).4H2O}n
_chemical_formula_sum            'C62 H56 Mn5 N22 O8'
_chemical_formula_weight         1511.98

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'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           55
_space_group_name_H-M_alt        'P b a m'
_space_group_name_Hall           '-P 2 2ab'

_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.
;

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

_cell_length_a                   16.2079(18)
_cell_length_b                   17.833(2)
_cell_length_c                   11.6508(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3367.6(6)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    9976
_cell_measurement_theta_min      2.56
_cell_measurement_theta_max      25.32

_exptl_crystal_description       block
_exptl_crystal_colour            brown
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.491
_exptl_crystal_F_000             1542
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.120
_exptl_crystal_size_min          0.070
_exptl_absorpt_coefficient_mu    0.982
_shelx_estimated_absorpt_T_min   0.828
_shelx_estimated_absorpt_T_max   0.934
_exptl_absorpt_correction_type   EMPIRICAL
_exptl_absorpt_correction_T_min  0.9142
_exptl_absorpt_correction_T_max  0.9576
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            56112
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_av_R_equivalents  0.0606
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.877
_diffrn_reflns_theta_max         28.345
_diffrn_reflns_theta_full        27.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             4394
_reflns_number_gt                3331
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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.
;

_computing_data_collection       'Bruker APEX3'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT  A'
_computing_structure_solution    'SHELXT (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0804P)²+1.2421P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   NOREF
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4394
_refine_ls_number_parameters     243
_refine_ls_number_restraints     24
_refine_ls_R_factor_all          0.0604
_refine_ls_R_factor_gt           0.0433
_refine_ls_wR_factor_ref         0.1353
_refine_ls_wR_factor_gt          0.1238
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_restrained_S_all      1.041
_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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.0884(2) 0.36889(19) 1.000000 0.0322(7) Uani 1 2 d S T P . .
C2 C 0.1667(2) 0.5012(2) 1.000000 0.0318(7) Uani 1 2 d S T P . .
C3 C 0.19890(15) 0.39990(13) 0.8357(2) 0.0392(6) Uani 1 1 d . . . . .
C4 C 0.2385(2) 0.2998(2) 1.000000 0.0298(7) Uani 1 2 d S T P . .
C5 C 0.3098(2) 0.43146(19) 1.000000 0.0312(7) Uani 1 2 d S T P . .
C6 C 0.4593(2) 0.4495(2) 0.7446(2) 0.0670(10) Uani 1 1 d . . . . .
H6 H 0.429639 0.413051 0.784164 0.080 Uiso 1 1 calc R U . . .
C7 C 0.4582(2) 0.4475(2) 0.6266(2) 0.0708(11) Uani 1 1 d . . . . .
H7 H 0.428698 0.410130 0.589031 0.085 Uiso 1 1 calc R U . . .
C8 C 0.500000 0.500000 0.5640(3) 0.0361(8) Uani 1 2 d S T P . .
C9 C 0.4339(3) 0.1300(2) 0.7457(3) 0.0780(11) Uani 1 1 d . U . . .
H9 H 0.460547 0.091980 0.785865 0.094 Uiso 1 1 calc R U . . .
C10 C 0.4388(3) 0.1300(2) 0.6269(3) 0.0773(11) Uani 1 1 d . U . . .
H10 H 0.468214 0.092487 0.589506 0.093 Uiso 1 1 calc R U . . .
C11 C 0.40016(18) 0.18545(17) 0.5637(2) 0.0481(7) Uani 1 1 d . U . . .
C12 C 0.3592(2) 0.23957(17) 0.6256(2) 0.0533(7) Uani 1 1 d . U . . .
H12 H 0.333106 0.278842 0.587710 0.064 Uiso 1 1 calc R U . . .
C13 C 0.3567(2) 0.23576(17) 0.7444(2) 0.0512(7) Uani 1 1 d . U . . .
H13 H 0.328285 0.272984 0.783835 0.061 Uiso 1 1 calc R U . . .
C14 C 0.3106(2) 0.5920(2) 0.7443(3) 0.0720(10) Uani 1 1 d . . . . .
H14 H 0.286930 0.552295 0.784304 0.086 Uiso 1 1 calc R U . . .
C15 C 0.3021(2) 0.5932(2) 0.6262(3) 0.0669(10) Uani 1 1 d . . . . .
H15 H 0.273998 0.554820 0.588916 0.080 Uiso 1 1 calc R U . . .
C16 C 0.33522(18) 0.65146(16) 0.5641(2) 0.0477(7) Uani 1 1 d . . . . .
C17 C 0.3717(3) 0.7074(2) 0.6271(3) 0.0777(11) Uani 1 1 d . . . . .
H17 H 0.392299 0.749537 0.590013 0.093 Uiso 1 1 calc R U . . .
C18 C 0.3781(3) 0.7017(2) 0.7456(3) 0.0839(13) Uani 1 1 d . . . . .
H18 H 0.403179 0.740585 0.785759 0.101 Uiso 1 1 calc R U . . .
N1 N 0.02051(19) 0.35099(18) 1.000000 0.0420(7) Uani 1 2 d S T P . .
N2 N 0.1506(2) 0.56365(17) 1.000000 0.0425(7) Uani 1 2 d S T P . .
N3 N 0.20029(19) 0.40081(16) 0.7367(2) 0.0679(9) Uani 1 1 d . . . . .
N4 N 0.27124(19) 0.24251(16) 1.000000 0.0354(6) Uani 1 2 d S T P . .
N5 N 0.37788(19) 0.44824(18) 1.000000 0.0398(7) Uani 1 2 d S T P . .
N6 N 0.500000 0.500000 0.8051(2) 0.0379(7) Uani 1 2 d S T P . .
N7 N 0.39288(15) 0.18172(13) 0.80501(19) 0.0460(6) Uani 1 1 d . . . . .
N8 N 0.3500(2) 0.64355(18) 0.8034(2) 0.0656(8) Uani 1 1 d . . . . .
O1W O 0.43960(18) 0.29312(16) 1.000000 0.0724(11) Uani 1 2 d S T P . .
H1O1 H 0.499051 0.304481 1.000000 0.109 Uiso 1 2 d R U P . .
H2O1 H 0.410911 0.331921 1.000000 0.109 Uiso 1 2 d R U P . .
O2W O 0.43063(16) 0.61000(14) 1.000000 0.0386(6) Uani 1 2 d S T P . .
H1O2 H 0.400489 0.620755 0.929510 0.058 Uiso 1 1 d R U . . .
O3W O 0.2704(3) 0.3966(3) 0.500000 0.1067(15) Uani 1 2 d S T P . .
H1O3 H 0.250747 0.388379 0.576370 0.160 Uiso 1 1 d R U . . .
O4W O 0.1044(8) 0.4552(10) 0.500000 0.465(11) Uani 1 2 d S T P . .
H1O4 H 0.113223 0.439707 0.578570 0.697 Uiso 1 1 d R U . . .
Mn1 Mn 0.19940(2) 0.39971(2) 1.000000 0.01962(14) Uani 1 2 d S T P . .
Mn2 Mn 0.500000 0.500000 1.000000 0.03051(19) Uani 1 4 d S T P . .
Mn3 Mn 0.38922(3) 0.17837(3) 1.000000 0.02669(15) Uani 1 2 d S T P . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 N1 1.146(5) . ?
C1 Mn1 1.881(4) . ?
C2 N2 1.144(5) . ?
C2 Mn1 1.885(3) . ?
C3 N3 1.154(4) . ?
C3 Mn1 1.914(3) . ?
C4 N4 1.152(4) . ?
C4 Mn1 1.891(4) . ?
C5 N5 1.143(4) . ?
C5 Mn1 1.877(3) . ?
C6 N6 1.320(3) . ?
C6 C7 1.376(4) . ?
C7 C8 1.366(3) . ?
C8 C8 1.492(6) 5_666 ?
C9 N7 1.331(4) . ?
C9 C10 1.386(4) . ?
C10 C11 1.383(4) . ?
C11 C12 1.376(4) . ?
C11 C11 1.484(5) 6_556 ?
C12 C13 1.385(4) . ?
C13 N7 1.331(4) . ?
C14 N8 1.315(5) . ?
C14 C15 1.383(5) . ?
C15 C16 1.375(4) . ?
C16 C17 1.372(5) . ?
C16 C16 1.493(5) 6_556 ?
C17 C18 1.388(5) . ?
C18 N8 1.318(5) . ?
N1 Mn3 2.191(3) 3_457 ?
N2 Mn3 2.145(3) 7_665 ?
N4 Mn3 2.228(3) . ?
N5 Mn2 2.184(3) . ?
N6 Mn2 2.271(3) . ?
N7 Mn3 2.273(2) . ?
O1W Mn3 2.203(3) . ?
O2W Mn2 2.261(2) . ?

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
N1 C1 Mn1 179.2(3) . . ?
N2 C2 Mn1 176.8(3) . . ?
N3 C3 Mn1 178.5(3) . . ?
N4 C4 Mn1 172.1(3) . . ?
N5 C5 Mn1 177.6(3) . . ?
N6 C6 C7 123.8(3) . . ?
C8 C7 C6 120.7(3) . . ?
C7 C8 C7 115.5(3) . 2_665 ?
C7 C8 C8 122.25(17) . 5_666 ?
C7 C8 C8 122.25(17) 2_665 5_666 ?
N7 C9 C10 123.2(3) . . ?
C11 C10 C9 120.4(3) . . ?
C12 C11 C10 116.1(3) . . ?
C12 C11 C11 121.64(16) . 6_556 ?
C10 C11 C11 122.18(18) . 6_556 ?
C11 C12 C13 120.2(3) . . ?
N7 C13 C12 123.6(3) . . ?
N8 C14 C15 123.9(3) . . ?
C16 C15 C14 119.8(3) . . ?
C17 C16 C15 115.8(3) . . ?
C17 C16 C16 122.4(2) . 6_556 ?
C15 C16 C16 121.76(19) . 6_556 ?
C16 C17 C18 120.8(4) . . ?
N8 C18 C17 122.7(4) . . ?
C1 N1 Mn3 177.6(3) . 3_457 ?
C2 N2 Mn3 175.6(3) . 7_665 ?
C4 N4 Mn3 148.3(3) . . ?
C5 N5 Mn2 170.2(3) . . ?
C6 N6 C6 115.5(3) . 2_665 ?
C6 N6 Mn2 122.24(16) . . ?
C6 N6 Mn2 122.25(16) 2_665 . ?
C13 N7 C9 116.5(2) . . ?
C13 N7 Mn3 122.56(19) . . ?
C9 N7 Mn3 120.91(19) . . ?
C14 N8 C18 116.8(3) . . ?
C5 Mn1 C1 179.43(14) . . ?
C5 Mn1 C2 88.78(14) . . ?
C1 Mn1 C2 90.64(14) . . ?
C5 Mn1 C4 87.99(14) . . ?
C1 Mn1 C4 92.59(14) . . ?
C2 Mn1 C4 176.77(14) . . ?
C5 Mn1 C3 90.20(8) . . ?
C1 Mn1 C3 89.80(8) . . ?
C2 Mn1 C3 89.84(7) . . ?
C4 Mn1 C3 90.18(7) . . ?
C5 Mn1 C3 90.20(8) . 6_557 ?
C1 Mn1 C3 89.80(8) . 6_557 ?
C2 Mn1 C3 89.83(7) . 6_557 ?
C4 Mn1 C3 90.18(7) . 6_557 ?
C3 Mn1 C3 179.47(16) . 6_557 ?
N5 Mn2 N5 180.0 . 5_667 ?
N5 Mn2 O2W 94.82(11) . 5_667 ?
N5 Mn2 O2W 85.19(11) 5_667 5_667 ?
N5 Mn2 O2W 85.18(11) . . ?
N5 Mn2 O2W 94.82(11) 5_667 . ?
O2W Mn2 O2W 180.00(11) 5_667 . ?
N5 Mn2 N6 90.0 . . ?
N5 Mn2 N6 90.0 5_667 . ?
O2W Mn2 N6 90.0 5_667 . ?
O2W Mn2 N6 90.0 . . ?
N5 Mn2 N6 90.000(1) . 5_667 ?
N5 Mn2 N6 90.000(1) 5_667 5_667 ?
O2W Mn2 N6 90.0 5_667 5_667 ?
O2W Mn2 N6 90.0 . 5_667 ?
N6 Mn2 N6 180.0 . 5_667 ?
N2 Mn3 N1 93.70(12) 7_655 3_557 ?
N2 Mn3 O1W 175.77(12) 7_655 . ?
N1 Mn3 O1W 82.07(12) 3_557 . ?
N2 Mn3 N4 103.37(12) 7_655 . ?
N1 Mn3 N4 162.94(12) 3_557 . ?
O1W Mn3 N4 80.87(11) . . ?
N2 Mn3 N7 91.89(6) 7_655 . ?
N1 Mn3 N7 88.91(6) 3_557 . ?
O1W Mn3 N7 88.05(6) . . ?
N4 Mn3 N7 90.51(6) . . ?
N2 Mn3 N7 91.89(6) 7_655 6_557 ?
N1 Mn3 N7 88.91(6) 3_557 6_557 ?
O1W Mn3 N7 88.05(6) . 6_557 ?
N4 Mn3 N7 90.51(6) . 6_557 ?
N7 Mn3 N7 175.75(13) . 6_557 ?

_refine_diff_density_max         0.815
_refine_diff_density_min         -0.569
_refine_diff_density_rms         0.079


_exptl_crystal_recrystallization_method 'room temperature reaction'
_chemical_properties_physical    
', Heat-sensitive,Light-sensitive,Photo-sensitive'
_exptl_crystal_preparation       ', Magnetic properties'
####################################################################### 
# 
# 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_compound1b
_database_code_depnum_ccdc_archive 'CCDC 1529647'
_audit_update_record             
;
2017-01-25 deposited with the CCDC.
2017-02-28 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        compound1b
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         {[Mn3(bipy)3(H2O)2][Mn(CN)6]2.2(bipy).2H2O}n
_chemical_formula_sum            'C62 H48 Mn5 N22 O4'
_chemical_formula_weight         1439.92

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'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           55
_space_group_name_H-M_alt        'P b a m'
_space_group_name_Hall           '-P 2 2ab'

_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.
;

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

_cell_length_a                   16.039(5)
_cell_length_b                   17.851(4)
_cell_length_c                   11.558(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3309.3(16)
_cell_formula_units_Z            2
_cell_measurement_temperature    408(2)
_cell_measurement_reflns_used    2634
_cell_measurement_theta_min      2.87
_cell_measurement_theta_max      25.01

_exptl_crystal_description       block
_exptl_crystal_colour            brown
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.445
_exptl_crystal_F_000             1462
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.120
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    0.991
_shelx_estimated_absorpt_T_min   0.866
_shelx_estimated_absorpt_T_max   0.907
_exptl_absorpt_correction_type   EMPIRICAL
_exptl_absorpt_correction_T_min  0.8912
_exptl_absorpt_correction_T_max  0.9683
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      408(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            18701
_diffrn_reflns_av_unetI/netI     0.2450
_diffrn_reflns_av_R_equivalents  0.1094
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         2.282
_diffrn_reflns_theta_max         24.996
_diffrn_reflns_theta_full        24.996
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measured_fraction_theta_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_point_group_measured_fraction_full 0.979
_reflns_number_total             3018
_reflns_number_gt                1400
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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.
;

_computing_data_collection       'Bruker APEX3'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT A'
_computing_structure_solution    'SHELXT (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1230P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   NOREF
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_extinction_coef       0.053(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         3018
_refine_ls_number_parameters     232
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.1379
_refine_ls_R_factor_gt           0.1098
_refine_ls_wR_factor_ref         0.2883
_refine_ls_wR_factor_gt          0.2647
_refine_ls_goodness_of_fit_ref   0.935
_refine_ls_restrained_S_all      0.935
_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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.0859(8) 0.3483(7) 1.000000 0.062(3) Uani 1 2 d S T P . .
C2 C 0.1569(9) 0.4982(7) 1.000000 0.071(3) Uani 1 2 d S TU P . .
C3 C 0.2001(6) 0.3924(6) 0.8215(10) 0.077(3) Uani 1 1 d . . . . .
C4 C 0.2519(8) 0.2895(8) 1.000000 0.065(3) Uani 1 2 d S T P . .
C5 C 0.3159(8) 0.4316(8) 1.000000 0.069(3) Uani 1 2 d S T P . .
C6 C 0.4602(7) 0.4506(6) 1.2554(8) 0.090(3) Uani 1 1 d . . . . .
H6 H 0.430109 0.414587 1.214971 0.108 Uiso 1 1 calc R U . . .
C7 C 0.4592(8) 0.4476(7) 1.3716(8) 0.101(4) Uani 1 1 d . . . . .
H7 H 0.430115 0.408946 1.407516 0.121 Uiso 1 1 calc R U . . .
C8 C 0.500000 0.500000 1.4402(9) 0.062(3) Uani 1 2 d S T P . .
C9 C 0.4435(10) 0.1319(8) 1.2553(11) 0.145(7) Uani 1 1 d . . . . .
H9 H 0.473363 0.095516 1.215394 0.174 Uiso 1 1 calc R U . . .
C10 C 0.4496(10) 0.1316(8) 1.3715(10) 0.135(6) Uani 1 1 d . . . . .
H10 H 0.482889 0.096167 1.408074 0.162 Uiso 1 1 calc R U . . .
C11 C 0.4072(6) 0.1832(6) 1.4357(8) 0.077(3) Uani 1 1 d . . . . .
C12 C 0.3658(7) 0.2360(6) 1.3750(8) 0.084(3) Uani 1 1 d . . . . .
H12 H 0.339090 0.274999 1.413454 0.101 Uiso 1 1 calc R U . . .
C13 C 0.3631(7) 0.2320(6) 1.2559(8) 0.086(3) Uani 1 1 d . . . . .
H13 H 0.334030 0.268875 1.215872 0.103 Uiso 1 1 calc R U . . .
C14 C 0.3096(10) 0.5901(10) 1.2543(15) 0.128(6) Uani 1 1 d . . . . .
H14 H 0.283895 0.551936 1.212655 0.154 Uiso 1 1 calc R U . . .
C15 C 0.3020(8) 0.5864(8) 1.3732(14) 0.116(4) Uani 1 1 d . . . . .
H15 H 0.277647 0.545000 1.408532 0.140 Uiso 1 1 calc R U . . .
C16 C 0.3320(6) 0.6467(6) 1.4397(8) 0.085(3) Uani 1 1 d . . . . .
C17 C 0.3628(10) 0.7036(8) 1.3754(13) 0.121(4) Uani 1 1 d . . . . .
H17 H 0.376832 0.748540 1.411256 0.145 Uiso 1 1 calc R U . . .
C18 C 0.3739(12) 0.6960(10) 1.2556(15) 0.142(6) Uani 1 1 d . . . . .
H18 H 0.401995 0.733601 1.215773 0.171 Uiso 1 1 calc R U . . .
N1 N 0.0202(8) 0.3220(7) 1.000000 0.080(3) Uani 1 2 d S T P . .
N2 N 0.1308(8) 0.5571(6) 1.000000 0.083(3) Uani 1 2 d S TU P . .
N3 N 0.2031(7) 0.3916(6) 0.7217(9) 0.117(4) Uani 1 1 d . . . . .
N4 N 0.2933(7) 0.2356(6) 1.000000 0.076(3) Uani 1 2 d S T P . .
N5 N 0.3819(6) 0.4472(9) 1.000000 0.093(4) Uani 1 2 d S T P . .
N6 N 0.500000 0.500000 1.1968(8) 0.071(3) Uani 1 2 d S T P . .
N7 N 0.4004(5) 0.1777(5) 1.1949(7) 0.075(2) Uani 1 1 d . . . . .
N8 N 0.3461(9) 0.6376(9) 1.1972(10) 0.122(4) Uani 1 1 d . . . . .
O2W O 0.4312(7) 0.6070(6) 1.000000 0.090(3) Uani 1 2 d S T P . .
H1O2 H 0.407883 0.614571 1.075980 0.135 Uiso 1 1 d R U . . .
O3W O 0.2787(11) 0.3874(12) 0.500000 0.203(8) Uani 1 2 d S T P . .
H1O3 H 0.259783 0.388434 0.576060 0.304 Uiso 1 1 d R U . . .
Mn1 Mn 0.19965(10) 0.39083(10) 1.000000 0.0573(7) Uani 1 2 d S T P . .
Mn2 Mn 0.500000 0.500000 1.000000 0.0639(8) Uani 1 4 d S T P . .
Mn3 Mn 0.39321(10) 0.16858(10) 1.000000 0.0553(7) Uani 1 2 d S T P . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 N1 1.155(15) . ?
C1 Mn1 1.976(13) . ?
C2 N2 1.131(17) . ?
C2 Mn1 2.036(13) . ?
C3 N3 1.154(13) . ?
C3 Mn1 2.064(12) . ?
C4 N4 1.169(16) . ?
C4 Mn1 1.994(15) . ?
C5 N5 1.093(15) . ?
C5 Mn1 2.002(13) . ?
C6 N6 1.282(10) . ?
C6 C7 1.345(13) . ?
C7 C8 1.390(12) . ?
C8 C8 1.38(2) 5_668 ?
C9 N7 1.277(14) . ?
C9 C10 1.346(15) . ?
C10 C11 1.364(15) . ?
C11 C12 1.350(13) . ?
C11 C11 1.487(18) 6_558 ?
C12 C13 1.380(12) . ?
C13 N7 1.340(12) . ?
C14 N8 1.224(18) . ?
C14 C15 1.381(19) . ?
C15 C16 1.408(16) . ?
C16 C17 1.352(16) . ?
C16 C16 1.39(2) 6_558 ?
C17 C18 1.403(18) . ?
C18 N8 1.32(2) . ?
N1 Mn3 2.043(13) 3_457 ?
N2 Mn3 2.028(12) 7_665 ?
N4 Mn3 2.000(10) . ?
N5 Mn2 2.116(10) . ?
N6 Mn2 2.274(10) . ?
N7 Mn3 2.261(8) . ?
O2W Mn2 2.206(11) . ?

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
N1 C1 Mn1 178.6(12) . . ?
N2 C2 Mn1 178.0(13) . . ?
N3 C3 Mn1 177.4(10) . . ?
N4 C4 Mn1 170.3(11) . . ?
N5 C5 Mn1 173.4(15) . . ?
N6 C6 C7 124.2(10) . . ?
C6 C7 C8 122.5(10) . . ?
C8 C8 C7 124.7(6) 5_668 . ?
C8 C8 C7 124.7(6) 5_668 2_665 ?
C7 C8 C7 110.5(11) . 2_665 ?
N7 C9 C10 126.0(11) . . ?
C9 C10 C11 120.2(11) . . ?
C12 C11 C10 115.7(9) . . ?
C12 C11 C11 121.3(6) . 6_558 ?
C10 C11 C11 123.0(6) . 6_558 ?
C11 C12 C13 119.8(10) . . ?
N7 C13 C12 123.3(10) . . ?
N8 C14 C15 127.7(17) . . ?
C14 C15 C16 118.4(14) . . ?
C17 C16 C16 123.3(8) . 6_558 ?
C17 C16 C15 113.6(12) . . ?
C16 C16 C15 123.1(9) 6_558 . ?
C16 C17 C18 121.1(14) . . ?
N8 C18 C17 122.6(16) . . ?
C1 N1 Mn3 151.2(12) . 3_457 ?
C2 N2 Mn3 169.2(13) . 7_665 ?
C4 N4 Mn3 161.3(11) . . ?
C5 N5 Mn2 168.3(16) . . ?
C6 N6 C6 116.2(12) 2_665 . ?
C6 N6 Mn2 121.9(6) 2_665 . ?
C6 N6 Mn2 121.9(6) . . ?
C9 N7 C13 114.6(9) . . ?
C9 N7 Mn3 121.8(7) . . ?
C13 N7 Mn3 123.6(7) . . ?
C14 N8 C18 115.7(16) . . ?
C1 Mn1 C4 92.3(5) . . ?
C1 Mn1 C5 178.7(5) . . ?
C4 Mn1 C5 86.5(5) . . ?
C1 Mn1 C2 92.9(5) . . ?
C4 Mn1 C2 174.8(5) . . ?
C5 Mn1 C2 88.4(6) . . ?
C1 Mn1 C3 90.5(3) . . ?
C4 Mn1 C3 90.6(3) . . ?
C5 Mn1 C3 89.5(3) . . ?
C2 Mn1 C3 89.4(3) . . ?
C1 Mn1 C3 90.5(3) . 6_557 ?
C4 Mn1 C3 90.6(3) . 6_557 ?
C5 Mn1 C3 89.5(3) . 6_557 ?
C2 Mn1 C3 89.4(3) . 6_557 ?
C3 Mn1 C3 178.4(6) . 6_557 ?
N5 Mn2 N5 180.0 . 5_667 ?
N5 Mn2 O2W 86.5(5) . . ?
N5 Mn2 O2W 93.5(5) 5_667 . ?
N5 Mn2 O2W 93.5(5) . 5_667 ?
N5 Mn2 O2W 86.5(5) 5_667 5_667 ?
O2W Mn2 O2W 180.0 . 5_667 ?
N5 Mn2 N6 90.000(2) . . ?
N5 Mn2 N6 90.000(2) 5_667 . ?
O2W Mn2 N6 90.0 . . ?
O2W Mn2 N6 90.0 5_667 . ?
N5 Mn2 N6 90.000(2) . 5_667 ?
N5 Mn2 N6 90.000(2) 5_667 5_667 ?
O2W Mn2 N6 90.0 . 5_667 ?
O2W Mn2 N6 90.0 5_667 5_667 ?
N6 Mn2 N6 180.0 . 5_667 ?
N4 Mn3 N2 115.8(5) . 7_655 ?
N4 Mn3 N1 138.5(5) . 3_557 ?
N2 Mn3 N1 105.7(5) 7_655 3_557 ?
N4 Mn3 N7 89.9(2) . 6_557 ?
N2 Mn3 N7 94.6(2) 7_655 6_557 ?
N1 Mn3 N7 86.7(2) 3_557 6_557 ?
N4 Mn3 N7 89.9(2) . . ?
N2 Mn3 N7 94.6(2) 7_655 . ?
N1 Mn3 N7 86.7(2) 3_557 . ?
N7 Mn3 N7 169.9(4) 6_557 . ?

_refine_diff_density_max         0.741
_refine_diff_density_min         -0.717
_refine_diff_density_rms         0.122


_chemical_properties_physical    
', Air-sensitive,Moisture-sensitive,Light-sensitive,Photo-sensitive'
_exptl_crystal_preparation       ', Magnetic properties'
