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

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#                                CCDC 
# 
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#  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.
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#  fide research purposes only. It may contain copyright material
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data_1
_audit_creation_date             2014-10-20
_audit_creation_method           
;
Olex2 1.2-alpha
(compiled 2014.10.08 svn.r3027 for OlexSys, GUI svn.r3563)
;
_shelxl_version_number           2014/6
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '0.5(C84 H60 Fe6 Mn6 N36 O6)'
_chemical_formula_sum            'C42 H32 Fe3 Mn3 N18 O4'
_chemical_formula_weight         1185.22
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0030 0.0020 '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'
Fe Fe 0.3460 0.8440 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn 0.3370 0.7280 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0060 0.0030 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0110 0.0060 '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      trigonal
_space_group_IT_number           148
_space_group_name_H-M_alt        'R -3'
_space_group_name_Hall           '-R 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'

_cell_length_a                   29.511(5)
_cell_length_b                   29.511(5)
_cell_length_c                   9.591(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     7234(4)
_cell_formula_units_Z            6
_cell_measurement_reflns_used    ?
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      ?
_cell_measurement_theta_min      ?
_shelx_estimated_absorpt_T_max   0.727
_shelx_estimated_absorpt_T_min   0.686
_exptl_absorpt_coefficient_mu    1.702
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.632
_exptl_crystal_density_meas      .
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             3570
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0624
_diffrn_reflns_av_unetI/netI     0.0534
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            16640
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.577
_diffrn_reflns_theta_min         2.268
_diffrn_reflns_v_R_equivalents   ?
_diffrn_ambient_temperature      296(2)
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_special_details          ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                2640
_reflns_number_total             3732
_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       ?
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        ?
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2008)'
_refine_diff_density_max         1.025
_refine_diff_density_min         -0.909
_refine_diff_density_rms         0.091
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     190
_refine_ls_number_reflns         3732
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0738
_refine_ls_R_factor_gt           0.0494
_refine_ls_restrained_S_all      1.051
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0610P)²+6.6253P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1188
_refine_ls_wR_factor_ref         0.1278
_refine_special_details          
"The solvent masking routine available from Olex2 has been used to deal with two completely disordered water molecules present in the cavities. The number of electrons present in each of the three cavities (per unit cell) was 37.7, which correlates very well with the number of electrons expected for two water molecules (36). The value of Z' was set to 6, thereby achieving and all-integral sum formula."
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Others
 Fixed U11: Fe1(0.030333) Mn2(0.032667) C1(0.042333)
 Fixed U12: Fe1(0.002887) Mn2(0.011547) C1(0.006351)
 Fixed U13: Fe1(-0) Mn2(0) C1(0.000577)
 Fixed U22: Fe1(0.035) Mn2(0.054) C1(0.099)
 Fixed U23: Fe1(0.002) Mn2(0) C1(0.015)
 Fixed U33: Fe1(0.016) Mn2(0.021) C1(0.034)
3.a Riding coordinates:
 O1(H1A,H1B)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_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
Fe1 Fe 0.49070(2) 0.12834(2) 0.61184(5) 0.027 Uani 1 1 d . . . . .
Mn2 Mn 0.53415(2) 0.17872(2) 0.12650(5) 0.036 Uani 1 1 d . . . . .
C1 C 0.38184(19) 0.1109(2) 0.6485(4) 0.058 Uani 1 1 d . . . . .
H1 H 0.3967 0.1470 0.6527 0.070 Uiso 1 1 calc R . . . .
C2 C 0.3278(2) 0.0792(3) 0.6582(5) 0.0755(19) Uani 1 1 d . . . . .
H2 H 0.3071 0.0945 0.6697 0.091 Uiso 1 1 calc R . . . .
C3 C 0.3048(2) 0.0265(3) 0.6514(5) 0.085(2) Uani 1 1 d . . . . .
H3 H 0.2686 0.0055 0.6547 0.102 Uiso 1 1 calc R . . . .
C4 C 0.33618(19) 0.0050(2) 0.6395(4) 0.0645(15) Uani 1 1 d . . . . .
H4 H 0.3213 -0.0312 0.6371 0.077 Uiso 1 1 calc R . . . .
C5 C 0.39045(16) 0.03695(18) 0.6309(4) 0.0438(10) Uani 1 1 d . . . . .
C6 C 0.42679(17) 0.01782(16) 0.6326(4) 0.0412(10) Uani 1 1 d . . . . .
C7 C 0.4131(2) -0.03428(18) 0.6390(4) 0.0604(14) Uani 1 1 d . . . . .
H7 H 0.3783 -0.0601 0.6276 0.072 Uiso 1 1 calc R . . . .
C8 C 0.4506(3) -0.0483(2) 0.6623(5) 0.0702(17) Uani 1 1 d . . . . .
H8 H 0.4416 -0.0833 0.6666 0.084 Uiso 1 1 calc R . . . .
C9 C 0.5015(2) -0.0092(2) 0.6788(5) 0.0601(13) Uani 1 1 d . . . . .
H9 H 0.5275 -0.0172 0.6995 0.072 Uiso 1 1 calc R . . . .
C10 C 0.51360(18) 0.04190(16) 0.6645(4) 0.0431(10) Uani 1 1 d . . . . .
H10 H 0.5485 0.0680 0.6722 0.052 Uiso 1 1 calc R . . . .
C11 C 0.49831(15) 0.13904(14) 0.8096(4) 0.0329(8) Uani 1 1 d . . . . .
C12 C 0.56355(16) 0.15750(15) 0.5888(3) 0.0331(8) Uani 1 1 d . . . . .
C13 C 0.49706(17) 0.19469(17) 0.5870(4) 0.0391(9) Uani 1 1 d . . . . .
C14 C 0.48652(14) 0.12209(14) 0.4115(4) 0.0322(8) Uani 1 1 d . . . . .
N1 N 0.41306(13) 0.08997(14) 0.6331(3) 0.0392(8) Uani 1 1 d . . . . .
N2 N 0.47782(13) 0.05621(12) 0.6398(3) 0.0331(7) Uani 1 1 d . . . . .
N3 N 0.50221(14) 0.14381(14) 0.9283(3) 0.0447(9) Uani 1 1 d . . . . .
N4 N 0.60799(14) 0.17452(14) 0.5679(3) 0.0468(9) Uani 1 1 d . . . . .
N5 N 0.50130(16) 0.23526(15) 0.5654(4) 0.0534(10) Uani 1 1 d . . . . .
N6 N 0.48856(13) 0.12484(13) 0.2910(3) 0.0383(8) Uani 1 1 d . . . . .
O1 O 0.58282(12) 0.23394(12) 0.3132(3) 0.0572(8) Uani 1 1 d . . . . .
H1A H 0.5745 0.2576 0.3247 0.086 Uiso 1 1 d R . . . .
H1B H 0.5763 0.2161 0.3883 0.086 Uiso 1 1 d 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
Fe1 C11 1.918(4) . ?
Fe1 C12 1.887(4) . ?
Fe1 C13 1.886(4) . ?
Fe1 C14 1.929(4) . ?
Fe1 N1 1.995(3) . ?
Fe1 N2 1.985(3) . ?
Mn2 N3 2.143(3) 1_554 ?
Mn2 N4 2.122(4) 17 ?
Mn2 N5 2.115(4) 18_545 ?
Mn2 N6 2.166(3) . ?
Mn2 O1 2.363(3) . ?
C1 H1 0.9300 . ?
C1 C2 1.392(7) . ?
C1 N1 1.349(5) . ?
C2 H2 0.9300 . ?
C2 C3 1.352(9) . ?
C3 H3 0.9300 . ?
C3 C4 1.364(8) . ?
C4 H4 0.9300 . ?
C4 C5 1.397(6) . ?
C5 C6 1.440(6) . ?
C5 N1 1.360(5) . ?
C6 C7 1.382(6) . ?
C6 N2 1.360(5) . ?
C7 H7 0.9300 . ?
C7 C8 1.380(8) . ?
C8 H8 0.9300 . ?
C8 C9 1.371(8) . ?
C9 H9 0.9300 . ?
C9 C10 1.372(6) . ?
C10 H10 0.9300 . ?
C10 N2 1.340(5) . ?
C11 N3 1.145(4) . ?
C12 N4 1.164(5) . ?
C13 N5 1.159(5) . ?
C14 N6 1.157(4) . ?
N3 Mn2 2.143(3) 1_556 ?
N4 Mn2 2.123(4) 18_545 ?
N5 Mn2 2.115(4) 17 ?
O1 H1A 0.8570 . ?
O1 H1B 0.8564 . ?

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
C11 Fe1 C14 176.39(16) . . ?
C11 Fe1 N1 89.95(14) . . ?
C11 Fe1 N2 89.23(13) . . ?
C12 Fe1 C11 91.59(15) . . ?
C12 Fe1 C14 86.03(15) . . ?
C12 Fe1 N1 173.78(16) . . ?
C12 Fe1 N2 93.92(15) . . ?
C13 Fe1 C11 90.67(16) . . ?
C13 Fe1 C12 90.72(17) . . ?
C13 Fe1 C14 86.66(15) . . ?
C13 Fe1 N1 95.29(17) . . ?
C13 Fe1 N2 175.37(16) . . ?
C14 Fe1 N1 92.70(14) . . ?
C14 Fe1 N2 93.63(13) . . ?
N2 Fe1 N1 80.08(14) . . ?
N3 Mn2 N6 109.33(13) 1_554 . ?
N3 Mn2 O1 166.72(13) 1_554 . ?
N4 Mn2 N3 90.78(13) 17 1_554 ?
N4 Mn2 N6 108.62(13) 17 . ?
N4 Mn2 O1 84.20(12) 17 . ?
N5 Mn2 N3 92.33(13) 18_545 1_554 ?
N5 Mn2 N4 143.52(16) 18_545 17 ?
N5 Mn2 N6 104.54(14) 18_545 . ?
N5 Mn2 O1 84.58(13) 18_545 . ?
N6 Mn2 O1 83.95(12) . . ?
C2 C1 H1 119.5 . . ?
N1 C1 H1 119.5 . . ?
N1 C1 C2 121.0(6) . . ?
C1 C2 H2 119.4 . . ?
C3 C2 C1 121.1(6) . . ?
C3 C2 H2 119.4 . . ?
C2 C3 H3 120.9 . . ?
C2 C3 C4 118.2(6) . . ?
C4 C3 H3 120.9 . . ?
C3 C4 H4 119.8 . . ?
C3 C4 C5 120.4(6) . . ?
C5 C4 H4 119.8 . . ?
C4 C5 C6 124.2(5) . . ?
N1 C5 C4 120.9(5) . . ?
N1 C5 C6 114.7(4) . . ?
C7 C6 C5 125.1(4) . . ?
N2 C6 C5 113.9(4) . . ?
N2 C6 C7 120.7(4) . . ?
C6 C7 H7 119.8 . . ?
C8 C7 C6 120.5(5) . . ?
C8 C7 H7 119.8 . . ?
C7 C8 H8 120.9 . . ?
C9 C8 C7 118.2(5) . . ?
C9 C8 H8 120.9 . . ?
C8 C9 H9 120.4 . . ?
C8 C9 C10 119.1(5) . . ?
C10 C9 H9 120.4 . . ?
C9 C10 H10 118.3 . . ?
N2 C10 C9 123.4(5) . . ?
N2 C10 H10 118.3 . . ?
N3 C11 Fe1 177.9(3) . . ?
N4 C12 Fe1 176.6(3) . . ?
N5 C13 Fe1 177.0(3) . . ?
N6 C14 Fe1 171.5(3) . . ?
C1 N1 Fe1 127.2(3) . . ?
C1 N1 C5 118.3(4) . . ?
C5 N1 Fe1 114.5(3) . . ?
C6 N2 Fe1 115.1(3) . . ?
C10 N2 Fe1 127.1(3) . . ?
C10 N2 C6 117.7(4) . . ?
C11 N3 Mn2 159.0(3) . 1_556 ?
C12 N4 Mn2 175.4(3) . 18_545 ?
C13 N5 Mn2 175.8(4) . 17 ?
C14 N6 Mn2 140.4(3) . . ?
Mn2 O1 H1A 109.7 . . ?
Mn2 O1 H1B 109.9 . . ?
H1A O1 H1B 109.1 . . ?

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
C1 C2 C3 C4 2.2(7) . . . . ?
C2 C1 N1 Fe1 178.1(3) . . . . ?
C2 C1 N1 C5 -1.7(5) . . . . ?
C2 C3 C4 C5 -1.7(7) . . . . ?
C3 C4 C5 C6 173.3(4) . . . . ?
C3 C4 C5 N1 -0.5(6) . . . . ?
C4 C5 C6 C7 1.9(6) . . . . ?
C4 C5 C6 N2 -172.6(3) . . . . ?
C4 C5 N1 Fe1 -177.6(3) . . . . ?
C4 C5 N1 C1 2.2(5) . . . . ?
C5 C6 C7 C8 -169.7(4) . . . . ?
C5 C6 N2 Fe1 -10.6(4) . . . . ?
C5 C6 N2 C10 169.5(3) . . . . ?
C6 C5 N1 Fe1 8.0(4) . . . . ?
C6 C5 N1 C1 -172.2(3) . . . . ?
C6 C7 C8 C9 0.1(6) . . . . ?
C7 C6 N2 Fe1 174.7(3) . . . . ?
C7 C6 N2 C10 -5.2(5) . . . . ?
C7 C8 C9 C10 -3.4(6) . . . . ?
C8 C9 C10 N2 2.6(6) . . . . ?
C9 C10 N2 Fe1 -178.1(3) . . . . ?
C9 C10 N2 C6 1.8(5) . . . . ?
N1 C1 C2 C3 -0.6(7) . . . . ?
N1 C5 C6 C7 176.1(4) . . . . ?
N1 C5 C6 N2 1.6(4) . . . . ?
N2 C6 C7 C8 4.4(6) . . . . ?

_smtbx_masks_special_details     ?
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 0.000 0.000 -0.327 229.1 34.7 ?
2 0.333 0.667 -0.228 229.1 34.7 ?
3 0.667 0.333 -0.561 229.1 34.7 ?

_olex2_submission_special_instructions 'No special instructions were received'
_database_code_depnum_ccdc_archive 'CCDC 994569'
