# Supplementary Material (ESI) for New Journal of Chemistry
# This journal is (c) The Royal Society of Chemistry and 
# The Centre National de la Recherche Scientifique, 2009

data_global
_journal_name_full               'New J.Chem.'

_journal_coden_Cambridge         0440
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Rodolphe Clerac'
_publ_contact_author_email       CLERAC@CRPP-BORDEAUX.CNRS.FR

_publ_section_title              
;
Bimetallic Cyanido-Bridged Magnetic Materials Derived
from Manganese(III) Schiff-Base Complexes and Pentacyanidonitrosylferrate(II)
precursor
;
loop_
_publ_author_name
'Rodolphe Clerac'
'Rodica Ababei'
'Nicolas Brefuel'
'Claude Coulon'
'Etienne Harte'
'Marguerite Kalisz'
;
Yang-Guang Li
;
'Xueting Liu.'
'Corine Mathoniere'
'Olivier Roubeau'

# Attachment 'complex_1.cif'

data_1
_database_code_depnum_ccdc_archive 'CCDC 720407'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C39 H36 Br4 Fe Mn2 N10 O9'
_chemical_formula_weight         1274.15

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'
Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Pbca

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

_cell_length_a                   14.851(3)
_cell_length_b                   23.826(5)
_cell_length_c                   28.135(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     9955(3)
_cell_formula_units_Z            8
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       block
_exptl_crystal_colour            brown
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.24
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.700
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             5024
_exptl_absorpt_coefficient_mu    4.057
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.3963
_exptl_absorpt_correction_T_max  0.4426
_exptl_absorpt_process_details   '(blessing, 1995, 1997)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      150(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  'Nonius KappaCCD diffractometer'
_diffrn_measurement_method       CCD
_diffrn_detector_area_resol_mean 9
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        none
_diffrn_reflns_number            16580
_diffrn_reflns_av_R_equivalents  0.0391
_diffrn_reflns_av_sigmaI/netI    0.0525
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_theta_min         2.17
_diffrn_reflns_theta_max         25.00
_reflns_number_total             8748
_reflns_number_gt                6552
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
During the refinement, the command 'omit-3 50' was used to omit the weak
data above 50 degree. The command 'isor' was used to restrain the N46 due
to its NPD problem, leading to a retraint number of 12.
The H atoms on coordinated water molecules were found from the residual
peaks according to the coordination environments of parent O atoms and
the H-bonding interactions between the adjacent O groups. The bond
distance of H-O and the angle of H-O-H were fixed with the ideal water
model. H atoms were refined isotropically with fixed thermal parameters
which are 1.5 time larger than its parent O atoms.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0609P)^2^+53.3797P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         8748
_refine_ls_number_parameters     607
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.0760
_refine_ls_R_factor_gt           0.0511
_refine_ls_wR_factor_ref         0.1479
_refine_ls_wR_factor_gt          0.1373
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_restrained_S_all      1.084
_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 0.42966(6) 0.82759(4) 0.14495(3) 0.0195(2) Uani 1 1 d . . .
Mn2 Mn 1.11666(6) 0.77042(4) 0.09207(3) 0.0205(2) Uani 1 1 d . . .
Fe1 Fe 0.78202(6) 0.82108(4) 0.12056(3) 0.0203(2) Uani 1 1 d . . .
Br1 Br 0.22530(5) 1.06938(3) 0.01945(3) 0.0352(2) Uani 1 1 d . . .
Br2 Br 0.28932(5) 0.54575(3) 0.22440(3) 0.0446(2) Uani 1 1 d . . .
Br3 Br 0.94363(5) 1.05882(3) 0.08094(3) 0.0366(2) Uani 1 1 d . . .
Br4 Br 1.05102(5) 0.55508(3) 0.27634(3) 0.0395(2) Uani 1 1 d . . .
O1W O 0.2929(3) 0.8415(2) 0.17493(15) 0.0271(11) Uani 1 1 d D . .
HW1A H 0.281(4) 0.827(3) 0.2019(12) 0.041 Uiso 1 1 d D . .
HW1B H 0.245(2) 0.847(3) 0.1592(18) 0.041 Uiso 1 1 d D . .
O2W O 1.2469(3) 0.7666(2) 0.05618(16) 0.0285(11) Uani 1 1 d D . .
HW2A H 1.260(4) 0.740(2) 0.038(2) 0.043 Uiso 1 1 d D . .
HW2B H 1.293(2) 0.779(3) 0.070(2) 0.043 Uiso 1 1 d D . .
O1 O 0.3795(3) 0.84953(18) 0.08565(14) 0.0219(10) Uani 1 1 d . . .
O2 O 0.4104(3) 0.75399(19) 0.12321(15) 0.0279(11) Uani 1 1 d . . .
O3 O 1.1492(3) 0.84406(18) 0.11102(15) 0.0227(10) Uani 1 1 d . . .
O4 O 1.1638(3) 0.74647(19) 0.15076(15) 0.0243(10) Uani 1 1 d . . .
N1 N 0.4520(3) 0.9091(2) 0.16259(18) 0.0230(12) Uani 1 1 d . . .
N2 N 0.4643(3) 0.7968(2) 0.21004(18) 0.0221(12) Uani 1 1 d . . .
N3 N 1.0609(3) 0.8027(2) 0.03158(18) 0.0249(12) Uani 1 1 d . . .
N4 N 1.0817(3) 0.6899(2) 0.07621(19) 0.0232(12) Uani 1 1 d . . .
C1 C 0.3546(4) 0.9472(3) 0.0999(2) 0.0260(15) Uani 1 1 d . . .
C2 C 0.3433(4) 0.8986(3) 0.0735(2) 0.0197(13) Uani 1 1 d . . .
C3 C 0.2936(5) 0.9015(3) 0.0309(2) 0.0290(16) Uani 1 1 d . . .
H3A H 0.2851 0.8685 0.0124 0.035 Uiso 1 1 calc R . .
C4 C 0.2574(4) 0.9515(3) 0.0158(2) 0.0284(16) Uani 1 1 d . . .
H4A H 0.2238 0.9530 -0.0129 0.034 Uiso 1 1 calc R . .
C5 C 0.2699(4) 0.9993(3) 0.0423(2) 0.0265(15) Uani 1 1 d . . .
C6 C 0.3184(4) 0.9982(3) 0.0836(2) 0.0256(15) Uani 1 1 d . . .
H6A H 0.3276 1.0318 0.1011 0.031 Uiso 1 1 calc R . .
C7 C 0.4136(4) 0.9503(3) 0.1419(2) 0.0238(14) Uani 1 1 d . . .
H7A H 0.4241 0.9865 0.1548 0.029 Uiso 1 1 calc R . .
C8 C 0.3930(4) 0.7054(3) 0.1968(2) 0.0249(15) Uani 1 1 d . . .
C9 C 0.3849(4) 0.7093(3) 0.1467(2) 0.0239(14) Uani 1 1 d . . .
C10 C 0.3486(4) 0.6638(3) 0.1216(3) 0.0310(16) Uani 1 1 d . . .
H10A H 0.3427 0.6661 0.0880 0.037 Uiso 1 1 calc R . .
C11 C 0.3215(4) 0.6162(3) 0.1447(3) 0.0342(17) Uani 1 1 d . . .
H11A H 0.2976 0.5856 0.1271 0.041 Uiso 1 1 calc R . .
C12 C 0.3287(4) 0.6124(3) 0.1940(3) 0.0330(17) Uani 1 1 d . . .
C13 C 0.3651(5) 0.6561(3) 0.2201(3) 0.0322(17) Uani 1 1 d . . .
H13A H 0.3713 0.6528 0.2536 0.039 Uiso 1 1 calc R . .
C14 C 0.4376(4) 0.7480(3) 0.2247(2) 0.0262(15) Uani 1 1 d . . .
H14A H 0.4486 0.7393 0.2572 0.031 Uiso 1 1 calc R . .
C15 C 0.5139(5) 0.9229(3) 0.2015(2) 0.0295(16) Uani 1 1 d . . .
H15A H 0.5104 0.9636 0.2082 0.035 Uiso 1 1 calc R . .
H15B H 0.5763 0.9143 0.1915 0.035 Uiso 1 1 calc R . .
C16 C 0.4928(5) 0.8908(3) 0.2465(2) 0.0279(15) Uani 1 1 d . . .
H16A H 0.4273 0.8934 0.2528 0.034 Uiso 1 1 calc R . .
H16B H 0.5246 0.9087 0.2734 0.034 Uiso 1 1 calc R . .
C17 C 0.5193(5) 0.8289(3) 0.2445(2) 0.0330(17) Uani 1 1 d . . .
H17A H 0.5836 0.8259 0.2356 0.040 Uiso 1 1 calc R . .
H17B H 0.5121 0.8122 0.2765 0.040 Uiso 1 1 calc R . .
C18 C 1.0431(4) 0.8969(3) 0.0642(2) 0.0212(14) Uani 1 1 d . . .
C19 C 1.1029(4) 0.8909(3) 0.1035(2) 0.0206(14) Uani 1 1 d . . .
C20 C 1.1154(4) 0.9364(3) 0.1338(2) 0.0236(14) Uani 1 1 d . . .
H20A H 1.1568 0.9335 0.1594 0.028 Uiso 1 1 calc R . .
C21 C 1.0679(4) 0.9858(3) 0.1270(2) 0.0227(14) Uani 1 1 d . . .
H21A H 1.0753 1.0162 0.1485 0.027 Uiso 1 1 calc R . .
C22 C 1.0089(4) 0.9909(3) 0.0882(2) 0.0256(15) Uani 1 1 d . . .
C23 C 0.9971(4) 0.9476(3) 0.0573(2) 0.0249(15) Uani 1 1 d . . .
H23A H 0.9576 0.9518 0.0309 0.030 Uiso 1 1 calc R . .
C24 C 1.0333(4) 0.8534(3) 0.0294(2) 0.0249(15) Uani 1 1 d . . .
H24A H 1.0025 0.8636 0.0011 0.030 Uiso 1 1 calc R . .
C25 C 1.0847(4) 0.6594(3) 0.1593(2) 0.0248(15) Uani 1 1 d . . .
C26 C 1.1335(4) 0.7051(3) 0.1775(2) 0.0227(14) Uani 1 1 d . . .
C27 C 1.1531(4) 0.7053(3) 0.2262(2) 0.0249(14) Uani 1 1 d . . .
H27A H 1.1850 0.7362 0.2394 0.030 Uiso 1 1 calc R . .
C28 C 1.1274(4) 0.6625(3) 0.2550(2) 0.0285(16) Uani 1 1 d . . .
H28A H 1.1414 0.6637 0.2879 0.034 Uiso 1 1 calc R . .
C29 C 1.0808(4) 0.6173(3) 0.2364(2) 0.0299(16) Uani 1 1 d . . .
C30 C 1.0587(4) 0.6159(3) 0.1889(2) 0.0298(16) Uani 1 1 d . . .
H30A H 1.0256 0.5851 0.1765 0.036 Uiso 1 1 calc R . .
C31 C 1.0683(4) 0.6535(3) 0.1091(2) 0.0276(15) Uani 1 1 d . . .
H31A H 1.0447 0.6184 0.0991 0.033 Uiso 1 1 calc R . .
C32 C 1.0485(5) 0.7668(3) -0.0116(2) 0.0308(16) Uani 1 1 d . . .
H32A H 1.1079 0.7601 -0.0265 0.037 Uiso 1 1 calc R . .
H32B H 1.0108 0.7873 -0.0349 0.037 Uiso 1 1 calc R . .
C33 C 1.0052(5) 0.7113(3) -0.0008(3) 0.0321(17) Uani 1 1 d . . .
H33A H 0.9500 0.7177 0.0181 0.039 Uiso 1 1 calc R . .
H33B H 0.9874 0.6930 -0.0310 0.039 Uiso 1 1 calc R . .
C34 C 1.0670(5) 0.6729(3) 0.0261(2) 0.0331(17) Uani 1 1 d . . .
H34A H 1.0416 0.6345 0.0256 0.040 Uiso 1 1 calc R . .
H34B H 1.1259 0.6717 0.0097 0.040 Uiso 1 1 calc R . .
N41 N 0.5746(4) 0.8279(2) 0.12008(19) 0.0288(13) Uani 1 1 d . . .
N42 N 0.9791(4) 0.7828(2) 0.12686(19) 0.0277(13) Uani 1 1 d . . .
N43 N 0.7474(5) 0.6940(3) 0.1206(3) 0.066(2) Uani 1 1 d . . .
N44 N 0.8071(4) 0.8061(3) 0.0126(2) 0.0344(14) Uani 1 1 d . . .
N45 N 0.7678(4) 0.8209(3) 0.2295(2) 0.0463(18) Uani 1 1 d . . .
N46 N 0.7999(4) 0.8895(3) 0.11890(19) 0.0283(13) Uani 1 1 d U . .
C41 C 0.6516(4) 0.8266(3) 0.1180(2) 0.0219(14) Uani 1 1 d . . .
C42 C 0.9059(4) 0.7984(3) 0.1257(2) 0.0231(14) Uani 1 1 d . . .
C43 C 0.7597(5) 0.7411(3) 0.1215(3) 0.0350(17) Uani 1 1 d . . .
C44 C 0.7947(4) 0.8112(3) 0.0531(2) 0.0218(14) Uani 1 1 d . . .
C45 C 0.7725(4) 0.8191(3) 0.1886(2) 0.0292(16) Uani 1 1 d . . .
O46 O 0.8118(4) 0.9368(2) 0.1186(2) 0.0573(17) Uani 1 1 d . . .
O11 O 0.5387(5) 1.0321(3) 0.0810(3) 0.0421(19) Uiso 0.67 1 d P A 1
O11A O 0.5674(11) 0.9836(7) 0.0574(6) 0.045(4) Uiso 0.33 1 d P B 2
O12 O 0.8046(6) 0.5834(3) 0.1056(3) 0.035(2) Uani 0.60 1 d P C 1
O12A O 0.7911(8) 0.5677(5) 0.1506(4) 0.035(3) Uani 0.40 1 d P D 2

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Mn1 0.0137(4) 0.0267(6) 0.0181(5) -0.0017(4) -0.0012(4) 0.0011(4)
Mn2 0.0138(4) 0.0265(6) 0.0212(5) -0.0024(4) -0.0027(4) -0.0004(4)
Fe1 0.0131(4) 0.0287(5) 0.0190(5) 0.0008(4) -0.0004(4) -0.0001(4)
Br1 0.0344(4) 0.0332(4) 0.0378(4) 0.0075(3) -0.0053(3) 0.0060(3)
Br2 0.0398(4) 0.0330(4) 0.0611(5) 0.0069(4) 0.0208(4) 0.0006(3)
Br3 0.0397(4) 0.0330(4) 0.0371(4) 0.0048(3) -0.0047(3) 0.0106(3)
Br4 0.0358(4) 0.0394(5) 0.0435(4) 0.0113(3) 0.0096(3) -0.0013(3)
O1W 0.015(2) 0.047(3) 0.019(2) 0.002(2) -0.0019(19) -0.001(2)
O2W 0.014(2) 0.038(3) 0.033(3) -0.014(2) 0.001(2) -0.001(2)
O1 0.022(2) 0.025(2) 0.019(2) -0.0004(18) 0.0004(19) 0.0057(19)
O2 0.030(3) 0.028(3) 0.026(2) -0.003(2) -0.002(2) 0.000(2)
O3 0.020(2) 0.024(2) 0.024(2) -0.0030(19) -0.0046(19) 0.0008(19)
O4 0.017(2) 0.031(3) 0.026(2) 0.001(2) -0.0075(19) -0.0029(19)
N1 0.015(3) 0.030(3) 0.024(3) -0.003(2) 0.002(2) -0.002(2)
N2 0.019(3) 0.026(3) 0.022(3) -0.001(2) -0.002(2) 0.001(2)
N3 0.021(3) 0.033(3) 0.021(3) -0.003(2) -0.002(2) 0.000(2)
N4 0.014(3) 0.025(3) 0.031(3) -0.005(2) -0.001(2) 0.001(2)
C1 0.016(3) 0.035(4) 0.027(3) 0.001(3) 0.003(3) 0.002(3)
C2 0.010(3) 0.027(4) 0.022(3) 0.004(3) 0.004(3) -0.005(3)
C3 0.029(4) 0.034(4) 0.024(4) 0.003(3) -0.001(3) -0.007(3)
C4 0.020(3) 0.038(4) 0.027(4) 0.006(3) -0.004(3) -0.008(3)
C5 0.024(4) 0.028(4) 0.028(4) 0.008(3) 0.002(3) 0.004(3)
C6 0.023(3) 0.025(4) 0.028(4) 0.000(3) -0.001(3) 0.002(3)
C7 0.019(3) 0.024(4) 0.028(3) -0.004(3) 0.001(3) -0.003(3)
C8 0.017(3) 0.027(4) 0.030(4) 0.002(3) 0.002(3) 0.008(3)
C9 0.013(3) 0.026(4) 0.033(4) 0.004(3) 0.001(3) 0.008(3)
C10 0.024(4) 0.033(4) 0.036(4) -0.002(3) -0.007(3) 0.004(3)
C11 0.021(3) 0.031(4) 0.050(5) -0.003(3) -0.004(3) 0.002(3)
C12 0.022(3) 0.025(4) 0.052(5) 0.003(3) 0.010(3) 0.000(3)
C13 0.025(4) 0.036(4) 0.035(4) 0.008(3) 0.008(3) 0.007(3)
C14 0.020(3) 0.040(4) 0.019(3) 0.000(3) 0.004(3) 0.006(3)
C15 0.026(3) 0.032(4) 0.030(4) -0.002(3) -0.008(3) -0.001(3)
C16 0.026(3) 0.034(4) 0.024(3) -0.010(3) -0.005(3) 0.001(3)
C17 0.026(4) 0.050(5) 0.023(4) 0.003(3) -0.003(3) 0.001(3)
C18 0.015(3) 0.027(4) 0.021(3) 0.000(3) 0.002(3) -0.002(3)
C19 0.014(3) 0.024(4) 0.023(3) 0.008(3) 0.003(3) -0.002(3)
C20 0.016(3) 0.032(4) 0.023(3) 0.000(3) -0.003(3) 0.001(3)
C21 0.018(3) 0.026(4) 0.024(3) -0.002(3) 0.003(3) -0.003(3)
C22 0.021(3) 0.027(4) 0.029(4) 0.005(3) 0.005(3) 0.002(3)
C23 0.019(3) 0.031(4) 0.025(3) 0.006(3) 0.001(3) 0.007(3)
C24 0.016(3) 0.038(4) 0.020(3) 0.001(3) -0.003(3) -0.001(3)
C25 0.015(3) 0.023(4) 0.036(4) -0.004(3) -0.001(3) 0.005(3)
C26 0.016(3) 0.026(4) 0.026(3) 0.001(3) 0.001(3) 0.010(3)
C27 0.019(3) 0.027(4) 0.029(4) -0.002(3) 0.000(3) 0.002(3)
C28 0.020(3) 0.036(4) 0.030(4) 0.001(3) 0.003(3) 0.007(3)
C29 0.022(3) 0.029(4) 0.039(4) 0.008(3) 0.008(3) -0.001(3)
C30 0.024(4) 0.028(4) 0.037(4) -0.001(3) -0.004(3) -0.001(3)
C31 0.020(3) 0.024(4) 0.039(4) -0.004(3) 0.001(3) 0.003(3)
C32 0.035(4) 0.035(4) 0.022(3) -0.004(3) -0.005(3) -0.002(3)
C33 0.025(4) 0.042(5) 0.029(4) -0.010(3) -0.008(3) 0.003(3)
C34 0.030(4) 0.041(4) 0.029(4) -0.009(3) 0.000(3) -0.001(3)
N41 0.018(3) 0.040(4) 0.029(3) 0.001(3) 0.002(2) 0.006(3)
N42 0.022(3) 0.038(4) 0.023(3) 0.000(2) 0.002(2) -0.002(3)
N43 0.047(4) 0.039(5) 0.111(7) 0.009(5) 0.015(4) 0.006(4)
N44 0.034(3) 0.041(4) 0.028(3) -0.005(3) -0.009(3) 0.012(3)
N45 0.027(3) 0.079(5) 0.033(4) 0.002(3) 0.001(3) -0.013(3)
N46 0.0280(15) 0.0288(15) 0.0280(15) -0.0004(10) 0.0011(10) -0.0006(10)
C41 0.024(4) 0.026(4) 0.016(3) -0.006(3) 0.000(3) 0.002(3)
C42 0.015(3) 0.037(4) 0.017(3) 0.002(3) -0.003(3) -0.003(3)
C43 0.020(3) 0.032(5) 0.053(5) 0.004(4) 0.006(3) -0.001(3)
C44 0.016(3) 0.025(4) 0.024(4) 0.002(3) -0.005(3) 0.005(3)
C45 0.012(3) 0.055(5) 0.021(4) 0.007(3) -0.002(3) -0.001(3)
O46 0.052(4) 0.033(3) 0.087(5) -0.003(3) 0.022(3) -0.006(3)
O12 0.039(5) 0.026(5) 0.040(5) -0.004(4) 0.002(4) 0.014(4)
O12A 0.037(7) 0.038(7) 0.029(7) -0.008(6) 0.010(6) 0.010(6)

_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 O2 1.879(5) . ?
Mn1 O1 1.900(4) . ?
Mn1 N1 2.032(5) . ?
Mn1 N2 2.039(5) . ?
Mn1 O1W 2.224(4) . ?
Mn1 N41 2.263(5) . ?
Mn2 O4 1.882(4) . ?
Mn2 O3 1.897(4) . ?
Mn2 N4 2.037(5) . ?
Mn2 N3 2.042(5) . ?
Mn2 O2W 2.184(4) . ?
Mn2 N42 2.285(6) . ?
Fe1 N46 1.652(6) . ?
Fe1 C45 1.921(7) . ?
Fe1 C44 1.922(7) . ?
Fe1 C42 1.923(6) . ?
Fe1 C43 1.935(8) . ?
Fe1 C41 1.943(7) . ?
Br1 C5 1.907(7) . ?
Br2 C12 1.896(7) . ?
Br3 C22 1.897(7) . ?
Br4 C29 1.911(7) . ?
O1W HW1A 0.850(10) . ?
O1W HW1B 0.851(10) . ?
O2W HW2A 0.848(10) . ?
O2W HW2B 0.846(10) . ?
O1 C2 1.332(7) . ?
O2 C9 1.308(8) . ?
O3 C19 1.328(7) . ?
O4 C26 1.318(8) . ?
N1 C7 1.275(8) . ?
N1 C15 1.467(8) . ?
N2 C14 1.296(9) . ?
N2 C17 1.481(8) . ?
N3 C24 1.277(9) . ?
N3 C32 1.497(8) . ?
N4 C31 1.284(9) . ?
N4 C34 1.483(8) . ?
C1 C2 1.386(9) . ?
C1 C6 1.407(9) . ?
C1 C7 1.472(9) . ?
C2 C3 1.409(9) . ?
C3 C4 1.375(10) . ?
C3 H3A 0.9500 . ?
C4 C5 1.373(10) . ?
C4 H4A 0.9500 . ?
C5 C6 1.367(9) . ?
C6 H6A 0.9500 . ?
C7 H7A 0.9500 . ?
C8 C13 1.408(10) . ?
C8 C9 1.418(9) . ?
C8 C14 1.444(10) . ?
C9 C10 1.403(10) . ?
C10 C11 1.369(10) . ?
C10 H10A 0.9500 . ?
C11 C12 1.395(10) . ?
C11 H11A 0.9500 . ?
C12 C13 1.384(10) . ?
C13 H13A 0.9500 . ?
C14 H14A 0.9500 . ?
C15 C16 1.512(10) . ?
C15 H15A 0.9900 . ?
C15 H15B 0.9900 . ?
C16 C17 1.527(10) . ?
C16 H16A 0.9900 . ?
C16 H16B 0.9900 . ?
C17 H17A 0.9900 . ?
C17 H17B 0.9900 . ?
C18 C23 1.402(9) . ?
C18 C19 1.423(9) . ?
C18 C24 1.435(9) . ?
C19 C20 1.393(9) . ?
C20 C21 1.386(9) . ?
C20 H20A 0.9500 . ?
C21 C22 1.405(9) . ?
C21 H21A 0.9500 . ?
C22 C23 1.361(9) . ?
C23 H23A 0.9500 . ?
C24 H24A 0.9500 . ?
C25 C30 1.385(10) . ?
C25 C26 1.405(9) . ?
C25 C31 1.439(9) . ?
C26 C27 1.401(9) . ?
C27 C28 1.356(9) . ?
C27 H27A 0.9500 . ?
C28 C29 1.384(10) . ?
C28 H28A 0.9500 . ?
C29 C30 1.376(10) . ?
C30 H30A 0.9500 . ?
C31 H31A 0.9500 . ?
C32 C33 1.501(10) . ?
C32 H32A 0.9900 . ?
C32 H32B 0.9900 . ?
C33 C34 1.501(10) . ?
C33 H33A 0.9900 . ?
C33 H33B 0.9900 . ?
C34 H34A 0.9900 . ?
C34 H34B 0.9900 . ?
N41 C41 1.145(8) . ?
N42 C42 1.149(8) . ?
N43 C43 1.137(10) . ?
N44 C44 1.161(8) . ?
N45 C45 1.154(9) . ?
N46 O46 1.141(7) . ?

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
O2 Mn1 O1 84.92(19) . . ?
O2 Mn1 N1 175.1(2) . . ?
O1 Mn1 N1 90.9(2) . . ?
O2 Mn1 N2 89.7(2) . . ?
O1 Mn1 N2 170.6(2) . . ?
N1 Mn1 N2 94.8(2) . . ?
O2 Mn1 O1W 97.10(19) . . ?
O1 Mn1 O1W 86.22(17) . . ?
N1 Mn1 O1W 85.06(19) . . ?
N2 Mn1 O1W 86.76(18) . . ?
O2 Mn1 N41 92.7(2) . . ?
O1 Mn1 N41 95.75(19) . . ?
N1 Mn1 N41 85.2(2) . . ?
N2 Mn1 N41 92.2(2) . . ?
O1W Mn1 N41 170.1(2) . . ?
O4 Mn2 O3 86.50(19) . . ?
O4 Mn2 N4 90.1(2) . . ?
O3 Mn2 N4 176.3(2) . . ?
O4 Mn2 N3 174.7(2) . . ?
O3 Mn2 N3 89.4(2) . . ?
N4 Mn2 N3 93.9(2) . . ?
O4 Mn2 O2W 93.66(18) . . ?
O3 Mn2 O2W 86.71(18) . . ?
N4 Mn2 O2W 94.89(19) . . ?
N3 Mn2 O2W 89.4(2) . . ?
O4 Mn2 N42 89.75(19) . . ?
O3 Mn2 N42 89.3(2) . . ?
N4 Mn2 N42 89.3(2) . . ?
N3 Mn2 N42 86.9(2) . . ?
O2W Mn2 N42 174.6(2) . . ?
N46 Fe1 C45 93.7(3) . . ?
N46 Fe1 C44 94.4(3) . . ?
C45 Fe1 C44 171.5(3) . . ?
N46 Fe1 C42 97.2(3) . . ?
C45 Fe1 C42 89.4(3) . . ?
C44 Fe1 C42 86.9(3) . . ?
N46 Fe1 C43 178.9(3) . . ?
C45 Fe1 C43 87.2(3) . . ?
C44 Fe1 C43 84.8(3) . . ?
C42 Fe1 C43 83.5(3) . . ?
N46 Fe1 C41 95.3(3) . . ?
C45 Fe1 C41 88.0(3) . . ?
C44 Fe1 C41 94.0(3) . . ?
C42 Fe1 C41 167.3(3) . . ?
C43 Fe1 C41 84.0(3) . . ?
Mn1 O1W HW1A 118(4) . . ?
Mn1 O1W HW1B 126(4) . . ?
HW1A O1W HW1B 110.7(18) . . ?
Mn2 O2W HW2A 121(4) . . ?
Mn2 O2W HW2B 119(4) . . ?
HW2A O2W HW2B 111.7(19) . . ?
C2 O1 Mn1 128.7(4) . . ?
C9 O2 Mn1 129.7(4) . . ?
C19 O3 Mn2 126.8(4) . . ?
C26 O4 Mn2 126.9(4) . . ?
C7 N1 C15 116.7(6) . . ?
C7 N1 Mn1 123.4(4) . . ?
C15 N1 Mn1 119.9(4) . . ?
C14 N2 C17 115.0(5) . . ?
C14 N2 Mn1 122.1(4) . . ?
C17 N2 Mn1 122.8(4) . . ?
C24 N3 C32 117.4(5) . . ?
C24 N3 Mn2 121.8(4) . . ?
C32 N3 Mn2 120.8(4) . . ?
C31 N4 C34 118.6(6) . . ?
C31 N4 Mn2 121.2(5) . . ?
C34 N4 Mn2 120.2(4) . . ?
C2 C1 C6 120.0(6) . . ?
C2 C1 C7 123.0(6) . . ?
C6 C1 C7 116.5(6) . . ?
O1 C2 C1 123.1(6) . . ?
O1 C2 C3 118.2(6) . . ?
C1 C2 C3 118.7(6) . . ?
C4 C3 C2 120.5(7) . . ?
C4 C3 H3A 119.7 . . ?
C2 C3 H3A 119.7 . . ?
C5 C4 C3 120.0(6) . . ?
C5 C4 H4A 120.0 . . ?
C3 C4 H4A 120.0 . . ?
C6 C5 C4 121.0(6) . . ?
C6 C5 Br1 119.1(5) . . ?
C4 C5 Br1 119.8(5) . . ?
C5 C6 C1 119.7(6) . . ?
C5 C6 H6A 120.1 . . ?
C1 C6 H6A 120.1 . . ?
N1 C7 C1 126.5(6) . . ?
N1 C7 H7A 116.8 . . ?
C1 C7 H7A 116.8 . . ?
C13 C8 C9 119.6(6) . . ?
C13 C8 C14 117.9(6) . . ?
C9 C8 C14 122.2(6) . . ?
O2 C9 C10 119.1(6) . . ?
O2 C9 C8 122.1(6) . . ?
C10 C9 C8 118.8(6) . . ?
C11 C10 C9 121.0(7) . . ?
C11 C10 H10A 119.5 . . ?
C9 C10 H10A 119.5 . . ?
C10 C11 C12 120.3(7) . . ?
C10 C11 H11A 119.9 . . ?
C12 C11 H11A 119.9 . . ?
C13 C12 C11 120.6(7) . . ?
C13 C12 Br2 120.8(6) . . ?
C11 C12 Br2 118.6(5) . . ?
C12 C13 C8 119.7(7) . . ?
C12 C13 H13A 120.1 . . ?
C8 C13 H13A 120.1 . . ?
N2 C14 C8 126.7(6) . . ?
N2 C14 H14A 116.6 . . ?
C8 C14 H14A 116.6 . . ?
N1 C15 C16 112.4(5) . . ?
N1 C15 H15A 109.1 . . ?
C16 C15 H15A 109.1 . . ?
N1 C15 H15B 109.1 . . ?
C16 C15 H15B 109.1 . . ?
H15A C15 H15B 107.9 . . ?
C15 C16 C17 113.9(6) . . ?
C15 C16 H16A 108.8 . . ?
C17 C16 H16A 108.8 . . ?
C15 C16 H16B 108.8 . . ?
C17 C16 H16B 108.8 . . ?
H16A C16 H16B 107.7 . . ?
N2 C17 C16 112.3(5) . . ?
N2 C17 H17A 109.1 . . ?
C16 C17 H17A 109.1 . . ?
N2 C17 H17B 109.1 . . ?
C16 C17 H17B 109.1 . . ?
H17A C17 H17B 107.9 . . ?
C23 C18 C19 120.0(6) . . ?
C23 C18 C24 118.6(6) . . ?
C19 C18 C24 121.3(6) . . ?
O3 C19 C20 119.1(5) . . ?
O3 C19 C18 122.2(6) . . ?
C20 C19 C18 118.7(6) . . ?
C21 C20 C19 120.5(6) . . ?
C21 C20 H20A 119.7 . . ?
C19 C20 H20A 119.7 . . ?
C20 C21 C22 120.0(6) . . ?
C20 C21 H21A 120.0 . . ?
C22 C21 H21A 120.0 . . ?
C23 C22 C21 120.7(6) . . ?
C23 C22 Br3 120.8(5) . . ?
C21 C22 Br3 118.5(5) . . ?
C22 C23 C18 120.1(6) . . ?
C22 C23 H23A 120.0 . . ?
C18 C23 H23A 120.0 . . ?
N3 C24 C18 128.2(6) . . ?
N3 C24 H24A 115.9 . . ?
C18 C24 H24A 115.9 . . ?
C30 C25 C26 120.3(6) . . ?
C30 C25 C31 118.1(6) . . ?
C26 C25 C31 121.3(6) . . ?
O4 C26 C27 118.9(6) . . ?
O4 C26 C25 123.3(6) . . ?
C27 C26 C25 117.8(6) . . ?
C28 C27 C26 121.5(6) . . ?
C28 C27 H27A 119.3 . . ?
C26 C27 H27A 119.3 . . ?
C27 C28 C29 120.1(6) . . ?
C27 C28 H28A 120.0 . . ?
C29 C28 H28A 120.0 . . ?
C30 C29 C28 120.3(6) . . ?
C30 C29 Br4 119.8(5) . . ?
C28 C29 Br4 119.9(5) . . ?
C29 C30 C25 120.0(6) . . ?
C29 C30 H30A 120.0 . . ?
C25 C30 H30A 120.0 . . ?
N4 C31 C25 128.0(6) . . ?
N4 C31 H31A 116.0 . . ?
C25 C31 H31A 116.0 . . ?
N3 C32 C33 113.0(6) . . ?
N3 C32 H32A 109.0 . . ?
C33 C32 H32A 109.0 . . ?
N3 C32 H32B 109.0 . . ?
C33 C32 H32B 109.0 . . ?
H32A C32 H32B 107.8 . . ?
C34 C33 C32 112.1(6) . . ?
C34 C33 H33A 109.2 . . ?
C32 C33 H33A 109.2 . . ?
C34 C33 H33B 109.2 . . ?
C32 C33 H33B 109.2 . . ?
H33A C33 H33B 107.9 . . ?
N4 C34 C33 113.8(6) . . ?
N4 C34 H34A 108.8 . . ?
C33 C34 H34A 108.8 . . ?
N4 C34 H34B 108.8 . . ?
C33 C34 H34B 108.8 . . ?
H34A C34 H34B 107.7 . . ?
C41 N41 Mn1 164.8(5) . . ?
C42 N42 Mn2 151.1(5) . . ?
O46 N46 Fe1 178.7(6) . . ?
N41 C41 Fe1 174.5(6) . . ?
N42 C42 Fe1 176.3(6) . . ?
N43 C43 Fe1 178.0(8) . . ?
N44 C44 Fe1 176.4(6) . . ?
N45 C45 Fe1 176.4(7) . . ?

_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         1.616
_refine_diff_density_min         -1.244
_refine_diff_density_rms         0.124

# Attachment 'complex_2.cif'

data_2
_database_code_depnum_ccdc_archive 'CCDC 720408'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C37 H28 Fe Mn2 N10 O6'
_chemical_formula_weight         874.42

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Tetragonal
_symmetry_space_group_name_H-M   P4/ncc

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

_cell_length_a                   14.751(2)
_cell_length_b                   14.751(2)
_cell_length_c                   17.063(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     3713.1(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       block
_exptl_crystal_colour            brown
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.23
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.564
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1776
_exptl_absorpt_coefficient_mu    1.116
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.7451
_exptl_absorpt_correction_T_max  0.7833
_exptl_absorpt_process_details   '(blessing, 1995, 1997)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      150(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  'Nonius KappaCCD diffractometer'
_diffrn_measurement_method       CCD
_diffrn_detector_area_resol_mean 9
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        none
_diffrn_reflns_number            5480
_diffrn_reflns_av_R_equivalents  0.0363
_diffrn_reflns_av_sigmaI/netI    0.0303
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         3.31
_diffrn_reflns_theta_max         25.00
_reflns_number_total             1635
_reflns_number_gt                1409
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
During the refinement, the command 'omit-3 50' was used to omit the weak
reflections above 50 degree. The command 'isor' was used to restrain the
non-H atoms with NPD and ADP problems. These atoms are as follows: O13,
O1w, O2w. This restraint command lead to a relative high restraint number
18.
The highest residual peak (3.354 e/A^3^) is very close to the Fe1 center
with the distance of 0.940 A, but featureless. This is mainly because of
the series termination errors.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0682P)^2^+17.2751P] where P=(Fo^2^+2Fc^2^)/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         1635
_refine_ls_number_parameters     137
_refine_ls_number_restraints     18
_refine_ls_R_factor_all          0.0564
_refine_ls_R_factor_gt           0.0496
_refine_ls_wR_factor_ref         0.1390
_refine_ls_wR_factor_gt          0.1318
_refine_ls_goodness_of_fit_ref   0.948
_refine_ls_restrained_S_all      0.969
_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
Fe1 Fe 0.2500 0.2500 0.24287(6) 0.0206(3) Uani 1 4 d S . .
Mn1 Mn 0.04730(4) 0.54730(4) 0.2500 0.0198(3) Uani 1 2 d S . .
O1 O 0.09314(18) 0.62188(19) 0.16931(16) 0.0277(6) Uani 1 1 d . . .
N1 N -0.0383(2) 0.4885(2) 0.1760(2) 0.0307(8) Uani 1 1 d . . .
C1 C -0.0236(3) 0.5979(3) 0.0722(2) 0.0282(9) Uani 1 1 d . . .
C2 C 0.0537(3) 0.6435(3) 0.1019(2) 0.0250(8) Uani 1 1 d . . .
C3 C 0.0913(3) 0.7133(3) 0.0561(2) 0.0308(9) Uani 1 1 d . . .
H3 H 0.1438 0.7442 0.0741 0.031 Uiso 1 1 calc R . .
C4 C 0.0529(3) 0.7376(3) -0.0148(3) 0.0369(11) Uani 1 1 d . . .
H4 H 0.0804 0.7841 -0.0452 0.037 Uiso 1 1 calc R . .
C5 C -0.0245(3) 0.6959(3) -0.0424(3) 0.0403(11) Uani 1 1 d . . .
H5 H -0.0514 0.7151 -0.0902 0.040 Uiso 1 1 calc R . .
C6 C -0.0619(3) 0.6264(3) 0.0001(3) 0.0389(11) Uani 1 1 d . . .
H6 H -0.1145 0.5967 -0.0192 0.039 Uiso 1 1 calc R . .
C7 C -0.0623(3) 0.5201(3) 0.1088(2) 0.0343(10) Uani 1 1 d . . .
H7 H -0.1092 0.4893 0.0815 0.034 Uiso 1 1 calc R . .
C8 C -0.0796(4) 0.4043(3) 0.2065(3) 0.0460(13) Uani 1 1 d . . .
H8A H -0.0383 0.3522 0.1986 0.046 Uiso 1 1 calc R . .
H8B H -0.1375 0.3916 0.1794 0.046 Uiso 1 1 calc R . .
N11 N 0.1508(2) 0.4331(2) 0.2277(2) 0.0338(8) Uani 1 1 d . . .
C11 C 0.1884(3) 0.3655(3) 0.2328(2) 0.0254(8) Uani 1 1 d . . .
C12 C 0.2500 0.2500 0.1299(5) 0.0238(16) Uani 1 4 d S . .
N12 N 0.2500 0.2500 0.0638(4) 0.0426(19) Uani 1 4 d S . .
N13 N 0.2500 0.2500 0.3402(4) 0.045(2) Uani 1 4 d S . .
O13 O 0.2500 0.2500 0.4051(6) 0.117(4) Uani 1 4 d SU . .
O1W O 0.2500 0.7500 0.2500 0.072(5) Uani 0.50 4 d SPU A 1
O2W O 0.2500 0.7500 0.1932(13) 0.057(5) Uani 0.25 2 d SPU B 2

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Fe1 0.0203(4) 0.0203(4) 0.0211(6) 0.000 0.000 0.000
Mn1 0.0183(3) 0.0183(3) 0.0229(5) 0.0007(2) -0.0007(2) 0.0000(3)
O1 0.0250(14) 0.0284(14) 0.0296(14) 0.0045(12) -0.0015(12) -0.0030(11)
N1 0.0352(19) 0.0304(19) 0.0267(17) 0.0054(15) -0.0012(15) -0.0112(15)
C1 0.031(2) 0.029(2) 0.0241(19) 0.0024(16) -0.0003(16) 0.0016(17)
C2 0.027(2) 0.0189(19) 0.0288(19) 0.0007(16) 0.0047(16) 0.0075(15)
C3 0.036(2) 0.0218(19) 0.035(2) 0.0025(17) 0.0026(18) 0.0016(17)
C4 0.052(3) 0.022(2) 0.038(2) 0.0106(18) 0.005(2) 0.0042(18)
C5 0.049(3) 0.038(3) 0.034(2) 0.0103(19) -0.007(2) 0.005(2)
C6 0.039(2) 0.043(3) 0.035(2) 0.008(2) -0.0085(19) -0.002(2)
C7 0.035(2) 0.040(2) 0.028(2) 0.0023(19) -0.0040(18) -0.0107(19)
C8 0.061(3) 0.047(3) 0.029(3) 0.009(2) -0.009(2) -0.030(3)
N11 0.034(2) 0.0261(18) 0.042(2) 0.0011(15) 0.0042(16) 0.0043(15)
C11 0.0204(19) 0.0224(19) 0.033(2) -0.0021(16) 0.0040(16) 0.0014(15)
C12 0.020(2) 0.020(2) 0.031(4) 0.000 0.000 0.000
N12 0.048(3) 0.048(3) 0.031(4) 0.000 0.000 0.000
N13 0.058(3) 0.058(3) 0.017(4) 0.000 0.000 0.000
O13 0.151(6) 0.151(6) 0.049(5) 0.000 0.000 0.000
O1W 0.068(6) 0.068(6) 0.079(9) 0.000 0.000 0.013(7)
O2W 0.026(7) 0.094(10) 0.051(9) 0.000 0.000 0.000(8)

_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 N13 1.661(7) . ?
Fe1 C12 1.928(8) . ?
Fe1 C11 1.938(4) 3 ?
Fe1 C11 1.938(4) . ?
Fe1 C11 1.938(4) 2 ?
Fe1 C11 1.938(4) 4 ?
Mn1 O1 1.888(3) 7_455 ?
Mn1 O1 1.888(3) . ?
Mn1 N1 1.985(3) . ?
Mn1 N1 1.985(3) 7_455 ?
Mn1 N11 2.305(4) 7_455 ?
Mn1 N11 2.305(4) . ?
O1 C2 1.328(5) . ?
N1 C7 1.287(5) . ?
N1 C8 1.478(5) . ?
C1 C6 1.417(6) . ?
C1 C2 1.418(6) . ?
C1 C7 1.426(6) . ?
C2 C3 1.407(6) . ?
C3 C4 1.383(6) . ?
C3 H3 0.9500 . ?
C4 C5 1.380(7) . ?
C4 H4 0.9500 . ?
C5 C6 1.372(7) . ?
C5 H5 0.9500 . ?
C6 H6 0.9500 . ?
C7 H7 0.9500 . ?
C8 C8 1.521(9) 7_455 ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
N11 C11 1.145(5) . ?
C12 N12 1.129(11) . ?
N13 O13 1.108(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
N13 Fe1 C12 180.000(1) . . ?
N13 Fe1 C11 95.09(12) . 3 ?
C12 Fe1 C11 84.91(12) . 3 ?
N13 Fe1 C11 95.09(12) . . ?
C12 Fe1 C11 84.91(12) . . ?
C11 Fe1 C11 89.55(2) 3 . ?
N13 Fe1 C11 95.09(12) . 2 ?
C12 Fe1 C11 84.91(12) . 2 ?
C11 Fe1 C11 89.55(2) 3 2 ?
C11 Fe1 C11 169.8(2) . 2 ?
N13 Fe1 C11 95.09(12) . 4 ?
C12 Fe1 C11 84.91(12) . 4 ?
C11 Fe1 C11 169.8(2) 3 4 ?
C11 Fe1 C11 89.55(2) . 4 ?
C11 Fe1 C11 89.55(2) 2 4 ?
O1 Mn1 O1 96.58(17) 7_455 . ?
O1 Mn1 N1 172.38(13) 7_455 . ?
O1 Mn1 N1 91.05(13) . . ?
O1 Mn1 N1 91.05(13) 7_455 7_455 ?
O1 Mn1 N1 172.37(13) . 7_455 ?
N1 Mn1 N1 81.3(2) . 7_455 ?
O1 Mn1 N11 93.92(12) 7_455 7_455 ?
O1 Mn1 N11 89.79(13) . 7_455 ?
N1 Mn1 N11 85.96(14) . 7_455 ?
N1 Mn1 N11 89.81(14) 7_455 7_455 ?
O1 Mn1 N11 89.79(13) 7_455 . ?
O1 Mn1 N11 93.92(12) . . ?
N1 Mn1 N11 89.81(14) . . ?
N1 Mn1 N11 85.96(14) 7_455 . ?
N11 Mn1 N11 174.43(18) 7_455 . ?
C2 O1 Mn1 128.0(2) . . ?
C7 N1 C8 120.3(4) . . ?
C7 N1 Mn1 125.7(3) . . ?
C8 N1 Mn1 113.9(3) . . ?
C6 C1 C2 119.4(4) . . ?
C6 C1 C7 117.3(4) . . ?
C2 C1 C7 123.1(4) . . ?
O1 C2 C3 119.0(4) . . ?
O1 C2 C1 123.3(3) . . ?
C3 C2 C1 117.7(4) . . ?
C4 C3 C2 120.9(4) . . ?
C4 C3 H3 119.5 . . ?
C2 C3 H3 119.5 . . ?
C5 C4 C3 121.5(4) . . ?
C5 C4 H4 119.3 . . ?
C3 C4 H4 119.3 . . ?
C6 C5 C4 119.1(4) . . ?
C6 C5 H5 120.5 . . ?
C4 C5 H5 120.5 . . ?
C5 C6 C1 121.3(4) . . ?
C5 C6 H6 119.3 . . ?
C1 C6 H6 119.3 . . ?
N1 C7 C1 124.9(4) . . ?
N1 C7 H7 117.6 . . ?
C1 C7 H7 117.6 . . ?
N1 C8 C8 106.1(3) . 7_455 ?
N1 C8 H8A 110.5 . . ?
C8 C8 H8A 110.5 7_455 . ?
N1 C8 H8B 110.5 . . ?
C8 C8 H8B 110.5 7_455 . ?
H8A C8 H8B 108.7 . . ?
C11 N11 Mn1 161.0(3) . . ?
N11 C11 Fe1 178.7(4) . . ?
N12 C12 Fe1 180.0 . . ?
O13 N13 Fe1 180.000(1) . . ?

_diffrn_measured_fraction_theta_max 0.993
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.993
_refine_diff_density_max         3.354
_refine_diff_density_min         -0.776
_refine_diff_density_rms         0.091

# Attachment 'complex_3.CIF'

data_rod1
_database_code_depnum_ccdc_archive 'CCDC 720409'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         
'C85 H88 Fe Mn4 N14 O9, 2(C H4 O), 2(Cl O4), H2 O'
_chemical_formula_sum            'C87 H98 Cl2 Fe Mn4 N14 O20'
_chemical_formula_weight         2006.30

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C -0.0020 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'
N N -0.0031 0.0040 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O -0.0041 0.0074 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn 0.2237 0.8587 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.2064 0.9930 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_H-M   I4/m

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

_cell_length_a                   18.5154(8)
_cell_length_b                   18.5154(8)
_cell_length_c                   27.4984(13)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     9427.0(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    4473
_cell_measurement_theta_min      2.34
_cell_measurement_theta_max      26.65

_exptl_crystal_description       plate
_exptl_crystal_colour            orange
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.02
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.414
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             4152
_exptl_absorpt_coefficient_mu    0.994
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.84
_exptl_absorpt_correction_T_max  0.98
_exptl_absorpt_process_details   'sadabs 2007/4'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.77490
_diffrn_radiation_type           synchrotron
_diffrn_radiation_source         'Advanced Light Source station 11.3.1'
_diffrn_radiation_monochromator  'silicon 111'
_diffrn_measurement_device_type  'Bruker APEX II CCD diffractometer'
_diffrn_measurement_method       '\w rotation with narrow frames'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_decay_%        .
_diffrn_reflns_number            26410
_diffrn_reflns_av_R_equivalents  0.0781
_diffrn_reflns_av_sigmaI/netI    0.0662
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_theta_min         2.34
_diffrn_reflns_theta_max         28.57
_reflns_number_total             4752
_reflns_number_gt                3724
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX 2'
_computing_cell_refinement       'Bruker SAINT v7.34a'
_computing_data_reduction        'Bruker SAINT v7.34a'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL & local programs'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger. All non-hydrogens were
refined anisotropically. The perchlorate ions occupy two crystallographic
sites with half occupancy. One of them presents a disorder over two
positions of its oxygen atoms. These were refined with displacement
parameters and distance restrains. Two methanol molecule with half
occupancy sit close to one of the two perchlorates. These proximity and
positional disorder result in unreal bond distances. Hydrogens were found
in difference Fourier maps and placed geometrically on their riding atom
except those of the water and methanol molecules, that are missing in this
structural model. Small voids remain in the structure that contain only
very diffuse electron density peaks. Use of PLATON/SQUEEZE to take
these into account did not improve significantly the quality of the
structure, and therefore it was left.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.1403P)^2^+28.2057P] where P=(Fo^2^+2Fc^2^)/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         4752
_refine_ls_number_parameters     367
_refine_ls_number_restraints     194
_refine_ls_R_factor_all          0.0855
_refine_ls_R_factor_gt           0.0699
_refine_ls_wR_factor_ref         0.2284
_refine_ls_wR_factor_gt          0.2085
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_restrained_S_all      1.061
_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
Fe1 Fe 0.0000 0.0000 0.23546(4) 0.0329(3) Uani 1 4 d S . .
Mn1 Mn 0.18451(3) 0.21060(3) 0.21408(2) 0.0338(3) Uani 1 1 d . . .
O1 O 0.0000 0.0000 0.3377(3) 0.062(2) Uani 1 4 d S . .
O2 O 0.20516(17) 0.20428(16) 0.28154(10) 0.0359(7) Uani 1 1 d . . .
O3 O 0.13227(17) 0.29655(17) 0.22084(12) 0.0411(7) Uani 1 1 d . . .
N1 N 0.0853(2) 0.1419(2) 0.22234(13) 0.0380(8) Uani 1 1 d . . .
N2 N 0.0000 0.0000 0.1237(3) 0.060(2) Uani 1 4 d S . .
N3 N 0.0000 0.0000 0.2959(3) 0.0409(17) Uani 1 4 d S . .
N4 N 0.24001(19) 0.12094(19) 0.20126(13) 0.0355(8) Uani 1 1 d . . .
N5 N 0.18958(19) 0.21760(19) 0.14258(13) 0.0360(8) Uani 1 1 d . . .
C1 C 0.0519(2) 0.0899(2) 0.22850(15) 0.0345(9) Uani 1 1 d . . .
C2 C 0.0000 0.0000 0.1645(4) 0.044(2) Uani 1 4 d S . .
C3 C 0.2018(2) 0.1407(2) 0.30521(16) 0.0360(9) Uani 1 1 d . . .
C4 C 0.1780(2) 0.1400(3) 0.35386(16) 0.0404(10) Uani 1 1 d . . .
H4A H 0.1622 0.1834 0.3689 0.048 Uiso 1 1 calc R . .
C5 C 0.1776(3) 0.0760(3) 0.37973(17) 0.0487(12) Uani 1 1 d . . .
H5A H 0.1616 0.0761 0.4126 0.058 Uiso 1 1 calc R . .
C6 C 0.2002(3) 0.0111(3) 0.35862(19) 0.0510(13) Uani 1 1 d . . .
H6A H 0.1999 -0.0324 0.3770 0.061 Uiso 1 1 calc R . .
C7 C 0.2230(3) 0.0110(2) 0.31099(18) 0.0427(10) Uani 1 1 d . . .
H7A H 0.2390 -0.0328 0.2966 0.051 Uiso 1 1 calc R . .
C8 C 0.2227(2) 0.0750(2) 0.28342(15) 0.0360(9) Uani 1 1 d . . .
C9 C 0.2472(2) 0.0704(2) 0.23324(16) 0.0375(9) Uani 1 1 d . . .
H9A H 0.2702 0.0270 0.2233 0.045 Uiso 1 1 calc R . .
C10 C 0.2717(3) 0.1144(2) 0.15091(16) 0.0402(10) Uani 1 1 d . . .
C11 C 0.2854(3) 0.0356(3) 0.13645(19) 0.0534(13) Uani 1 1 d . . .
H11A H 0.3211 0.0143 0.1585 0.080 Uiso 1 1 calc R . .
H11B H 0.3037 0.0338 0.1030 0.080 Uiso 1 1 calc R . .
H11C H 0.2401 0.0084 0.1386 0.080 Uiso 1 1 calc R . .
C12 C 0.3431(3) 0.1550(3) 0.15220(18) 0.0480(11) Uani 1 1 d . . .
H12A H 0.3767 0.1300 0.1741 0.072 Uiso 1 1 calc R . .
H12B H 0.3350 0.2042 0.1640 0.072 Uiso 1 1 calc R . .
H12C H 0.3637 0.1567 0.1194 0.072 Uiso 1 1 calc R . .
C13 C 0.2148(3) 0.1504(2) 0.11649(16) 0.0409(10) Uani 1 1 d . . .
C14 C 0.2471(3) 0.1682(3) 0.06666(18) 0.0535(13) Uani 1 1 d . . .
H14A H 0.2102 0.1909 0.0462 0.080 Uiso 1 1 calc R . .
H14B H 0.2640 0.1236 0.0511 0.080 Uiso 1 1 calc R . .
H14C H 0.2879 0.2014 0.0708 0.080 Uiso 1 1 calc R . .
C15 C 0.1478(3) 0.1022(3) 0.11001(18) 0.0514(12) Uani 1 1 d . . .
H15A H 0.1132 0.1263 0.0885 0.077 Uiso 1 1 calc R . .
H15B H 0.1253 0.0937 0.1418 0.077 Uiso 1 1 calc R . .
H15C H 0.1623 0.0559 0.0957 0.077 Uiso 1 1 calc R . .
C16 C 0.1697(2) 0.2740(2) 0.11838(17) 0.0399(10) Uani 1 1 d . . .
H16A H 0.1753 0.2724 0.0841 0.048 Uiso 1 1 calc R . .
C17 C 0.1398(2) 0.3391(2) 0.13864(17) 0.0403(10) Uani 1 1 d . . .
C18 C 0.1258(3) 0.3966(3) 0.1061(2) 0.0507(12) Uani 1 1 d . . .
H18A H 0.1362 0.3908 0.0726 0.061 Uiso 1 1 calc R . .
C19 C 0.0972(3) 0.4611(3) 0.1225(2) 0.0570(14) Uani 1 1 d . . .
H19A H 0.0881 0.4994 0.1003 0.068 Uiso 1 1 calc R . .
C20 C 0.0823(3) 0.4694(3) 0.1710(2) 0.0519(13) Uani 1 1 d . . .
H20A H 0.0640 0.5143 0.1824 0.062 Uiso 1 1 calc R . .
C21 C 0.0931(2) 0.4140(2) 0.20371(19) 0.0437(10) Uani 1 1 d . . .
H21A H 0.0804 0.4203 0.2369 0.052 Uiso 1 1 calc R . .
C22 C 0.1230(2) 0.3477(2) 0.18789(17) 0.0362(9) Uani 1 1 d . . .
Cl1 Cl 0.5586(3) -0.2360(3) 0.5000 0.0822(13) Uani 0.50 2 d SPDU . 1
O4 O 0.6244(7) -0.2050(7) 0.5000 0.084(3) Uani 0.50 2 d SPDU . 1
O5 O 0.5506(10) -0.2775(11) 0.4585(5) 0.085(4) Uani 0.25 1 d PDU . 1
O6 O 0.5052(9) -0.1827(10) 0.5000 0.124(5) Uani 0.50 2 d SPDU . 1
Cl2 Cl 0.2431(4) -0.0625(3) 0.5000 0.0889(15) Uani 0.50 2 d SPDU . 2
O7 O 0.2273(15) 0.0127(7) 0.5000 0.100(3) Uani 0.25 2 d SPDU . 2
O9 O 0.2033(10) -0.1063(10) 0.5336(7) 0.100(3) Uani 0.25 1 d PDU . 2
O10 O 0.3196(8) -0.0769(13) 0.5000 0.099(3) Uani 0.25 2 d SPDU . 2
O8 O 0.2382(10) -0.1038(10) 0.5441(6) 0.097(3) Uani 0.25 1 d PDU . 2
O11 O 0.1807(10) -0.0138(11) 0.5000 0.098(3) Uani 0.25 2 d SPDU . 2
O12 O 0.3061(11) -0.0155(12) 0.5000 0.100(3) Uani 0.25 2 d SPDU . 2
O1S O 0.4658(8) -0.1014(8) 0.5000 0.083(4) Uani 0.50 2 d SPU A 2
C1S C 0.4497(17) -0.0268(17) 0.5000 0.120(9) Uani 0.50 2 d SPU A 2
O2S O 0.5430(15) -0.3653(12) 0.5000 0.149(8) Uani 0.50 2 d SPU . 2
C2S C 0.5198(18) -0.4361(14) 0.5290(9) 0.077(7) Uani 0.25 1 d PU . 2
O1W O 0.1608(6) -0.2676(7) 0.5000 0.142(4) Uani 1 2 d SU . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Fe1 0.0340(4) 0.0340(4) 0.0306(6) 0.000 0.000 0.000
Mn1 0.0377(4) 0.0327(4) 0.0310(4) 0.0032(2) 0.0041(2) 0.0061(2)
O1 0.078(3) 0.078(3) 0.030(4) 0.000 0.000 0.000
O2 0.0418(16) 0.0350(15) 0.0310(15) 0.0043(11) 0.0052(12) 0.0024(12)
O3 0.0412(17) 0.0373(16) 0.0447(17) 0.0017(13) 0.0054(13) 0.0085(13)
N1 0.0375(19) 0.041(2) 0.0361(18) 0.0006(15) 0.0039(15) 0.0047(16)
N2 0.075(4) 0.075(4) 0.031(4) 0.000 0.000 0.000
N3 0.041(3) 0.041(3) 0.040(4) 0.000 0.000 0.000
N4 0.0368(18) 0.0359(18) 0.0337(18) 0.0030(14) 0.0044(14) 0.0038(14)
N5 0.0408(19) 0.0350(18) 0.0321(19) 0.0031(14) 0.0049(14) 0.0018(14)
C1 0.034(2) 0.037(2) 0.032(2) 0.0000(17) 0.0011(16) 0.0038(18)
C2 0.045(3) 0.045(3) 0.042(5) 0.000 0.000 0.000
C3 0.031(2) 0.041(2) 0.036(2) 0.0060(18) -0.0019(16) -0.0042(17)
C4 0.039(2) 0.046(2) 0.036(2) 0.0042(18) 0.0022(18) -0.0096(19)
C5 0.054(3) 0.059(3) 0.033(2) 0.009(2) -0.002(2) -0.013(2)
C6 0.060(3) 0.047(3) 0.046(3) 0.017(2) -0.014(2) -0.012(2)
C7 0.046(2) 0.035(2) 0.047(3) 0.0090(19) -0.011(2) -0.0031(18)
C8 0.033(2) 0.038(2) 0.037(2) 0.0062(17) -0.0040(17) -0.0022(17)
C9 0.037(2) 0.033(2) 0.042(2) 0.0036(18) 0.0007(18) 0.0016(17)
C10 0.049(3) 0.035(2) 0.037(2) 0.0029(17) 0.0107(19) 0.0086(18)
C11 0.072(3) 0.041(3) 0.047(3) 0.002(2) 0.015(2) 0.017(2)
C12 0.046(3) 0.051(3) 0.048(3) 0.008(2) 0.013(2) 0.011(2)
C13 0.054(3) 0.035(2) 0.033(2) 0.0001(17) 0.0074(19) 0.0069(19)
C14 0.068(3) 0.054(3) 0.039(2) 0.005(2) 0.010(2) 0.015(2)
C15 0.067(3) 0.048(3) 0.039(2) -0.010(2) 0.000(2) 0.001(2)
C16 0.039(2) 0.040(2) 0.041(2) 0.0067(18) -0.0006(18) 0.0013(18)
C17 0.034(2) 0.036(2) 0.050(3) 0.0057(19) -0.0016(19) -0.0018(17)
C18 0.055(3) 0.042(3) 0.055(3) 0.015(2) -0.003(2) 0.005(2)
C19 0.059(3) 0.036(2) 0.076(4) 0.014(2) -0.006(3) 0.005(2)
C20 0.043(3) 0.034(2) 0.078(4) -0.002(2) -0.010(2) 0.0018(19)
C21 0.035(2) 0.039(2) 0.057(3) -0.004(2) -0.005(2) 0.0032(18)
C22 0.0283(19) 0.033(2) 0.048(2) 0.0027(18) -0.0037(17) 0.0009(16)
Cl1 0.089(3) 0.097(3) 0.061(2) 0.000 0.000 0.027(2)
O4 0.099(5) 0.089(7) 0.063(6) 0.000 0.000 0.017(4)
O5 0.076(9) 0.121(10) 0.058(7) -0.004(6) 0.027(7) -0.011(7)
O6 0.112(7) 0.114(10) 0.146(13) 0.000 0.000 0.045(7)
Cl2 0.152(5) 0.066(2) 0.049(2) 0.000 0.000 0.021(3)
O7 0.164(7) 0.066(3) 0.069(6) 0.000 0.000 0.020(4)
O9 0.145(6) 0.086(5) 0.068(6) 0.019(4) 0.000(4) 0.021(5)
O10 0.147(5) 0.071(6) 0.081(7) 0.000 0.000 0.012(5)
O8 0.154(7) 0.087(5) 0.051(5) 0.011(4) -0.004(4) 0.023(5)
O11 0.158(6) 0.068(6) 0.068(7) 0.000 0.000 0.025(4)
O12 0.158(6) 0.072(5) 0.071(7) 0.000 0.000 0.014(4)
O1S 0.085(7) 0.086(7) 0.078(7) 0.000 0.000 -0.023(6)
C1S 0.121(12) 0.122(12) 0.117(12) 0.000 0.000 -0.009(9)
O2S 0.186(12) 0.129(10) 0.131(11) 0.000 0.000 -0.017(9)
C2S 0.111(11) 0.063(10) 0.057(10) 0.000(8) 0.002(8) -0.019(9)
O1W 0.122(6) 0.181(8) 0.122(7) 0.000 0.000 0.001(6)

_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 N3 1.662(8) . ?
Fe1 C1 1.931(4) 2 ?
Fe1 C1 1.931(4) . ?
Fe1 C1 1.931(4) 3 ?
Fe1 C1 1.931(4) 4 ?
Fe1 C2 1.952(10) . ?
Mn1 O3 1.872(3) . ?
Mn1 O2 1.898(3) . ?
Mn1 N5 1.973(4) . ?
Mn1 N4 1.984(4) . ?
Mn1 N1 2.246(4) . ?
O1 N3 1.149(10) . ?
O2 C3 1.346(5) . ?
O3 C22 1.321(5) . ?
N1 C1 1.157(6) . ?
N2 C2 1.123(13) . ?
N4 C9 1.291(6) . ?
N4 C10 1.508(5) . ?
N5 C16 1.293(6) . ?
N5 C13 1.510(5) . ?
C3 C4 1.408(6) . ?
C3 C8 1.411(6) . ?
C4 C5 1.381(7) . ?
C4 H4A 0.9500 . ?
C5 C6 1.399(8) . ?
C5 H5A 0.9500 . ?
C6 C7 1.376(7) . ?
C6 H6A 0.9500 . ?
C7 C8 1.408(6) . ?
C7 H7A 0.9500 . ?
C8 C9 1.455(6) . ?
C9 H9A 0.9500 . ?
C10 C12 1.521(7) . ?
C10 C11 1.533(6) . ?
C10 C13 1.566(6) . ?
C11 H11A 0.9800 . ?
C11 H11B 0.9800 . ?
C11 H11C 0.9800 . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
C13 C14 1.531(6) . ?
C13 C15 1.538(7) . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?
C16 C17 1.439(6) . ?
C16 H16A 0.9500 . ?
C17 C22 1.398(6) . ?
C17 C18 1.413(6) . ?
C18 C19 1.382(7) . ?
C18 H18A 0.9500 . ?
C19 C20 1.372(8) . ?
C19 H19A 0.9500 . ?
C20 C21 1.378(7) . ?
C20 H20A 0.9500 . ?
C21 C22 1.416(6) . ?
C21 H21A 0.9500 . ?
Cl1 O4 1.346(12) . ?
Cl1 O5 1.384(12) 10_556 ?
Cl1 O5 1.384(12) . ?
Cl1 O6 1.397(12) . ?
Cl2 O7 1.424(12) . ?
Cl2 O9 1.433(11) 10_556 ?
Cl2 O9 1.433(11) . ?
Cl2 O8 1.435(11) . ?
Cl2 O8 1.436(11) 10_556 ?
Cl2 O10 1.440(12) . ?
Cl2 O12 1.455(12) . ?
Cl2 O11 1.466(12) . ?
O7 O11 0.99(3) . ?
O7 O12 1.55(3) . ?
O9 O8 0.71(3) . ?
O10 O12 1.16(3) . ?
O1S C1S 1.41(3) . ?
O2S C2S 1.59(3) . ?
O2S C2S 1.59(3) 10_556 ?

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
N3 Fe1 C1 95.69(13) . 2 ?
N3 Fe1 C1 95.69(13) . . ?
C1 Fe1 C1 168.6(3) 2 . ?
N3 Fe1 C1 95.69(13) . 3 ?
C1 Fe1 C1 89.44(3) 2 3 ?
C1 Fe1 C1 89.44(3) . 3 ?
N3 Fe1 C1 95.69(13) . 4 ?
C1 Fe1 C1 89.44(3) 2 4 ?
C1 Fe1 C1 89.44(3) . 4 ?
C1 Fe1 C1 168.6(3) 3 4 ?
N3 Fe1 C2 180.000(1) . . ?
C1 Fe1 C2 84.31(13) 2 . ?
C1 Fe1 C2 84.31(13) . . ?
C1 Fe1 C2 84.31(13) 3 . ?
C1 Fe1 C2 84.31(13) 4 . ?
O3 Mn1 O2 93.41(14) . . ?
O3 Mn1 N5 93.88(14) . . ?
O2 Mn1 N5 165.65(15) . . ?
O3 Mn1 N4 175.44(14) . . ?
O2 Mn1 N4 91.02(14) . . ?
N5 Mn1 N4 81.56(15) . . ?
O3 Mn1 N1 92.78(14) . . ?
O2 Mn1 N1 91.78(13) . . ?
N5 Mn1 N1 100.18(14) . . ?
N4 Mn1 N1 88.16(14) . . ?
C3 O2 Mn1 121.1(3) . . ?
C22 O3 Mn1 127.4(3) . . ?
C1 N1 Mn1 157.4(3) . . ?
O1 N3 Fe1 180.000(1) . . ?
C9 N4 C10 121.8(4) . . ?
C9 N4 Mn1 122.6(3) . . ?
C10 N4 Mn1 115.6(3) . . ?
C16 N5 C13 120.6(4) . . ?
C16 N5 Mn1 123.6(3) . . ?
C13 N5 Mn1 115.7(3) . . ?
N1 C1 Fe1 176.2(4) . . ?
N2 C2 Fe1 180.0 . . ?
O2 C3 C4 118.9(4) . . ?
O2 C3 C8 122.4(4) . . ?
C4 C3 C8 118.7(4) . . ?
C5 C4 C3 120.0(4) . . ?
C5 C4 H4A 120.0 . . ?
C3 C4 H4A 120.0 . . ?
C4 C5 C6 121.4(4) . . ?
C4 C5 H5A 119.3 . . ?
C6 C5 H5A 119.3 . . ?
C7 C6 C5 119.2(4) . . ?
C7 C6 H6A 120.4 . . ?
C5 C6 H6A 120.4 . . ?
C6 C7 C8 120.7(5) . . ?
C6 C7 H7A 119.6 . . ?
C8 C7 H7A 119.6 . . ?
C7 C8 C3 119.9(4) . . ?
C7 C8 C9 117.4(4) . . ?
C3 C8 C9 122.6(4) . . ?
N4 C9 C8 124.9(4) . . ?
N4 C9 H9A 117.6 . . ?
C8 C9 H9A 117.6 . . ?
N4 C10 C12 106.1(4) . . ?
N4 C10 C11 112.2(4) . . ?
C12 C10 C11 109.4(4) . . ?
N4 C10 C13 105.0(3) . . ?
C12 C10 C13 112.9(4) . . ?
C11 C10 C13 111.1(4) . . ?
C10 C11 H11A 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C10 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C10 C12 H12A 109.5 . . ?
C10 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C10 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
N5 C13 C14 111.7(4) . . ?
N5 C13 C15 106.5(4) . . ?
C14 C13 C15 109.7(4) . . ?
N5 C13 C10 105.7(3) . . ?
C14 C13 C10 111.7(4) . . ?
C15 C13 C10 111.4(4) . . ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C13 C15 H15A 109.5 . . ?
C13 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C13 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
N5 C16 C17 126.0(4) . . ?
N5 C16 H16A 117.0 . . ?
C17 C16 H16A 117.0 . . ?
C22 C17 C18 119.1(4) . . ?
C22 C17 C16 123.7(4) . . ?
C18 C17 C16 117.2(4) . . ?
C19 C18 C17 121.0(5) . . ?
C19 C18 H18A 119.5 . . ?
C17 C18 H18A 119.5 . . ?
C20 C19 C18 119.3(5) . . ?
C20 C19 H19A 120.3 . . ?
C18 C19 H19A 120.3 . . ?
C19 C20 C21 121.5(5) . . ?
C19 C20 H20A 119.3 . . ?
C21 C20 H20A 119.3 . . ?
C20 C21 C22 120.1(5) . . ?
C20 C21 H21A 119.9 . . ?
C22 C21 H21A 119.9 . . ?
O3 C22 C17 123.7(4) . . ?
O3 C22 C21 117.5(4) . . ?
C17 C22 C21 118.8(4) . . ?
O4 Cl1 O5 109.5(8) . 10_556 ?
O4 Cl1 O5 109.5(8) . . ?
O5 Cl1 O5 111.2(17) 10_556 . ?
O4 Cl1 O6 109.8(12) . . ?
O5 Cl1 O6 108.4(10) 10_556 . ?
O5 Cl1 O6 108.4(10) . . ?
O7 Cl2 O9 116.6(9) . 10_556 ?
O7 Cl2 O9 116.6(9) . . ?
O7 Cl2 O8 120.5(9) . . ?
O9 Cl2 O8 102.1(12) 10_556 . ?
O7 Cl2 O8 120.5(9) . 10_556 ?
O9 Cl2 O8 102.1(12) . 10_556 ?
O7 Cl2 O10 112.5(10) . . ?
O9 Cl2 O10 113.7(8) 10_556 . ?
O9 Cl2 O10 113.7(8) . . ?
O8 Cl2 O10 88.0(9) . . ?
O8 Cl2 O10 88.0(9) 10_556 . ?
O9 Cl2 O12 138.7(10) 10_556 . ?
O9 Cl2 O12 138.7(10) . . ?
O8 Cl2 O12 111.7(8) . . ?
O8 Cl2 O12 111.7(8) 10_556 . ?
O10 Cl2 O12 47.4(12) . . ?
O9 Cl2 O11 86.7(11) 10_556 . ?
O9 Cl2 O11 86.7(11) . . ?
O8 Cl2 O11 106.0(8) . . ?
O8 Cl2 O11 106.0(8) 10_556 . ?
O10 Cl2 O11 152.6(13) . . ?
O12 Cl2 O11 105.3(9) . . ?
O11 O7 O12 130.7(10) . . ?
O10 O12 O7 122.1(9) . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        28.50
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         1.652
_refine_diff_density_min         -0.787
_refine_diff_density_rms         0.116