# Electronic Supplementary Material (ESI) for Dalton Transactions
# This journal is © The Royal Society of Chemistry 2012


data_global
_journal_name_full               'Dalton Trans.'
_journal_coden_cambridge         0222
_journal_year                    ?
_journal_volume                  ?
_journal_page_first              ?
loop_
_publ_author_name
_publ_author_address
L.A.Kushch
;
Institute of Problems of Chemical Physics, RAS,
Chernogolovka, MD, 142432, Russia
;
V.D.Sasnovskaya
;
Institute of Problems of Chemical Physics, RAS,
Chernogolovka, MD, 142432, Russia
;
A.I.Dmitriev
;
Institute of Problems of Chemical Physics, RAS,
Chernogolovka, MD, 142432, Russia
;
E.B.Yagubskii
;
Institute of Problems of Chemical Physics, RAS,
Chernogolovka, MD, 142432, Russia
;
;
O.V.Koplak
;
;
Educational and Scientific Center of National
Academy of Sciences and T. Shevchenko National
University, Kiev 01033, Ukraine
;
L.V.Zorina
;
Institute of Solid State Physics, RAS,
Chernogolovka, MD, 142432, Russia
;
D.W.Boukhvalov
;
School of Computational Sciences, Korea Institute
for Advanced Study, Seoul 130-722, Korea
;
_publ_contact_author_address     
;
Institute of Problems of Chemical Physics, RAS,
Chernogolovka, MD, 142432, Russia
;
_publ_contact_author_email       lkushch@icp.ac.ru
#TrackingRef 'Mn12-final.cif'

_publ_contact_author_name        'Kushch, Ludmila A.'

_publ_requested_category         FA

data_Mn12_i41_a
_database_code_depnum_ccdc_archive 'CCDC 885545'

_vrf_PLAT029_ALERT_3_A           
;
PROBLEM: _diffrn_measured_fraction_theta_full Low ....... 0.908
RESPONSE: The crystal is unstable in air conditions due to solvent
loss and weakly diffracting at high theta angles.
;

_vrf_PLAT601_ALERT_2_A           
;
PROBLEM: Structure Contains Solvent Accessible VOIDS of 362 A**3
RESPONSE: There are large spaces in the structure between the Mn12 units
which are filled by solvent CH2Cl2 molecules disordered throughout several
sites of 20-60% occupancies. The analysis of additional solvent accessible
voids in the structure with the PLATON program shows four cavities in the
unit cell, each being of 400 A3 in size and involving 90 electrons. The
amount of electrons and the cavity volume correspond to two dichloromethane
molecules per this void, therefore more accurate chemical formula of the
compound should be apparently written as
[Mn12O12(CN-o-C6H4CO2)12(CH3CO2)4(H2O)4]10CH2Cl2. However, these additional
solvent molecules are not localized because of very strong positional disorder:
different electron density peaks within the void do not exceed 1.5 e/A3.
;

_vrf_PLAT022_ALERT_3_B           
;
PROBLEM: Ratio Unique / Expected Reflections (too) Low .. 0.882
RESPONSE: The crystal is unstable in air conditions due to solvent
loss and weakly diffracting at high theta angles.
;

_audit_creation_method           
;
CrysAlis RED (Oxford Diffraction Ltd.),
SHELXL-97 and WinGX routine-INITIALISE
;

_chemical_compound_source        'synthesis as described'
_chemical_melting_point          ?
_chemical_name_common            ?
_chemical_formula_moiety         'C104 H68 Mn12 N12 O48, 8(C H2 Cl2)'
_chemical_formula_sum            'C112 H84 Cl16 Mn12 N12 O48'
_chemical_formula_weight         3592.39

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'
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'
N N 0.0061 0.0033 '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'

_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_H-M   'I 41/a'
_symmetry_space_group_name_Hall  '-I 4ad'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y+1/2, z'
'-y+3/4, x+1/4, z+1/4'
'y+1/4, -x+1/4, z+1/4'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1, z+1/2'
'-y+5/4, x+3/4, z+3/4'
'y+3/4, -x+3/4, z+3/4'
'-x, -y, -z'
'x, y-1/2, -z'
'y-3/4, -x-1/4, -z-1/4'
'-y-1/4, x-1/4, -z-1/4'
'-x+1/2, -y+1/2, -z+1/2'
'x+1/2, y, -z+1/2'
'y-1/4, -x+1/4, -z+1/4'
'-y+1/4, x+1/4, -z+1/4'

_cell_length_a                   21.0064(15)
_cell_length_b                   21.0064(15)
_cell_length_c                   42.006(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     18536(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    8940
_cell_measurement_theta_min      2.6
_cell_measurement_theta_max      25.5

_exptl_crystal_description       bulky
_exptl_crystal_colour            black
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             7184
_exptl_absorpt_coefficient_mu    1.084
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.36360
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.5 (release 08-05-2007 CrysAlis171 .NET)
(compiled May 8 2007,13:10:02)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'Enhance (Mo) X-ray Source'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       \w-scan
_diffrn_detector_area_resol_mean 10.4752
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            46525
_diffrn_reflns_av_R_equivalents  0.1408
_diffrn_reflns_av_sigmaI/netI    0.0929
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_l_min       -49
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_theta_min         4.23
_diffrn_reflns_theta_max         25.58
_reflns_number_total             7694
_reflns_number_gt                4072
_reflns_threshold_expression     >2\s(I)

_computing_data_collection       'CrysAlis CCD, Oxford Diffraction Ltd.'
_computing_cell_refinement       'CrysAlis RED, Oxford Diffraction Ltd.'
_computing_data_reduction        'CrysAlis RED, Oxford Diffraction Ltd.'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'DIAMOND 3.1 (Crystal Impact GbR 2005)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'

_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^ > 2\s(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.
One of three independent CN-o-C6H4CO2 ligands in the Mn12 molecule is
disordered between two slightly different orientations with 70 / 30%
occupancy. A combination of the restraints was used to have close to
reality geometry of this disordered fragments: FLAT and ISOR were used
for C6H4CN part, SAME and SADI for CCN part. Hydrogen atoms in terminal
water ligands of the Mn12 complex were refined with restrained O-H bonds
to be of equal length (SADI instruction). SADI restrains were applied
for C-C bonds in phenyl cycles of two ordered CN-o-C6H4CO2 ligands, as
well as for C-Cl and Cl-Cl distances in the solvent CH2Cl2 molecules.
DELU restraints were used for all non-hydrogen atoms of the Mn12 molecule.
;

_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^)+(0.1065P)^2^+256.3578P] 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         7694
_refine_ls_number_parameters     531
_refine_ls_number_restraints     413
_refine_ls_R_factor_all          0.1913
_refine_ls_R_factor_gt           0.1125
_refine_ls_wR_factor_ref         0.2939
_refine_ls_wR_factor_gt          0.2607
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_restrained_S_all      1.004
_refine_ls_shift/su_max          0.005
_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 0.01504(6) 0.18159(6) 0.14758(2) 0.0473(4) Uani 1 1 d U . .
Mn2 Mn 0.05485(8) 0.05575(7) 0.14852(3) 0.0592(4) Uani 1 1 d U . .
Mn3 Mn 0.17397(7) 0.15605(7) 0.13285(3) 0.0573(4) Uani 1 1 d U . .
O1 O 0.0133(3) 0.1938(3) 0.10305(10) 0.0433(12) Uani 1 1 d U . .
O2 O 0.0063(3) 0.1748(3) 0.19295(12) 0.0546(14) Uani 1 1 d U . .
O3 O 0.0904(3) 0.1363(3) 0.14706(11) 0.0523(8) Uani 1 1 d U . .
O4 O -0.0211(3) 0.1022(3) 0.14196(12) 0.0529(9) Uani 1 1 d U . .
O5 O 0.0765(3) 0.0380(3) 0.09939(13) 0.0625(13) Uani 1 1 d U . .
O6 O 0.0388(3) 0.0739(3) 0.19921(13) 0.0663(16) Uani 1 1 d U . .
O7 O 0.1331(4) 0.0111(3) 0.16176(15) 0.0701(13) Uani 1 1 d U A .
O8 O 0.0147(4) -0.0262(3) 0.15072(15) 0.0698(14) Uani 1 1 d U . .
O9 O 0.1676(3) 0.0932(3) 0.09370(14) 0.0679(16) Uani 1 1 d U . .
O10 O 0.1905(3) 0.2108(3) 0.17564(14) 0.0620(16) Uani 1 1 d DU . .
H10D H 0.158(4) 0.221(5) 0.186(3) 0.093 Uiso 1 1 d D . .
H10E H 0.203(5) 0.247(4) 0.172(3) 0.093 Uiso 1 1 d D . .
O11 O 0.2624(3) 0.1695(4) 0.12212(16) 0.0701(15) Uani 1 1 d U . .
O12 O 0.2092(3) 0.0855(3) 0.15734(16) 0.0710(14) Uani 1 1 d U A .
C1 C 0.0180(5) 0.1248(4) 0.20927(19) 0.058(2) Uani 1 1 d U . .
C2 C 0.0074(4) 0.1303(4) 0.24436(18) 0.062(2) Uani 1 1 d DU . .
C3 C 0.0420(6) 0.0909(5) 0.26418(18) 0.084(3) Uani 1 1 d DU . .
H3 H 0.0717 0.0617 0.2554 0.101 Uiso 1 1 calc R . .
C4 C 0.0334(6) 0.0940(6) 0.2966(2) 0.098(4) Uani 1 1 d DU . .
H4 H 0.0571 0.0669 0.3103 0.118 Uiso 1 1 calc R . .
C5 C -0.0094(6) 0.1362(5) 0.3092(2) 0.096(4) Uani 1 1 d DU . .
H5 H -0.0148 0.1381 0.3316 0.115 Uiso 1 1 calc R . .
C6 C -0.0452(5) 0.1761(5) 0.29009(15) 0.078(3) Uani 1 1 d DU . .
H6 H -0.0749 0.2050 0.2991 0.093 Uiso 1 1 calc R . .
C7 C -0.0365(4) 0.1729(4) 0.25736(15) 0.062(2) Uani 1 1 d DU . .
C8 C -0.0746(5) 0.2141(5) 0.2385(2) 0.063(2) Uani 1 1 d DU . .
N1 N -0.1083(4) 0.2484(4) 0.22533(18) 0.075(2) Uani 1 1 d DU . .
C9 C -0.0373(6) -0.0455(5) 0.1405(2) 0.073(3) Uani 1 1 d U . .
C10 C -0.0511(7) -0.1172(6) 0.1430(3) 0.104(4) Uani 1 1 d U . .
H10A H -0.0931 -0.1262 0.1338 0.156 Uiso 1 1 calc R . .
H10B H -0.0506 -0.1301 0.1654 0.156 Uiso 1 1 calc R . .
H10C H -0.0186 -0.1410 0.1312 0.156 Uiso 1 1 calc R . .
C11 C 0.1228(5) 0.0587(5) 0.0836(2) 0.062(2) Uani 1 1 d U . .
C12 C 0.1251(4) 0.0430(4) 0.0484(2) 0.062(2) Uani 1 1 d DU . .
C13 C 0.1593(5) 0.0821(5) 0.02837(18) 0.071(2) Uani 1 1 d DU . .
H13 H 0.1823 0.1170 0.0370 0.085 Uiso 1 1 calc R . .
C14 C 0.1604(5) 0.0711(5) -0.0042(2) 0.083(3) Uani 1 1 d DU . .
H14 H 0.1861 0.0967 -0.0178 0.100 Uiso 1 1 calc R . .
C15 C 0.1239(5) 0.0226(5) -0.0167(2) 0.088(3) Uani 1 1 d DU . .
H15 H 0.1204 0.0179 -0.0391 0.105 Uiso 1 1 calc R . .
C16 C 0.0924(5) -0.0192(5) 0.00323(18) 0.081(3) Uani 1 1 d DU . .
H16 H 0.0714 -0.0554 -0.0054 0.097 Uiso 1 1 calc R . .
C17 C 0.0916(5) -0.0084(5) 0.0356(2) 0.070(2) Uani 1 1 d DU . .
C18 C 0.0589(6) -0.0540(6) 0.0547(3) 0.078(3) Uani 1 1 d U . .
N2 N 0.0299(5) -0.0912(5) 0.0682(2) 0.092(3) Uani 1 1 d DU . .
C21 C 0.1889(6) 0.0324(5) 0.1648(2) 0.0704(18) Uani 1 1 d U . .
C22A C 0.2440(5) -0.0103(5) 0.1771(3) 0.077(3) Uani 0.70 1 d PGDU A 1
C23A C 0.3072(5) 0.0056(5) 0.1713(3) 0.091(4) Uani 0.70 1 d PGDU A 1
H23A H 0.3173 0.0440 0.1605 0.110 Uiso 0.70 1 calc PR A 1
C24A C 0.3556(5) -0.0348(7) 0.1814(4) 0.112(5) Uani 0.70 1 d PGDU A 1
H24A H 0.3988 -0.0240 0.1775 0.134 Uiso 0.70 1 calc PR A 1
C25A C 0.3408(6) -0.0910(7) 0.1972(4) 0.131(6) Uani 0.70 1 d PGDU A 1
H25A H 0.3739 -0.1186 0.2041 0.158 Uiso 0.70 1 calc PR A 1
C26A C 0.2776(6) -0.1069(5) 0.2030(4) 0.130(6) Uani 0.70 1 d PGDU A 1
H26A H 0.2675 -0.1453 0.2138 0.156 Uiso 0.70 1 calc PR A 1
C27A C 0.2292(5) -0.0665(5) 0.1929(3) 0.106(5) Uani 0.70 1 d PGDU A 1
C28A C 0.1660(8) -0.0857(10) 0.1996(6) 0.128(6) Uani 0.70 1 d PDU A 1
N3A N 0.1172(8) -0.1085(11) 0.2053(6) 0.184(9) Uani 0.70 1 d PDU A 1
C22B C 0.2236(12) -0.0223(12) 0.1860(7) 0.078(6) Uani 0.30 1 d PGDU A 2
C23B C 0.2883(12) -0.0208(14) 0.1789(8) 0.098(7) Uani 0.30 1 d PGDU A 2
H23B H 0.3044 0.0102 0.1645 0.117 Uiso 0.30 1 calc PR A 2
C24B C 0.3293(11) -0.0645(15) 0.1929(8) 0.105(8) Uani 0.30 1 d PGDU A 2
H24B H 0.3735 -0.0635 0.1880 0.126 Uiso 0.30 1 calc PR A 2
C25B C 0.3057(13) -0.1097(15) 0.2140(9) 0.121(9) Uani 0.30 1 d PGDU A 2
H25B H 0.3338 -0.1396 0.2235 0.145 Uiso 0.30 1 calc PR A 2
C26B C 0.2411(13) -0.1113(13) 0.2211(7) 0.117(9) Uani 0.30 1 d PGDU A 2
H26B H 0.2250 -0.1422 0.2355 0.141 Uiso 0.30 1 calc PR A 2
C27B C 0.2001(11) -0.0675(11) 0.2071(6) 0.107(8) Uani 0.30 1 d PGDU A 2
C28B C 0.1360(13) -0.0703(18) 0.2178(10) 0.115(9) Uani 0.30 1 d PDU A 2
N3B N 0.0837(13) -0.080(2) 0.2245(12) 0.177(14) Uani 0.30 1 d PDU A 2
Cl1 Cl 0.3094(4) 0.1631(4) 0.0265(2) 0.147(3) Uiso 0.60 1 d PDU . .
Cl2 Cl 0.3311(4) 0.2592(4) -0.0196(2) 0.166(3) Uiso 0.60 1 d PDU . .
C31 C 0.3157(12) 0.2418(7) 0.0194(4) 0.110(7) Uiso 0.60 1 d PDU . .
H31A H 0.3503 0.2594 0.0328 0.132 Uiso 0.60 1 calc PR . .
H31B H 0.2756 0.2629 0.0258 0.132 Uiso 0.60 1 calc PR . .
Cl3 Cl 0.2320(13) -0.0527(12) 0.2928(6) 0.160(9) Uiso 0.20 1 d PDU B 1
Cl4 Cl 0.2737(16) -0.1380(15) 0.3408(8) 0.205(13) Uiso 0.20 1 d PDU B 1
C32 C 0.268(3) -0.0613(15) 0.3286(9) 0.093(18) Uiso 0.20 1 d PDU B 1
H32A H 0.2435 -0.0369 0.3447 0.112 Uiso 0.20 1 calc PR B 1
H32B H 0.3111 -0.0427 0.3274 0.112 Uiso 0.20 1 calc PR B 1
Cl5 Cl 0.0356(9) 0.1462(10) 0.3966(5) 0.180(7) Uiso 0.30 1 d PDU C 1
Cl6 Cl 0.1228(9) 0.0578(8) 0.3698(5) 0.158(6) Uiso 0.30 1 d PDU C 1
C33 C 0.0522(13) 0.0695(12) 0.3871(10) 0.075(12) Uiso 0.30 1 d PDU C 1
H33A H 0.0504 0.0436 0.4068 0.090 Uiso 0.30 1 calc PR C 1
H33B H 0.0186 0.0536 0.3726 0.090 Uiso 0.30 1 calc PR C 1
Cl7 Cl 0.1567(5) 0.0553(5) 0.3565(3) 0.108(3) Uiso 0.40 1 d PDU D 2
Cl8 Cl 0.0506(6) 0.0995(9) 0.3919(4) 0.157(5) Uiso 0.40 1 d PDU D 2
C34 C 0.1211(9) 0.1185(10) 0.3750(6) 0.082(8) Uiso 0.40 1 d PDU D 2
H34A H 0.1501 0.1351 0.3916 0.098 Uiso 0.40 1 calc PR D 2
H34B H 0.1142 0.1529 0.3593 0.098 Uiso 0.40 1 calc PR D 2
Cl9 Cl 0.1935(8) -0.0233(8) 0.2827(4) 0.146(5) Uiso 0.30 1 d PDU E 3
Cl10 Cl 0.1901(8) 0.0275(7) 0.3451(3) 0.130(4) Uiso 0.30 1 d PDU E 3
C35 C 0.222(3) -0.028(2) 0.3205(6) 0.16(2) Uiso 0.30 1 d PDU E 3
H35A H 0.2126 -0.0710 0.3291 0.198 Uiso 0.30 1 calc PR E 3
H35B H 0.2688 -0.0229 0.3201 0.198 Uiso 0.30 1 calc PR E 3
Cl11 Cl 0.3418(15) -0.2353(16) 0.2650(7) 0.198(12) Uiso 0.20 1 d PDU . .
Cl12 Cl 0.4191(16) -0.2519(17) 0.2104(8) 0.212(13) Uiso 0.20 1 d PDU . .
C36 C 0.349(2) -0.269(3) 0.2285(10) 0.11(2) Uiso 0.20 1 d PDU . .
H36A H 0.3140 -0.2532 0.2148 0.135 Uiso 0.20 1 calc PR . .
H36B H 0.3449 -0.3153 0.2305 0.135 Uiso 0.20 1 calc PR . .

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 0.0652(9) 0.0569(8) 0.0198(6) -0.0004(5) 0.0007(5) 0.0016(6)
Mn2 0.0867(10) 0.0584(8) 0.0325(7) -0.0043(6) 0.0012(6) 0.0081(7)
Mn3 0.0639(9) 0.0745(10) 0.0336(7) -0.0090(6) -0.0066(6) 0.0091(7)
O1 0.055(3) 0.060(3) 0.0145(15) -0.0049(18) 0.001(2) -0.001(2)
O2 0.086(4) 0.056(3) 0.0218(15) 0.0016(16) 0.002(2) 0.006(3)
O3 0.0701(16) 0.0642(18) 0.023(2) -0.0026(18) -0.0055(17) 0.0058(13)
O4 0.074(2) 0.058(2) 0.026(2) 0.0015(18) 0.003(2) -0.0032(14)
O5 0.083(4) 0.067(3) 0.0369(17) -0.010(2) 0.004(2) 0.004(3)
O6 0.111(5) 0.060(3) 0.0286(16) 0.0062(16) 0.001(2) 0.016(3)
O7 0.095(2) 0.064(3) 0.052(3) -0.007(3) -0.006(3) 0.0161(19)
O8 0.102(4) 0.0604(18) 0.047(3) 0.001(2) 0.003(3) 0.002(2)
O9 0.071(4) 0.089(5) 0.045(3) -0.022(2) 0.000(2) 0.006(3)
O10 0.077(4) 0.072(4) 0.037(3) -0.008(2) -0.011(3) 0.004(3)
O11 0.061(2) 0.093(5) 0.056(4) -0.016(3) -0.009(2) 0.011(3)
O12 0.080(3) 0.075(3) 0.058(3) -0.010(2) -0.019(3) 0.016(2)
C1 0.088(7) 0.058(4) 0.026(2) 0.003(2) 0.002(4) 0.006(4)
C2 0.096(7) 0.064(6) 0.026(2) 0.005(3) 0.000(3) 0.008(4)
C3 0.129(10) 0.091(8) 0.034(3) 0.014(4) -0.002(5) 0.029(5)
C4 0.150(12) 0.113(9) 0.032(3) 0.008(5) -0.011(5) 0.033(7)
C5 0.149(12) 0.109(9) 0.029(4) 0.004(4) -0.001(5) 0.022(6)
C6 0.117(9) 0.087(7) 0.029(3) -0.004(4) 0.003(4) 0.008(5)
C7 0.093(7) 0.064(6) 0.030(3) 0.004(3) 0.009(3) 0.001(4)
C8 0.082(7) 0.076(7) 0.032(4) -0.002(4) 0.012(4) 0.010(4)
N1 0.094(7) 0.087(6) 0.044(5) 0.007(4) 0.010(4) 0.017(4)
C9 0.102(6) 0.067(5) 0.049(6) 0.002(5) 0.008(5) -0.006(4)
C10 0.139(11) 0.074(5) 0.100(10) 0.013(7) -0.006(8) -0.022(6)
C11 0.077(5) 0.071(6) 0.039(3) -0.015(3) 0.003(3) 0.005(4)
C12 0.063(6) 0.083(6) 0.039(3) -0.017(3) 0.003(3) 0.004(4)
C13 0.077(7) 0.092(7) 0.043(3) -0.014(4) 0.006(4) -0.004(4)
C14 0.101(8) 0.105(8) 0.044(3) -0.015(4) 0.016(5) -0.006(5)
C15 0.104(9) 0.117(9) 0.042(4) -0.026(4) 0.008(5) -0.003(6)
C16 0.089(8) 0.104(8) 0.050(3) -0.029(4) -0.001(5) -0.007(5)
C17 0.076(7) 0.086(6) 0.048(3) -0.022(3) 0.003(4) 0.000(4)
C18 0.096(9) 0.078(7) 0.059(5) -0.024(4) 0.008(5) -0.004(5)
N2 0.117(9) 0.088(7) 0.072(6) -0.014(5) 0.009(5) -0.012(5)
C21 0.095(3) 0.069(4) 0.048(5) -0.020(4) -0.008(5) 0.017(3)
C22A 0.097(3) 0.075(6) 0.059(8) -0.011(6) -0.007(6) 0.020(5)
C23A 0.093(4) 0.095(8) 0.087(10) -0.013(7) -0.023(8) 0.010(5)
C24A 0.099(5) 0.117(10) 0.119(12) -0.003(8) -0.015(9) 0.025(6)
C25A 0.131(6) 0.129(11) 0.134(13) 0.020(10) -0.031(10) 0.030(8)
C26A 0.142(7) 0.111(10) 0.136(13) 0.040(9) -0.012(10) 0.028(7)
C27A 0.123(6) 0.099(9) 0.095(11) 0.021(8) 0.002(9) 0.022(6)
C28A 0.131(6) 0.127(12) 0.127(13) 0.036(10) -0.001(10) 0.000(8)
N3A 0.163(10) 0.182(15) 0.209(16) 0.021(12) 0.025(12) -0.040(10)
C22B 0.093(5) 0.066(9) 0.075(13) -0.012(9) -0.017(7) 0.010(7)
C23B 0.090(7) 0.102(14) 0.101(15) -0.007(11) -0.018(10) 0.014(9)
C24B 0.095(8) 0.105(15) 0.116(16) 0.001(12) -0.008(11) 0.022(10)
C25B 0.128(10) 0.116(15) 0.119(17) 0.010(11) -0.017(12) 0.009(11)
C26B 0.133(11) 0.104(14) 0.115(16) 0.031(11) -0.009(12) 0.005(10)
C27B 0.124(9) 0.102(14) 0.095(15) 0.016(10) -0.014(10) 0.002(10)
C28B 0.133(9) 0.107(16) 0.104(16) 0.023(13) 0.003(11) 0.006(9)
N3B 0.148(12) 0.19(2) 0.19(2) 0.006(14) 0.037(14) -0.012(13)

_geom_special_details            
;
All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell s.u.'s are taken
into account individually in the estimation of s.u.'s in distances, angles
and torsion angles; correlations between s.u.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell s.u.'s is used for estimating s.u.'s 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 O4 1.847(6) . ?
Mn1 O3 1.847(6) . ?
Mn1 O1 1.888(5) . ?
Mn1 O1 1.892(6) 15 ?
Mn1 O2 1.920(5) . ?
Mn1 O1 1.923(6) 16 ?
Mn1 Mn2 2.7727(19) . ?
Mn1 Mn1 2.816(2) 15 ?
Mn1 Mn1 2.816(2) 16 ?
Mn1 Mn1 2.943(3) 2 ?
Mn2 O3 1.851(6) . ?
Mn2 O4 1.889(6) . ?
Mn2 O8 1.920(7) . ?
Mn2 O7 1.972(7) . ?
Mn2 O5 2.146(6) . ?
Mn2 O6 2.189(6) . ?
Mn3 O3 1.900(6) . ?
Mn3 O4 1.932(6) 16 ?
Mn3 O11 1.932(7) . ?
Mn3 O12 1.949(7) . ?
Mn3 O9 2.113(6) . ?
Mn3 O10 2.162(6) . ?
O1 Mn1 1.892(6) 16 ?
O1 Mn1 1.923(5) 15 ?
O2 C1 1.279(10) . ?
O4 Mn3 1.932(6) 15 ?
O5 C11 1.256(11) . ?
O6 C1 1.230(10) . ?
O7 C21 1.261(12) . ?
O8 C9 1.241(13) . ?
O9 C11 1.261(11) . ?
O11 C9 1.260(13) 16 ?
O12 C21 1.236(12) . ?
C1 C2 1.496(11) . ?
C2 C3 1.380(9) . ?
C2 C7 1.395(8) . ?
C3 C4 1.377(9) . ?
C4 C5 1.368(9) . ?
C5 C6 1.382(9) . ?
C6 C7 1.388(6) . ?
C7 C8 1.422(12) . ?
C8 N1 1.150(10) . ?
C9 O11 1.260(13) 15 ?
C9 C10 1.538(15) . ?
C11 C12 1.515(12) . ?
C12 C13 1.377(9) . ?
C12 C17 1.395(9) . ?
C13 C14 1.389(9) . ?
C14 C15 1.378(9) . ?
C15 C16 1.382(9) . ?
C16 C17 1.381(9) . ?
C17 C18 1.425(15) . ?
C18 N2 1.140(13) . ?
C21 C22A 1.552(14) . ?
C21 C22B 1.63(2) . ?
C22A C23A 1.3900 . ?
C22A C27A 1.3900 . ?
C23A C24A 1.3900 . ?
C24A C25A 1.3900 . ?
C25A C26A 1.3900 . ?
C26A C27A 1.3900 . ?
C27A C28A 1.415(12) . ?
C28A N3A 1.157(12) . ?
C22B C23B 1.3900 . ?
C22B C27B 1.3900 . ?
C23B C24B 1.3900 . ?
C24B C25B 1.3900 . ?
C25B C26B 1.3900 . ?
C26B C27B 1.3900 . ?
C27B C28B 1.421(13) . ?
C28B N3B 1.154(13) . ?
Cl1 C31 1.684(13) . ?
Cl2 C31 1.709(13) . ?
Cl3 C32 1.691(15) . ?
Cl4 C32 1.695(15) . ?
Cl5 C33 1.696(14) . ?
Cl6 C33 1.670(14) . ?
Cl7 C34 1.711(13) . ?
Cl8 C34 1.690(13) . ?
Cl9 C35 1.700(15) . ?
Cl10 C35 1.697(15) . ?
Cl11 C36 1.691(15) . ?
Cl12 C36 1.691(15) . ?

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
O4 Mn1 O3 83.4(3) . . ?
O4 Mn1 O1 89.3(2) . . ?
O3 Mn1 O1 94.3(2) . . ?
O4 Mn1 O1 103.0(3) . 15 ?
O3 Mn1 O1 173.1(3) . 15 ?
O1 Mn1 O1 83.6(2) . 15 ?
O4 Mn1 O2 91.2(2) . . ?
O3 Mn1 O2 93.2(2) . . ?
O1 Mn1 O2 172.5(3) . . ?
O1 Mn1 O2 89.0(2) 15 . ?
O4 Mn1 O1 171.5(2) . 16 ?
O3 Mn1 O1 94.2(3) . 16 ?
O1 Mn1 O1 82.7(2) . 16 ?
O1 Mn1 O1 79.0(3) 15 16 ?
O2 Mn1 O1 97.1(2) . 16 ?
O4 Mn1 Mn2 42.68(19) . . ?
O3 Mn1 Mn2 41.49(19) . . ?
O1 Mn1 Mn2 98.57(17) . . ?
O1 Mn1 Mn2 145.25(18) 15 . ?
O2 Mn1 Mn2 86.82(18) . . ?
O1 Mn1 Mn2 135.71(17) 16 . ?
O4 Mn1 Mn1 91.02(19) . 15 ?
O3 Mn1 Mn1 136.94(16) . 15 ?
O1 Mn1 Mn1 42.85(17) . 15 ?
O1 Mn1 Mn1 41.80(13) 15 15 ?
O2 Mn1 Mn1 129.67(19) . 15 ?
O1 Mn1 Mn1 85.13(15) 16 15 ?
Mn2 Mn1 Mn1 125.23(7) . 15 ?
O4 Mn1 Mn1 129.75(17) . 16 ?
O3 Mn1 Mn1 88.35(19) . 16 ?
O1 Mn1 Mn1 41.91(17) . 16 ?
O1 Mn1 Mn1 85.69(15) 15 16 ?
O2 Mn1 Mn1 138.84(19) . 16 ?
O1 Mn1 Mn1 41.89(13) 16 16 ?
Mn2 Mn1 Mn1 118.88(7) . 16 ?
Mn1 Mn1 Mn1 63.01(5) 15 16 ?
O4 Mn1 Mn1 142.5(2) . 2 ?
O3 Mn1 Mn1 133.4(2) . 2 ?
O1 Mn1 Mn1 82.16(17) . 2 ?
O1 Mn1 Mn1 39.91(17) 15 2 ?
O2 Mn1 Mn1 92.95(17) . 2 ?
O1 Mn1 Mn1 39.15(16) 16 2 ?
Mn2 Mn1 Mn1 174.78(9) . 2 ?
Mn1 Mn1 Mn1 58.50(2) 15 2 ?
Mn1 Mn1 Mn1 58.50(2) 16 2 ?
O3 Mn2 O4 82.2(3) . . ?
O3 Mn2 O8 177.6(3) . . ?
O4 Mn2 O8 95.7(3) . . ?
O3 Mn2 O7 96.2(3) . . ?
O4 Mn2 O7 171.8(2) . . ?
O8 Mn2 O7 85.8(3) . . ?
O3 Mn2 O5 92.4(2) . . ?
O4 Mn2 O5 97.4(2) . . ?
O8 Mn2 O5 89.1(3) . . ?
O7 Mn2 O5 90.7(3) . . ?
O3 Mn2 O6 86.3(2) . . ?
O4 Mn2 O6 85.5(2) . . ?
O8 Mn2 O6 92.4(3) . . ?
O7 Mn2 O6 86.4(3) . . ?
O5 Mn2 O6 176.6(3) . . ?
O3 Mn2 Mn1 41.36(18) . . ?
O4 Mn2 Mn1 41.52(18) . . ?
O8 Mn2 Mn1 136.3(2) . . ?
O7 Mn2 Mn1 135.1(2) . . ?
O5 Mn2 Mn1 102.47(18) . . ?
O6 Mn2 Mn1 78.55(16) . . ?
O3 Mn3 O4 94.6(2) . 16 ?
O3 Mn3 O11 173.4(3) . . ?
O4 Mn3 O11 91.8(3) 16 . ?
O3 Mn3 O12 91.1(3) . . ?
O4 Mn3 O12 174.2(3) 16 . ?
O11 Mn3 O12 82.5(3) . . ?
O3 Mn3 O9 92.8(2) . . ?
O4 Mn3 O9 93.3(3) 16 . ?
O11 Mn3 O9 88.3(3) . . ?
O12 Mn3 O9 87.7(3) . . ?
O3 Mn3 O10 90.2(3) . . ?
O4 Mn3 O10 94.2(2) 16 . ?
O11 Mn3 O10 87.8(3) . . ?
O12 Mn3 O10 84.5(3) . . ?
O9 Mn3 O10 171.7(3) . . ?
Mn1 O1 Mn1 96.3(2) . 16 ?
Mn1 O1 Mn1 95.3(2) . 15 ?
Mn1 O1 Mn1 100.9(3) 16 15 ?
C1 O2 Mn1 125.0(5) . . ?
Mn1 O3 Mn2 97.2(3) . . ?
Mn1 O3 Mn3 133.1(3) . . ?
Mn2 O3 Mn3 125.6(3) . . ?
Mn1 O4 Mn2 95.8(3) . . ?
Mn1 O4 Mn3 130.6(3) . 15 ?
Mn2 O4 Mn3 126.9(3) . 15 ?
C11 O5 Mn2 127.8(6) . . ?
C1 O6 Mn2 122.7(5) . . ?
C21 O7 Mn2 129.5(7) . . ?
C9 O8 Mn2 131.5(7) . . ?
C11 O9 Mn3 132.0(6) . . ?
C9 O11 Mn3 137.2(7) 16 . ?
C21 O12 Mn3 133.6(7) . . ?
O6 C1 O2 126.8(7) . . ?
O6 C1 C2 117.3(7) . . ?
O2 C1 C2 115.8(7) . . ?
C3 C2 C7 119.7(8) . . ?
C3 C2 C1 118.0(7) . . ?
C7 C2 C1 122.3(7) . . ?
C4 C3 C2 120.0(9) . . ?
C5 C4 C3 119.9(10) . . ?
C4 C5 C6 121.7(9) . . ?
C5 C6 C7 118.3(8) . . ?
C6 C7 C2 120.4(7) . . ?
C6 C7 C8 116.7(7) . . ?
C2 C7 C8 122.9(6) . . ?
N1 C8 C7 174.5(9) . . ?
O8 C9 O11 126.8(10) . 15 ?
O8 C9 C10 117.5(11) . . ?
O11 C9 C10 115.6(11) 15 . ?
O9 C11 O5 126.7(8) . . ?
O9 C11 C12 115.5(8) . . ?
O5 C11 C12 117.7(8) . . ?
C13 C12 C17 119.3(8) . . ?
C13 C12 C11 118.8(7) . . ?
C17 C12 C11 121.8(8) . . ?
C12 C13 C14 120.9(9) . . ?
C15 C14 C13 119.1(9) . . ?
C14 C15 C16 120.5(9) . . ?
C17 C16 C15 119.9(9) . . ?
C16 C17 C12 120.0(9) . . ?
C16 C17 C18 116.7(8) . . ?
C12 C17 C18 123.2(8) . . ?
N2 C18 C17 175.2(13) . . ?
O12 C21 O7 127.9(10) . . ?
O12 C21 C22A 110.4(10) . . ?
O7 C21 C22A 121.5(10) . . ?
O12 C21 C22B 128.5(14) . . ?
O7 C21 C22B 102.9(13) . . ?
C23A C22A C27A 120.0 . . ?
C23A C22A C21 121.1(8) . . ?
C27A C22A C21 118.9(8) . . ?
C22A C23A C24A 120.0 . . ?
C25A C24A C23A 120.0 . . ?
C24A C25A C26A 120.0 . . ?
C27A C26A C25A 120.0 . . ?
C26A C27A C22A 120.0 . . ?
C26A C27A C28A 116.9(10) . . ?
C22A C27A C28A 123.1(10) . . ?
N3A C28A C27A 172(2) . . ?
C23B C22B C27B 120.0 . . ?
C23B C22B C21 107.7(14) . . ?
C27B C22B C21 132.2(14) . . ?
C24B C23B C22B 120.0 . . ?
C23B C24B C25B 120.0 . . ?
C26B C25B C24B 120.0 . . ?
C27B C26B C25B 120.0 . . ?
C26B C27B C22B 120.0 . . ?
C26B C27B C28B 115.3(13) . . ?
C22B C27B C28B 124.5(13) . . ?
N3B C28B C27B 171(4) . . ?
Cl1 C31 Cl2 113.2(11) . . ?
Cl3 C32 Cl4 113.7(15) . . ?
Cl6 C33 Cl5 115.2(14) . . ?
Cl8 C34 Cl7 113.0(13) . . ?
Cl10 C35 Cl9 112.9(14) . . ?
Cl11 C36 Cl12 113.7(15) . . ?

_diffrn_measured_fraction_theta_max 0.882
_diffrn_reflns_theta_full        25.25
_diffrn_measured_fraction_theta_full 0.908
_refine_diff_density_max         1.236
_refine_diff_density_min         -0.747
_refine_diff_density_rms         0.142