# Supplementary Material (ESI) for Dalton Transactions
# This journal is (c) The Royal Society of Chemistry 2009

data_global
_journal_name_full               'Dalton Trans.'

_journal_coden_Cambridge         0222
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Debasis Das'
_publ_contact_author_email       DASDEBASIS2001@YAHOO.COM

_publ_section_title              
;
Mono- and dinuclear manganese(III)
complexes showing efficient catechol oxidase activity:
syntheses, characterization and spectroscopic studies
;
loop_
_publ_author_name
'Debasis Das'
'Arpita Banerjee'
'Kazi Sabnam Banu'
'Santanu Bhattacharya'
'Tanmay Chattopadhyay'
;
M.Mukherjee
;
'Goutam Kumar Patra'
'Ennio Zangrando'

# Attachment 'SB3new.cif'

data_2
_database_code_depnum_ccdc_archive 'CCDC 718546'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '2(C21 H24 Mn N2 O6, 2(Cl), 4(H2 O), (C2 H3 N)'
_chemical_formula_sum            'C44 H59 Cl2 Mn2 N5 O16 '
_chemical_formula_weight         1094.74

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'
Cl Cl 0.1484 0.1585 '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'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   'C cca'

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

_cell_length_a                   26.701(5)
_cell_length_b                   19.466(4)
_cell_length_c                   10.047(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     5222(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       block
_exptl_crystal_colour            black
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.30
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.392
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2280
_exptl_absorpt_coefficient_mu    0.655
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(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  'image plate dip1030'
_diffrn_measurement_method       'laser scanner'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            28162
_diffrn_reflns_av_R_equivalents  0.0795
_diffrn_reflns_av_sigmaI/netI    0.0644
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.09
_diffrn_reflns_theta_max         25.02
_reflns_number_total             2206
_reflns_number_gt                1104
_reflns_threshold_expression     >2\s(I)

_computing_data_collection       'Nonius Xpress'
_computing_cell_refinement       'Denzo (Otwinowski & Minor 1997)'
_computing_data_reduction        'Denzo and Scalepack (Otwinowski & Minor 1997)'
_computing_structure_solution    'SHELX97 (Sheldrick, 1998)'
_computing_structure_refinement  'SHELX97 (Sheldrick, 1998)'
_computing_molecular_graphics    'Ortep3/windows (Farrugia,1997)'
_computing_publication_material  'Wingx 1.70.00 (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.
;

_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^)+(0.0836P)^2^+0.0000P] 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         2206
_refine_ls_number_parameters     171
_refine_ls_number_restraints     13
_refine_ls_R_factor_all          0.0965
_refine_ls_R_factor_gt           0.0480
_refine_ls_wR_factor_ref         0.1457
_refine_ls_wR_factor_gt          0.1285
_refine_ls_goodness_of_fit_ref   0.859
_refine_ls_restrained_S_all      0.871
_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
Mn Mn 0.12998(3) 0.2500 0.7500 0.0672(3) Uani 1 2 d S . .
O1W O 0.13314(12) 0.32555(18) 0.5811(4) 0.0999(11) Uani 1 1 d D . .
H2W H 0.1040(12) 0.335(3) 0.554(6) 0.150 Uiso 1 1 d D . .
H1W H 0.1591(15) 0.350(2) 0.590(6) 0.150 Uiso 1 1 d D . .
N1 N 0.18581(13) 0.2002(2) 0.6643(4) 0.0803(11) Uani 1 1 d D . .
O1 O 0.08115(10) 0.19947(14) 0.6584(3) 0.0751(8) Uani 1 1 d . . .
C1 C 0.18133(18) 0.1558(3) 0.5710(5) 0.0808(13) Uani 1 1 d . . .
H1 H 0.2106 0.1372 0.5363 0.097 Uiso 1 1 calc R . .
C2 C 0.13502(18) 0.1325(2) 0.5161(4) 0.0701(12) Uani 1 1 d . . .
C3 C 0.1370(2) 0.0844(2) 0.4123(5) 0.0835(14) Uani 1 1 d . . .
H3 H 0.1683 0.0709 0.3816 0.100 Uiso 1 1 calc R . .
C4 C 0.0952(2) 0.0557(2) 0.3528(5) 0.0845(14) Uani 1 1 d . . .
C5 C 0.04952(19) 0.0767(2) 0.4017(5) 0.0819(13) Uani 1 1 d . . .
H5 H 0.0207 0.0579 0.3648 0.098 Uiso 1 1 calc R . .
C6 C 0.04436(17) 0.1244(2) 0.5035(4) 0.0671(11) Uani 1 1 d . . .
C7 C 0.08713(17) 0.15358(19) 0.5614(4) 0.0658(11) Uani 1 1 d . . .
C8 C 0.0992(2) 0.0041(3) 0.2405(5) 0.1171(19) Uani 1 1 d . . .
H8A H 0.0953 -0.0415 0.2754 0.176 Uiso 1 1 calc R . .
H8B H 0.1314 0.0082 0.1988 0.176 Uiso 1 1 calc R . .
H8C H 0.0734 0.0130 0.1761 0.176 Uiso 1 1 calc R . .
C9 C -0.0052(2) 0.1447(2) 0.5472(5) 0.0842(14) Uani 1 1 d . . .
H9 H -0.0075 0.1781 0.6131 0.101 Uiso 1 1 calc R . .
O2 O -0.04377(15) 0.1211(2) 0.5039(4) 0.1217(14) Uani 1 1 d . . .
C10A C 0.2349(3) 0.2114(4) 0.7457(11) 0.095(2) Uiso 0.50 1 d PD . 1
H10A H 0.2336 0.1895 0.8335 0.114 Uiso 0.50 1 calc PR . 1
C11 C 0.2822(3) 0.1979(4) 0.6762(9) 0.086(3) Uani 0.50 1 d PD . 1
H11A H 0.2861 0.1493 0.6635 0.129 Uiso 0.50 1 calc PR . 1
H11B H 0.3096 0.2150 0.7284 0.129 Uiso 0.50 1 calc PR . 1
H11C H 0.2819 0.2204 0.5912 0.129 Uiso 0.50 1 calc PR . 1
C10B C 0.2346(3) 0.2304(5) 0.6893(9) 0.095(2) Uiso 0.50 1 d PD . 2
H10D H 0.2595 0.1943 0.6952 0.114 Uiso 0.50 1 calc PR . 2
H10E H 0.2436 0.2602 0.6155 0.114 Uiso 0.50 1 calc PR . 2
O2W O 0.20871(14) 0.41890(16) 0.5663(3) 0.0937(10) Uani 1 1 d D . .
H3W H 0.217(2) 0.443(3) 0.499(4) 0.140 Uiso 1 1 d D . .
H4W H 0.214(2) 0.445(2) 0.633(4) 0.140 Uiso 1 1 d D . .
Cl1 Cl 0.2500 0.0000 0.68393(17) 0.0901(6) Uani 1 2 d S . .
N20 N -0.0179(10) 0.2500 0.2500 0.186(4) Uiso 0.50 2 d SPD . .
C20 C 0.0259(11) 0.2500 0.2500 0.186(4) Uiso 0.50 2 d SPD . .
C21 C 0.0826(7) 0.2500 0.2500 0.158(7) Uiso 0.50 2 d SPD . .
H21A H 0.0863 0.2035 0.2500 0.236 Uiso 0.25 1 d PR . .
H21B H 0.0863 0.2733 0.3280 0.236 Uiso 0.25 1 d PR . .
H21C H 0.0863 0.2733 0.1720 0.236 Uiso 0.25 1 d 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
Mn 0.0556(6) 0.0711(5) 0.0749(7) 0.0046(5) 0.000 0.000
O1W 0.067(2) 0.114(2) 0.119(3) 0.048(2) -0.016(2) -0.0099(19)
N1 0.059(2) 0.093(3) 0.089(3) 0.005(2) 0.004(2) -0.0047(19)
O1 0.0621(19) 0.0824(18) 0.081(2) -0.0133(16) 0.0096(15) -0.0016(14)
C1 0.062(3) 0.092(3) 0.088(4) 0.019(3) 0.016(3) 0.010(2)
C2 0.066(3) 0.075(2) 0.069(3) 0.012(2) 0.015(3) 0.014(2)
C3 0.086(4) 0.091(3) 0.074(3) 0.007(3) 0.018(3) 0.024(3)
C4 0.100(4) 0.082(3) 0.072(3) -0.007(2) 0.008(3) 0.024(3)
C5 0.085(4) 0.091(3) 0.069(3) -0.014(2) -0.003(3) 0.018(3)
C6 0.059(3) 0.081(3) 0.062(3) -0.003(2) 0.006(2) 0.005(2)
C7 0.071(3) 0.064(2) 0.062(3) 0.011(2) 0.009(2) 0.006(2)
C8 0.127(5) 0.128(4) 0.097(4) -0.039(3) 0.003(4) 0.044(4)
C9 0.074(4) 0.094(3) 0.085(3) -0.024(3) 0.002(3) -0.002(3)
O2 0.072(3) 0.153(3) 0.140(3) -0.076(3) 0.005(2) -0.005(2)
C11 0.073(6) 0.086(6) 0.098(7) -0.022(5) 0.023(5) 0.019(5)
O2W 0.103(3) 0.094(2) 0.085(3) 0.0008(19) 0.009(2) -0.0183(19)
Cl1 0.1008(13) 0.0963(11) 0.0731(11) 0.000 0.000 -0.0009(9)

_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
Mn O1 1.875(3) . ?
Mn O1 1.875(3) 7_456 ?
Mn N1 1.976(4) 7_456 ?
Mn N1 1.976(4) . ?
Mn O1W 2.247(3) 7_456 ?
Mn O1W 2.247(3) . ?
N1 C1 1.281(6) . ?
N1 C10B 1.452(8) . ?
N1 C10A 1.560(9) . ?
O1 C7 1.332(4) . ?
C1 C2 1.428(6) . ?
C2 C3 1.403(6) . ?
C2 C7 1.418(6) . ?
C3 C4 1.383(6) . ?
C4 C5 1.377(6) . ?
C4 C8 1.514(6) . ?
C5 C6 1.388(6) . ?
C6 C7 1.402(6) . ?
C6 C9 1.449(6) . ?
C9 O2 1.208(5) . ?
C10A C11 1.468(10) . ?
C10A C10A 1.506(14) 7_456 ?
C10B C10B 1.438(14) 7_456 ?
N20 C20 1.170(15) . ?
C20 C21 1.51(2) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 Mn O1 91.89(17) . 7_456 ?
O1 Mn N1 174.96(15) . 7_456 ?
O1 Mn N1 93.06(14) 7_456 7_456 ?
O1 Mn N1 93.06(14) . . ?
O1 Mn N1 174.96(15) 7_456 . ?
N1 Mn N1 82.0(2) 7_456 . ?
O1 Mn O1W 93.07(13) . 7_456 ?
O1 Mn O1W 89.92(13) 7_456 7_456 ?
N1 Mn O1W 87.91(14) 7_456 7_456 ?
N1 Mn O1W 88.84(14) . 7_456 ?
O1 Mn O1W 89.92(13) . . ?
O1 Mn O1W 93.07(13) 7_456 . ?
N1 Mn O1W 88.84(14) 7_456 . ?
N1 Mn O1W 87.91(14) . . ?
O1W Mn O1W 175.69(16) 7_456 . ?
C1 N1 C10B 119.0(5) . . ?
C1 N1 C10A 123.8(5) . . ?
C10B N1 C10A 25.7(6) . . ?
C1 N1 Mn 125.4(3) . . ?
C10B N1 Mn 113.8(4) . . ?
C10A N1 Mn 109.7(4) . . ?
C7 O1 Mn 128.9(3) . . ?
N1 C1 C2 125.3(4) . . ?
C3 C2 C7 117.7(5) . . ?
C3 C2 C1 117.8(4) . . ?
C7 C2 C1 124.4(4) . . ?
C4 C3 C2 124.1(4) . . ?
C5 C4 C3 116.1(4) . . ?
C5 C4 C8 121.6(5) . . ?
C3 C4 C8 122.2(5) . . ?
C4 C5 C6 123.3(5) . . ?
C5 C6 C7 119.7(4) . . ?
C5 C6 C9 119.8(4) . . ?
C7 C6 C9 120.5(4) . . ?
O1 C7 C6 118.5(4) . . ?
O1 C7 C2 122.5(4) . . ?
C6 C7 C2 119.0(4) . . ?
O2 C9 C6 124.4(4) . . ?
C11 C10A C10A 101.9(6) . 7_456 ?
C11 C10A N1 116.7(8) . . ?
C10A C10A N1 99.7(6) 7_456 . ?
C10B C10B N1 111.2(5) 7_456 . ?
N20 C20 C21 180.000(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
O1 Mn N1 C1 5.9(4) . . . . ?
O1 Mn N1 C1 174.7(14) 7_456 . . . ?
N1 Mn N1 C1 -173.1(5) 7_456 . . . ?
O1W Mn N1 C1 98.9(4) 7_456 . . . ?
O1W Mn N1 C1 -83.9(4) . . . . ?
O1 Mn N1 C10B 170.1(5) . . . . ?
O1 Mn N1 C10B -21.0(17) 7_456 . . . ?
N1 Mn N1 C10B -8.8(5) 7_456 . . . ?
O1W Mn N1 C10B -96.9(5) 7_456 . . . ?
O1W Mn N1 C10B 80.3(5) . . . . ?
O1 Mn N1 C10A -162.5(4) . . . . ?
O1 Mn N1 C10A 6.3(17) 7_456 . . . ?
N1 Mn N1 C10A 18.5(4) 7_456 . . . ?
O1W Mn N1 C10A -69.5(4) 7_456 . . . ?
O1W Mn N1 C10A 107.7(4) . . . . ?
O1 Mn O1 C7 174.4(4) 7_456 . . . ?
N1 Mn O1 C7 5.5(17) 7_456 . . . ?
N1 Mn O1 C7 -6.6(3) . . . . ?
O1W Mn O1 C7 -95.6(3) 7_456 . . . ?
O1W Mn O1 C7 81.3(3) . . . . ?
C10B N1 C1 C2 -166.0(6) . . . . ?
C10A N1 C1 C2 164.3(5) . . . . ?
Mn N1 C1 C2 -2.5(6) . . . . ?
N1 C1 C2 C3 178.9(4) . . . . ?
N1 C1 C2 C7 -2.7(7) . . . . ?
C7 C2 C3 C4 -0.8(6) . . . . ?
C1 C2 C3 C4 177.7(4) . . . . ?
C2 C3 C4 C5 -0.4(7) . . . . ?
C2 C3 C4 C8 179.7(4) . . . . ?
C3 C4 C5 C6 0.9(7) . . . . ?
C8 C4 C5 C6 -179.2(4) . . . . ?
C4 C5 C6 C7 -0.1(6) . . . . ?
C4 C5 C6 C9 178.7(4) . . . . ?
Mn O1 C7 C6 -177.1(3) . . . . ?
Mn O1 C7 C2 3.8(5) . . . . ?
C5 C6 C7 O1 179.7(3) . . . . ?
C9 C6 C7 O1 0.9(6) . . . . ?
C5 C6 C7 C2 -1.2(6) . . . . ?
C9 C6 C7 C2 -180.0(4) . . . . ?
C3 C2 C7 O1 -179.4(3) . . . . ?
C1 C2 C7 O1 2.2(6) . . . . ?
C3 C2 C7 C6 1.6(5) . . . . ?
C1 C2 C7 C6 -176.9(4) . . . . ?
C5 C6 C9 O2 2.5(8) . . . . ?
C7 C6 C9 O2 -178.7(5) . . . . ?
C1 N1 C10A C11 30.7(9) . . . . ?
C10B N1 C10A C11 -56.6(11) . . . . ?
Mn N1 C10A C11 -160.7(6) . . . . ?
C1 N1 C10A C10A 139.4(7) . . . 7_456 ?
C10B N1 C10A C10A 52.1(9) . . . 7_456 ?
Mn N1 C10A C10A -52.0(9) . . . 7_456 ?
C1 N1 C10B C10B -169.9(9) . . . 7_456 ?
C10A N1 C10B C10B -61.5(11) . . . 7_456 ?
Mn N1 C10B C10B 24.7(13) . . . 7_456 ?

_diffrn_measured_fraction_theta_max 0.960
_diffrn_reflns_theta_full        25.02
_diffrn_measured_fraction_theta_full 0.960
_refine_diff_density_max         0.325
_refine_diff_density_min         -0.309
_refine_diff_density_rms         0.049