# 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

_publ_contact_author_name        'Tapas Maji'
_publ_contact_author_email       AJI@JNCASR.AC.IN

_publ_section_title              
;
A bimetallic pillared-layer metal-organic coordination
framework with a 3D biporous structure
;
loop_
_publ_author_name
'Tapas Maji'
'A Govindaraj'
'K. L. Gurunatha'
'Suchetan Pal'
'C. N. R. Rao'

# Attachment 'complex1.cif'

data_complex1
_database_code_depnum_ccdc_archive 'CCDC 705856'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C62 H54 Fe2 Mn3 N22 O7'
_chemical_formula_weight         1495.74

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'
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           Orthorhombic
_symmetry_space_group_name_H-M   Pbam

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

_cell_length_a                   16.3148(8)
_cell_length_b                   17.8861(11)
_cell_length_c                   11.6284(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     3393.3(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       'block shape'
_exptl_crystal_colour            brown
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.458
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1514
_exptl_absorpt_coefficient_mu    1.028
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.8178
_exptl_absorpt_correction_T_max  0.9912
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      100(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  ?
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            24867
_diffrn_reflns_av_R_equivalents  0.1089
_diffrn_reflns_av_sigmaI/netI    0.0772
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         1.69
_diffrn_reflns_theta_max         24.89
_reflns_number_total             3109
_reflns_number_gt                2077
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (Bruker,2000)'
_computing_cell_refinement       SMART
_computing_data_reduction        'SAINT (Bruker,2000)'
_computing_structure_solution    'SIR-92 (Altomare et al. 1994)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Mercury 1.4.1'
_computing_publication_material  'PLATON (Spek, 2003)'

_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.
;

_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^)+(0.0466P)^2^+2.2806P] 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    noref
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3109
_refine_ls_number_parameters     243
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0881
_refine_ls_R_factor_gt           0.0471
_refine_ls_wR_factor_ref         0.1130
_refine_ls_wR_factor_gt          0.0981
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_restrained_S_all      1.020
_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
C1 C 0.8027(2) 0.0984(2) 0.3310(4) 0.0251(10) Uani 1 1 d . . .
C2 C 0.8356(3) -0.0038(3) 0.5000 0.0138(12) Uani 1 2 d S . .
C3 C 0.6897(3) 0.0663(3) 0.5000 0.0188(13) Uani 1 2 d S . .
C4 C 0.7616(3) 0.2019(3) 0.5000 0.0160(13) Uani 1 2 d S . .
C5 C 0.9144(3) 0.1326(3) 0.5000 0.0152(12) Uani 1 2 d S . .
C6 C 0.8561(2) -0.2391(2) 0.7558(3) 0.0272(11) Uani 1 1 d . . .
H4 H 0.8279 -0.2761 0.7160 0.033 Uiso 1 1 calc R . .
C7 C 0.8582(3) -0.2433(2) 0.8735(3) 0.0302(11) Uani 1 1 d . . .
H5 H 0.8321 -0.2824 0.9114 0.036 Uiso 1 1 calc R . .
C8 C 0.9325(3) -0.1334(3) 0.7545(3) 0.0413(13) Uani 1 1 d . . .
H6 H 0.9588 -0.0955 0.7141 0.050 Uiso 1 1 calc R . .
C9 C 0.9375(3) -0.1331(3) 0.8729(3) 0.0417(13) Uani 1 1 d . . .
H7 H 0.9664 -0.0955 0.9103 0.050 Uiso 1 1 calc R . .
C10 C 0.8994(2) -0.1888(2) 0.9359(3) 0.0241(10) Uani 1 1 d . . .
C11 C 0.5431(3) 0.0477(3) 0.2449(4) 0.0614(13) Uani 1 1 d U . .
H8 H 0.5747 0.0824 0.2845 0.074 Uiso 1 1 calc R . .
C12 C 0.5446(3) 0.0497(3) 0.1265(4) 0.0616(13) Uani 1 1 d U . .
H9 H 0.5764 0.0853 0.0890 0.074 Uiso 1 1 calc R . .
C13 C 0.5000 0.0000 0.0641(4) 0.0206(14) Uani 1 2 d S . .
C14 C 0.3796(3) 0.1984(3) 0.2442(4) 0.0559(16) Uani 1 1 d . . .
H10 H 0.4057 0.2366 0.2843 0.067 Uiso 1 1 calc R . .
C15 C 0.3743(3) 0.2049(3) 0.1270(4) 0.0510(15) Uani 1 1 d . . .
H11 H 0.3972 0.2461 0.0903 0.061 Uiso 1 1 calc R . .
C16 C 0.3091(3) 0.0920(3) 0.2449(4) 0.0443(14) Uani 1 1 d . . .
H12 H 0.2845 0.0531 0.2852 0.053 Uiso 1 1 calc R . .
C17 C 0.2999(3) 0.0939(3) 0.1269(4) 0.0451(14) Uani 1 1 d . . .
H13 H 0.2700 0.0567 0.0898 0.054 Uiso 1 1 calc R . .
C18 C 0.3353(2) 0.1510(2) 0.0638(3) 0.0208(10) Uani 1 1 d . . .
N1 N 0.8022(2) 0.0977(2) 0.2318(3) 0.0358(10) Uani 1 1 d . . .
N2 N 0.8515(3) -0.0662(3) 0.5000 0.0196(11) Uani 1 2 d S . .
N3 N 0.6217(3) 0.0500(2) 0.5000 0.0191(11) Uani 1 2 d S . .
N4 N 0.7294(3) 0.2594(3) 0.5000 0.0155(11) Uani 1 2 d S . .
N6 N 0.89208(19) -0.18530(18) 0.6950(3) 0.0224(8) Uani 1 1 d . . .
N7 N 0.5000 0.0000 0.3052(4) 0.0177(11) Uani 1 2 d S . .
N8 N 0.3505(2) 0.1421(2) 0.3037(3) 0.0288(9) Uani 1 1 d . . .
N5 N 0.9809(3) 0.1514(3) 0.5000 0.0219(11) Uani 1 2 d S . .
O1 O 0.9378(2) -0.2966(2) 0.5000 0.0383(12) Uani 1 2 d S . .
H1 H 0.9894 -0.3136 0.5000 0.046 Uiso 1 2 d SR . .
H2 H 0.8982 -0.3308 0.5000 0.046 Uiso 1 2 d SR . .
O2 O 0.4324(2) 0.11049(19) 0.5000 0.0167(9) Uani 1 2 d S . .
H3 H 0.4013 0.1232 0.4335 0.020 Uiso 1 1 d R . .
O3 O 0.7297(3) 0.1012(2) 0.0000 0.0383(12) Uani 1 2 d S . .
O4 O 0.9042(7) 0.0437(6) 0.0000 0.079(4) Uani 0.50 2 d SP . .
Mn1 Mn 0.88958(5) -0.18173(4) 0.5000 0.0128(2) Uani 1 2 d S . .
Mn2 Mn 0.5000 0.0000 0.5000 0.0137(3) Uani 1 4 d S . .
Fe1 Fe 0.80206(5) 0.09956(4) 0.5000 0.0151(2) Uani 1 2 d S . .

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
C1 0.020(2) 0.017(2) 0.038(3) 0.003(2) -0.003(2) -0.0012(19)
C2 0.008(3) 0.019(4) 0.014(3) 0.000 0.000 0.001(3)
C3 0.022(3) 0.012(3) 0.022(3) 0.000 0.000 0.008(3)
C4 0.013(3) 0.013(4) 0.022(3) 0.000 0.000 -0.005(3)
C5 0.019(3) 0.013(3) 0.014(3) 0.000 0.000 0.007(3)
C6 0.036(3) 0.028(3) 0.018(2) -0.0008(19) -0.0045(19) -0.012(2)
C7 0.046(3) 0.025(3) 0.019(2) 0.008(2) 0.003(2) -0.008(2)
C8 0.062(3) 0.042(3) 0.019(2) 0.002(2) -0.002(2) -0.027(3)
C9 0.064(4) 0.042(3) 0.019(2) -0.002(2) -0.009(2) -0.027(3)
C10 0.028(2) 0.031(3) 0.013(2) 0.0011(18) -0.0016(17) 0.004(2)
C11 0.093(3) 0.077(3) 0.0138(18) 0.0011(18) 0.0003(19) -0.063(3)
C12 0.093(3) 0.078(3) 0.0141(18) 0.0017(18) 0.0007(19) -0.063(3)
C13 0.021(3) 0.028(4) 0.013(3) 0.000 0.000 0.012(3)
C14 0.100(5) 0.038(4) 0.029(3) -0.001(2) -0.022(3) -0.021(3)
C15 0.091(4) 0.036(3) 0.026(3) 0.009(2) -0.012(3) -0.022(3)
C16 0.043(3) 0.067(4) 0.023(2) 0.013(2) -0.004(2) -0.020(3)
C17 0.052(3) 0.059(4) 0.024(2) 0.003(2) -0.005(2) -0.029(3)
C18 0.019(2) 0.024(3) 0.020(2) -0.0050(18) 0.0022(16) 0.0070(19)
N1 0.043(2) 0.038(3) 0.026(2) 0.0070(19) -0.0083(19) -0.001(2)
N2 0.019(3) 0.023(3) 0.017(2) 0.000 0.000 0.000(2)
N3 0.013(3) 0.017(3) 0.027(3) 0.000 0.000 -0.001(2)
N4 0.014(3) 0.013(3) 0.019(2) 0.000 0.000 -0.002(2)
N6 0.029(2) 0.022(2) 0.0165(18) 0.0049(15) -0.0018(15) -0.0038(17)
N7 0.013(2) 0.023(3) 0.016(3) 0.000 0.000 0.001(2)
N8 0.032(2) 0.034(3) 0.0200(19) 0.0005(18) -0.0001(16) 0.0124(19)
N5 0.018(3) 0.020(3) 0.028(3) 0.000 0.000 -0.003(2)
O1 0.013(2) 0.019(3) 0.082(3) 0.000 0.000 0.0023(18)
O2 0.015(2) 0.023(2) 0.0123(18) 0.000 0.000 0.0001(18)
O3 0.051(3) 0.040(3) 0.024(2) 0.000 0.000 -0.009(2)
O4 0.076(9) 0.083(10) 0.078(9) 0.000 0.000 0.003(7)
Mn1 0.0125(4) 0.0126(5) 0.0133(4) 0.000 0.000 -0.0005(4)
Mn2 0.0120(6) 0.0180(7) 0.0110(6) 0.000 0.000 -0.0028(5)
Fe1 0.0110(4) 0.0125(5) 0.0217(4) 0.000 0.000 0.0002(4)

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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 N1 1.154(5) . ?
C1 Fe1 1.965(4) . ?
C2 N2 1.147(6) . ?
C2 Fe1 1.927(6) . ?
C3 N3 1.147(6) . ?
C3 Fe1 1.928(6) . ?
C4 N4 1.156(6) . ?
C4 Fe1 1.945(6) . ?
C5 N5 1.136(6) . ?
C5 Fe1 1.926(6) . ?
C6 N6 1.330(5) . ?
C6 C7 1.372(5) . ?
C6 H4 0.9300 . ?
C7 C10 1.388(5) . ?
C7 H5 0.9300 . ?
C8 N6 1.332(5) . ?
C8 C9 1.379(5) . ?
C8 H6 0.9300 . ?
C9 C10 1.384(6) . ?
C9 H7 0.9300 . ?
C10 C10 1.490(7) 6_557 ?
C11 N7 1.309(5) . ?
C11 C12 1.377(6) . ?
C11 H8 0.9300 . ?
C12 C13 1.359(5) . ?
C12 H9 0.9300 . ?
C13 C12 1.359(5) 2_655 ?
C13 C13 1.492(10) 5_655 ?
C14 N8 1.311(6) . ?
C14 C15 1.370(6) . ?
C14 H10 0.9300 . ?
C15 C18 1.368(6) . ?
C15 H11 0.9300 . ?
C16 N8 1.313(5) . ?
C16 C17 1.381(6) . ?
C16 H12 0.9300 . ?
C17 C18 1.385(6) . ?
C17 H13 0.9300 . ?
C18 C18 1.484(7) 6 ?
N2 Mn1 2.157(5) . ?
N3 Mn2 2.177(5) . ?
N4 Mn1 2.208(4) 7_765 ?
N6 Mn1 2.269(3) . ?
N7 C11 1.309(5) 2_655 ?
N7 Mn2 2.265(4) . ?
N5 Mn1 2.181(5) 5_756 ?
O1 Mn1 2.200(4) . ?
O1 H1 0.8948 . ?
O1 H2 0.8898 . ?
O2 Mn2 2.263(3) . ?
O2 H3 0.9528 . ?
Mn1 N5 2.181(5) 5_756 ?
Mn1 N4 2.208(4) 7_755 ?
Mn1 N6 2.269(3) 6_556 ?
Mn2 N3 2.177(5) 5_656 ?
Mn2 O2 2.263(3) 5_656 ?
Mn2 N7 2.265(4) 5_656 ?
Fe1 C1 1.965(4) 6_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
N1 C1 Fe1 179.3(4) . . ?
N2 C2 Fe1 176.6(5) . . ?
N3 C3 Fe1 176.7(5) . . ?
N4 C4 Fe1 172.8(5) . . ?
N5 C5 Fe1 179.4(5) . . ?
N6 C6 C7 124.0(4) . . ?
N6 C6 H4 118.0 . . ?
C7 C6 H4 118.0 . . ?
C6 C7 C10 119.7(4) . . ?
C6 C7 H5 120.2 . . ?
C10 C7 H5 120.2 . . ?
N6 C8 C9 123.4(4) . . ?
N6 C8 H6 118.3 . . ?
C9 C8 H6 118.3 . . ?
C8 C9 C10 120.0(4) . . ?
C8 C9 H7 120.0 . . ?
C10 C9 H7 120.0 . . ?
C9 C10 C7 116.4(4) . . ?
C9 C10 C10 122.0(2) . 6_557 ?
C7 C10 C10 121.5(2) . 6_557 ?
N7 C11 C12 124.3(5) . . ?
N7 C11 H8 117.9 . . ?
C12 C11 H8 117.9 . . ?
C13 C12 C11 120.4(5) . . ?
C13 C12 H9 119.8 . . ?
C11 C12 H9 119.8 . . ?
C12 C13 C12 115.5(5) 2_655 . ?
C12 C13 C13 122.2(3) 2_655 5_655 ?
C12 C13 C13 122.2(3) . 5_655 ?
N8 C14 C15 124.6(5) . . ?
N8 C14 H10 117.7 . . ?
C15 C14 H10 117.7 . . ?
C18 C15 C14 120.2(4) . . ?
C18 C15 H11 119.9 . . ?
C14 C15 H11 119.9 . . ?
N8 C16 C17 123.9(4) . . ?
N8 C16 H12 118.1 . . ?
C17 C16 H12 118.1 . . ?
C16 C17 C18 119.9(4) . . ?
C16 C17 H13 120.0 . . ?
C18 C17 H13 120.0 . . ?
C15 C18 C17 115.4(4) . . ?
C15 C18 C18 122.5(3) . 6 ?
C17 C18 C18 122.0(2) . 6 ?
C2 N2 Mn1 176.3(4) . . ?
C3 N3 Mn2 170.4(5) . . ?
C4 N4 Mn1 145.5(4) . 7_765 ?
C6 N6 C8 116.5(4) . . ?
C6 N6 Mn1 122.9(3) . . ?
C8 N6 Mn1 120.6(3) . . ?
C11 N7 C11 115.2(5) 2_655 . ?
C11 N7 Mn2 122.4(3) 2_655 . ?
C11 N7 Mn2 122.4(3) . . ?
C14 N8 C16 115.8(4) . . ?
C5 N5 Mn1 177.1(5) . 5_756 ?
Mn1 O1 H1 130.8 . . ?
Mn1 O1 H2 112.5 . . ?
H1 O1 H2 116.7 . . ?
Mn2 O2 H3 118.0 . . ?
N2 Mn1 N5 92.36(17) . 5_756 ?
N2 Mn1 O1 175.79(16) . . ?
N5 Mn1 O1 83.43(16) 5_756 . ?
N2 Mn1 N4 101.72(17) . 7_755 ?
N5 Mn1 N4 165.92(17) 5_756 7_755 ?
O1 Mn1 N4 82.49(15) . 7_755 ?
N2 Mn1 N6 91.84(9) . . ?
N5 Mn1 N6 89.40(8) 5_756 . ?
O1 Mn1 N6 88.13(9) . . ?
N4 Mn1 N6 90.14(8) 7_755 . ?
N2 Mn1 N6 91.84(9) . 6_556 ?
N5 Mn1 N6 89.40(8) 5_756 6_556 ?
O1 Mn1 N6 88.13(9) . 6_556 ?
N4 Mn1 N6 90.14(8) 7_755 6_556 ?
N6 Mn1 N6 176.17(17) . 6_556 ?
N3 Mn2 N3 180.0 5_656 . ?
N3 Mn2 O2 94.90(15) 5_656 5_656 ?
N3 Mn2 O2 85.10(15) . 5_656 ?
N3 Mn2 O2 85.10(15) 5_656 . ?
N3 Mn2 O2 94.90(15) . . ?
O2 Mn2 O2 180.0 5_656 . ?
N3 Mn2 N7 90.0 5_656 . ?
N3 Mn2 N7 90.0 . . ?
O2 Mn2 N7 90.0 5_656 . ?
O2 Mn2 N7 90.0 . . ?
N3 Mn2 N7 90.0 5_656 5_656 ?
N3 Mn2 N7 90.0 . 5_656 ?
O2 Mn2 N7 90.0 5_656 5_656 ?
O2 Mn2 N7 90.0 . 5_656 ?
N7 Mn2 N7 180.0 . 5_656 ?
C5 Fe1 C3 179.9(2) . . ?
C5 Fe1 C2 91.4(2) . . ?
C3 Fe1 C2 88.5(2) . . ?
C5 Fe1 C4 92.0(2) . . ?
C3 Fe1 C4 88.2(2) . . ?
C2 Fe1 C4 176.7(2) . . ?
C5 Fe1 C1 89.90(12) . . ?
C3 Fe1 C1 90.10(12) . . ?
C2 Fe1 C1 89.34(12) . . ?
C4 Fe1 C1 90.67(12) . . ?
C5 Fe1 C1 89.90(12) . 6_556 ?
C3 Fe1 C1 90.10(12) . 6_556 ?
C2 Fe1 C1 89.34(12) . 6_556 ?
C4 Fe1 C1 90.67(12) . 6_556 ?
C1 Fe1 C1 178.7(2) . 6_556 ?

_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full        24.89
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         0.428
_refine_diff_density_min         -0.458
_refine_diff_density_rms         0.087