# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2003

data_global
_publ_contact_author_email       ICNRC@MAHENDRA.IACS.RES.IN
_publ_contact_author_name        'Prof Nirmalendu Ray Chaudhuri'
_journal_name_full               Chem.Commun.
_journal_coden_Cambridge         0182
_journal_year                    ?
_journal_volume                  ?
_journal_page_first              ?
loop_
_publ_author_name
N.R.Chaudhuri
M.Corbella
S.Konar
J.Ribas
E.Zangrando

data_B302076B
_database_code_CSD               203690

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
(4,4'-bipyridine)-(squarate)-(bis-aquo)-iron(II) trihydrated
;
_chemical_name_common            
"(4,4'-bipyridine)-(squarate)-(bis-aquo)-iron(ii) trihydrated"
_chemical_melting_point          ?
_chemical_formula_moiety         
'[(C10 H8 N2) (C4 O4 2-) 2(H2 O) Fe 2+] 3(H2 O)'
_chemical_formula_sum            'C14 H18 Fe N2 O9'
_chemical_formula_weight         414.15

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'
O O 0.0106 0.0060 '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'
Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   C2/c

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

_cell_length_a                   20.198(4)
_cell_length_b                   11.456(3)
_cell_length_c                   8.099(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 109.07(2)
_cell_angle_gamma                90.00
_cell_volume                     1771.2(7)
_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       prism
_exptl_crystal_colour            'orange brown'
_exptl_crystal_size_max          0.55
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.20
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.553
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             856
_exptl_absorpt_coefficient_mu    0.902
_exptl_absorpt_correction_type   refdelf
_exptl_absorpt_correction_T_min  0.6301
_exptl_absorpt_correction_T_max  0.8657
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
Parkin S,Moezzi B & Hope H, (1995) J. Appl. Cryst. 28, 53-56
Cubic fit to sin(theta)/lambda - 24 parameters
;

_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            4065
_diffrn_reflns_av_R_equivalents  0.0266
_diffrn_reflns_av_sigmaI/netI    0.0404
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         3.09
_diffrn_reflns_theta_max         28.60
_reflns_number_total             2119
_reflns_number_gt                1757
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Nonius xpress'
_computing_cell_refinement       'Mosflm (J. Appl. Cryst., 1993, 21, 67)'
_computing_data_reduction        'Mosflm (J. Appl. Cryst., 1993, 21, 67)'
_computing_structure_solution    'Shelxs-97 (Sheldrick, 1990)'
_computing_structure_refinement  'Shelxl-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Ortep3/windows (Farrugia,1997)'
_computing_publication_material  'Wingx 1.63 (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^ > 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^)+(0.0562P)^2^+3.9880P] 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         2119
_refine_ls_number_parameters     135
_refine_ls_number_restraints     19
_refine_ls_R_factor_all          0.0585
_refine_ls_R_factor_gt           0.0502
_refine_ls_wR_factor_ref         0.1431
_refine_ls_wR_factor_gt          0.1358
_refine_ls_goodness_of_fit_ref   1.123
_refine_ls_restrained_S_all      1.289
_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
Fe Fe 0.2500 0.2500 0.0000 0.0316(2) Uani 1 2 d S . .
N1 N 0.34818(15) 0.1556(3) 0.0058(4) 0.0447(7) Uani 1 1 d . . .
C1 C 0.4080(2) 0.2075(4) 0.0231(7) 0.0593(11) Uani 1 1 d . . .
H1 H 0.4102 0.2881 0.0380 0.071 Uiso 1 1 calc R . .
C2 C 0.4681(2) 0.1497(4) 0.0204(7) 0.0624(12) Uani 1 1 d . . .
H2 H 0.5087 0.1920 0.0322 0.075 Uiso 1 1 calc R . .
C3 C 0.46816(18) 0.0326(3) 0.0008(5) 0.0459(8) Uani 1 1 d . . .
C4 C 0.4064(3) -0.0215(5) -0.0175(14) 0.124(3) Uani 1 1 d U . .
H4 H 0.4032 -0.1021 -0.0303 0.149 Uiso 1 1 calc R . .
C5 C 0.3482(3) 0.0425(5) -0.0173(13) 0.119(3) Uani 1 1 d U . .
H5 H 0.3064 0.0025 -0.0348 0.142 Uiso 1 1 calc R . .
C6 C 0.26754(17) 0.2673(3) 0.3966(4) 0.0346(6) Uani 1 1 d . . .
C7 C 0.28139(17) 0.3162(3) 0.5708(4) 0.0354(6) Uani 1 1 d . . .
O1 O 0.29056(14) 0.2908(2) 0.2731(3) 0.0447(6) Uani 1 1 d . . .
O2 O 0.31909(14) 0.3977(2) 0.6558(3) 0.0442(6) Uani 1 1 d . . .
O1W O 0.20370(14) 0.0948(2) 0.0416(3) 0.0430(6) Uani 1 1 d D . .
H12 H 0.193(3) 0.028(3) -0.019(5) 0.064 Uiso 1 1 d D . .
H11 H 0.193(3) 0.094(4) 0.141(4) 0.064 Uiso 1 1 d D . .
O2W O 0.0000 0.0257(7) 0.2500 0.0874(17) Uani 1 2 d SD . .
H21 H 0.034(3) -0.019(6) 0.235(11) 0.131 Uiso 1 1 d D . .
O3W O 0.5706(2) 0.3843(4) 0.0835(6) 0.0813(11) Uani 1 1 d D . .
H31 H 0.6155(15) 0.365(7) 0.122(8) 0.122 Uiso 1 1 d D . .
H32 H 0.550(3) 0.399(7) -0.029(4) 0.122 Uiso 1 1 d D . .

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
Fe 0.0352(3) 0.0329(3) 0.0295(4) -0.0009(2) 0.0143(2) 0.0019(2)
N1 0.0411(15) 0.0422(15) 0.0546(19) -0.0050(13) 0.0209(13) 0.0031(12)
C1 0.045(2) 0.0386(18) 0.095(3) -0.006(2) 0.025(2) 0.0042(16)
C2 0.0385(19) 0.045(2) 0.105(4) -0.005(2) 0.025(2) 0.0011(16)
C3 0.0380(17) 0.0460(19) 0.055(2) -0.0089(15) 0.0165(15) 0.0043(14)
C4 0.065(3) 0.050(3) 0.280(8) -0.036(4) 0.087(4) -0.006(2)
C5 0.059(3) 0.055(3) 0.266(8) -0.032(4) 0.085(4) -0.007(2)
C6 0.0389(15) 0.0387(16) 0.0285(16) 0.0006(11) 0.0143(12) -0.0002(12)
C7 0.0420(16) 0.0337(15) 0.0328(16) 0.0022(11) 0.0153(12) 0.0005(12)
O1 0.0506(14) 0.0524(14) 0.0338(13) -0.0042(10) 0.0176(10) -0.0123(11)
O2 0.0584(15) 0.0418(13) 0.0350(13) -0.0038(9) 0.0188(10) -0.0134(11)
O1W 0.0588(15) 0.0369(12) 0.0413(14) -0.0037(9) 0.0276(11) -0.0044(10)
O2W 0.066(3) 0.122(5) 0.079(4) 0.000 0.031(3) 0.000
O3W 0.062(2) 0.100(3) 0.082(3) 0.009(2) 0.0243(18) 0.012(2)

_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
Fe O1W 2.087(2) . ?
Fe O1W 2.087(2) 7 ?
Fe O1 2.145(2) . ?
Fe O1 2.145(2) 7 ?
Fe N1 2.246(3) . ?
Fe N1 2.246(3) 7 ?
N1 C5 1.309(6) . ?
N1 C1 1.312(5) . ?
C1 C2 1.390(5) . ?
C2 C3 1.350(6) . ?
C3 C4 1.356(6) . ?
C3 C3 1.492(7) 5_655 ?
C4 C5 1.386(7) . ?
C6 O1 1.262(4) . ?
C6 C7 1.458(4) . ?
C6 C7 1.460(4) 7_556 ?
C7 O2 1.259(4) . ?
C7 C6 1.460(4) 7_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
O1W Fe O1W 180.00(15) . 7 ?
O1W Fe O1 93.42(10) . . ?
O1W Fe O1 86.58(10) 7 . ?
O1W Fe O1 86.58(10) . 7 ?
O1W Fe O1 93.42(10) 7 7 ?
O1 Fe O1 180.0 . 7 ?
O1W Fe N1 91.46(10) . . ?
O1W Fe N1 88.54(10) 7 . ?
O1 Fe N1 92.65(11) . . ?
O1 Fe N1 87.35(11) 7 . ?
O1W Fe N1 88.54(10) . 7 ?
O1W Fe N1 91.46(10) 7 7 ?
O1 Fe N1 87.35(11) . 7 ?
O1 Fe N1 92.65(11) 7 7 ?
N1 Fe N1 180.00(16) . 7 ?
C5 N1 C1 114.8(4) . . ?
C5 N1 Fe 121.0(3) . . ?
C1 N1 Fe 124.0(3) . . ?
N1 C1 C2 124.1(4) . . ?
C3 C2 C1 120.6(4) . . ?
C2 C3 C4 115.5(4) . . ?
C2 C3 C3 122.2(4) . 5_655 ?
C4 C3 C3 122.3(5) . 5_655 ?
C3 C4 C5 120.5(5) . . ?
N1 C5 C4 124.3(5) . . ?
O1 C6 C7 132.9(3) . . ?
O1 C6 C7 136.8(3) . 7_556 ?
C7 C6 C7 90.2(3) . 7_556 ?
O2 C7 C6 134.8(3) . . ?
O2 C7 C6 135.4(3) . 7_556 ?
C6 C7 C6 89.8(3) . 7_556 ?
C6 O1 Fe 130.9(2) . . ?

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
O1W Fe N1 C5 18.6(6) . . . . ?
O1W Fe N1 C5 -161.4(6) 7 . . . ?
O1 Fe N1 C5 112.1(6) . . . . ?
O1 Fe N1 C5 -67.9(6) 7 . . . ?
N1 Fe N1 C5 -3(45) 7 . . . ?
O1W Fe N1 C1 -165.0(4) . . . . ?
O1W Fe N1 C1 15.0(4) 7 . . . ?
O1 Fe N1 C1 -71.5(4) . . . . ?
O1 Fe N1 C1 108.5(4) 7 . . . ?
N1 Fe N1 C1 173(42) 7 . . . ?
C5 N1 C1 C2 -1.0(8) . . . . ?
Fe N1 C1 C2 -177.6(4) . . . . ?
N1 C1 C2 C3 -0.7(8) . . . . ?
C1 C2 C3 C4 0.8(8) . . . . ?
C1 C2 C3 C3 -179.4(5) . . . 5_655 ?
C2 C3 C4 C5 0.6(12) . . . . ?
C3 C3 C4 C5 -179.2(8) 5_655 . . . ?
C1 N1 C5 C4 2.5(12) . . . . ?
Fe N1 C5 C4 179.2(7) . . . . ?
C3 C4 C5 N1 -2.5(15) . . . . ?
O1 C6 C7 O2 1.4(7) . . . . ?
C7 C6 C7 O2 -179.0(5) 7_556 . . . ?
O1 C6 C7 C6 -179.6(5) . . . 7_556 ?
C7 C6 C7 C6 0.0 7_556 . . 7_556 ?
C7 C6 O1 Fe -161.3(3) . . . . ?
C7 C6 O1 Fe 19.3(6) 7_556 . . . ?
O1W Fe O1 C6 -30.5(3) . . . . ?
O1W Fe O1 C6 149.5(3) 7 . . . ?
O1 Fe O1 C6 -151(100) 7 . . . ?
N1 Fe O1 C6 -122.2(3) . . . . ?
N1 Fe O1 C6 57.8(3) 7 . . . ?

_diffrn_measured_fraction_theta_max 0.933
_diffrn_reflns_theta_full        28.60
_diffrn_measured_fraction_theta_full 0.933
_refine_diff_density_max         0.750
_refine_diff_density_min         -0.720
_refine_diff_density_rms         0.076