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


data_global

_journal_coden_Cambridge         182

loop_
_publ_author_name
'Richard Winpenny'
'Abd-Alhakeem H, Abu-Nawwas'
'Joan Cano'
'Paul Christian'
'Talal Mallah'
'Gopalan Rajaraman'
'Simon J Teat'
'Yasuhiko Yukawa'

_publ_contact_author_name        'Prof Richard Winpenny'
_publ_contact_author_address     
;
Chemistry
University of Manchester
Oxford Road
Manchester
M13 9PL
UNITED KINGDOM
;

_publ_contact_author_email       RICHARD.WINPENNY@MAN.AC.UK

_publ_requested_journal          'Chemical Communications'

_publ_section_title              
;
An Fe(III) Wheel With a Zwitterionic Ligand: The
Structure and Magnetic Properties of [Fe(OMe)2(proline)]12[ClO4]12
;

data_yp61
_database_code_depnum_ccdc_archive 'CCDC 222686'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C84 H180 Cl12 Fe12 N12 O96'
_chemical_formula_weight         3990.00

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'
Fe Fe 0.3463 0.8444 '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           hexagonal
_symmetry_space_group_name_H-M   P622

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-x, -y, z'
'y, -x+y, z'
'x-y, x, z'
'y, x, -z'
'x-y, -y, -z'
'-x, -x+y, -z'
'-y, -x, -z'
'-x+y, y, -z'
'x, x-y, -z'

_cell_length_a                   25.0265(17)
_cell_length_b                   25.0265(17)
_cell_length_c                   7.7474(11)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     4202.3(7)
_cell_formula_units_Z            1
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    17768
_cell_measurement_theta_min      2.43
_cell_measurement_theta_max      25.72

_exptl_crystal_description       needle
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.577
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2052
_exptl_absorpt_coefficient_mu    1.296
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.65
_exptl_absorpt_correction_T_max  0.92
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.6938
_diffrn_radiation_type           synchrotron
_diffrn_radiation_source         'Daresbury SRS station 9.8'
_diffrn_radiation_monochromator  'silicon 111'
_diffrn_measurement_device_type  'Bruker SMART 1K 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_%        10
_diffrn_reflns_number            23070
_diffrn_reflns_av_R_equivalents  0.0468
_diffrn_reflns_av_sigmaI/netI    0.0267
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         1.83
_diffrn_reflns_theta_max         25.70
_reflns_number_total             2883
_reflns_number_gt                2554
_reflns_threshold_expression     I>2\s(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL and 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.
The data were cut to a resolution of 0.8 Angstroms, as above this the average
I/sigma were less than 2 and thereby considered to be unobserved. All non-
hydrogens were found in the difference map and were refined anistropically,
except for the disorder oxygen of the ClO4 group. One of the methoxide
carbons has a ratio of approx 6:1 between the maximum and minimum
displacement parameter, it was consider whether to split it but since no
additional chemical information would be gained, it was decided not to split
it. The ClO4 group was refined with geometrical and displacement parameters
restraints. All hydrogen atoms were placed geometrically, except for the
methyl on the methoxides which where found in the rotational difference map.
The hydrogens were refined using a riding model. Two hydrogen position were
found in the difference map for N6, it was therefore modelled geometrical
hydrogen placement as NH2.
;

_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^)+(0.1237P)^2^+7.6404P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.06(7)
_refine_ls_number_reflns         2883
_refine_ls_number_parameters     162
_refine_ls_number_restraints     99
_refine_ls_R_factor_all          0.0783
_refine_ls_R_factor_gt           0.0722
_refine_ls_wR_factor_ref         0.2187
_refine_ls_wR_factor_gt          0.2139
_refine_ls_goodness_of_fit_ref   1.132
_refine_ls_restrained_S_all      1.168
_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 0.86384(2) 0.72768(5) 1.0000 0.0454(4) Uani 1 2 d S . .
Fe2 Fe 0.76831(4) 0.76831(4) 1.0000 0.0470(4) Uani 1 2 d S . .
O1M O 0.9280(2) 0.7341(2) 0.8395(7) 0.0502(11) Uani 1 1 d . . .
C1M C 0.9184(5) 0.6988(5) 0.6854(13) 0.071(2) Uani 1 1 d . . .
H1M1 H 0.9294 0.6669 0.7067 0.107 Uiso 1 1 calc R . .
H1M2 H 0.9442 0.7260 0.5925 0.107 Uiso 1 1 calc R . .
H1M3 H 0.8749 0.6792 0.6516 0.107 Uiso 1 1 calc R . .
O2M O 0.8466(2) 0.7893(2) 0.8839(7) 0.0459(11) Uani 1 1 d . . .
C2M C 0.8717(7) 0.8208(8) 0.7283(19) 0.123(6) Uani 1 1 d . . .
H2M1 H 0.8510 0.8437 0.6955 0.184 Uiso 1 1 calc R . .
H2M2 H 0.8656 0.7910 0.6375 0.184 Uiso 1 1 calc R . .
H2M3 H 0.9159 0.8496 0.7435 0.184 Uiso 1 1 calc R . .
O1 O 0.7245(2) 0.6898(2) 0.8548(9) 0.0627(15) Uani 1 1 d . . .
O2 O 0.7930(2) 0.6566(2) 0.8600(8) 0.0559(13) Uani 1 1 d . . .
C1 C 0.7415(4) 0.6517(3) 0.8222(13) 0.0575(19) Uani 1 1 d . . .
C2 C 0.6947(4) 0.5948(3) 0.7239(13) 0.061(2) Uani 1 1 d . . .
H2A H 0.6972 0.6052 0.5984 0.074 Uiso 1 1 calc R . .
C3 C 0.6284(4) 0.5674(5) 0.7828(19) 0.091(3) Uani 1 1 d . . .
H3A H 0.6263 0.5715 0.9094 0.109 Uiso 1 1 calc R . .
H3B H 0.6084 0.5882 0.7255 0.109 Uiso 1 1 calc R . .
C4 C 0.5986(5) 0.5025(5) 0.733(2) 0.109(4) Uani 1 1 d . . .
H4A H 0.5852 0.4974 0.6108 0.130 Uiso 1 1 calc R . .
H4B H 0.5620 0.4775 0.8062 0.130 Uiso 1 1 calc R . .
C5 C 0.6454(5) 0.4829(4) 0.7570(16) 0.082(3) Uani 1 1 d . . .
H5A H 0.6422 0.4540 0.6650 0.099 Uiso 1 1 calc R . .
H5B H 0.6405 0.4628 0.8707 0.099 Uiso 1 1 calc R . .
N6 N 0.7073(3) 0.5442(3) 0.7460(11) 0.0634(19) Uani 1 1 d . . .
H6A H 0.7297 0.5500 0.8453 0.076 Uiso 1 1 calc R . .
H6B H 0.7300 0.5431 0.6541 0.076 Uiso 1 1 calc R . .
Cl1 Cl 0.68282(12) 0.51695(15) 0.2495(4) 0.0913(9) Uani 1 1 d D . .
O11 O 0.6470(6) 0.4534(4) 0.1939(17) 0.095(5) Uiso 0.50 1 d PDU A 1
O12 O 0.7183(5) 0.5538(5) 0.1086(13) 0.084(4) Uiso 0.50 1 d PDU A 1
O13 O 0.7211(5) 0.5212(6) 0.3909(14) 0.095(5) Uiso 0.50 1 d PDU A 1
O14 O 0.6401(5) 0.5366(6) 0.3041(16) 0.091(4) Uiso 0.50 1 d PDU A 1
O11' O 0.6357(6) 0.4579(5) 0.307(2) 0.150(9) Uiso 0.50 1 d PDU A 2
O12' O 0.7177(6) 0.5080(7) 0.1129(16) 0.105(5) Uiso 0.50 1 d PDU A 2
O13' O 0.7260(5) 0.5482(6) 0.3880(13) 0.073(3) Uiso 0.50 1 d PDU A 2
O14' O 0.6586(8) 0.5534(7) 0.186(2) 0.160(8) Uiso 0.50 1 d PDU A 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 0.0330(4) 0.0295(5) 0.0724(8) 0.000 0.0072(7) 0.0148(3)
Fe2 0.0310(4) 0.0310(4) 0.0768(9) -0.0043(4) 0.0043(4) 0.0139(4)
O1M 0.040(2) 0.040(2) 0.073(3) -0.004(2) 0.006(2) 0.022(2)
C1M 0.076(6) 0.077(6) 0.076(5) -0.011(5) -0.007(4) 0.049(5)
O2M 0.036(2) 0.033(2) 0.069(3) 0.000(2) 0.009(2) 0.0167(18)
C2M 0.118(10) 0.191(16) 0.128(11) 0.082(11) 0.060(9) 0.129(12)
O1 0.043(3) 0.032(2) 0.111(4) -0.015(3) -0.010(3) 0.017(2)
O2 0.040(2) 0.036(2) 0.086(4) -0.002(2) 0.008(3) 0.015(2)
C1 0.046(4) 0.038(4) 0.083(5) 0.002(3) 0.002(4) 0.017(3)
C2 0.052(4) 0.036(3) 0.084(6) -0.004(4) -0.002(4) 0.013(3)
C3 0.054(5) 0.068(6) 0.131(10) -0.030(6) -0.015(6) 0.016(4)
C4 0.069(6) 0.053(5) 0.172(14) -0.009(7) 0.005(8) 0.007(5)
C5 0.072(6) 0.041(4) 0.092(7) -0.002(5) 0.004(5) -0.004(4)
N6 0.049(4) 0.042(3) 0.075(4) -0.011(3) 0.010(3) 0.004(3)
Cl1 0.0573(13) 0.115(2) 0.0766(15) 0.0016(16) 0.0008(12) 0.0246(14)

_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 O1M 1.974(5) . ?
Fe1 O1M 1.974(5) 11_657 ?
Fe1 O2M 2.009(5) . ?
Fe1 O2M 2.009(5) 11_657 ?
Fe1 O2 2.081(5) . ?
Fe1 O2 2.081(5) 11_657 ?
Fe2 O1M 1.995(5) 11_657 ?
Fe2 O1M 1.995(5) 5_565 ?
Fe2 O2M 1.974(4) . ?
Fe2 O2M 1.974(4) 7_557 ?
Fe2 O1 2.043(5) . ?
Fe2 O1 2.043(5) 7_557 ?
O1M Fe2 1.995(5) 6_655 ?
O1M C1M 1.433(11) . ?
O2M C2M 1.404(13) . ?
O1 C1 1.249(9) . ?
O2 C1 1.266(9) . ?
C1 C2 1.520(11) . ?
C2 C3 1.514(13) . ?
C2 N6 1.460(11) . ?
C3 C4 1.460(15) . ?
C4 C5 1.490(18) . ?
C5 N6 1.545(10) . ?
Cl1 O11 1.447(8) . ?
Cl1 O12 1.418(8) . ?
Cl1 O13 1.424(8) . ?
Cl1 O14 1.446(8) . ?
Cl1 O11' 1.424(9) . ?
Cl1 O12' 1.459(9) . ?
Cl1 O13' 1.444(8) . ?
Cl1 O14' 1.412(9) . ?

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
O1M Fe1 O1M 171.9(3) . 11_657 ?
O1M Fe1 O2M 97.7(2) . . ?
O1M Fe1 O2M 76.9(2) . 11_657 ?
O1M Fe1 O2M 97.7(2) 11_657 11_657 ?
O1M Fe1 O2M 76.9(2) 11_657 . ?
O1M Fe1 O2 93.0(2) . . ?
O1M Fe1 O2 93.0(2) 11_657 . ?
O1M Fe1 O2 93.0(2) . 11_657 ?
O1M Fe1 O2 93.0(2) 11_657 11_657 ?
O2M Fe1 O2M 96.7(3) . 11_657 ?
O2M Fe1 O2 90.2(2) . . ?
O2M Fe1 O2 168.36(18) 11_657 . ?
O2M Fe1 O2 90.2(2) 11_657 11_657 ?
O2M Fe1 O2 168.36(18) . 11_657 ?
O2 Fe1 O2 84.5(3) . 11_657 ?
O1M Fe2 O1M 177.4(3) 11_657 5_565 ?
O1M Fe2 O2M 101.2(2) 11_657 7_557 ?
O1M Fe2 O2M 77.2(2) 11_657 . ?
O1M Fe2 O2M 77.2(2) 5_565 7_557 ?
O1M Fe2 O2M 101.2(2) 5_565 . ?
O1M Fe2 O1 94.1(2) 11_657 . ?
O1M Fe2 O1 87.8(2) 5_565 . ?
O1M Fe2 O1 87.8(2) 11_657 7_557 ?
O1M Fe2 O1 94.1(2) 5_565 7_557 ?
O2M Fe2 O2M 102.0(3) . 7_557 ?
O2M Fe2 O1 89.4(2) . . ?
O2M Fe2 O1 162.6(2) 7_557 . ?
O2M Fe2 O1 89.4(2) 7_557 7_557 ?
O2M Fe2 O1 162.6(2) . 7_557 ?
O1 Fe2 O1 82.9(4) . 7_557 ?
Fe1 O1M Fe2 99.5(2) . 6_655 ?
Fe1 O1M C1M 126.5(5) . . ?
Fe2 O1M C1M 128.4(5) 6_655 . ?
Fe1 O2M Fe2 99.1(2) . . ?
Fe1 O2M C2M 127.5(5) . . ?
Fe2 O2M C2M 130.2(5) . . ?
Fe2 O1 C1 128.4(5) . . ?
Fe1 O2 C1 126.5(5) . . ?
O1 C1 O2 126.7(8) . . ?
O1 C1 C2 114.7(7) . . ?
O2 C1 C2 118.6(7) . . ?
C1 C2 C3 115.5(8) . . ?
C1 C2 N6 110.7(7) . . ?
C3 C2 N6 103.5(8) . . ?
C2 C3 C4 105.0(9) . . ?
C3 C4 C5 106.6(9) . . ?
C4 C5 N6 103.1(8) . . ?
C2 N6 C5 108.9(8) . . ?
O11 Cl1 O12 109.2(5) . . ?
O11 Cl1 O13 109.5(5) . . ?
O11 Cl1 O14 107.7(5) . . ?
O11 Cl1 O11' 38.3(8) . . ?
O11 Cl1 O12' 72.9(7) . . ?
O11 Cl1 O13' 134.5(7) . . ?
O11 Cl1 O14' 112.1(9) . . ?
O12 Cl1 O13 111.4(5) . . ?
O12 Cl1 O14 109.4(5) . . ?
O12 Cl1 O11' 146.9(8) . . ?
O12 Cl1 O12' 46.7(7) . . ?
O12 Cl1 O13' 99.5(7) . . ?
O12 Cl1 O14' 69.1(8) . . ?
O13 Cl1 O14 109.5(5) . . ?
O13 Cl1 O11' 90.8(9) . . ?
O13 Cl1 O12' 97.9(8) . . ?
O13 Cl1 O13' 25.2(7) . . ?
O13 Cl1 O14' 135.2(8) . . ?
O14 Cl1 O11' 83.9(9) . . ?
O14 Cl1 O12' 150.0(7) . . ?
O14 Cl1 O13' 94.5(7) . . ?
O14 Cl1 O14' 41.6(8) . . ?
O11' Cl1 O12' 108.3(6) . . ?
O11' Cl1 O13' 109.8(6) . . ?
O11' Cl1 O14' 112.3(6) . . ?
O12' Cl1 O13' 106.2(5) . . ?
O12' Cl1 O14' 109.3(6) . . ?
O13' Cl1 O14' 110.8(6) . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N6 H6A O12 0.92 2.07 2.821(14) 138.1 1_556
N6 H6A O12' 0.92 2.26 2.866(16) 123.0 11_656
N6 H6A O12' 0.92 2.28 3.034(17) 139.5 1_556
N6 H6A O12 0.92 2.63 3.296(15) 130.1 11_656
N6 H6B O13' 0.92 2.07 2.806(13) 135.9 .
N6 H6B O13 0.92 2.09 2.867(15) 140.8 .
N6 H6B O13 0.92 2.11 2.863(15) 137.9 11_656
N6 H6B O13' 0.92 2.27 3.014(14) 137.4 11_656

_diffrn_measured_fraction_theta_max 0.992
_diffrn_reflns_theta_full        25.70
_diffrn_measured_fraction_theta_full 0.992
_refine_diff_density_max         0.941
_refine_diff_density_min         -0.501
_refine_diff_density_rms         0.119