Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004

data_global
_journal_name_full               'Dalton Trans.'

_journal_coden_Cambridge         0222

_publ_contact_author_name        'Prof. Dante Gatteschi'
_publ_contact_author_address     
;
Dipartimento di Chimica, Universita' di Firenze,
Via della Lastruccia 3
50019 Sesto Fiorentino (Firenze), Italy
;
_publ_contact_author_email       dante.gatteschi@unifi.it
_publ_contact_author_phone       +390554573336
_publ_contact_author_fax         +390554573372
_publ_requested_category         FM

_publ_section_title              
;
Antiferromagnetic coupling between Rare Earth Ions
and Semiquinones in a series of 1:1 complexes
;
loop_
_publ_author_name
'Dante Gatteschi'
'Andrea Caneschi'
'Andrea Dei'
'Sandrine Poussereau'
'Lorenzo Sorace'

data_hotrp43
_database_code_depnum_ccdc_archive 'CCDC 221177'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            Ho(HBPz)3(TRP)
_chemical_melting_point          ?
_chemical_formula_moiety         'C12.5 H12.5 B1 Ho.5 N6 O1'
_chemical_formula_sum            'C12.50 H12.50 B Ho0.50 N6 O'
_chemical_formula_weight         356.06

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'
B B 0.0013 0.0007 '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'
Ho Ho -0.2175 4.6783 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_H-M   P43212

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

_cell_length_a                   9.416(5)
_cell_length_b                   9.416(5)
_cell_length_c                   32.226(5)
_cell_angle_alpha                90.000(5)
_cell_angle_beta                 90.000(5)
_cell_angle_gamma                90.000(5)
_cell_volume                     2857(2)
_cell_formula_units_Z            8
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    25
_cell_measurement_theta_min      2.25
_cell_measurement_theta_max      12.48

_exptl_crystal_description       'elongated octahedron'
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.655
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1408
_exptl_absorpt_coefficient_mu    2.816
_exptl_absorpt_correction_type   psi-scan
_exptl_absorpt_correction_T_min  .6113
_exptl_absorpt_correction_T_max  .9921
_exptl_absorpt_process_details   '(North, Phillips & Mathews, 1968)'

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71069
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'enraf nonius cad4'
_diffrn_measurement_method       omega-2theta
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         78
_diffrn_standards_interval_count 400
_diffrn_standards_interval_time  120
_diffrn_standards_decay_%        3.8
_diffrn_reflns_number            4849
_diffrn_reflns_av_R_equivalents  0.0461
_diffrn_reflns_av_sigmaI/netI    0.0529
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_theta_min         2.25
_diffrn_reflns_theta_max         26.98
_reflns_number_total             3099
_reflns_number_gt                2630
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SIR97 (Altomare, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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^)+(0.0223P)^2^+3.6652P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.003(2)
_refine_ls_number_reflns         3099
_refine_ls_number_parameters     192
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0504
_refine_ls_R_factor_gt           0.0295
_refine_ls_wR_factor_ref         0.0885
_refine_ls_wR_factor_gt          0.0669
_refine_ls_goodness_of_fit_ref   1.312
_refine_ls_restrained_S_all      1.312
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_chemical_absolute_configuration ad

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
Ho1 Ho 0.89466(3) 0.10534(3) 0.7500 0.03220(11) Uani 1 2 d S . .
O1 O 0.8284(5) 0.3244(5) 0.77444(14) 0.0416(10) Uani 1 1 d . . .
N12 N 0.9702(6) -0.1898(6) 0.80981(16) 0.0420(12) Uani 1 1 d . . .
C13 C 1.0016(7) -0.2558(6) 0.7470(3) 0.0492(16) Uani 1 1 d . . .
H13 H 1.0029 -0.2568 0.7182 0.059 Uiso 1 1 calc R . .
N21 N 0.7300(6) 0.0295(6) 0.80679(18) 0.0438(14) Uani 1 1 d . . .
C23 C 0.5904(7) 0.0409(7) 0.8101(2) 0.0455(16) Uani 1 1 d . . .
H23 H 0.5331 0.0894 0.7913 0.055 Uiso 1 1 calc R . .
N31 N 1.0294(6) 0.1338(6) 0.81476(19) 0.0446(14) Uani 1 1 d . . .
C12 C 1.0512(8) -0.3646(8) 0.7714(3) 0.059(2) Uani 1 1 d . . .
H12 H 1.0910 -0.4502 0.7629 0.071 Uiso 1 1 calc R . .
N32 N 1.0249(6) 0.0399(7) 0.84685(17) 0.0444(13) Uani 1 1 d . . .
C1 C 0.7085(6) 0.3790(7) 0.7637(2) 0.0416(15) Uani 1 1 d . . .
N11 N 0.9512(6) -0.1480(5) 0.76977(17) 0.0418(12) Uani 1 1 d . . .
N22 N 0.7725(6) -0.0477(6) 0.8404(2) 0.0501(15) Uani 1 1 d . . .
C32 C 1.1850(9) 0.2034(9) 0.8634(3) 0.065(2) Uani 1 1 d . . .
H32 H 1.2549 0.2548 0.8771 0.078 Uiso 1 1 calc R . .
C21 C 0.6584(8) -0.0833(8) 0.8634(2) 0.056(2) Uani 1 1 d . . .
H21 H 0.6604 -0.1363 0.8877 0.067 Uiso 1 1 calc R . .
C33 C 1.1244(8) 0.2319(8) 0.8252(3) 0.0541(19) Uani 1 1 d . . .
H33 H 1.1473 0.3099 0.8088 0.065 Uiso 1 1 calc R . .
C22 C 0.5403(8) -0.0293(9) 0.8453(2) 0.0544(19) Uani 1 1 d . . .
H22 H 0.4468 -0.0372 0.8543 0.065 Uiso 1 1 calc R . .
B1 B 0.9281(8) -0.0924(9) 0.8463(2) 0.0486(18) Uani 1 1 d . . .
C31 C 1.1178(8) 0.0814(8) 0.8763(2) 0.060(2) Uani 1 1 d . . .
H31 H 1.1339 0.0351 0.9014 0.072 Uiso 1 1 calc R . .
C2 C 0.6744(9) 0.5152(8) 0.7782(3) 0.0548(18) Uani 1 1 d . . .
H2 H 0.7440 0.5577 0.7945 0.066 Uiso 1 1 calc R . .
C3 C 0.5532(8) 0.5965(8) 0.7722(3) 0.064(2) Uani 1 1 d . . .
H3 H 0.5542 0.6844 0.7854 0.076 Uiso 1 1 calc R . .
C4 C 0.4318(7) 0.5682(7) 0.7500 0.068(3) Uani 1 2 d S . .
H4 H 0.3620 0.6380 0.7500 0.082 Uiso 1 2 calc SR . .
C11 C 1.0285(8) -0.3181(8) 0.8111(3) 0.055(2) Uani 1 1 d . . .
H11 H 1.0504 -0.3684 0.8351 0.065 Uiso 1 1 calc R . .
H2B H 0.9413 -0.1588 0.8797 0.10(3) Uiso 1 1 d R . .

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
Ho1 0.03200(13) 0.03200(13) 0.03260(18) -0.00107(13) -0.00107(13) 0.00359(16)
O1 0.039(2) 0.041(2) 0.045(3) -0.007(2) -0.006(2) 0.009(2)
N12 0.044(3) 0.043(3) 0.039(3) 0.009(3) -0.006(2) 0.001(2)
C13 0.059(4) 0.041(3) 0.048(4) -0.006(4) -0.008(4) 0.007(3)
N21 0.035(3) 0.052(3) 0.044(3) 0.004(3) 0.000(2) 0.003(3)
C23 0.042(4) 0.059(4) 0.036(3) -0.004(3) 0.006(3) 0.002(3)
N31 0.042(3) 0.046(4) 0.046(4) -0.004(3) -0.006(3) 0.004(3)
C12 0.057(4) 0.041(4) 0.078(6) -0.007(4) -0.018(4) 0.011(3)
N32 0.042(3) 0.057(4) 0.034(3) -0.005(3) -0.008(2) 0.007(2)
C1 0.037(3) 0.046(4) 0.042(4) 0.003(3) 0.007(3) 0.006(3)
N11 0.054(3) 0.035(3) 0.037(3) 0.003(2) -0.001(3) 0.005(2)
N22 0.046(3) 0.055(4) 0.049(4) 0.009(3) 0.008(3) 0.004(3)
C32 0.059(5) 0.064(5) 0.072(5) -0.022(4) -0.032(4) 0.008(4)
C21 0.055(4) 0.058(5) 0.054(5) 0.000(4) 0.013(4) -0.010(4)
C33 0.048(4) 0.046(4) 0.067(5) -0.011(3) -0.015(4) 0.001(3)
C22 0.042(4) 0.078(5) 0.043(4) -0.004(4) 0.009(3) -0.007(4)
B1 0.046(4) 0.055(5) 0.044(4) 0.016(4) -0.004(3) 0.008(3)
C31 0.058(4) 0.075(5) 0.046(4) -0.011(4) -0.023(4) 0.015(4)
C2 0.055(4) 0.041(4) 0.068(5) -0.008(3) 0.008(4) 0.007(3)
C3 0.067(5) 0.048(4) 0.076(6) -0.006(4) 0.007(4) 0.017(4)
C4 0.058(4) 0.058(4) 0.089(9) 0.008(6) 0.008(6) 0.027(5)
C11 0.049(4) 0.042(4) 0.073(6) 0.013(4) -0.016(4) 0.004(3)

_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
Ho1 O1 2.295(4) . ?
Ho1 O1 2.295(4) 8_666 ?
Ho1 N31 2.457(6) . ?
Ho1 N31 2.457(6) 8_666 ?
Ho1 N21 2.503(6) . ?
Ho1 N21 2.503(6) 8_666 ?
Ho1 N11 2.526(5) 8_666 ?
Ho1 N11 2.526(5) . ?
O1 C1 1.288(7) . ?
N12 C11 1.328(9) . ?
N12 N11 1.361(7) . ?
N12 B1 1.544(11) . ?
C13 N11 1.338(8) . ?
C13 C12 1.374(10) . ?
N21 C23 1.323(9) . ?
N21 N22 1.364(8) . ?
C23 C22 1.395(10) . ?
N31 C33 1.328(9) . ?
N31 N32 1.361(8) . ?
C12 C11 1.367(12) . ?
N32 C31 1.349(8) . ?
N32 B1 1.544(10) . ?
C1 C2 1.403(9) . ?
C1 C1 1.461(13) 8_666 ?
N22 C21 1.348(9) . ?
N22 B1 1.536(10) . ?
C32 C31 1.376(12) . ?
C32 C33 1.383(11) . ?
C21 C22 1.355(11) . ?
C2 C3 1.388(10) . ?
C3 C4 1.375(9) . ?
C4 C3 1.375(9) 8_666 ?

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 Ho1 O1 68.2(2) . 8_666 ?
O1 Ho1 N31 75.56(17) . . ?
O1 Ho1 N31 136.57(17) 8_666 . ?
O1 Ho1 N31 136.57(17) . 8_666 ?
O1 Ho1 N31 75.56(17) 8_666 8_666 ?
N31 Ho1 N31 146.5(3) . 8_666 ?
O1 Ho1 N21 80.63(18) . . ?
O1 Ho1 N21 76.79(17) 8_666 . ?
N31 Ho1 N21 74.3(2) . . ?
N31 Ho1 N21 114.0(2) 8_666 . ?
O1 Ho1 N21 76.79(17) . 8_666 ?
O1 Ho1 N21 80.63(18) 8_666 8_666 ?
N31 Ho1 N21 114.0(2) . 8_666 ?
N31 Ho1 N21 74.3(2) 8_666 8_666 ?
N21 Ho1 N21 152.7(3) . 8_666 ?
O1 Ho1 N11 122.19(18) . 8_666 ?
O1 Ho1 N11 145.07(18) 8_666 8_666 ?
N31 Ho1 N11 75.49(19) . 8_666 ?
N31 Ho1 N11 77.30(18) 8_666 8_666 ?
N21 Ho1 N11 135.19(18) . 8_666 ?
N21 Ho1 N11 71.13(19) 8_666 8_666 ?
O1 Ho1 N11 145.07(18) . . ?
O1 Ho1 N11 122.19(18) 8_666 . ?
N31 Ho1 N11 77.30(18) . . ?
N31 Ho1 N11 75.49(19) 8_666 . ?
N21 Ho1 N11 71.13(19) . . ?
N21 Ho1 N11 135.19(18) 8_666 . ?
N11 Ho1 N11 70.5(3) 8_666 . ?
C1 O1 Ho1 120.3(4) . . ?
C11 N12 N11 110.3(6) . . ?
C11 N12 B1 128.6(6) . . ?
N11 N12 B1 121.2(5) . . ?
N11 C13 C12 111.9(8) . . ?
C23 N21 N22 105.7(6) . . ?
C23 N21 Ho1 130.6(5) . . ?
N22 N21 Ho1 123.4(4) . . ?
N21 C23 C22 111.3(7) . . ?
C33 N31 N32 106.3(6) . . ?
C33 N31 Ho1 129.6(5) . . ?
N32 N31 Ho1 123.9(4) . . ?
C11 C12 C13 104.1(7) . . ?
C31 N32 N31 109.1(6) . . ?
C31 N32 B1 128.6(6) . . ?
N31 N32 B1 122.3(5) . . ?
O1 C1 C2 118.4(6) . . ?
O1 C1 C1 115.6(4) . 8_666 ?
C2 C1 C1 126.0(4) . 8_666 ?
C13 N11 N12 104.7(6) . . ?
C13 N11 Ho1 130.7(5) . . ?
N12 N11 Ho1 122.7(4) . . ?
C21 N22 N21 109.6(6) . . ?
C21 N22 B1 128.6(6) . . ?
N21 N22 B1 121.7(6) . . ?
C31 C32 C33 104.0(6) . . ?
N22 C21 C22 108.9(7) . . ?
N31 C33 C32 111.6(7) . . ?
C21 C22 C23 104.5(7) . . ?
N22 B1 N32 110.1(6) . . ?
N22 B1 N12 108.2(6) . . ?
N32 B1 N12 109.6(6) . . ?
N32 C31 C32 109.0(7) . . ?
C3 C2 C1 130.2(8) . . ?
C4 C3 C2 130.5(8) . . ?
C3 C4 C3 126.4(10) 8_666 . ?
N12 C11 C12 109.1(7) . . ?

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        26.98
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         1.148
_refine_diff_density_min         -2.122
_refine_diff_density_rms         0.159