# 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
'Kevin John'
'e Da Re,Ryan'
'Christopher J. Kuehl'
'David E. Morris'
'Brian L. Scott'

_publ_contact_author_name        'Dr Kevin John'
_publ_contact_author_address     
;
Chemistry Division
Los Alamos National Laboratory
MS 582
Los Alamos
NM
87545
UNITED STATES OF AMERICA
;

_publ_contact_author_email       KJOHN@LANL.GOV

_publ_requested_journal          'Chemical Communications'

_publ_section_title              
;
Toward new paradigms in mixed-valency:
ytterbocene-terpyridine charge-transfer complexes
;

data_ccd586a
_database_code_CSD               212458

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
bis-pentamethylcyclopentadienyl ytterbium terpyridine
;

_chemical_name_common            'ytterbocene terpyridine'
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C35 H41 N3 Yb'
_chemical_formula_weight         676.74

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'
Yb Yb -0.3850 5.5486 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Pbna

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

_cell_length_a                   14.214(9)
_cell_length_b                   14.214(9)
_cell_length_c                   14.682(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2966(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    203(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       block
_exptl_crystal_colour            purple
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.11
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.513
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1364
_exptl_crystal_preparation       'crystallized from toluene'
_exptl_absorpt_coefficient_mu    3.180
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.60
_exptl_absorpt_correction_T_max  0.70
_exptl_absorpt_process_details   'SADABS (Sheldrick, 1996)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      203(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  'Bruker P4/CCD'
_diffrn_measurement_method       '\w and \f scan'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_decay_%        '< 2'
_diffrn_reflns_number            14555
_diffrn_reflns_av_R_equivalents  0.0853
_diffrn_reflns_av_sigmaI/netI    0.0405
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.99
_diffrn_reflns_theta_max         23.33
_reflns_number_total             2143
_reflns_number_gt                1771
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Siemens SMART (v. 4.202, Siemens 1996)'
_computing_cell_refinement       'Bruker SAINT (v. 5.00, Bruker 1998)'
_computing_data_reduction        'Bruker SAINT (v. 5.00, Bruker 1998)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker AXS SHEXTL (v. 5.10)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'

_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^)+(0.1038P)^2^+31.7318P] 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         2143
_refine_ls_number_parameters     178
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0888
_refine_ls_R_factor_gt           0.0795
_refine_ls_wR_factor_ref         0.2036
_refine_ls_wR_factor_gt          0.1966
_refine_ls_goodness_of_fit_ref   1.201
_refine_ls_restrained_S_all      1.201
_refine_ls_shift/su_max          0.018
_refine_ls_shift/su_mean         0.002

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
Yb Yb 0.76391(5) 0.2500 0.5000 0.0269(4) Uani 1 2 d S . .
N1 N 0.6974(6) 0.1077(7) 0.5643(6) 0.033(2) Uani 1 1 d . . .
N2 N 0.5947(11) 0.2500 0.5000 0.042(4) Uani 1 2 d S . .
C1 C 0.8286(10) 0.1089(9) 0.3907(9) 0.045(3) Uani 1 1 d . . .
C2 C 0.9021(8) 0.1765(10) 0.3908(9) 0.043(3) Uani 1 1 d . . .
C3 C 0.8700(9) 0.2563(9) 0.3439(9) 0.040(3) Uani 1 1 d . . .
C4 C 0.7753(8) 0.2382(8) 0.3152(11) 0.036(3) Uani 1 1 d . . .
C5 C 0.7498(8) 0.1477(10) 0.3475(9) 0.040(3) Uani 1 1 d . . .
C6 C 0.8424(16) 0.0059(10) 0.4095(12) 0.087(7) Uani 1 1 d . . .
H6A H 0.8667 -0.0243 0.3560 0.130 Uiso 1 1 calc R . .
H6B H 0.7832 -0.0219 0.4257 0.130 Uiso 1 1 calc R . .
H6C H 0.8861 -0.0017 0.4588 0.130 Uiso 1 1 calc R . .
C7 C 1.0050(11) 0.1558(16) 0.4181(11) 0.086(6) Uani 1 1 d . . .
H7A H 1.0385 0.1311 0.3666 0.129 Uiso 1 1 calc R . .
H7B H 1.0059 0.1105 0.4667 0.129 Uiso 1 1 calc R . .
H7C H 1.0346 0.2129 0.4381 0.129 Uiso 1 1 calc R . .
C8 C 0.9339(10) 0.3358(11) 0.3139(10) 0.062(4) Uani 1 1 d . . .
H8A H 0.9626 0.3199 0.2567 0.093 Uiso 1 1 calc R . .
H8B H 0.9820 0.3454 0.3589 0.093 Uiso 1 1 calc R . .
H8C H 0.8977 0.3923 0.3071 0.093 Uiso 1 1 calc R . .
C9 C 0.7189(11) 0.2981(12) 0.2491(9) 0.059(4) Uani 1 1 d . . .
H9A H 0.7352 0.2813 0.1877 0.089 Uiso 1 1 calc R . .
H9B H 0.7330 0.3633 0.2591 0.089 Uiso 1 1 calc R . .
H9C H 0.6529 0.2875 0.2586 0.089 Uiso 1 1 calc R . .
C10 C 0.6567(10) 0.0988(13) 0.3296(11) 0.081(6) Uani 1 1 d . . .
H10A H 0.6606 0.0642 0.2736 0.121 Uiso 1 1 calc R . .
H10B H 0.6076 0.1450 0.3251 0.121 Uiso 1 1 calc R . .
H10C H 0.6431 0.0564 0.3788 0.121 Uiso 1 1 calc R . .
C11 C 0.7491(10) 0.0343(9) 0.5927(9) 0.040(3) Uani 1 1 d . . .
H11A H 0.8136 0.0360 0.5822 0.048 Uiso 1 1 calc R . .
C12 C 0.7129(12) -0.0428(9) 0.6360(9) 0.052(4) Uani 1 1 d . . .
H12A H 0.7526 -0.0907 0.6558 0.063 Uiso 1 1 calc R . .
C13 C 0.6175(12) -0.0491(11) 0.6501(9) 0.062(5) Uani 1 1 d . . .
H13A H 0.5919 -0.1015 0.6788 0.074 Uiso 1 1 calc R . .
C14 C 0.5600(10) 0.0235(10) 0.6210(9) 0.050(4) Uani 1 1 d . . .
H14A H 0.4956 0.0215 0.6319 0.060 Uiso 1 1 calc R . .
C15 C 0.5999(9) 0.0998(9) 0.5753(8) 0.038(3) Uani 1 1 d . . .
C16 C 0.5447(8) 0.1779(10) 0.5387(9) 0.042(3) Uani 1 1 d . . .
C17 C 0.4465(10) 0.1776(12) 0.5409(11) 0.056(4) Uani 1 1 d . . .
H17A H 0.4146 0.1289 0.5698 0.067 Uiso 1 1 calc R . .
C18 C 0.3966(15) 0.2500 0.5000 0.075(8) Uani 1 2 d S . .
H18A H 0.3311 0.2500 0.5000 0.090 Uiso 1 2 calc SR . .

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
Yb 0.0123(5) 0.0299(5) 0.0387(5) 0.0014(3) 0.000 0.000
N1 0.020(5) 0.043(6) 0.037(5) -0.003(4) 0.001(4) -0.007(5)
N2 0.017(8) 0.060(11) 0.049(9) -0.005(7) 0.000 0.000
C1 0.050(9) 0.036(7) 0.048(8) 0.004(6) 0.022(6) 0.008(7)
C2 0.016(6) 0.062(9) 0.051(8) -0.009(7) 0.003(5) 0.019(6)
C3 0.025(7) 0.048(8) 0.047(7) -0.002(6) 0.005(6) 0.001(6)
C4 0.016(7) 0.028(7) 0.062(9) -0.003(5) 0.001(6) 0.007(5)
C5 0.019(6) 0.046(8) 0.054(8) -0.023(6) 0.009(6) -0.010(6)
C6 0.146(19) 0.037(8) 0.078(12) 0.009(7) 0.048(12) 0.033(11)
C7 0.036(9) 0.150(19) 0.072(10) 0.002(11) -0.003(8) 0.047(11)
C8 0.040(8) 0.064(10) 0.081(11) -0.010(8) 0.027(7) -0.030(8)
C9 0.073(11) 0.075(10) 0.029(7) -0.008(7) -0.017(7) 0.037(9)
C10 0.035(9) 0.114(14) 0.094(13) -0.056(11) 0.017(8) -0.039(10)
C11 0.044(7) 0.037(8) 0.040(8) -0.001(6) -0.005(6) -0.002(6)
C12 0.074(11) 0.030(7) 0.053(9) 0.001(6) -0.002(8) -0.012(7)
C13 0.083(13) 0.055(10) 0.047(8) -0.004(7) 0.011(8) -0.038(9)
C14 0.042(8) 0.056(9) 0.053(8) -0.006(7) 0.009(7) -0.026(8)
C15 0.033(7) 0.041(7) 0.040(7) -0.001(6) 0.005(6) -0.016(6)
C16 0.021(6) 0.062(9) 0.044(7) -0.020(6) 0.006(6) -0.022(7)
C17 0.026(8) 0.073(10) 0.069(9) -0.016(8) 0.005(7) -0.009(8)
C18 0.012(10) 0.11(2) 0.099(19) -0.030(15) 0.000 0.000

_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
Yb N2 2.405(15) . ?
Yb N1 2.424(10) . ?
Yb N1 2.424(10) 3_556 ?
Yb C5 2.678(12) . ?
Yb C5 2.678(12) 3_556 ?
Yb C4 2.724(16) . ?
Yb C4 2.724(16) 3_556 ?
Yb C1 2.728(12) . ?
Yb C1 2.728(12) 3_556 ?
Yb C2 2.743(11) 3_556 ?
Yb C2 2.743(11) . ?
Yb C3 2.745(13) . ?
N1 C11 1.343(16) . ?
N1 C15 1.399(15) . ?
N2 C16 1.370(15) 3_556 ?
N2 C16 1.370(15) . ?
C1 C5 1.400(19) . ?
C1 C2 1.419(18) . ?
C1 C6 1.503(18) . ?
C2 C3 1.403(18) . ?
C2 C7 1.545(18) . ?
C3 C4 1.434(18) . ?
C3 C8 1.515(18) . ?
C4 C5 1.418(18) . ?
C4 C9 1.52(2) . ?
C5 C10 1.517(17) . ?
C11 C12 1.368(19) . ?
C12 C13 1.38(2) . ?
C13 C14 1.38(2) . ?
C14 C15 1.396(17) . ?
C15 C16 1.462(19) . ?
C16 C17 1.397(18) . ?
C17 C18 1.39(2) . ?
C18 C17 1.39(2) 3_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
N2 Yb N1 67.0(2) . . ?
N2 Yb N1 67.0(2) . 3_556 ?
N1 Yb N1 134.1(5) . 3_556 ?
N2 Yb C5 85.7(2) . . ?
N1 Yb C5 81.0(4) . . ?
N1 Yb C5 95.6(4) 3_556 . ?
N2 Yb C5 85.7(2) . 3_556 ?
N1 Yb C5 95.6(4) . 3_556 ?
N1 Yb C5 81.0(4) 3_556 3_556 ?
C5 Yb C5 171.4(5) . 3_556 ?
N2 Yb C4 93.4(3) . . ?
N1 Yb C4 111.1(3) . . ?
N1 Yb C4 71.7(3) 3_556 . ?
C5 Yb C4 30.4(4) . . ?
C5 Yb C4 150.6(4) 3_556 . ?
N2 Yb C4 93.4(3) . 3_556 ?
N1 Yb C4 71.7(3) . 3_556 ?
N1 Yb C4 111.1(3) 3_556 3_556 ?
C5 Yb C4 150.6(4) . 3_556 ?
C5 Yb C4 30.4(4) 3_556 3_556 ?
C4 Yb C4 173.2(5) . 3_556 ?
N2 Yb C1 109.7(3) . . ?
N1 Yb C1 75.4(3) . . ?
N1 Yb C1 121.0(3) 3_556 . ?
C5 Yb C1 30.0(4) . . ?
C5 Yb C1 156.4(4) 3_556 . ?
C4 Yb C1 49.3(4) . . ?
C4 Yb C1 127.7(4) 3_556 . ?
N2 Yb C1 109.7(3) . 3_556 ?
N1 Yb C1 121.0(3) . 3_556 ?
N1 Yb C1 75.4(3) 3_556 3_556 ?
C5 Yb C1 156.4(4) . 3_556 ?
C5 Yb C1 30.0(4) 3_556 3_556 ?
C4 Yb C1 127.7(4) . 3_556 ?
C4 Yb C1 49.3(4) 3_556 3_556 ?
C1 Yb C1 140.6(6) . 3_556 ?
N2 Yb C2 135.7(3) . 3_556 ?
N1 Yb C2 111.7(4) . 3_556 ?
N1 Yb C2 100.9(4) 3_556 3_556 ?
C5 Yb C2 138.6(4) . 3_556 ?
C5 Yb C2 50.0(4) 3_556 3_556 ?
C4 Yb C2 124.3(4) . 3_556 ?
C4 Yb C2 49.6(4) 3_556 3_556 ?
C1 Yb C2 112.5(4) . 3_556 ?
C1 Yb C2 30.1(4) 3_556 3_556 ?
N2 Yb C2 135.7(3) . . ?
N1 Yb C2 100.9(4) . . ?
N1 Yb C2 111.7(4) 3_556 . ?
C5 Yb C2 50.0(4) . . ?
C5 Yb C2 138.6(4) 3_556 . ?
C4 Yb C2 49.6(4) . . ?
C4 Yb C2 124.3(4) 3_556 . ?
C1 Yb C2 30.1(4) . . ?
C1 Yb C2 112.5(4) 3_556 . ?
C2 Yb C2 88.5(5) 3_556 . ?
N2 Yb C3 123.3(3) . . ?
N1 Yb C3 124.5(3) . . ?
N1 Yb C3 82.1(3) 3_556 . ?
C5 Yb C3 50.2(4) . . ?
C5 Yb C3 136.2(4) 3_556 . ?
C4 Yb C3 30.4(4) . . ?
C4 Yb C3 142.9(4) 3_556 . ?
C1 Yb C3 49.3(4) . . ?
C1 Yb C3 106.4(4) 3_556 . ?
C2 Yb C3 94.7(4) 3_556 . ?
C2 Yb C3 29.6(4) . . ?
C11 N1 C15 116.4(11) . . ?
C11 N1 Yb 123.7(8) . . ?
C15 N1 Yb 119.9(8) . . ?
C16 N2 C16 117.5(16) 3_556 . ?
C16 N2 Yb 121.2(8) 3_556 . ?
C16 N2 Yb 121.2(8) . . ?
C5 C1 C2 108.9(11) . . ?
C5 C1 C6 124.8(15) . . ?
C2 C1 C6 124.2(14) . . ?
C5 C1 Yb 73.0(7) . . ?
C2 C1 Yb 75.5(7) . . ?
C6 C1 Yb 130.7(9) . . ?
C3 C2 C1 107.9(11) . . ?
C3 C2 C7 126.1(14) . . ?
C1 C2 C7 124.6(14) . . ?
C3 C2 Yb 75.3(7) . . ?
C1 C2 Yb 74.4(7) . . ?
C7 C2 Yb 126.7(9) . . ?
C2 C3 C4 107.7(11) . . ?
C2 C3 C8 123.4(13) . . ?
C4 C3 C8 127.7(13) . . ?
C2 C3 Yb 75.1(7) . . ?
C4 C3 Yb 74.0(8) . . ?
C8 C3 Yb 126.6(9) . . ?
C5 C4 C3 107.7(11) . . ?
C5 C4 C9 126.0(13) . . ?
C3 C4 C9 125.6(12) . . ?
C5 C4 Yb 73.0(8) . . ?
C3 C4 Yb 75.6(8) . . ?
C9 C4 Yb 124.8(9) . . ?
C1 C5 C4 107.7(11) . . ?
C1 C5 C10 126.6(14) . . ?
C4 C5 C10 125.4(14) . . ?
C1 C5 Yb 77.0(8) . . ?
C4 C5 Yb 76.6(8) . . ?
C10 C5 Yb 117.3(8) . . ?
N1 C11 C12 124.1(13) . . ?
C11 C12 C13 119.5(15) . . ?
C12 C13 C14 119.3(13) . . ?
C13 C14 C15 119.1(13) . . ?
C14 C15 N1 121.3(12) . . ?
C14 C15 C16 123.3(12) . . ?
N1 C15 C16 115.3(10) . . ?
N2 C16 C17 122.0(15) . . ?
N2 C16 C15 116.2(11) . . ?
C17 C16 C15 121.7(13) . . ?
C18 C17 C16 119.9(16) . . ?
C17 C18 C17 118.4(19) . 3_556 ?

_diffrn_measured_fraction_theta_max 0.992
_diffrn_reflns_theta_full        23.33
_diffrn_measured_fraction_theta_full 0.992
_refine_diff_density_max         4.327
_refine_diff_density_min         -5.209
_refine_diff_density_rms         0.251