# Supplementary Material (ESI) for Chemical Communications
# This journal is (c) The Royal Society of Chemistry 2008

data_global
_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182

_publ_contact_author_name        'Karin Ruhlandt-Senge'
_publ_contact_author_address     
;
1-014C Center for Science and Techn
Syracuse University
Syracuse
NY
13244-4100
UNITED STATES OF AMERICA
;

_publ_contact_author_email       KRUHLAND@SYR.EDU

_publ_section_title              
;
A unique heterobimetallic benzyl calciate - an
organometallic mixed metal species involving a heavy alkaline earth
metal
;
loop_
_publ_author_name
'Karin Ruhlandt-Senge'
'Charles F. Campana'
'Marites A. Guino-o'

data_data0x
_database_code_depnum_ccdc_archive 'CCDC 663415'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C47 H68 Ca Li2 N4'
_chemical_formula_weight         743.02

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'
Li Li -0.0003 0.0001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ca Ca 0.2262 0.3064 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Tetragonal
_symmetry_space_group_name_H-M   I-42d

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'y, -x, -z'
'-x, -y, z'
'-y, x, -z'
'x, -y+1/2, -z+1/4'
'-y+1/2, -x, z+3/4'
'-x, y+1/2, -z+1/4'
'y+1/2, x, z+3/4'
'x+1/2, y+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, -y+1, -z+3/4'
'-y+1, -x+1/2, z+5/4'
'-x+1/2, y+1, -z+3/4'
'y+1, x+1/2, z+5/4'

_cell_length_a                   13.6240(7)
_cell_length_b                   13.6240(7)
_cell_length_c                   28.4840(14)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     5287.0(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    4191
_cell_measurement_theta_min      2.55
_cell_measurement_theta_max      28.28

_exptl_crystal_description       cube
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.50
_exptl_crystal_size_mid          0.50
_exptl_crystal_size_min          0.50
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    0.818
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1416
_exptl_absorpt_coefficient_mu    0.142
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9326
_exptl_absorpt_correction_T_max  0.9326
_exptl_absorpt_process_details   'R. Blessing, Acta Cryst. (1995) A51 33-38.'

_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  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        no
_diffrn_reflns_number            13194
_diffrn_reflns_av_R_equivalents  0.0820
_diffrn_reflns_av_sigmaI/netI    0.0446
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_theta_min         2.55
_diffrn_reflns_theta_max         22.49
_reflns_number_total             1738
_reflns_number_gt                1349
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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^)+(0.1200P)^2^+0.0000P] 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    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   0.08(10)
_refine_ls_number_reflns         1738
_refine_ls_number_parameters     109
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0786
_refine_ls_R_factor_gt           0.0656
_refine_ls_wR_factor_ref         0.1837
_refine_ls_wR_factor_gt          0.1753
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_restrained_S_all      1.121
_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
Ca1 Ca 0.0000 0.0000 0.0000 0.0582(5) Uani 1 4 d S . .
C1 C 0.2343(3) 0.0342(3) 0.01126(15) 0.0648(12) Uani 1 1 d . . .
H1A H 0.2257 -0.0332 0.0187 0.078 Uiso 1 1 calc R . .
C2 C 0.2849(4) 0.0949(6) 0.04178(18) 0.0939(17) Uani 1 1 d . . .
H2A H 0.3081 0.0689 0.0707 0.113 Uiso 1 1 calc R . .
C3 C 0.3023(4) 0.1908(6) 0.0315(3) 0.101(2) Uani 1 1 d . . .
H3A H 0.3390 0.2307 0.0524 0.122 Uiso 1 1 calc R . .
C4 C 0.2678(4) 0.2279(4) -0.0079(2) 0.0870(18) Uani 1 1 d . . .
H4A H 0.2787 0.2952 -0.0148 0.104 Uiso 1 1 calc R . .
C5 C 0.2166(3) 0.1713(4) -0.03886(19) 0.0723(14) Uani 1 1 d . . .
H5A H 0.1941 0.2001 -0.0673 0.087 Uiso 1 1 calc R . .
C6 C 0.1958(3) 0.0718(3) -0.03025(17) 0.0581(11) Uani 1 1 d . . .
C7 C 0.1393(2) 0.0123(4) -0.06240(13) 0.0590(11) Uani 1 1 d . . .
H7A H 0.1353 -0.0496 -0.0443 0.071 Uiso 1 1 calc R . .
H7B H 0.1895 -0.0010 -0.0867 0.071 Uiso 1 1 calc R . .
Li1 Li 0.0000 0.0000 -0.1064(3) 0.057(2) Uani 1 2 d S . .
N1 N 0.0188(3) -0.1052(3) -0.15997(12) 0.0708(11) Uani 1 1 d . . .
C8 C -0.0161(5) -0.0528(4) -0.20110(17) 0.0901(16) Uani 1 1 d . . .
H8A H -0.0886 -0.0557 -0.2020 0.108 Uiso 1 1 calc R . .
H8B H 0.0092 -0.0855 -0.2297 0.108 Uiso 1 1 calc R . .
C9 C 0.1230(4) -0.1329(4) -0.1646(2) 0.0877(16) Uani 1 1 d . . .
H9A H 0.1341 -0.1619 -0.1957 0.132 Uiso 1 1 calc R . .
H9B H 0.1399 -0.1809 -0.1403 0.132 Uiso 1 1 calc R . .
H9C H 0.1642 -0.0745 -0.1610 0.132 Uiso 1 1 calc R . .
C10 C -0.0428(4) -0.1977(4) -0.15439(18) 0.0898(17) Uani 1 1 d . . .
H10A H -0.0383 -0.2372 -0.1831 0.135 Uiso 1 1 calc R . .
H10B H -0.1114 -0.1795 -0.1488 0.135 Uiso 1 1 calc R . .
H10C H -0.0183 -0.2359 -0.1277 0.135 Uiso 1 1 calc 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
Ca1 0.0591(7) 0.0591(7) 0.0565(9) 0.000 0.000 0.000
C1 0.051(2) 0.077(3) 0.067(3) 0.009(2) -0.002(2) -0.005(2)
C2 0.065(3) 0.145(6) 0.071(3) -0.004(4) -0.003(3) -0.005(4)
C3 0.064(4) 0.122(6) 0.118(6) -0.045(5) 0.012(4) -0.019(3)
C4 0.056(3) 0.082(4) 0.123(6) -0.030(4) 0.007(3) -0.013(3)
C5 0.054(3) 0.065(3) 0.098(4) 0.000(3) 0.011(3) -0.001(2)
C6 0.032(2) 0.063(3) 0.080(3) 0.003(2) 0.008(2) -0.0013(19)
C7 0.043(2) 0.069(3) 0.065(2) 0.013(3) -0.0013(18) 0.001(2)
Li1 0.051(5) 0.067(5) 0.053(5) 0.000 0.000 0.015(6)
N1 0.052(2) 0.089(3) 0.072(2) -0.013(2) -0.0046(18) 0.002(2)
C8 0.099(4) 0.108(4) 0.064(3) -0.009(2) 0.002(3) -0.009(3)
C9 0.071(3) 0.099(4) 0.093(4) -0.030(3) 0.001(3) 0.024(3)
C10 0.083(3) 0.096(4) 0.091(4) -0.012(3) -0.016(3) 0.002(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
Ca1 C7 2.605(4) 4 ?
Ca1 C7 2.605(4) . ?
Ca1 C7 2.605(4) 3 ?
Ca1 C7 2.606(4) 2 ?
Ca1 C6 2.970(4) 2 ?
Ca1 C6 2.970(4) 4 ?
Ca1 C6 2.970(4) 3 ?
Ca1 C6 2.970(4) . ?
Ca1 Li1 3.030(7) 2 ?
Ca1 Li1 3.030(7) . ?
C1 C2 1.383(7) . ?
C1 C6 1.391(6) . ?
C1 H1A 0.9500 . ?
C2 C3 1.361(9) . ?
C2 H2A 0.9500 . ?
C3 C4 1.316(9) . ?
C3 H3A 0.9500 . ?
C4 C5 1.364(7) . ?
C4 H4A 0.9500 . ?
C5 C6 1.405(6) . ?
C5 H5A 0.9500 . ?
C6 C7 1.446(6) . ?
C7 Li1 2.280(5) . ?
C7 H7A 0.9900 . ?
C7 H7B 0.9900 . ?
Li1 N1 2.109(6) . ?
Li1 N1 2.109(6) 3 ?
Li1 C7 2.280(5) 3 ?
N1 C8 1.452(6) . ?
N1 C9 1.475(6) . ?
N1 C10 1.523(6) . ?
C8 C8 1.504(10) 3 ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
C9 H9A 0.9800 . ?
C9 H9B 0.9800 . ?
C9 H9C 0.9800 . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?

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
C7 Ca1 C7 117.74(9) 4 . ?
C7 Ca1 C7 117.74(9) 4 3 ?
C7 Ca1 C7 93.96(16) . 3 ?
C7 Ca1 C7 93.97(16) 4 2 ?
C7 Ca1 C7 117.74(9) . 2 ?
C7 Ca1 C7 117.74(9) 3 2 ?
C7 Ca1 C6 118.53(13) 4 2 ?
C7 Ca1 C6 90.91(14) . 2 ?
C7 Ca1 C6 112.34(14) 3 2 ?
C7 Ca1 C6 29.13(13) 2 2 ?
C7 Ca1 C6 29.13(13) 4 4 ?
C7 Ca1 C6 112.34(14) . 4 ?
C7 Ca1 C6 90.91(14) 3 4 ?
C7 Ca1 C6 118.53(13) 2 4 ?
C6 Ca1 C6 146.26(18) 2 4 ?
C7 Ca1 C6 112.34(14) 4 3 ?
C7 Ca1 C6 118.53(13) . 3 ?
C7 Ca1 C6 29.13(13) 3 3 ?
C7 Ca1 C6 90.91(14) 2 3 ?
C6 Ca1 C6 94.83(5) 2 3 ?
C6 Ca1 C6 94.83(5) 4 3 ?
C7 Ca1 C6 90.91(14) 4 . ?
C7 Ca1 C6 29.13(13) . . ?
C7 Ca1 C6 118.53(13) 3 . ?
C7 Ca1 C6 112.34(14) 2 . ?
C6 Ca1 C6 94.83(5) 2 . ?
C6 Ca1 C6 94.83(5) 4 . ?
C6 Ca1 C6 146.26(18) 3 . ?
C7 Ca1 Li1 46.98(8) 4 2 ?
C7 Ca1 Li1 133.02(8) . 2 ?
C7 Ca1 Li1 133.02(8) 3 2 ?
C7 Ca1 Li1 46.98(8) 2 2 ?
C6 Ca1 Li1 73.13(9) 2 2 ?
C6 Ca1 Li1 73.13(9) 4 2 ?
C6 Ca1 Li1 106.87(9) 3 2 ?
C6 Ca1 Li1 106.87(9) . 2 ?
C7 Ca1 Li1 133.02(8) 4 . ?
C7 Ca1 Li1 46.98(8) . . ?
C7 Ca1 Li1 46.98(8) 3 . ?
C7 Ca1 Li1 133.02(8) 2 . ?
C6 Ca1 Li1 106.87(9) 2 . ?
C6 Ca1 Li1 106.87(9) 4 . ?
C6 Ca1 Li1 73.13(9) 3 . ?
C6 Ca1 Li1 73.13(9) . . ?
Li1 Ca1 Li1 180.0 2 . ?
C2 C1 C6 120.1(5) . . ?
C2 C1 H1A 119.9 . . ?
C6 C1 H1A 119.9 . . ?
C3 C2 C1 121.7(6) . . ?
C3 C2 H2A 119.2 . . ?
C1 C2 H2A 119.2 . . ?
C4 C3 C2 119.3(6) . . ?
C4 C3 H3A 120.3 . . ?
C2 C3 H3A 120.3 . . ?
C3 C4 C5 121.1(6) . . ?
C3 C4 H4A 119.4 . . ?
C5 C4 H4A 119.4 . . ?
C4 C5 C6 122.4(6) . . ?
C4 C5 H5A 118.8 . . ?
C6 C5 H5A 118.8 . . ?
C1 C6 C5 115.3(4) . . ?
C1 C6 C7 122.2(4) . . ?
C5 C6 C7 122.5(4) . . ?
C1 C6 Ca1 88.3(2) . . ?
C5 C6 Ca1 123.3(3) . . ?
C7 C6 Ca1 61.3(2) . . ?
C6 C7 Li1 146.4(3) . . ?
C6 C7 Ca1 89.5(2) . . ?
Li1 C7 Ca1 76.34(19) . . ?
C6 C7 H7A 100.2 . . ?
Li1 C7 H7A 100.2 . . ?
Ca1 C7 H7A 63.3 . . ?
C6 C7 H7B 100.2 . . ?
Li1 C7 H7B 100.2 . . ?
Ca1 C7 H7B 165.6 . . ?
H7A C7 H7B 104.2 . . ?
N1 Li1 N1 87.3(3) . 3 ?
N1 Li1 C7 116.66(16) . 3 ?
N1 Li1 C7 110.27(15) 3 3 ?
N1 Li1 C7 110.27(15) . . ?
N1 Li1 C7 116.66(16) 3 . ?
C7 Li1 C7 113.4(4) 3 . ?
N1 Li1 Ca1 136.36(17) . . ?
N1 Li1 Ca1 136.36(17) 3 . ?
C7 Li1 Ca1 56.68(18) 3 . ?
C7 Li1 Ca1 56.68(18) . . ?
C8 N1 C9 111.6(4) . . ?
C8 N1 C10 108.1(4) . . ?
C9 N1 C10 109.1(4) . . ?
C8 N1 Li1 102.1(3) . . ?
C9 N1 Li1 110.9(3) . . ?
C10 N1 Li1 114.8(3) . . ?
N1 C8 C8 112.0(4) . 3 ?
N1 C8 H8A 109.2 . . ?
C8 C8 H8A 109.2 3 . ?
N1 C8 H8B 109.2 . . ?
C8 C8 H8B 109.2 3 . ?
H8A C8 H8B 107.9 . . ?
N1 C9 H9A 109.5 . . ?
N1 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
N1 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
N1 C10 H10A 109.5 . . ?
N1 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
N1 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        22.49
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.205
_refine_diff_density_min         -0.227
_refine_diff_density_rms         0.050