# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2004

data_global

_journal_coden_Cambridge         182

loop_
_publ_author_name
'Anjana Devi'
'Arne Baunemann'
'Ralf Becker'
'Peter Ehrhart'
'Roland A. Fischer'
'Reji Thomas'
'Rainer Waser'
'Manuela Winter'

_publ_contact_author_name        'Prof Anjana Devi'
_publ_contact_author_address     
;
Lehrstuhl fur Anorganische Chemie II
Ruhr-University Bochum
Inorganic Materials Chemistry Group
Universitatsstr. 150
Bochum
NRW
D-44780
GERMANY
;

_publ_contact_author_email       ANJANA.DEVI@RUHR-UNI-BOCHUM.DE

_publ_requested_journal          'Chemical Communications'

_publ_section_title              
;
Mononuclear precursor for MOCVD of HfO2 thin films
;

data_raf40
_database_code_depnum_ccdc_archive 'CCDC 236724'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C22 H40 Hf O8'
_chemical_formula_weight         611.03

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'
Hf Hf -0.5830 6.1852 '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                   9.872(3)
_cell_length_b                   15.312(4)
_cell_length_c                   18.599(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 97.548(7)
_cell_angle_gamma                90.00
_cell_volume                     2787.1(12)
_cell_formula_units_Z            4
_cell_measurement_temperature    213(2)
_cell_measurement_reflns_used    60
_cell_measurement_theta_min      10.0
_cell_measurement_theta_max      15.0

_exptl_crystal_description       prism
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.42
_exptl_crystal_size_min          0.38
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.456
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1232
_exptl_absorpt_coefficient_mu    3.780
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.449
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      213(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  'Bruke axs CCD 1000'
_diffrn_measurement_method       \w-scans
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            7901
_diffrn_reflns_av_R_equivalents  0.1274
_diffrn_reflns_av_sigmaI/netI    0.1312
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         2.21
_diffrn_reflns_theta_max         25.13
_reflns_number_total             2471
_reflns_number_gt                1751
_reflns_threshold_expression     >2sigma(I)

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

_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^)+(0.0000P)^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    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2471
_refine_ls_number_parameters     147
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0800
_refine_ls_R_factor_gt           0.0481
_refine_ls_wR_factor_ref         0.0954
_refine_ls_wR_factor_gt          0.0864
_refine_ls_goodness_of_fit_ref   0.891
_refine_ls_restrained_S_all      0.891
_refine_ls_shift/su_max          0.082
_refine_ls_shift/su_mean         0.004

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
Hf1 Hf 0.5000 0.30020(3) 0.7500 0.03817(19) Uani 1 2 d S . .
O1 O 0.7000(6) 0.3260(3) 0.7951(3) 0.0477(14) Uani 1 1 d . . .
C2 C 0.7593(8) 0.3860(6) 0.8388(4) 0.043(2) Uani 1 1 d . . .
C3 C 0.6943(8) 0.4480(5) 0.8711(4) 0.042(2) Uani 1 1 d . . .
H3 H 0.7469 0.4864 0.9028 0.050 Uiso 1 1 calc R . .
C4 C 0.5509(9) 0.4596(5) 0.8605(4) 0.041(2) Uani 1 1 d . . .
O4 O 0.5063(5) 0.5275(3) 0.8958(3) 0.0448(14) Uani 1 1 d . . .
C41 C 0.3639(9) 0.5564(6) 0.8881(4) 0.053(2) Uani 1 1 d . . .
C411 C 0.3708(10) 0.6336(6) 0.9386(4) 0.065(3) Uani 1 1 d . . .
H41A H 0.4022 0.6145 0.9877 0.097 Uiso 1 1 calc R . .
H41B H 0.2807 0.6595 0.9368 0.097 Uiso 1 1 calc R . .
H41C H 0.4339 0.6766 0.9238 0.097 Uiso 1 1 calc R . .
C413 C 0.2785(9) 0.4834(6) 0.9159(5) 0.072(3) Uani 1 1 d . . .
H41D H 0.2689 0.4358 0.8811 0.108 Uiso 1 1 calc R . .
H41E H 0.1888 0.5057 0.9220 0.108 Uiso 1 1 calc R . .
H41F H 0.3235 0.4622 0.9621 0.108 Uiso 1 1 calc R . .
C412 C 0.3186(11) 0.5839(7) 0.8115(5) 0.088(4) Uani 1 1 d . . .
H41G H 0.3852 0.6237 0.7958 0.132 Uiso 1 1 calc R . .
H41H H 0.2307 0.6128 0.8087 0.132 Uiso 1 1 calc R . .
H41I H 0.3105 0.5328 0.7803 0.132 Uiso 1 1 calc R . .
C21 C 0.9148(8) 0.3783(7) 0.8513(5) 0.065(3) Uani 1 1 d . . .
H21A H 0.9403 0.3193 0.8666 0.098 Uiso 1 1 calc R . .
H21B H 0.9516 0.4193 0.8886 0.098 Uiso 1 1 calc R . .
H21C H 0.9513 0.3914 0.8065 0.098 Uiso 1 1 calc R . .
O5 O 0.4680(5) 0.4112(4) 0.8210(3) 0.0420(13) Uani 1 1 d . . .
O6 O 0.5538(5) 0.2218(3) 0.6784(3) 0.0499(15) Uani 1 1 d . . .
C61 C 0.6281(10) 0.1817(9) 0.6296(6) 0.098(4) Uani 1 1 d . . .
H61 H 0.6460 0.1230 0.6510 0.118 Uiso 1 1 calc R . .
C611 C 0.5499(11) 0.1625(8) 0.5609(5) 0.089(4) Uani 1 1 d . . .
H61A H 0.4799 0.1199 0.5676 0.134 Uiso 1 1 calc R . .
H61B H 0.6097 0.1391 0.5282 0.134 Uiso 1 1 calc R . .
H61C H 0.5072 0.2156 0.5405 0.134 Uiso 1 1 calc R . .
C612 C 0.7632(10) 0.2171(7) 0.6306(6) 0.091(4) Uani 1 1 d . . .
H61D H 0.7589 0.2696 0.6012 0.136 Uiso 1 1 calc R . .
H61E H 0.8212 0.1743 0.6111 0.136 Uiso 1 1 calc R . .
H61F H 0.8007 0.2311 0.6800 0.136 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
Hf1 0.0414(3) 0.0333(3) 0.0416(3) 0.000 0.0126(2) 0.000
O1 0.054(4) 0.039(4) 0.053(3) 0.003(3) 0.019(3) 0.011(3)
C2 0.044(5) 0.042(5) 0.042(5) 0.013(4) 0.008(4) -0.002(4)
C3 0.039(5) 0.053(6) 0.034(5) -0.010(4) 0.007(4) -0.013(4)
C4 0.051(6) 0.045(5) 0.029(5) 0.006(4) 0.012(4) -0.007(5)
O4 0.046(4) 0.037(3) 0.054(3) -0.008(3) 0.015(3) -0.005(3)
C41 0.049(6) 0.060(6) 0.051(6) -0.015(4) 0.018(4) 0.007(5)
C411 0.081(7) 0.055(6) 0.065(6) -0.021(5) 0.034(5) -0.005(5)
C413 0.047(6) 0.063(7) 0.110(8) -0.025(6) 0.029(5) -0.013(5)
C412 0.116(10) 0.075(8) 0.073(7) -0.021(6) 0.007(6) 0.037(7)
C21 0.036(6) 0.090(8) 0.070(6) 0.002(5) 0.006(4) -0.003(5)
O5 0.034(3) 0.046(4) 0.046(3) -0.009(3) 0.005(2) -0.001(3)
O6 0.055(4) 0.047(4) 0.051(3) -0.008(3) 0.021(3) 0.000(3)
C61 0.053(7) 0.163(12) 0.083(8) -0.067(8) 0.025(6) -0.002(7)
C611 0.078(8) 0.126(10) 0.065(7) -0.026(6) 0.010(6) 0.000(7)
C612 0.053(7) 0.106(10) 0.120(9) -0.028(7) 0.038(6) 0.003(6)

_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
Hf1 O6 1.919(5) . ?
Hf1 O6 1.919(5) 2_656 ?
Hf1 O1 2.079(6) 2_656 ?
Hf1 O1 2.079(6) . ?
Hf1 O5 2.200(5) 2_656 ?
Hf1 O5 2.200(5) . ?
O1 C2 1.312(9) . ?
C2 C3 1.333(10) . ?
C2 C21 1.526(11) . ?
C3 C4 1.414(10) . ?
C3 H3 0.9400 . ?
C4 O5 1.266(9) . ?
C4 O4 1.335(9) . ?
O4 C41 1.462(9) . ?
C41 C412 1.497(11) . ?
C41 C411 1.505(11) . ?
C41 C413 1.531(12) . ?
C411 H41A 0.9700 . ?
C411 H41B 0.9700 . ?
C411 H41C 0.9700 . ?
C413 H41D 0.9700 . ?
C413 H41E 0.9700 . ?
C413 H41F 0.9700 . ?
C412 H41G 0.9700 . ?
C412 H41H 0.9700 . ?
C412 H41I 0.9700 . ?
C21 H21A 0.9700 . ?
C21 H21B 0.9700 . ?
C21 H21C 0.9700 . ?
O6 C61 1.384(10) . ?
C61 C611 1.433(13) . ?
C61 C612 1.438(13) . ?
C61 H61 0.9900 . ?
C611 H61A 0.9700 . ?
C611 H61B 0.9700 . ?
C611 H61C 0.9700 . ?
C612 H61D 0.9700 . ?
C612 H61E 0.9700 . ?
C612 H61F 0.9700 . ?

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
O6 Hf1 O6 102.6(3) . 2_656 ?
O6 Hf1 O1 100.0(2) . 2_656 ?
O6 Hf1 O1 93.7(2) 2_656 2_656 ?
O6 Hf1 O1 93.7(2) . . ?
O6 Hf1 O1 100.0(2) 2_656 . ?
O1 Hf1 O1 158.1(3) 2_656 . ?
O6 Hf1 O5 89.5(2) . 2_656 ?
O6 Hf1 O5 166.97(19) 2_656 2_656 ?
O1 Hf1 O5 79.31(18) 2_656 2_656 ?
O1 Hf1 O5 83.81(19) . 2_656 ?
O6 Hf1 O5 167.0(2) . . ?
O6 Hf1 O5 89.5(2) 2_656 . ?
O1 Hf1 O5 83.81(19) 2_656 . ?
O1 Hf1 O5 79.31(18) . . ?
O5 Hf1 O5 78.9(3) 2_656 . ?
C2 O1 Hf1 134.9(5) . . ?
O1 C2 C3 125.1(8) . . ?
O1 C2 C21 113.5(7) . . ?
C3 C2 C21 121.4(8) . . ?
C2 C3 C4 124.0(8) . . ?
C2 C3 H3 118.0 . . ?
C4 C3 H3 118.0 . . ?
O5 C4 O4 120.8(7) . . ?
O5 C4 C3 124.5(7) . . ?
O4 C4 C3 114.7(7) . . ?
C4 O4 C41 124.3(6) . . ?
O4 C41 C412 109.9(6) . . ?
O4 C41 C411 102.3(7) . . ?
C412 C41 C411 110.9(8) . . ?
O4 C41 C413 108.1(7) . . ?
C412 C41 C413 114.6(8) . . ?
C411 C41 C413 110.2(6) . . ?
C41 C411 H41A 109.5 . . ?
C41 C411 H41B 109.5 . . ?
H41A C411 H41B 109.5 . . ?
C41 C411 H41C 109.5 . . ?
H41A C411 H41C 109.5 . . ?
H41B C411 H41C 109.5 . . ?
C41 C413 H41D 109.5 . . ?
C41 C413 H41E 109.5 . . ?
H41D C413 H41E 109.5 . . ?
C41 C413 H41F 109.5 . . ?
H41D C413 H41F 109.5 . . ?
H41E C413 H41F 109.5 . . ?
C41 C412 H41G 109.5 . . ?
C41 C412 H41H 109.5 . . ?
H41G C412 H41H 109.5 . . ?
C41 C412 H41I 109.5 . . ?
H41G C412 H41I 109.5 . . ?
H41H C412 H41I 109.5 . . ?
C2 C21 H21A 109.5 . . ?
C2 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C2 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C4 O5 Hf1 132.0(5) . . ?
C61 O6 Hf1 162.2(6) . . ?
O6 C61 C611 114.0(9) . . ?
O6 C61 C612 113.3(8) . . ?
C611 C61 C612 118.6(10) . . ?
O6 C61 H61 102.7 . . ?
C611 C61 H61 102.7 . . ?
C612 C61 H61 102.7 . . ?
C61 C611 H61A 109.4 . . ?
C61 C611 H61B 109.5 . . ?
H61A C611 H61B 109.5 . . ?
C61 C611 H61C 109.5 . . ?
H61A C611 H61C 109.5 . . ?
H61B C611 H61C 109.5 . . ?
C61 C612 H61D 109.5 . . ?
C61 C612 H61E 109.4 . . ?
H61D C612 H61E 109.5 . . ?
C61 C612 H61F 109.5 . . ?
H61D C612 H61F 109.5 . . ?
H61E C612 H61F 109.5 . . ?

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
O6 Hf1 O1 C2 164.2(6) . . . . ?
O6 Hf1 O1 C2 -92.3(7) 2_656 . . . ?
O1 Hf1 O1 C2 35.5(6) 2_656 . . . ?
O5 Hf1 O1 C2 75.1(6) 2_656 . . . ?
O5 Hf1 O1 C2 -4.7(6) . . . . ?
Hf1 O1 C2 C3 5.0(12) . . . . ?
Hf1 O1 C2 C21 -175.9(5) . . . . ?
O1 C2 C3 C4 -2.4(12) . . . . ?
C21 C2 C3 C4 178.6(7) . . . . ?
C2 C3 C4 O5 2.1(12) . . . . ?
C2 C3 C4 O4 -177.7(7) . . . . ?
O5 C4 O4 C41 -5.2(10) . . . . ?
C3 C4 O4 C41 174.6(6) . . . . ?
C4 O4 C41 C412 -61.9(9) . . . . ?
C4 O4 C41 C411 -179.8(6) . . . . ?
C4 O4 C41 C413 63.9(9) . . . . ?
O4 C4 O5 Hf1 175.7(4) . . . . ?
C3 C4 O5 Hf1 -4.0(11) . . . . ?
O6 Hf1 O5 C4 -54.0(12) . . . . ?
O6 Hf1 O5 C4 104.5(6) 2_656 . . . ?
O1 Hf1 O5 C4 -161.8(6) 2_656 . . . ?
O1 Hf1 O5 C4 4.2(6) . . . . ?
O5 Hf1 O5 C4 -81.5(6) 2_656 . . . ?
O6 Hf1 O6 C61 -130(2) 2_656 . . . ?
O1 Hf1 O6 C61 134(2) 2_656 . . . ?
O1 Hf1 O6 C61 -28(2) . . . . ?
O5 Hf1 O6 C61 55(2) 2_656 . . . ?
O5 Hf1 O6 C61 28(3) . . . . ?
Hf1 O6 C61 C611 -133.9(18) . . . . ?
Hf1 O6 C61 C612 6(3) . . . . ?

_diffrn_measured_fraction_theta_max 0.992
_diffrn_reflns_theta_full        25.13
_diffrn_measured_fraction_theta_full 0.992
_refine_diff_density_max         1.273
_refine_diff_density_min         -0.938
_refine_diff_density_rms         0.147