Supplementary Material (ESI) for Dalton Transactions
This journal is (c) The Royal Society of Chemistry 2001
data_global
#===========================================================================
# 0. AUDIT DETAILS
_audit_creation_date 8-Apr-00
_audit_creation_method 'PLATON
option'
_audit_update_record
;
8-Apr-00 Updated by the Author E.H.
10-Apr-00 Updated by the Author E.H.
12-Oct-00 Updated by the Author E.H.
6-Dec-00 Updated by the Author E.H.
;
#===========================================================================
# 1. SUBMISSION DETAILS
#===========================================================================
# Name and address of author for X-ray correspondence
_publ_contact_author
;
Dr Fritz E Kuhn
Anorganisch-Chemisches Institut
Technishe Universitat Munchen
Litchtenbergstr 4
Muchen
D-85747 Garching bei M\"unchen
GERMANY
;
_publ_requested_journal 'J.C.S., Dalton Trans.'
_publ_requested_coeditor_name ?
_publ_contact_letter # Include date of submission
;
Date of submission: 10-Nov-00
;
#===========================================================================
# 2. PROCESSING SUMMARY (JOURNAL OFFICE ONLY)
#===========================================================================
_journal_date_recd_electronic ?
_journal_date_to_coeditor ?
_journal_date_from_coeditor ?
_journal_date_accepted ?
_journal_date_printers_first ?
_journal_date_printers_final ?
_journal_date_proofs_out ?
_journal_date_proofs_in ?
_journal_coeditor_name ?
_journal_coeditor_code ?
_journal_coeditor_notes
;
?
;
_journal_techeditor_code ?
_journal_techeditor_notes
;
?
;
_journal_coden_Cambridge 186
_journal_name_full ?
_journal_year ?
_journal_volume ?
_journal_issue ?
_journal_page_first ?
_journal_page_last ?
_journal_suppl_publ_number ?
_journal_suppl_publ_pages ?
#===========================================================================
# 3. TITLE AND AUTHOR LIST
#===========================================================================
_publ_section_title
;
Molybdenum(VI) cis-Dioxo Complexes Bearing (poly)-Pyrazolyl Methane and
(poly)-Pyrazolyl Borate Ligands: Syntheses, Characterization and Catalytic
Applications
;
# The loop structure below should contain the names and adresses of all
# authors, in the required order of publication. Repeat as necessary.
loop_
_publ_author_name
_publ_author_address
'Santos, A. M.'
;
Anorganisch-chemisches Institut der
Technischen Universit\"at M\"unchen
Lichtenbergstrasse 4
D-85747 Garching bei M\"unchen
;
'K\"uhn, F. E.'
;
Anorganisch-chemisches Institut der
Technischen Universit\"at M\"unchen
Lichtenbergstrasse 4
D-85747 Garching bei M\"unchen
;
'Lucas, I.'
;
Instituto de Tecnologia Quimica e Biologica
da Universidade Nova de Lisboa,
Quinta do Marques, EAN, Apt 127,
2781-901 Oeiras
Portugal
;
'Rom\"ao, C. C.'
;
Instituto de Tecnologia Quimica e Biologica
da Universidade Nova de Lisboa,
Quinta do Marques, EAN, Apt 127,
2781-901 Oeiras
Portugal
;
'Herdtweck, E.'
;
Anorganisch-chemisches Institut der
Technischen Universit\"at M\"unchen
Lichtenbergstrasse 4
D-85747 Garching bei M\"unchen
;
#===========================================================================
# 4. TEXT
#===========================================================================
_publ_section_abstract
;
Reaction of MoOCl2(THF)2 with mono- and bidentate nitrogen donor ligands of the pyrazole type leads to octahedral complexes of the formula MoO2Cl2L2. One of these compounds has been examined by X-ray crystallography. Reaction of MoO2X2(THF)2 (X == Cl, Br) with tridentate ligands, e. g. trispyrazolylmethane or trispyrazolyborate leads to the replacement of both coordinated solvent molecules and one of the chlorine ligands. Depending on the donor ability and the steric bulk of the ligand rapid ligand rotation is observed at room temperature in some cases. At lower temperatures the structures are more rigid. 95Mo-NMR spectroscopy proves to be a straightforward mean to distinguish between the different ligand environment of the Mo(VI) centre. The turnover frequencies of the described complexes in olefin epoxidation with t-butyl hydroperoxide as oxidizing agent are in the range of 200 - 400 1/h. This relatively low activity is compensated by the ease of handling and the stability of the complexes.
;
# Insert blank lines between paragraphs
_publ_section_comment
;
none
;
_publ_section_experimental
;
none
;
# Insert blank lines between references
_publ_section_references
;
Allen, F.H., Kennard, O. & Taylor, R. (1983).
Acc. Chem. Res. 16, 146-153.
Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A.
(1993) J. Appl. Cryst. 26, 343-350.
Sheldrick, G.M. SHELXL97. Program for crystal structure
refinement. University of G\"ottingen, Germany, 1997.
Spek, A.L. (1997). HELENA, Program for Datareduction, Utrecht
University, The Netherlands.
Wilson, A.J.C. (1992) Ed. International Tables for Crystallography,
Volume C, Kluwer Academic Publishers, Dordrecht, The Netherlands.
;
_publ_section_figure_captions
;
none
;
_publ_section_acknowledgements
;
none
;
_publ_section_table_legends
;
none
;
#===========================================================================
data_ANAE-4073-173
_database_code_CSD 154166
#===========================================================================
# 5. CHEMICAL DATA
#===========================================================================
_chemical_name_systematic
;
?
;
_chemical_name_common ?
_chemical_formula_moiety 'C9 H12 Cl2 Mo N4 O2'
_chemical_formula_structural ?
_chemical_formula_analytical ?
_chemical_formula_sum 'C9 H12 Cl2 Mo N4 O2'
_chemical_formula_weight 375.07
_chemical_compound_source 'see text'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
O O 0.0106 0.0060
'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'
Mo Mo -1.6832 0.6857
'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'
H H 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
#===========================================================================
# 6. CRYSTAL DATA
#===========================================================================
_symmetry_cell_setting Orthorhombic
_symmetry_space_group_name_Hall '-P 2ac 2ab'
_symmetry_space_group_name_H-M 'P b c a'
loop_
_symmetry_equiv_pos_as_xyz
x,y,z
1/2-x,-y,1/2+z
1/2+x,1/2-y,-z
-x,1/2+y,1/2-z
-x,-y,-z
1/2+x,y,1/2-z
1/2-x,1/2+y,z
x,1/2-y,1/2+z
_cell_length_a 12.0163(2)
_cell_length_b 15.8867(4)
_cell_length_c 14.4079(3)
_cell_angle_alpha 90
_cell_angle_beta 90
_cell_angle_gamma 90
_cell_volume 2750.5(1)
_cell_formula_units_Z 8
_cell_measurement_temperature 173(1)
_cell_measurement_reflns_used 42799
_cell_measurement_theta_min 1.00
_cell_measurement_theta_max 25.35
_exptl_crystal_description 'prism'
_exptl_crystal_colour 'colorless'
_exptl_crystal_size_max 0.38
_exptl_crystal_size_mid 0.30
_exptl_crystal_size_min 0.23
_exptl_crystal_density_meas none
_exptl_crystal_density_diffrn 1.812
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000 1488
_exptl_absorpt_coefficient_mu 1.341
_exptl_absorpt_correction_type 'empirical'
_exptl_absorpt_correction_T_min 0.625
_exptl_absorpt_correction_T_max 0.735
_exptl_special_details
;
Diffractometer operator E. Herdtweck
scanspeed 2x10 s per film
repetition 1
425 films measured in 6 data sets with delta_phi=1 and with delta_omega=1
;
_exptl_absorpt_process_details
;
Denzo-SNM; Scale-Pack
;
_publ_section_exptl_prep
;
The crystal was fixed in a capillary with perfluorinated ether and transfered
to the diffractometer.
;
_publ_section_exptl_refinement
;
Straight forward.
Hydrogen atoms could be located in the difference Fourier maps and refined
freely.
;
#===========================================================================
# 7. EXPERIMENTAL DATA
#===========================================================================
_diffrn_ambient_temperature 173(1)
_diffrn_radiation_wavelength 0.71073
_diffrn_radiation_type 'Mo K\a'
_diffrn_radiation_source 'NONIUS FR 591 rotating anode'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device 'four-circle diffractometer'
_diffrn_measurement_device_type 'Kappa CCD (Nonius)'
_diffrn_measurement_method ' phi- and omega-rotation '
_diffrn_detector 'CCD plate'
_diffrn_detector_area_resol_mean 18 # 9 for binned mode
_diffrn_standards_number none
_diffrn_standards_interval_count none
_diffrn_standards_interval_time none
_diffrn_standards_decay_% 0
# number of measured reflections (redundant set)
_diffrn_reflns_number 24230
_diffrn_reflns_av_R_equivalents 0.039
_diffrn_reflns_av_sigmaI/netI 0.0195
_diffrn_reflns_limit_h_min -14
_diffrn_reflns_limit_h_max 14
_diffrn_reflns_limit_k_min -19
_diffrn_reflns_limit_k_max 19
_diffrn_reflns_limit_l_min -17
_diffrn_reflns_limit_l_max 17
_diffrn_reflns_theta_min 2.55
_diffrn_reflns_theta_max 25.40
_reflns_number_total 2519
_reflns_number_gt 2275
_reflns_threshold_expression >2sigma(I)
_diffrn_reflns_reduction_process
;
with the Kappa CCD software Scale-Pack
;
_computing_data_collection 'Kappa CCD (Nonius)'
_computing_cell_refinement 'Denzo and HKL'
_computing_data_reduction 'Denzo and HKL'
_computing_structure_solution 'SHELXS-86 (Sheldrick, 1987)'
_computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics 'PLATON (Spek, 1999)'
_computing_publication_material 'PLATON (Spek, 1999)'
#===========================================================================
# 8. REFINEMENT DATA
#===========================================================================
_refine_special_details
;
Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^
or flagged by the user for potential systematic errors. Weighted R-factors
wR and all goodnesses 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 observed criterion
of F^2^ > 2sigma(F^2^) is used only for calculating R_factor_obs 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 sigma
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0245P)^2^+2.8893P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens difmap
_refine_ls_hydrogen_treatment refall
_refine_ls_extinction_method none
_refine_ls_extinction_coef ?
_refine_ls_number_reflns 2519
_refine_ls_number_parameters 211
_refine_ls_number_restraints 0
_refine_ls_R_factor_all 0.0277
_refine_ls_R_factor_gt 0.0243
_refine_ls_wR_factor_ref 0.0602
_refine_ls_wR_factor_gt 0.0585
_refine_ls_goodness_of_fit_ref 1.108
_refine_ls_restrained_S_all 1.108
_refine_ls_shift/su_max 0.001
_refine_ls_shift/su_mean 0.000
_diffrn_measured_fraction_theta_max 0.993
_diffrn_reflns_theta_full 25.40
_diffrn_measured_fraction_theta_full 0.993
_refine_diff_density_max 0.466
_refine_diff_density_min -0.521
_refine_diff_density_rms 0.065
#===========================================================================
# 9. ATOMIC COORDINATES AND THERMAL PARAMETERS
#===========================================================================
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_thermal_displace_type
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_U_iso_or_equiv
Mo Mo Uani 0.19840(2) -0.38007(1) 0.35760(1) 1.000 0.0221(1)
Cl1 Cl Uani 0.20586(6) -0.23189(4) 0.35236(5) 1.000 0.0364(2)
Cl2 Cl Uani 0.22284(5) -0.52366(3) 0.40211(4) 1.000 0.0298(2)
O1 O Uani 0.25308(16) -0.39546(11) 0.25065(12) 1.000 0.0356(6)
O2 O Uani 0.05917(15) -0.38619(11) 0.34269(12) 1.000 0.0334(6)
N11 N Uani 0.41382(15) -0.37239(12) 0.50679(14) 1.000 0.0254(6)
N12 N Uani 0.37488(15) -0.36786(12) 0.41817(13) 1.000 0.0245(6)
N21 N Uani 0.23917(15) -0.38306(11) 0.58616(13) 1.000 0.0210(6)
N22 N Uani 0.16443(15) -0.36967(11) 0.51603(13) 1.000 0.0214(6)
C1 C Uani 0.34824(18) -0.34080(15) 0.58669(16) 1.000 0.0254(7)
C2 C Uani 0.4091(2) -0.3634(2) 0.6758(2) 1.000 0.0392(10)
C3 C Uani 0.3321(2) -0.24645(17) 0.5787(2) 1.000 0.0353(8)
C13 C Uani 0.4627(2) -0.38369(17) 0.36362(19) 1.000 0.0347(9)
C14 C Uani 0.5573(2) -0.3977(2) 0.4159(2) 1.000 0.0428(10)
C15 C Uani 0.5240(2) -0.38932(19) 0.5061(2) 1.000 0.0413(9)
C23 C Uani 0.0686(2) -0.40203(15) 0.54717(18) 1.000 0.0274(7)
C24 C Uani 0.0806(2) -0.43458(17) 0.63480(18) 1.000 0.0331(8)
C25 C Uani 0.1885(2) -0.42161(16) 0.65845(18) 1.000 0.0293(8)
H21 H Uiso 0.423(2) -0.423(2) 0.679(2) 1.000 0.042(8)
H22 H Uiso 0.367(2) -0.3430(18) 0.726(2) 1.000 0.044(8)
H23 H Uiso 0.474(3) -0.3364(18) 0.677(2) 1.000 0.041(8)
H31 H Uiso 0.405(3) -0.2202(19) 0.580(2) 1.000 0.050(9)
H32 H Uiso 0.290(2) -0.2269(18) 0.631(2) 1.000 0.038(8)
H33 H Uiso 0.297(2) -0.2308(18) 0.524(2) 1.000 0.036(8)
H131 H Uiso 0.455(2) -0.3863(16) 0.302(2) 1.000 0.037(8)
H141 H Uiso 0.628(3) -0.410(2) 0.398(2) 1.000 0.055(9)
H151 H Uiso 0.565(3) -0.3930(18) 0.559(2) 1.000 0.048(9)
H231 H Uiso 0.009(2) -0.4005(14) 0.5085(18) 1.000 0.022(6)
H241 H Uiso 0.031(2) -0.4589(18) 0.667(2) 1.000 0.043(8)
H251 H Uiso 0.228(2) -0.4330(17) 0.712(2) 1.000 0.036(7)
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
Mo 0.0282(1) 0.0218(1) 0.0164(1) 0.0005(1) -0.0026(1) 0.0015(1)
Cl1 0.0516(4) 0.0208(3) 0.0367(4) 0.0056(2) 0.0044(3) 0.0032(2)
Cl2 0.0371(3) 0.0204(3) 0.0320(3) -0.0003(2) -0.0030(2) 0.0026(2)
O1 0.0498(11) 0.0366(9) 0.0205(9) -0.0006(8) 0.0017(8) 0.0058(8)
O2 0.0327(10) 0.0371(10) 0.0305(10) 0.0040(7) -0.0113(8) 0.0010(7)
N11 0.0191(9) 0.0362(11) 0.0209(10) -0.0068(8) 0.0020(8) -0.0023(8)
N12 0.0238(10) 0.0326(10) 0.0172(10) -0.0028(8) 0.0021(8) -0.0026(8)
N21 0.0213(9) 0.0263(10) 0.0153(10) -0.0011(7) 0.0013(7) -0.0013(8)
N22 0.0197(9) 0.0267(10) 0.0177(10) -0.0001(8) -0.0011(7) -0.0002(8)
C1 0.0199(11) 0.0349(13) 0.0213(12) -0.0079(10) 0.0016(9) -0.0046(10)
C2 0.0277(14) 0.063(2) 0.0270(15) -0.0080(14) -0.0043(12) -0.0028(14)
C3 0.0386(14) 0.0332(14) 0.0342(15) -0.0124(12) 0.0060(13) -0.0107(12)
C13 0.0366(15) 0.0400(15) 0.0274(15) -0.0073(12) 0.0137(11) -0.0062(11)
C14 0.0204(13) 0.0611(18) 0.0468(18) -0.0176(14) 0.0095(12) -0.0041(12)
C15 0.0223(13) 0.0598(18) 0.0419(17) -0.0136(14) -0.0016(12) 0.0010(12)
C23 0.0207(11) 0.0328(13) 0.0287(13) -0.0035(10) 0.0021(10) -0.0012(10)
C24 0.0334(14) 0.0377(14) 0.0281(14) 0.0008(11) 0.0092(11) -0.0108(12)
C25 0.0369(14) 0.0313(13) 0.0196(13) 0.0026(10) 0.0009(10) -0.0030(10)
#===========================================================================
# 10. MOLECULAR GEOMETRY
#===========================================================================
_geom_special_details
;
Bond distances, angles etc. have been calculated using the
rounded fractional coordinates. All esds are estimated
from the variances of the (full) variance-covariance matrix.
The cell esds are taken into account in the estimation of
distances, angles and torsion angles
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_1
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Mo Cl1 2.3570(7) . . yes
Mo Cl2 2.3877(5) . . yes
Mo O1 1.6929(18) . . yes
Mo O2 1.6896(18) . . yes
Mo N12 2.3014(18) . . yes
Mo N22 2.3247(19) . . yes
N11 N12 1.362(3) . . yes
N11 C1 1.483(3) . . yes
N11 C15 1.351(3) . . yes
N12 C13 1.340(3) . . yes
N21 N22 1.368(3) . . yes
N21 C1 1.473(3) . . yes
N21 C25 1.353(3) . . yes
N22 C23 1.339(3) . . yes
C1 C2 1.521(4) . . no
C1 C3 1.516(4) . . no
C13 C14 1.382(4) . . no
C14 C15 1.366(4) . . no
C23 C24 1.372(4) . . no
C24 C25 1.356(3) . . no
C2 H21 0.96(3) . . no
C2 H22 0.94(3) . . no
C2 H23 0.89(3) . . no
C3 H31 0.97(4) . . no
C3 H32 0.96(3) . . no
C3 H33 0.93(3) . . no
C13 H131 0.89(3) . . no
C14 H141 0.91(4) . . no
C15 H151 0.91(3) . . no
C23 H231 0.91(2) . . no
C24 H241 0.85(3) . . no
C25 H251 0.92(3) . . no
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_2
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
Cl1 Mo Cl2 163.36(2) . . . yes
Cl1 Mo O1 95.76(6) . . . yes
Cl1 Mo O2 95.22(6) . . . yes
Cl1 Mo N12 83.85(5) . . . yes
Cl1 Mo N22 88.12(5) . . . yes
Cl2 Mo O1 93.37(6) . . . yes
Cl2 Mo O2 95.80(6) . . . yes
Cl2 Mo N12 82.26(5) . . . yes
Cl2 Mo N22 79.97(5) . . . yes
O1 Mo O2 105.09(9) . . . yes
O1 Mo N12 89.98(8) . . . yes
O1 Mo N22 166.45(8) . . . yes
O2 Mo N12 164.91(8) . . . yes
O2 Mo N22 87.42(7) . . . yes
N12 Mo N22 77.50(6) . . . yes
N12 N11 C1 121.84(17) . . . yes
N12 N11 C15 109.9(2) . . . yes
C1 N11 C15 126.4(2) . . . yes
Mo N12 N11 131.89(14) . . . yes
Mo N12 C13 119.18(16) . . . yes
N11 N12 C13 105.63(18) . . . yes
N22 N21 C1 121.13(17) . . . yes
N22 N21 C25 110.09(18) . . . yes
C1 N21 C25 127.08(19) . . . yes
Mo N22 N21 126.78(13) . . . yes
Mo N22 C23 116.93(15) . . . yes
N21 N22 C23 104.92(18) . . . yes
N11 C1 N21 108.34(18) . . . yes
N11 C1 C2 108.67(19) . . . yes
N11 C1 C3 110.11(19) . . . yes
N21 C1 C2 108.95(19) . . . yes
N21 C1 C3 109.67(18) . . . yes
C2 C1 C3 111.0(2) . . . no
N12 C13 C14 111.0(2) . . . yes
C13 C14 C15 105.2(2) . . . no
N11 C15 C14 108.3(2) . . . yes
N22 C23 C24 111.3(2) . . . yes
C23 C24 C25 105.9(2) . . . no
N21 C25 C24 107.8(2) . . . yes
C1 C2 H21 110.9(17) . . . no
C1 C2 H22 108.0(16) . . . no
C1 C2 H23 108.9(19) . . . no
H21 C2 H22 113(2) . . . no
H21 C2 H23 109(2) . . . no
H22 C2 H23 107(2) . . . no
C1 C3 H31 107.9(19) . . . no
C1 C3 H32 109.1(17) . . . no
C1 C3 H33 112.8(18) . . . no
H31 C3 H32 109(2) . . . no
H31 C3 H33 108(2) . . . no
H32 C3 H33 110(2) . . . no
N12 C13 H131 120.7(16) . . . no
C14 C13 H131 128.3(16) . . . no
C13 C14 H141 130.5(19) . . . no
C15 C14 H141 124.4(19) . . . no
N11 C15 H151 123(2) . . . no
C14 C15 H151 129(2) . . . no
N22 C23 H231 117.6(16) . . . no
C24 C23 H231 131.1(16) . . . no
C23 C24 H241 126.9(18) . . . no
C25 C24 H241 127.1(18) . . . no
N21 C25 H251 120.0(16) . . . no
C24 C25 H251 132.2(16) . . . no
# End of Crystallographic Information File
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