# 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
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Guido Pampaloni'
_publ_contact_author_email       PAMPA@DCCI.UNIPI.IT

_publ_section_title              
;
From 1,2-Dialkoxyalkanes to 1,4-Dioxanes. A
Transformation Mediated by NbCl5 via Multiple C-O Bond Cleavage at Room
Temperature
;
loop_
_publ_author_name
'Guido Pampaloni'
'Fabio Marchetti'
'Stefano Zacchini'

# Attachment 'Nbocl3dme.CIF'

data_pbca
_database_code_depnum_ccdc_archive 'CCDC 679568'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            trichloro(1,2dimethoxyethane)oxoniobium(V)
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C4 H10 Cl3 Nb O3'
_chemical_formula_weight         305.38

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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Nb Nb -2.0727 0.6215 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   Pbca

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

_cell_length_a                   7.3270(7)
_cell_length_b                   11.9741(11)
_cell_length_c                   23.187(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2034.2(3)
_cell_formula_units_Z            8
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    3394
_cell_measurement_theta_min      3.289
_cell_measurement_theta_max      28.127

_exptl_crystal_description       prism
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.11
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.994
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1200
_exptl_absorpt_coefficient_mu    1.932
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.7474
_exptl_absorpt_correction_T_max  0.8155
_exptl_absorpt_process_details   
;
G. M. Sheldrick, SADABS, Universitat
Gottingen, Gottingen, Germany
;

_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_%        ?
_diffrn_reflns_number            10475
_diffrn_reflns_av_R_equivalents  0.0323
_diffrn_reflns_av_sigmaI/netI    0.0266
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_theta_min         3.29
_diffrn_reflns_theta_max         26.97
_reflns_number_total             2150
_reflns_number_gt                1784
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_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^)+(0.0274P)^2^+0.3857P] 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_number_reflns         2150
_refine_ls_number_parameters     102
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0338
_refine_ls_R_factor_gt           0.0239
_refine_ls_wR_factor_ref         0.0562
_refine_ls_wR_factor_gt          0.0526
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_restrained_S_all      1.042
_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
C1 C 0.9000(4) 0.8452(2) 0.29940(10) 0.0260(6) Uani 1 1 d . . .
H1A H 0.8762 0.8124 0.2614 0.039 Uiso 1 1 calc R . .
H1B H 1.0285 0.8674 0.3019 0.039 Uiso 1 1 calc R . .
H1C H 0.8221 0.9109 0.3048 0.039 Uiso 1 1 calc R . .
C2 C 0.6670(4) 0.7316(2) 0.34401(11) 0.0224(6) Uani 1 1 d . . .
H2A H 0.6373 0.6888 0.3087 0.027 Uiso 1 1 calc R . .
H2B H 0.5891 0.7992 0.3451 0.027 Uiso 1 1 calc R . .
C3 C 0.6354(4) 0.6616(2) 0.39645(11) 0.0250(6) Uani 1 1 d . . .
H3A H 0.6515 0.7070 0.4318 0.030 Uiso 1 1 calc R . .
H3B H 0.5098 0.6311 0.3962 0.030 Uiso 1 1 calc R . .
C4 C 0.7414(5) 0.4966(2) 0.44358(11) 0.0326(7) Uani 1 1 d . . .
H4A H 0.7500 0.5387 0.4797 0.049 Uiso 1 1 calc R . .
H4B H 0.8360 0.4388 0.4428 0.049 Uiso 1 1 calc R . .
H4C H 0.6209 0.4615 0.4409 0.049 Uiso 1 1 calc R . .
Cl2 Cl 1.06147(10) 0.70864(6) 0.45859(3) 0.02847(17) Uani 1 1 d . . .
Cl3 Cl 0.95493(9) 0.55691(6) 0.27534(2) 0.02273(15) Uani 1 1 d . . .
Cl4 Cl 1.20043(10) 0.46628(6) 0.39137(3) 0.02900(17) Uani 1 1 d . . .
Nb1 Nb 1.06010(3) 0.633007(19) 0.364033(9) 0.01766(8) Uani 1 1 d . . .
O1 O 1.2349(3) 0.70922(15) 0.33689(7) 0.0247(4) Uani 1 1 d . . .
O2 O 0.8600(2) 0.76305(14) 0.34413(7) 0.0187(4) Uani 1 1 d . . .
O3 O 0.7669(3) 0.57206(15) 0.39510(7) 0.0217(4) Uani 1 1 d . . .

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
C1 0.0280(17) 0.0233(15) 0.0265(12) 0.0076(11) 0.0012(11) 0.0024(13)
C2 0.0159(15) 0.0236(15) 0.0277(12) -0.0012(10) -0.0014(11) 0.0009(12)
C3 0.0201(15) 0.0282(16) 0.0268(12) 0.0001(11) 0.0025(11) 0.0025(13)
C4 0.0386(19) 0.0333(17) 0.0260(12) 0.0092(11) 0.0033(12) -0.0031(15)
Cl2 0.0370(4) 0.0268(4) 0.0216(3) -0.0030(2) -0.0083(3) -0.0006(3)
Cl3 0.0240(4) 0.0237(4) 0.0204(3) -0.0049(2) 0.0023(2) -0.0025(3)
Cl4 0.0293(4) 0.0199(3) 0.0378(3) 0.0022(3) -0.0049(3) 0.0057(3)
Nb1 0.01665(14) 0.01595(13) 0.02038(11) -0.00066(8) -0.00188(9) 0.00086(10)
O1 0.0202(11) 0.0221(11) 0.0317(9) -0.0011(8) 0.0013(8) -0.0017(9)
O2 0.0175(10) 0.0155(9) 0.0230(8) 0.0020(7) -0.0006(7) 0.0026(8)
O3 0.0225(11) 0.0214(10) 0.0211(8) 0.0023(7) 0.0027(7) -0.0004(8)

_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
C1 O2 1.459(3) . ?
C1 H1A 0.9800 . ?
C1 H1B 0.9800 . ?
C1 H1C 0.9800 . ?
C2 O2 1.463(3) . ?
C2 C3 1.495(3) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C3 O3 1.442(3) . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C4 O3 1.454(3) . ?
C4 H4A 0.9800 . ?
C4 H4B 0.9800 . ?
C4 H4C 0.9800 . ?
Cl2 Nb1 2.3721(6) . ?
Cl3 Nb1 2.3777(6) . ?
Cl4 Nb1 2.3334(7) . ?
Nb1 O1 1.6939(18) . ?
Nb1 O2 2.1879(17) . ?
Nb1 O3 2.3801(18) . ?

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
O2 C1 H1A 109.5 . . ?
O2 C1 H1B 109.5 . . ?
H1A C1 H1B 109.5 . . ?
O2 C1 H1C 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
O2 C2 C3 107.0(2) . . ?
O2 C2 H2A 110.3 . . ?
C3 C2 H2A 110.3 . . ?
O2 C2 H2B 110.3 . . ?
C3 C2 H2B 110.3 . . ?
H2A C2 H2B 108.6 . . ?
O3 C3 C2 107.2(2) . . ?
O3 C3 H3A 110.3 . . ?
C2 C3 H3A 110.3 . . ?
O3 C3 H3B 110.3 . . ?
C2 C3 H3B 110.3 . . ?
H3A C3 H3B 108.5 . . ?
O3 C4 H4A 109.5 . . ?
O3 C4 H4B 109.5 . . ?
H4A C4 H4B 109.5 . . ?
O3 C4 H4C 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?
O1 Nb1 O2 92.57(8) . . ?
O1 Nb1 Cl4 103.22(7) . . ?
O2 Nb1 Cl4 164.05(5) . . ?
O1 Nb1 Cl2 97.73(6) . . ?
O2 Nb1 Cl2 85.76(5) . . ?
Cl4 Nb1 Cl2 94.23(2) . . ?
O1 Nb1 Cl3 97.48(6) . . ?
O2 Nb1 Cl3 82.71(5) . . ?
Cl4 Nb1 Cl3 92.86(2) . . ?
Cl2 Nb1 Cl3 161.28(3) . . ?
O1 Nb1 O3 163.73(8) . . ?
O2 Nb1 O3 71.18(6) . . ?
Cl4 Nb1 O3 93.04(5) . . ?
Cl2 Nb1 O3 80.86(4) . . ?
Cl3 Nb1 O3 81.48(4) . . ?
C1 O2 C2 111.46(19) . . ?
C1 O2 Nb1 119.69(15) . . ?
C2 O2 Nb1 117.71(15) . . ?
C3 O3 C4 111.0(2) . . ?
C3 O3 Nb1 112.45(15) . . ?
C4 O3 Nb1 122.73(17) . . ?

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
O2 C2 C3 O3 -53.7(3) . . . . ?
C3 C2 O2 C1 -171.6(2) . . . . ?
C3 C2 O2 Nb1 44.6(2) . . . . ?
O1 Nb1 O2 C1 22.61(17) . . . . ?
Cl4 Nb1 O2 C1 -149.28(16) . . . . ?
Cl2 Nb1 O2 C1 120.17(17) . . . . ?
Cl3 Nb1 O2 C1 -74.61(16) . . . . ?
O3 Nb1 O2 C1 -158.05(18) . . . . ?
O1 Nb1 O2 C2 163.42(16) . . . . ?
Cl4 Nb1 O2 C2 -8.5(3) . . . . ?
Cl2 Nb1 O2 C2 -99.01(15) . . . . ?
Cl3 Nb1 O2 C2 66.21(15) . . . . ?
O3 Nb1 O2 C2 -17.23(14) . . . . ?
C2 C3 O3 C4 -177.7(2) . . . . ?
C2 C3 O3 Nb1 40.5(2) . . . . ?
O1 Nb1 O3 C3 -11.6(3) . . . . ?
O2 Nb1 O3 C3 -13.89(14) . . . . ?
Cl4 Nb1 O3 C3 168.51(14) . . . . ?
Cl2 Nb1 O3 C3 74.71(14) . . . . ?
Cl3 Nb1 O3 C3 -99.05(14) . . . . ?
O1 Nb1 O3 C4 -148.2(3) . . . . ?
O2 Nb1 O3 C4 -150.53(19) . . . . ?
Cl4 Nb1 O3 C4 31.87(18) . . . . ?
Cl2 Nb1 O3 C4 -61.93(18) . . . . ?
Cl3 Nb1 O3 C4 124.31(18) . . . . ?

_diffrn_measured_fraction_theta_max 0.968
_diffrn_reflns_theta_full        26.97
_diffrn_measured_fraction_theta_full 0.968
_refine_diff_density_max         0.679
_refine_diff_density_min         -0.315
_refine_diff_density_rms         0.081