Synthesis, Characterization, X-ray and Electronic Structures of Diethyl Ether and 1,2-Dimethoxyethane Adducts of Molybdenum(IV) Chloride and Tungsten(IV) Chloride
Shaw, Thomas E.; Diethrich, Timothy J. J.; Stern, Charlotte L.; Scott, Brian; Jurca, Titel; Gilbert, Thomas M.; Sattelberger, Alfred P.; Dalton Transactions  (2022) –; doi:10.1039/D2DT00787H

data_7710168
_publ_section_title
;
 Synthesis, Characterization, X-ray and Electronic Structures of Diethyl
 Ether and 1,2-Dimethoxyethane Adducts of Molybdenum(IV) Chloride and
 Tungsten(IV) Chloride
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00787H
_journal_year                    2022
_chemical_formula_moiety         'C8 H20 Cl4 Mo O2'
_chemical_formula_sum            'C8 H20 Cl4 Mo O2'
_chemical_formula_weight         385.98
_chemical_name_systematic        'Tetrachlorobis(diethyl ether)molybdenum(IV)'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Heat-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-27
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-02-09 deposited with the CCDC.	2022-04-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.347(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.5956(2)
_cell_length_b                   11.4732(4)
_cell_length_c                   9.0193(3)
_cell_measurement_reflns_used    4082
_cell_measurement_temperature    298.1(5)
_cell_measurement_theta_max      30.3800
_cell_measurement_theta_min      2.9410
_cell_volume                     754.22(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      298.1(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.963
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -74.00  -9.00   0.50    5.00    --   20.00  54.00 150.00  130
  2  \w     14.00  40.00   0.50    5.00    --   20.00  54.00 150.00   52
  3  \w    -25.00  31.00   0.50    5.00    --   20.00  54.00-150.00  112
  4  \w    -74.00  76.00   0.50    5.00    --   20.00  54.00 -60.00  300
  5  \w     -1.00  48.00   0.50    5.00    --   20.00  54.00-120.00   98
  6  \w     55.00  81.00   0.50    5.00    --   20.00  54.00-120.00   52
  7  \w    -46.00  53.00   0.50    5.00    --   20.00  54.00  60.00  198
  8  \w     48.00  73.00   0.50    5.00    --   20.00  54.00-180.00   50
  9  \w     28.00  54.00   0.50    5.00    --   20.00  54.00 -90.00   52
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini II'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0948812000
_diffrn_orient_matrix_UB_12      -0.0072611000
_diffrn_orient_matrix_UB_13      0.0074650000
_diffrn_orient_matrix_UB_21      0.0203771000
_diffrn_orient_matrix_UB_22      0.0481687000
_diffrn_orient_matrix_UB_23      0.0512072000
_diffrn_orient_matrix_UB_31      0.0077147000
_diffrn_orient_matrix_UB_32      -0.0380284000
_diffrn_orient_matrix_UB_33      0.0635407000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0199
_diffrn_reflns_av_unetI/netI     0.0218
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            6900
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.612
_diffrn_reflns_theta_min         2.948
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.560
_exptl_absorpt_correction_T_max  0.944
_exptl_absorpt_correction_T_min  0.869
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.700
_exptl_crystal_description       trapezoid
_exptl_crystal_F_000             388
_exptl_crystal_preparation
'Molybdenum pentachloride was dissolved in diethyl ether and cooled to -35 C. After cooling for approximately 10 minutes, allyltrimethylsilane was added to the solution which was then allowed to stir for 2 hours, during which the product precipitated as a red-orange powder.'
_exptl_crystal_recrystallization_method
'The red-orange powder from the synthetic step was dissolved in a minimal amount of toluene and allowed to sit, unperturbed, in the glovebox freezer at -35 C overnight.'
_exptl_crystal_size_max          0.431
_exptl_crystal_size_mid          0.287
_exptl_crystal_size_min          0.147
_refine_diff_density_max         0.440
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.057
_refine_ls_extinction_coef       0.0173(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     73
_refine_ls_number_reflns         2234
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0272
_refine_ls_R_factor_gt           0.0212
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0209P)^2^+0.1730P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0494
_refine_ls_wR_factor_ref         0.0516
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1935
_reflns_number_total             2234
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00787h2.cif
_cod_data_source_block           exp_235
_cod_database_code               7710168
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Mo C Cl O'
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C1(H1A,H1B)
2.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C)
;
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on the diffractometer using a MiteGen mount. '
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.183
_oxdiff_exptl_absorpt_empirical_full_min 0.863