Volatile Hexavalent Oxo-amidinate Complexes: Molybdenum and Tungsten Precursors for Atomic Layer Deposition
Mouat, Aidan R.; Mane, Anil U.; Elam, Jeffrey W.; Delferro, Massimiliano; Marks, Tobin J.; Stair, Peter C.; Chemistry of Materials 28 (2016) 1907–; doi:10.1021/acs.chemmater.6b00248

data_4003229
_publ_section_title
;
 Volatile Hexavalent Oxo-amidinate Complexes: Molybdenum and Tungsten
 Precursors for Atomic Layer Deposition
;
_journal_issue                   6
_journal_name_full               'Chemistry of Materials'
_journal_page_first              1907
_journal_paper_doi               10.1021/acs.chemmater.6b00248
_journal_volume                  28
_journal_year                    2016
_chemical_formula_moiety         'C20 H42 N4 O2 W'
_chemical_formula_sum            'C20 H42 N4 O2 W'
_chemical_formula_weight         554.42
_chemical_name_systematic        WO2(tBuNC(Me)CtBu)2
_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
_audit_creation_date             2015-07-20
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.14(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.122(2)
_cell_length_b                   16.708(3)
_cell_length_c                   14.856(3)
_cell_measurement_reflns_used    5145
_cell_measurement_temperature    100
_cell_measurement_theta_max      68.288
_cell_measurement_theta_min      4.099
_cell_volume                     2387.6(9)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0297
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            4331
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.357
_diffrn_reflns_theta_min         1.888
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.858
_exptl_absorpt_correction_T_max  0.753048
_exptl_absorpt_correction_T_min  0.472891
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1036 before and 0.0451 after correction.
 The Ratio of minimum to maximum transmission not present.
 The \l/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.1398 before and 0.0543 after correction.
 The Ratio of minimum to maximum transmission is 0.62.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 36196 reflections, Rint = 0.0548
 (28734 with I > 3sig(I), Rint = 0.0540)
;
_exptl_crystal_colour            'dull dark red'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.542
_exptl_crystal_description       needle
_exptl_crystal_F_000             1120
_exptl_crystal_preparation
;
The compound was prepared by reaction of WO2Cl2(dme) 
with two equivalents of Li(tBuNC(Me)NtBu)*OEt2.
;
_exptl_crystal_recrystallization_method
;
The compound was crystallized from a concentrated 
pentane solution at -30 C.
;
_exptl_crystal_size_max          0.601
_exptl_crystal_size_mid          0.124
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.905
_refine_diff_density_min         -0.951
_refine_diff_density_rms         0.204
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     313
_refine_ls_number_reflns         4331
_refine_ls_number_restraints     291
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0359
_refine_ls_R_factor_gt           0.0338
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0808P)^2^+1.6654P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1079
_refine_ls_wR_factor_ref         0.1105
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4031
_reflns_number_total             4331
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm6b00248_si_003.cif
_cod_data_source_block           3am074_a
_cod_database_code               4003229
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.40(2) 0.274(9) 0.33(2)
2. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(1)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(1)
 Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C18A)=Sof(H18D)=Sof(H18E)=
 Sof(H18F)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(2)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(2)
 Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(3)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(3)
5.a Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,
 H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,
 H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C16A(H16D,H16E,H16F), C19A(H19D,H19E,
 H19F), C15A(H15D,H15E,H15F), C18A(H18D,H18E,H18F), C20A(H20D,H20E,H20F)
;
_shelx_res_checksum              77827
_shelx_hkl_checksum              6885
_shelx_shelxl_version_number     2014/7
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'
_olex2_date_sample_completion    2014-04-22
_olex2_date_sample_data_collection 2014-04-21
_olex2_date_sample_submission    2014-04-21
_olex2_exptl_crystal_mounting_method
;
The compound was mounted under air-free conditions 
in Paratone-N on a brass tip.
;
_olex2_submission_original_sample_id WO2(tBuAMD)2
_olex2_submission_special_instructions 'No special instructions were received'