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_4003230
_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 Mo N4 O2'
_chemical_formula_sum            'C20 H42 Mo N4 O2'
_chemical_formula_weight         466.51
_chemical_name_systematic        (tBuNC(Me)NtBu)2MoO2
_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                 107.80(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.129(2)
_cell_length_b                   16.708(3)
_cell_length_c                   14.870(3)
_cell_measurement_temperature    100
_cell_volume                     2396.1(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 0.985
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0362
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_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            4330
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.351
_diffrn_reflns_theta_max         25.351
_diffrn_reflns_theta_min         1.885
_diffrn_source                   microsource
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.568
_exptl_absorpt_correction_T_max  0.753050
_exptl_absorpt_correction_T_min  0.572957
_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 0.1553 before and 0.0555 after correction.
 The Ratio of minimum to maximum transmission is 0.76.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 40879 reflections, Rint = 0.0429
 (23622 with I > 3sig(I), Rint = 0.0411)
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_description       plate
_exptl_crystal_F_000             992
_exptl_crystal_preparation
;
The compound was prepared by reacting MoO2Cl2(dme) 
with 2 equivalents of Li(tBuNC(Me)NtBu).
;
_exptl_crystal_recrystallization_method
;
The compound was recrystallized from slow evaporation 
of pentane at room temperature.
;
_exptl_crystal_size_max          0.363
_exptl_crystal_size_mid          0.131
_exptl_crystal_size_min          0.124
_refine_diff_density_max         1.038
_refine_diff_density_min         -0.766
_refine_diff_density_rms         0.130
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.107
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     303
_refine_ls_number_reflns         4330
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.127
_refine_ls_R_factor_all          0.0406
_refine_ls_R_factor_gt           0.0397
_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^)+(0.0768P)^2^+2.0098P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1199
_refine_ls_wR_factor_ref         0.1213
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4164
_reflns_number_total             4330
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm6b00248_si_002.cif
_cod_data_source_block           MoO2(tBuAMD)2
_cod_original_cell_volume        2396.0(9)
_cod_database_code               4003230
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9808(12) 0.0192(12)
2. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C3-C6 \\sim C3-C5 \\sim C3-C4
 with sigma of 0.02
 N1-C6 \\sim N1-C5 \\sim N1-C4
 with sigma of 0.02
 C5-C4 \\sim C4-C6 \\sim C5-C6
 with sigma of 0.02
 C7-C8 \\sim C7-C10 \\sim C7-C9
 with sigma of 0.02
 N2-C8 \\sim N2-C10 \\sim N2-C9
 with sigma of 0.02
 C10-C8 \\sim C8-C9 \\sim C10-C9
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C8) = Uanis(C8A)
Uanis(C9) = Uanis(C9A)
Uanis(C10) = Uanis(C10A)
5. Others
 Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=1-FVAR(1)
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=
 Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(1)
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=1-FVAR(2)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(2)
6.a Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), 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), C4A(H4AA,H4AB,H4AC), C5A(H5AA,H5AB,H5AC), C6A(H6AA,H6AB,H6AC),
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C10(H10A,
 H10B,H10C), C9(H9A,H9B,H9C), C9A(H9AA,H9AB,H9AC), C10A(H10D,H10E,H10F),
 C8A(H8AA,H8AB,H8AC)
;
_shelx_res_checksum              57315
_shelx_hkl_checksum              78407
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 1/15/15
_olex2_date_sample_submission    1/15/15
_olex2_exptl_crystal_mounting_method
;
The crystal was mounted in Paratone-N under air-free 
conditions on a brass mount.
;
_olex2_submission_original_sample_id MoO2(tBuAMD)2
_olex2_submission_special_instructions 'No special instructions were received'