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_4003231
_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 O4 W2, C5 H11'
_chemical_formula_sum            'C25 H53 N4 O4 W2'
_chemical_formula_weight         841.41
_chemical_name_systematic        W2O2(u2-O)2(tBuAMD)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             2015-07-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.80(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.760(2)
_cell_length_b                   24.074(5)
_cell_length_c                   12.908(3)
_cell_measurement_temperature    100
_cell_volume                     3312.7(12)
_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 0.944
_diffrn_measured_fraction_theta_max 0.944
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.1137
_diffrn_reflns_Laue_measured_fraction_full 0.944
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            12169
_diffrn_reflns_point_group_measured_fraction_full 0.944
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        25.733
_diffrn_reflns_theta_max         25.733
_diffrn_reflns_theta_min         2.315
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.970
_exptl_absorpt_correction_T_max  0.745263
_exptl_absorpt_correction_T_min  0.485413
_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 0.1281 before and 0.0960 after correction.
 The Ratio of minimum to maximum transmission is 0.67.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 30004 reflections, Rint = 0.1027
 (11314 with I > 3sig(I), Rint = 0.0854)
;
_exptl_crystal_colour            'dull dark green'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.687
_exptl_crystal_description       plate
_exptl_crystal_F_000             1644
_exptl_crystal_preparation
;
The compound was prepared via the reaction of two equivalents 
of Li(tBUAMD) with WO2Cl2(dme) in THF.
;
_exptl_crystal_recrystallization_method
;
The compound was crystallized via vapor diffusion of pentane 
into THF at room temperature.
;
_exptl_crystal_size_max          0.213
_exptl_crystal_size_mid          0.157
_exptl_crystal_size_min          0.102
_refine_diff_density_max         2.291
_refine_diff_density_min         -2.498
_refine_diff_density_rms         0.408
_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     333
_refine_ls_number_reflns         7192
_refine_ls_number_restraints     289
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0987
_refine_ls_R_factor_gt           0.0780
_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^)+(0.0986P)^2^+84.6347P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1952
_refine_ls_wR_factor_ref         0.2111
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5812
_reflns_number_total             7192
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm6b00248_si_004.cif
_cod_data_source_block           3am064_a
_cod_original_cell_volume        3312.8(12)
_cod_database_code               4003231
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9406(11) 0.0594(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.04
5.a Secondary CH2 refined with riding coordinates:
 C3A(H3AA,H3AB), C2A(H2AA,H2AB)
5.b Aromatic/amide H refined with riding coordinates:
 C4A(H4AA)
5.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C13(H13A,H13B,H13C), C4(H4A,H4B,H4C), C12(H12A,H12B,
 H12C), C8(H8A,H8B,H8C), C20(H20A,H20B,H20C), C6(H6A,H6B,H6C), C2(H2A,H2B,H2C),
 C3(H3A,H3B,H3C), C10(H10A,H10B,H10C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C),
  C19(H19A,H19B,H19C), C9(H9A,H9B,H9C), C5A(H5AA,H5AB,H5AC), C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              58082
_shelx_hkl_checksum              90411
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_completion    2014-04-09
_olex2_date_sample_data_collection 2014-04-08
_olex2_date_sample_submission    2014-04-08
_olex2_exptl_crystal_mounting_method
;
The crystal was mounted under air-free conditions in 
Paratone-N on a brass mount.
;
_olex2_submission_original_sample_id WO2(u2-O)2(tBuAMD)2
_olex2_submission_special_instructions 'No special instructions were received'