Synthesis and characterisation of fifteen-electron dihalo(carbonyl)tungsten(iii) complexes, Tp*WX<sub>2</sub>(CO) (X = Br, I).
Thomas, Simon; Gable, Robert W.; Young, Charles G.; Chemical communications (Cambridge, England) 56 (2020) 10349–10352; doi:10.1039/d0cc04607h

data_7126926
_publ_section_title
;
 Synthesis and characterisation of fifteen-electron
 dihalo(carbonyl)tungsten(iii) complexes, Tp*WX<sub>2</sub>(CO) (X = Br,
 I).
;
_journal_issue                   71
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              10349
_journal_page_last               10352
_journal_paper_doi               10.1039/d0cc04607h
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C16 H22 B Br2 N6 O1 W'
_chemical_formula_sum            'C16 H22 B Br2 N6 O W'
_chemical_formula_weight         668.87
_chemical_name_systematic
;
Dibromocarbonyl{hydrotris(3,5-dimethylpyrazol-1-yl)borato)tungsten(III)
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-05-24
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2019-09-16 deposited with the CCDC.	2020-07-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.18(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.123(2)
_cell_length_b                   14.145(2)
_cell_length_c                   18.726(2)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    293(1)
_cell_measurement_theta_max      15.4
_cell_measurement_theta_min      8.5
_cell_volume                     2117.7(7)
_computing_cell_refinement       'CAD-4 Software'
_computing_data_collection       'CAD-4 Software (Enraf-Nonius, 1989)'
_computing_data_reduction        'PROCESS_DATA (Gable et al., 1993)'
_computing_molecular_graphics    'ORTEPII (Johnson, 1976)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293(1)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'Enraf-Nonius CAD-4MachS diffractometer'
_diffrn_measurement_device_type  'Enraf-Nonius CAD-4MachS diffractometer'
_diffrn_measurement_method       \w:2\q
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0362
_diffrn_reflns_av_unetI/netI     0.0397
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -1
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -1
_diffrn_reflns_number            5724
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.492
_diffrn_reflns_theta_min         2.210
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_decay_%        0
_diffrn_standards_interval_time  160
_diffrn_standards_number         3
_exptl_absorpt_coefficient_mu    9.247
_exptl_absorpt_correction_T_max  0.2527
_exptl_absorpt_correction_T_min  0.1236
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   'SHELX76 (Sheldrick, 1976)'
_exptl_crystal_colour            'dark brown'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    2.098
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    none
_exptl_crystal_description       plate
_exptl_crystal_F_000             1268
_exptl_crystal_recrystallization_method
'were obtained by slow evaporation from dichloromethane/Hexane'
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.18
_refine_diff_density_max         3.415
_refine_diff_density_min         -4.116
_refine_ls_extinction_coef       0.0014(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     299
_refine_ls_number_reflns         4863
_refine_ls_number_restraints     46
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0884
_refine_ls_R_factor_gt           0.0671
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1100P)^2^+8.6248P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1699
_refine_ls_wR_factor_ref         0.1826
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3743
_reflns_number_total             4863
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc04607h1.cif
_cod_data_source_block           cy_3
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_crystal_density_meas' value 'Not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

 Adding full bibliography for 7126926--7126927.cif.
;
_cod_database_code               7126926
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 W-C1 = W-C1A = W-C1B
 1.9 with sigma of 0.01
 C1-O1 = C1A-O1A = C1B-O1B
 1.16 with sigma of 0.01
 W-O1 = W-O1A = W-O1B
 3.06 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(O1B) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(O1)
\\sim Ueq, Uanis(O1A) \\sim Ueq, Uanis(C1A) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
4. Others
 1*[Sof(Br2)+Sof(C1B)+Sof(O1B)]+1*[Sof(Br1)+Sof(C1A)+Sof(O1A)]+1*[Sof(C1)+
 Sof(O1)+Sof(Br3)]=1.999 with esd of 0.001
 Sof(C1B)=Sof(O1B)=1-FVAR(1)
 Sof(Br2)=FVAR(1)
 Sof(C1A)=Sof(O1A)=1-FVAR(2)
 Sof(Br1)=FVAR(2)
 Sof(C1)=Sof(O1)=1-FVAR(3)
 Sof(Br3)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 B(H)
5.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C23(H23), C33(H33)
5.c Idealised Me refined as rotating group:
 C11(H11a,H11b,H11c), C15(H15a,H15b,H15c), C21(H21a,H21b,H21c), C25(H25a,H25b,
 H25c), C31(H31a,H31b,H31c), C35(H35a,H35b,H35c)
;
_shelx_res_checksum              56092
_shelx_hkl_checksum              98998
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method mounted
_olex2_submission_special_instructions 'No special instructions were received'
_rwg_local_checkcif_report
;
PLAT972_ALERT_2_A Check Calcd Residual Density 0.92A From W -4.27 eA-3 
PLAT971_ALERT_2_B Check Calcd Residual Density 0.93A From W 3.39 eA-3 
PLAT971_ALERT_2_B Check Calcd Residual Density 1.00A From W 3.24 eA-3 
PLAT971_ALERT_2_B Check Calcd Residual Density 0.87A From W 3.11 eA-3 
PLAT971_ALERT_2_B Check Calcd Residual Density 0.99A From W 3.06 eA-3 
PLAT971_ALERT_2_B Check Calcd Residual Density 0.91A From W 2.88 eA-3 
PLAT971_ALERT_2_B Check Calcd Residual Density 0.79A From W 2.85 eA-3 
PLAT972_ALERT_2_B Check Calcd Residual Density 0.83A From W -2.92 eA-3 
PLAT972_ALERT_2_B Check Calcd Residual Density 0.86A From W -2.79 eA-3 

  The crystal was disordered, attempts to model this disorder were not
 successful

PLAT220_ALERT_2_C Non-Solvent Resd 1 C Ueq(max)/Ueq(min) Range 4.4 Ratio 

  The disordered CO molecules had higher ADP than the other molecules

PLAT234_ALERT_4_C Large Hirshfeld Difference W --C1A .. 0.21 Ang. 
PLAT234_ALERT_4_C Large Hirshfeld Difference C13 --C14 .. 0.18 Ang. 

  These atome were correctly assigned, these atoms were affected by the
 disorder

PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds ............... 0.01892 Ang. 

  Partly disorder, partly due the presence of W & Br atoms

PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 6.127 Check 

  This occurs with the weaker reflections, these were measured with pre-scan

PLAT972_ALERT_2_C Check Calcd Residual Density 0.94A From W -1.84 eA-3 

   See PLAT971_ALERT_2_B above

PLAT977_ALERT_2_C Check the Negative Difference Density on H25C -0.32 eA-3 

  The crystal was disordered, attempts to model this disorder were not
 successful

PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density 0 Note 

The crystal was disordered

PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 7 Note 

  Due the disorder, the CO molecules were restrained to geometrical estimates

PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ... 6 Report 

  Due the disorder, the ADPs of the CO molecules were restrained to near
isotropic values

PLAT072_ALERT_2_G SHELXL First Parameter in WGHT Unusually Large 0.11 Report 
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large 8.62 Why ? 

   This is due to the crystal being disordered, 

PLAT153_ALERT_1_G The s.u. values on the Cell Axes are Equal (Note) 0.002 Ang. 

   Correct, after rounding off

PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records 3 Report 
PLAT186_ALERT_4_G The CIF-Embedded .res File Contains ISOR Records 1 Report 

   See PLAT002_ALERT_2_G & PLAT003_ALERT_2_G  above

PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K) 293 Check 
PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature   ..... (K) 293 Check 

   Correct

PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) W --Br2 .. 5.8 s.u. 

   These atoms were correctly assigned, due to disorder

PLAT301_ALERT_3_G Main Residue Disorder ............ Percentage = 15 Note 

  The Br & CO molecules were disordered over the three positions

PLAT860_ALERT_3_G Number of Least-Squares Restraints ............. 46 Note 

   See PLAT002_ALERT_2_G and PLAT003_ALERT_2_G above
 
PLAT910_ALERT_3_G Missing No, of FCF Reflection(s) Below Theta(Min) 1 Note 

   Behind beam stop
;