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_7126927
_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 I2 N6 O1 W'
_chemical_formula_sum            'C16 H22 B I2 N6 O W'
_chemical_formula_weight         762.85
_chemical_name_systematic
;
 carbonyl{hydrotris(3,5-dimethylpyrazol-1-yl)borato)diiodotungsten(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     direct
_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                 99.627(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.1399(11)
_cell_length_b                   14.223(2)
_cell_length_c                   19.364(4)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    293(1)
_cell_measurement_theta_max      13.7
_cell_measurement_theta_min      9.5
_cell_volume                     2210.3(6)
_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    'ShelXS-1986 (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(1)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0577
_diffrn_reflns_av_unetI/netI     0.0473
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -1
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -1
_diffrn_reflns_number            4624
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.992
_diffrn_reflns_theta_max         24.992
_diffrn_reflns_theta_min         2.133
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_decay_%        2
_diffrn_standards_interval_time  160
_diffrn_standards_number         3
_exptl_absorpt_coefficient_mu    8.038
_exptl_absorpt_correction_T_max  0.9216
_exptl_absorpt_correction_T_min  0.3669
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   'SHELX76 (Sheldrick, 1976)'
_exptl_crystal_colour            'Dark Red'
_exptl_crystal_density_diffrn    2.292
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    none
_exptl_crystal_description       plate
_exptl_crystal_F_000             1412
_exptl_crystal_recrystallization_method
'was obtained by slow evaporation from dichloromethane/Hexane'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.01
_refine_diff_density_max         2.692
_refine_diff_density_min         -1.994
_refine_diff_density_rms         0.271
_refine_ls_extinction_coef       0.0009(2)
_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   1.187
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         3888
_refine_ls_number_restraints     46
_refine_ls_restrained_S_all      1.179
_refine_ls_R_factor_all          0.0903
_refine_ls_R_factor_gt           0.0755
_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^)+(0.0757P)^2^+44.4031P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1799
_refine_ls_wR_factor_ref         0.1873
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3242
_reflns_number_total             3888
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc04607h1.cif
_cod_data_source_block           cy_4
_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               7126927
_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 0.001
 C1-O1 = C1A-O1A = C1B-O1B
 1.16 with sigma of 0.001
 W-O1 = W-O1A = W-O1B
 3.06 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(O1A)
\\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(O1B) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(O1) = Uanis(O1A) = Uanis(O1B)
Uanis(C1) = Uanis(C1A) = Uanis(C1B)
4. Others
 1*[Sof(I2)+Sof(C1B)+Sof(O1B)]+1*[Sof(I1)+Sof(C1A)+Sof(O1A)]+1*[Sof(C1)+
 Sof(O1)+Sof(I3)]=2 with esd of 0.001
 Sof(C1B)=Sof(O1B)=1-FVAR(1)
 Sof(I2)=FVAR(1)
 Sof(C1A)=Sof(O1A)=1-FVAR(2)
 Sof(I1)=FVAR(2)
 Sof(C1)=Sof(O1)=1-FVAR(3)
 Sof(I3)=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              97373
_shelx_hkl_checksum              97935
_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
;
PLAT234_ALERT_4_B Large Hirshfeld Difference O1 --C1 .. 0.28 Ang. 

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

PLAT342_ALERT_3_B Low Bond Precision on C-C Bonds ............... 0.03 Ang. 

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

PLAT971_ALERT_2_B Check Calcd Residual Density 0.92A From C1 2.58 eA-3 
PLAT971_ALERT_2_B Check Calcd Residual Density 1.01A From N11 2.51 eA-3 

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

PLAT234_ALERT_4_C Large Hirshfeld Difference C23 --C24 .. 0.20 Ang. 

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

PLAT241_ALERT_2_C High MainMol Ueq as Compared to Neighbors of C13 Check 
PLAT242_ALERT_2_C Low  MainMol Ueq as Compared to Neighbors of C24 Check 

   Due to some disorder

PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 7.939 Check 
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 2.190 Check 

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

PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.594 4 Report 

   Not measured

PLAT971_ALERT_2_C Check Calcd Residual Density 1.15A From W 2.44 eA-3 
PLAT971_ALERT_2_C Check Calcd Residual Density 0.93A From W 2.15 eA-3 
PLAT971_ALERT_2_C Check Calcd Residual Density 1.02A From C1B 2.15 eA-3 
PLAT971_ALERT_2_C Check Calcd Residual Density 1.02A From W 2.04 eA-3 
PLAT972_ALERT_2_C Check Calcd Residual Density 0.77A From W -2.03 eA-3 
PLAT972_ALERT_2_C Check Calcd Residual Density 0.86A From W -1.80 eA-3 
PLAT977_ALERT_2_C Check the Negative Difference Density on H -0.58 eA-3 
PLAT977_ALERT_2_C Check the Negative Difference Density on H35B -0.34 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 

   Noted

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

PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large 44.39 Why ? 

   This is due to the crystal being disordered, 

PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records 2 Report 
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 2 Report 

   The CO molecules are disordered over the three positions, overlapping
 with the Iodine atoms.  These needed to be constrained to geometrical
 estimates with the ADP restrained to near isotropic values

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

   Correct

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

  The I & 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

PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) Still 66 % 

   True

PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min) 1 Note 

   Behind beam stop
;