Niobium and Tantalum complexes derived from the acids Ph2C(X)CO2H (X = OH, NH2): synthesis, structure and ROP capability
Zhang, Xin; Prior, Timothy J.; Redshaw, Carl; New Journal of Chemistry 46 (2022) 14146–14154; doi:10.1039/D2NJ02527B

data_7061661
_publ_section_title
;
 Niobium and Tantalum complexes derived from the acids Ph2C(X)CO2H (X =
 OH, NH2): synthesis, structure and ROP capability
;
_journal_issue                   29
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              14146
_journal_page_last               14154
_journal_paper_doi               10.1039/D2NJ02527B
_journal_volume                  46
_journal_year                    2022
_chemical_formula_moiety         'C72 H80 O22 Ta4, 0.5[CH3CN]'
_chemical_formula_sum            'C73 H81.5 N0.5 O22 Ta4'
_chemical_formula_weight         2041.68
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6257)
;
_audit_update_record
;
2022-02-04 deposited with the CCDC.	2022-07-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.593(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.2617(4)
_cell_length_b                   14.3187(2)
_cell_length_c                   25.8451(8)
_cell_measurement_reflns_used    56281
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      31.5280
_cell_measurement_theta_min      1.8260
_cell_volume                     7491.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'hybrid pixel detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000HE'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -73.00  -7.00   0.50    0.40    --  -18.74 119.00 -17.00  132
  2  \w     13.00  76.00   0.50    0.40    --   21.24-119.00-101.00  126
  3  \w     22.00  63.00   0.50    0.40    --  -18.74  19.00-150.00   82
  4  \w     22.00  63.00   0.50    0.40    --  -18.74  19.00 -60.00   82
  5  \w    -16.00  63.00   0.50    0.40    --  -18.74  38.00  90.00  158
  6  \w     22.00  63.00   0.50    0.40    --  -18.74  19.00-180.00   82
  7  \w     22.00  63.00   0.50    0.40    --  -18.74  19.00  30.00   82
  8  \w     22.00  63.00   0.50    0.40    --  -18.74  19.00 -30.00   82
  9  \w      0.00  65.00   0.50    0.40    --   21.24 -99.00   0.00  130
 10  \w      0.00  65.00   0.50    0.40    --   21.24 -99.00 -90.00  130
 11  \w    -56.00   6.00   0.50    0.40    --  -18.74 -57.00   0.00  124
 12  \w    -49.00   9.00   0.50    0.40    --   21.24 -59.00 -31.00  116
 13  \w    -54.00   6.00   0.50    0.40    --  -18.74 -57.00 150.00  120
 14  \w    -19.00   7.00   0.50    0.40    --  -18.74 -38.00-120.00   52
 15  \w   -103.00 -40.00   0.50    0.40    --  -18.74 -19.00 -60.00  126
 16  \w    -50.00   1.00   0.50    0.40    --  -18.74 -57.00-120.00  102
 17  \w   -100.00 -23.00   0.50    0.40    --  -18.74 -38.00-120.00  154
 18  \w    -29.00  -1.00   0.50    0.40    --   21.24 111.00-178.58   56
 19  \w     24.00 104.00   0.50    0.40    --   21.24  19.00  90.00  160
 20  \w     22.00  48.00   0.50    0.40    --   21.24  19.00-180.00   52
 21  \w     52.00 104.00   0.50    0.40    --   21.24  19.00-180.00  104
 22  \w    -10.00  53.00   0.50    0.40    --   21.24 -77.00 150.00  126
 23  \w     21.00  48.00   0.50    0.40    --   21.24 -59.00 -31.00   54
 24  \w     -6.00  62.00   0.50    0.40    --   21.24  57.00-150.00  136
 25  \w     22.00  96.00   0.50    0.40    --   21.24  19.00  90.00  148
 26  \w    -40.00 -14.00   0.50    0.40    --   21.24 131.00 127.75   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, UG2 \k goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ equipped with Arc)Sec VHF Varimax confocal mirrors and an UG2 goniometer and HyPix 6000HE detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0127540000
_diffrn_orient_matrix_UB_12      -0.0249280000
_diffrn_orient_matrix_UB_13      -0.0165394000
_diffrn_orient_matrix_UB_21      0.0026866000
_diffrn_orient_matrix_UB_22      0.0423596000
_diffrn_orient_matrix_UB_23      -0.0128991000
_diffrn_orient_matrix_UB_31      0.0329964000
_diffrn_orient_matrix_UB_32      0.0061637000
_diffrn_orient_matrix_UB_33      0.0216886000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, Arc)Sec VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0431
_diffrn_reflns_av_unetI/netI     0.0184
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            104958
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.700
_diffrn_reflns_theta_min         1.733
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FRE+'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    5.896
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50908
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.810
_exptl_crystal_description       prism
_exptl_crystal_F_000             3964
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.274
_refine_diff_density_min         -1.128
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     480
_refine_ls_number_reflns         9677
_refine_ls_number_restraints     124
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0226
_refine_ls_R_factor_gt           0.0194
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0233P)^2^+20.1069P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0464
_refine_ls_wR_factor_ref         0.0475
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8869
_reflns_number_total             9677
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj02527b2.cif
_cod_data_source_block           2021ncs0504s
_cod_original_formula_sum        'C73 H81.50 N0.50 O22 Ta4'
_cod_database_code               7061661
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         (C14H12NO2)5Ta(OC2H5)5
_chemical_oxdiff_usercomment     dpgTa
_shelx_estimated_absorpt_t_max   0.619
_shelx_estimated_absorpt_t_min   0.254
_reflns_odcompleteness_completeness 99.99
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.64
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C30-C29 \\sim C30A-C29
 with sigma of 0.02
 C36A-C35A \\sim C36-C35
 with sigma of 0.02
 C34A-C33 \\sim C34-C33
 with sigma of 0.02
 C32A-C31 \\sim C32-C31
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C35: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C33: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C29 \\sim C30A \\sim C30: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C32 \\sim C31 \\sim C32A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C35A \\sim C35: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(C30) \\sim Ueq, Uanis(C30A) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C32A)
\\sim Ueq: with sigma of 0.0125 and sigma for terminal atoms of 0.025
Uanis(C36) \\sim Ueq, Uanis(C36A) \\sim Ueq, Uanis(C34A) \\sim Ueq, Uanis(C34)
\\sim Ueq: with sigma of 0.0024 and sigma for terminal atoms of 0.0048
Uanis(C36) = Uanis(C36A)
Uanis(C34) = Uanis(C34A)
4. Rigid body (RIGU) restrains
 C33, O11, O12, C35, O10, C29, C30, C31, C32, C30A, C32A, O9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H29C)=Sof(H29D)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(1)
 Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
 Sof(H31C)=Sof(H31D)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(2)
 Sof(H31A)=Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(2)
 Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(C35A)=Sof(H35C)=Sof(H35D)=1-FVAR(3)
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(3)
 Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(4)
 Sof(H33C)=Sof(H33D)=Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C29(H29C,H29D), C31(H31A,H31B), C31(H31C,H31D), C33(H33C,
 H33D), C33(H33A,H33B), C35(H35A,H35B), C35A(H35C,H35D)
6.b Me refined with riding coordinates:
 C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C30A(H30D,H30E,H30F), C32A(H32D,
 H32E,H32F), C34A(H34A,H34B,H34C), C34(H34D,H34E,H34F), C36(H36A,H36B,H36C),
 C36A(H36D,H36E,H36F)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24),
  C25(H25), C26(H26), C27(H27), C28(H28)
;
_smtbx_masks_special_details
;
A solvent mask was employed to model a small amount of electron
density. This equates to partial filling of voids by CH3CN and
gives and overall formula of 0.5CH3CN for each four-Ta cluster
and hence 2 CH3CN extra in each unit cell. 
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              19437
_shelx_fab_checksum              89209
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.880
_oxdiff_exptl_absorpt_empirical_full_min 0.639