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_7061662
_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         'C64 H68 N4 O13 Ta2, 2.25[C2H3N]'
_chemical_formula_sum            'C68.5 H74.75 N6.25 O13 Ta2'
_chemical_formula_weight         1555.49
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-20
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-02-04 deposited with the CCDC.	2022-07-07 downloaded from the CCDC.
;
_cell_angle_alpha                90.0
_cell_angle_beta                 92.7533(14)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   54.1856(8)
_cell_length_b                   10.7080(2)
_cell_length_c                   22.4972(4)
_cell_measurement_reflns_used    36467
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      31.1100
_cell_measurement_theta_min      1.8500
_cell_volume                     13038.2(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.119a (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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   -107.00 -29.00   0.50    5.00    --  -20.30 -24.00-133.00  156
  2  \w    -64.00  -3.00   0.50    5.00    --   22.65 -24.00-133.00  122
  3  \w     16.00 102.00   0.50    5.00    --   22.65  24.00  30.00  172
  4  \w     33.00  62.00   0.50    5.00    --  -20.30  19.00 -60.00   58
  5  \w    -30.00  -2.00   0.50    5.00    --  -20.30  57.00-150.00   56
  6  \w     32.00  68.00   0.50    5.00    --   22.65 -99.00-150.00   72
  7  \w      0.00  64.00   0.50    5.00    --   22.65 -99.00 -90.00  128
  8  \w     17.00  68.00   0.50    5.00    --   22.65 -99.00  60.00  102
  9  \w    -65.00 -20.00   0.50    5.00    --   22.65 -19.00   0.00   90
 10  \w     18.00  68.00   0.50    5.00    --   22.65 -99.00  90.00  100
 11  \w      0.00  60.00   0.50    5.00    --   22.65  57.00   0.00  120
 12  \w      1.00  62.00   0.50    5.00    --   22.65 -99.00 150.00  122
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0017118000
_diffrn_orient_matrix_UB_12      0.0467399000
_diffrn_orient_matrix_UB_13      0.0221059000
_diffrn_orient_matrix_UB_21      -0.0032776000
_diffrn_orient_matrix_UB_22      0.0465562000
_diffrn_orient_matrix_UB_23      -0.0214349000
_diffrn_orient_matrix_UB_31      -0.0125710000
_diffrn_orient_matrix_UB_32      -0.0055660000
_diffrn_orient_matrix_UB_33      0.0070235000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0681
_diffrn_reflns_av_unetI/netI     0.0458
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       65
_diffrn_reflns_limit_h_min       -74
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            84692
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.351
_diffrn_reflns_theta_min         1.813
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.416
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77322
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.119a (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    1.585
_exptl_crystal_description       block
_exptl_crystal_F_000             6236
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         5.350
_refine_diff_density_min         -3.280
_refine_diff_density_rms         0.195
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     940
_refine_ls_number_reflns         17841
_refine_ls_number_restraints     1027
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0694
_refine_ls_R_factor_gt           0.0561
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0680P)^2^+137.4773P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1420
_refine_ls_wR_factor_ref         0.1510
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14138
_reflns_number_total             17841
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj02527b2.cif
_cod_data_source_block           2021ncs0560z
_cod_original_formula_sum        'C68.50 H74.75 N6.25 O13 Ta2'
_cod_database_code               7061662
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C68 H74 N6 O3 Ta2'
_chemical_oxdiff_usercomment     'Ta dpg new'
_cell_oxdiff_angle_alpha         89.9064(10)
_cell_oxdiff_angle_beta          92.7483(7)
_cell_oxdiff_angle_gamma         89.8417(9)
_cell_oxdiff_length_a            54.1899(4)
_cell_oxdiff_length_b            10.71359(16)
_cell_oxdiff_length_c            22.4837(2)
_cell_oxdiff_measurement_reflns_used 36442
_cell_oxdiff_volume              13038.2(2)
_shelx_estimated_absorpt_t_max   0.848
_shelx_estimated_absorpt_t_min   0.482
_reflns_odcompleteness_completeness 99.95
_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, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N3-H3A = N3-H3B
 0.91726 with sigma of 0.02
 H3B-H42
 -1.95 with sigma of 0.02
 H3A-H3B
 1.485961 with sigma of 0.04
 C16-C23 \\sim C16-C23A
 with sigma of 0.02
 C28-C24 \\sim C28A-C24A
 with sigma of 0.04
 C23-C28 \\sim C23A-C28A
 with sigma of 0.02
 C23-C24 \\sim C23A-C24A
 with sigma of 0.02
 C24-C26 \\sim C24A-C26A
 with sigma of 0.04
 C28-C27 \\sim C28A-C27A
 with sigma of 0.02
 C24-C25 \\sim C24A-C25A
 with sigma of 0.02
 C27-C26 \\sim C27A-C26A
 with sigma of 0.02
 C28-C26 \\sim C28A-C26A
 with sigma of 0.04
 C26-C25 \\sim C26A-C25A
 with sigma of 0.02
 C27-C25 \\sim C27A-C25A
 with sigma of 0.04
 C16-C28 \\sim C16-C28A
 with sigma of 0.04
 C16-C24 \\sim C16-C24A
 with sigma of 0.04
 C23-C27 \\sim C23A-C27A
 with sigma of 0.04
 C23-C25 \\sim C23A-C25A
 with sigma of 0.04
 C18-C22 \\sim C18A-C22A
 with sigma of 0.04
 C16-C22 \\sim C16-C22A
 with sigma of 0.04
 C19-C21 \\sim C19A-C21A
 with sigma of 0.04
 C17-C21 \\sim C17A-C21A
 with sigma of 0.04
 C16-C17 \\sim C16-C17A
 with sigma of 0.02
 C17-C18 \\sim C17A-C18A
 with sigma of 0.02
 C17-C22 \\sim C17A-C22A
 with sigma of 0.02
 C16-C18 \\sim C16-C18A
 with sigma of 0.04
 C17-C19 \\sim C17A-C19A
 with sigma of 0.04
 C18-C19 \\sim C18A-C19A
 with sigma of 0.02
 C18-C20 \\sim C18A-C20A
 with sigma of 0.04
 C19-C20 \\sim C19A-C20A
 with sigma of 0.02
 C22-C20 \\sim C22A-C20A
 with sigma of 0.04
 C22-C21 \\sim C22A-C21A
 with sigma of 0.02
 C21-C20 \\sim C21A-C20A
 with sigma of 0.02
 C61-C62A \\sim C61-C62
 with sigma of 0.02
 C63-C64 \\sim C63A-C64A
 with sigma of 0.02
 O13-C64 \\sim O13-C64A
 with sigma of 0.04
 O13-C63 \\sim O13-C63A
 with sigma of 0.02
 C11-C12 \\sim C11-C12A
 with sigma of 0.02
 C12-C13 \\sim C12A-C13A
 with sigma of 0.02
 C11-C13 \\sim C11-C13A
 with sigma of 0.04
 C2-C9 \\sim C2-C9A
 with sigma of 0.02
 C9-C13 \\sim C9A-C13A
 with sigma of 0.04
 C12-C14 \\sim C12A-C14A
 with sigma of 0.04
 C2-C10 \\sim C2-C10A
 with sigma of 0.04
 C2-C14 \\sim C2-C14A
 with sigma of 0.04
 C10-C9 \\sim C10A-C9A
 with sigma of 0.02
 C9-C14 \\sim C9A-C14A
 with sigma of 0.02
 C10-C14 \\sim C10A-C14A
 with sigma of 0.04
 C14-C13 \\sim C14A-C13A
 with sigma of 0.02
 C9-C11 \\sim C9A-C11
 with sigma of 0.04
 C10-C11 \\sim C10A-C11
 with sigma of 0.02
 C57-C58 \\sim C57-C58A
 with sigma of 0.02
 C59-C60 \\sim C59-C60A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C17 \\sim C18 \\sim C19 \\sim C22 \\sim C21 \\sim C20 \\sim C25A \\sim C24A
\\sim C22A \\sim C21A \\sim C20A \\sim C19A \\sim C18A \\sim C17A \\sim C16
\\sim C23 \\sim C28 \\sim C24 \\sim C27 \\sim C26 \\sim C25 \\sim C23A \\sim
C28A \\sim C27A \\sim C26A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C64A \\sim C63 \\sim C63A \\sim C64: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C10 \\sim C9 \\sim C11 \\sim C12 \\sim C14 \\sim C13 \\sim C13A \\sim C12A
\\sim C10A \\sim C9A \\sim C14A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C62 \\sim C62A \\sim C61: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C58A \\sim C57 \\sim C58: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C60A \\sim C60 \\sim C59: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C10 \\sim H10 \\sim C9 \\sim C11 \\sim C12 \\sim C14 \\sim C13 \\sim H13 \\sim
C13A \\sim C12A \\sim C10A \\sim H10A \\sim C9A \\sim C14A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C63A) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C64A) \\sim Ueq, Uanis(C64)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C62) = Uanis(C62A)
Uanis(C9A) = Uanis(C9)
Uanis(C10) = Uanis(C10A)
4. Rigid body (RIGU) restrains
 C28, C24, C27, C26, C25, C28A, C27A, C26A, C25A, C24A, C23, C23A, C17, C18,
 C19, C22, C21, C20, C22A, C21A, C20A, C19A, C18A, C17A, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C63, C63A, C64, C64A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10, C9, C11, C12, C14, C13, C13A, C12A, C10A, C9A, C14A, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C62, C62A, C61
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C58, C57, C58A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C59, C60A, C60
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C23A)=Sof(C28A)=Sof(H28A)=Sof(C27A)=Sof(H27A)=Sof(C26A)=Sof(H26A)=
 Sof(C25A)=Sof(H25A)=Sof(C24A)=Sof(H24A)=Sof(C22A)=Sof(H22A)=Sof(C21A)=
 Sof(H21A)=Sof(C20A)=Sof(H20A)=Sof(C19A)=Sof(H19A)=Sof(C18A)=Sof(H18A)=
 Sof(C17A)=1-FVAR(1)
 Sof(C23)=Sof(C28)=Sof(H28)=Sof(C17)=Sof(C18)=Sof(H18)=Sof(C24)=Sof(H24)=
 Sof(C27)=Sof(H27)=Sof(C26)=Sof(H26)=Sof(C25)=Sof(H25)=Sof(C19)=Sof(H19)=
 Sof(C22)=Sof(H22)=Sof(C21)=Sof(H21)=Sof(C20)=Sof(H20)=FVAR(1)
 Sof(H61C)=Sof(H61D)=Sof(C62)=Sof(H62D)=Sof(H62E)=Sof(H62F)=1-FVAR(2)
 Sof(H61A)=Sof(H61B)=Sof(C62A)=Sof(H62A)=Sof(H62B)=Sof(H62C)=FVAR(2)
 Sof(C63A)=Sof(H63C)=Sof(H63D)=Sof(C64A)=Sof(H64D)=Sof(H64E)=Sof(H64F)=1-FVAR(3)
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=FVAR(3)
 Sof(H11A)=Sof(C13A)=Sof(H13A)=Sof(C12A)=Sof(H12A)=Sof(C10A)=Sof(H10A)=
 Sof(C9A)=Sof(C14A)=Sof(H14A)=1-FVAR(4)
 Sof(C10)=Sof(H10)=Sof(C9)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(C14)=Sof(H14)=
 Sof(C13)=Sof(H13)=FVAR(4)
 Sof(H59C)=Sof(H59D)=Sof(C60A)=Sof(H60D)=Sof(H60E)=Sof(H60F)=1-FVAR(5)
 Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(5)
 Sof(H57C)=Sof(H57D)=Sof(C58A)=Sof(H58D)=Sof(H58E)=Sof(H58F)=1-FVAR(6)
 Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=1(DFIX)=FVAR(6)
 1(DFIX)=1.62*FVAR(7)
6.a Secondary CH2 refined with riding coordinates:
 N4(H4A,H4B), N2(H2A,H2B), N1(H1A,H1B), C57(H57A,H57B), C57(H57C,H57D),
 C59(H59A,H59B), C59(H59C,H59D), C61(H61A,H61B), C61(H61C,H61D), C63(H63A,H63B),
  C63A(H63C,H63D)
6.b Me refined with riding coordinates:
 C58(H58A,H58B,H58C), C60(H60A,H60B,H60C), C62A(H62A,H62B,H62C), C64(H64A,H64B,
 H64C), C62(H62D,H62E,H62F), C64A(H64D,H64E,H64F), C60A(H60D,H60E,H60F),
 C58A(H58D,H58E,H58F)
6.c Aromatic/amide H refined with riding coordinates:
 C52(H52), C38(H38), C42(H42), C10(H10), C39(H39), C40(H40), C8(H8), C36(H36),
 C41(H41), C56(H56), C32(H32), C46(H46), C11(H11), C11(H11A), C50(H50), C4(H4),
 C7(H7), C53(H53), C6(H6), C12(H12), C5(H5), C47(H47), C55(H55), C33(H33),
 C14(H14), C35(H35), C49(H49), C28(H28), C34(H34), C54(H54), C48(H48), C18(H18),
  C13(H13), C24(H24), C27(H27), C26(H26), C25(H25), C19(H19), C22(H22),
 C21(H21), C20(H20), C28A(H28A), C27A(H27A), C26A(H26A), C25A(H25A), C24A(H24A),
  C22A(H22A), C21A(H21A), C20A(H20A), C19A(H19A), C18A(H18A), C13A(H13A),
 C12A(H12A), C10A(H10A), C14A(H14A)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 420 electrons were 
found in a volume of 1212\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
18[C2H3N] per Unit Cell 
which account for 396 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              65531
_shelx_fab_checksum              98392
_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 5.050
_oxdiff_exptl_absorpt_empirical_full_min 0.406