#------------------------------------------------------------------------------
#$Date: 2016-03-22 23:53:12 +0200 (Tue, 22 Mar 2016) $
#$Revision: 179082 $
#$URL: svn://www.crystallography.net/cod/cif/4/30/44/4304403.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4304403
loop_
_publ_author_name
'Yuji Tooyama'
'Henrik Braband'
'Bernhard Spingler'
'Ulrich Abram'
'Roger Alberto'
_publ_section_title
;
High-Valent Technetium Complexes with the [99TcO3]+ Core from in Situ
Prepared Mixed Anhydrides of [99TcO4]- and Their Reactivities
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              257
_journal_page_last               264
_journal_paper_doi               10.1021/ic701908q
_journal_volume                  47
_journal_year                    2008
_chemical_formula_moiety         '[TcO3(bpza)]'
_chemical_formula_sum            'C8 H7 N4 O5 Tc'
_chemical_formula_weight         337.18
_chemical_name_common            '[TcO3(bpza)]'
_chemical_name_systematic
;
(bis(pyrazol-1-yl)acetato-N,N',O)-trioxo-technetium(VII)
;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 91.119(11)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   11.7406(12)
_cell_length_b                   8.1846(8)
_cell_length_c                   11.3273(9)
_cell_measurement_reflns_used    7998
_cell_measurement_temperature    183(2)
_cell_measurement_theta_max      26
_cell_measurement_theta_min      2.4
_cell_volume                     1088.26(18)
_computing_cell_refinement       'IPDS (Stoe, 1999)'
_computing_data_collection       'IPDS (Stoe, 1999)'
_computing_data_reduction        'X-RED (Stoe, 1999)'
_computing_molecular_graphics    'ORTEP-3 (Farrugia, 1997)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SIR-97 (Altomare, 1999)'
_diffrn_ambient_temperature      183(2)
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_device_type  'Stoe IPDS'
_diffrn_measurement_method       '/f oscillation scan'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_sigmaI/netI    0.0233
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            15009
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         26.00
_diffrn_reflns_theta_min         2.47
_diffrn_standards_interval_count 'every image'
_diffrn_standards_interval_time  5.5
_diffrn_standards_number         50-200
_exptl_absorpt_coefficient_mu    1.344
_exptl_absorpt_correction_T_max  0.7912
_exptl_absorpt_correction_T_min  0.6619
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   none
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    2.058
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             664
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.566
_refine_diff_density_min         -0.732
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     163
_refine_ls_number_reflns         2073
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0490
_refine_ls_R_factor_gt           0.0448
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0715P)²+1.1416P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1084
_refine_ls_wR_factor_ref         0.1103
_reflns_number_gt                1759
_reflns_number_total             2073
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic701908q-file004.cif
_cod_data_source_block           yt050107
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4304403
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Tc1 Tc 0.56437(3) 0.16650(4) 0.77475(3) 0.03985(17) Uani 1 1 d . . .
O4 O 0.3891(3) 0.1765(3) 0.8273(3) 0.0384(6) Uani 1 1 d . . .
O5 O 0.2238(3) 0.2955(4) 0.8623(3) 0.0492(8) Uani 1 1 d . . .
N4 N 0.4521(3) 0.5214(4) 0.8091(3) 0.0337(7) Uani 1 1 d . . .
O2 O 0.5374(3) -0.0131(4) 0.7070(3) 0.0544(8) Uani 1 1 d . . .
N2 N 0.5453(3) 0.4304(4) 0.8332(3) 0.0361(7) Uani 1 1 d . . .
C7 C 0.3560(3) 0.4447(5) 0.7489(3) 0.0333(8) Uani 1 1 d . . .
H7 H 0.2916 0.5244 0.7429 0.040 Uiso 1 1 calc R . .
N3 N 0.3872(3) 0.3941(4) 0.6317(3) 0.0347(7) Uani 1 1 d . . .
N1 N 0.4718(3) 0.2832(4) 0.6189(3) 0.0361(7) Uani 1 1 d . . .
O1 O 0.6001(3) 0.1195(4) 0.9159(3) 0.0495(8) Uani 1 1 d . . .
O3 O 0.6867(3) 0.2317(5) 0.7158(3) 0.0552(8) Uani 1 1 d . . .
C3 C 0.3380(4) 0.4320(5) 0.5260(4) 0.0416(9) Uani 1 1 d . . .
H3 H 0.2771 0.5065 0.5122 0.050 Uiso 1 1 calc R . .
C5 C 0.4657(4) 0.6758(5) 0.8471(4) 0.0387(9) Uani 1 1 d . . .
H5 H 0.4120 0.7622 0.8394 0.046 Uiso 1 1 calc R . .
C2 C 0.3936(4) 0.3411(5) 0.4426(4) 0.0455(10) Uani 1 1 d . . .
H2 H 0.3786 0.3393 0.3599 0.055 Uiso 1 1 calc R . .
C6 C 0.6190(3) 0.5294(5) 0.8877(4) 0.0403(9) Uani 1 1 d . . .
H6 H 0.6929 0.4985 0.9149 0.048 Uiso 1 1 calc R . .
C8 C 0.3180(3) 0.2943(5) 0.8202(4) 0.0351(8) Uani 1 1 d . . .
C4 C 0.5723(4) 0.6848(5) 0.8993(4) 0.0418(10) Uani 1 1 d . . .
H4 H 0.6068 0.7775 0.9356 0.050 Uiso 1 1 calc R . .
C1 C 0.4766(4) 0.2521(5) 0.5045(4) 0.0414(9) Uani 1 1 d . . .
H1 H 0.5291 0.1793 0.4695 0.050 Uiso 1 1 calc R . .
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Tc Tc -1.4390 0.7593 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O3 Tc1 O2 104.51(18) . . ?
O3 Tc1 O1 104.45(17) . . ?
O2 Tc1 O1 105.84(16) . . ?
O3 Tc1 O4 157.65(14) . . ?
O2 Tc1 O4 89.25(15) . . ?
O1 Tc1 O4 88.16(14) . . ?
O3 Tc1 N1 87.55(15) . . ?
O2 Tc1 N1 86.00(14) . . ?
O1 Tc1 N1 160.01(14) . . ?
O4 Tc1 N1 75.73(12) . . ?
O3 Tc1 N2 84.47(15) . . ?
O2 Tc1 N2 160.62(14) . . ?
O1 Tc1 N2 88.00(15) . . ?
O4 Tc1 N2 77.49(11) . . ?
N1 Tc1 N2 77.14(12) . . ?
C8 O4 Tc1 129.6(3) . . ?
C5 N4 N2 111.3(3) . . ?
C5 N4 C7 130.2(3) . . ?
N2 N4 C7 118.5(3) . . ?
C6 N2 N4 106.0(3) . . ?
C6 N2 Tc1 130.4(3) . . ?
N4 N2 Tc1 123.4(2) . . ?
N3 C7 N4 110.3(3) . . ?
N3 C7 C8 109.5(3) . . ?
N4 C7 C8 109.2(3) . . ?
N1 N3 C3 111.1(3) . . ?
N1 N3 C7 119.4(3) . . ?
C3 N3 C7 129.4(4) . . ?
C1 N1 N3 106.2(3) . . ?
C1 N1 Tc1 130.8(3) . . ?
N3 N1 Tc1 122.7(2) . . ?
N3 C3 C2 106.4(4) . . ?
N4 C5 C4 106.8(4) . . ?
C3 C2 C1 105.9(4) . . ?
N2 C6 C4 110.3(4) . . ?
O5 C8 O4 125.5(4) . . ?
O5 C8 C7 118.3(4) . . ?
O4 C8 C7 116.1(3) . . ?
C5 C4 C6 105.5(4) . . ?
N1 C1 C2 110.4(4) . . ?
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Tc1 O3 1.683(3) . ?
Tc1 O2 1.685(3) . ?
Tc1 O1 1.690(3) . ?
Tc1 O4 2.155(3) . ?
Tc1 N1 2.266(3) . ?
Tc1 N2 2.272(3) . ?
O4 C8 1.277(5) . ?
O5 C8 1.214(5) . ?
N4 C5 1.343(5) . ?
N4 N2 1.347(4) . ?
N4 C7 1.450(5) . ?
N2 C6 1.328(5) . ?
C7 N3 1.444(5) . ?
C7 C8 1.543(5) . ?
N3 N1 1.355(5) . ?
N3 C3 1.356(5) . ?
N1 C1 1.323(6) . ?
C3 C2 1.377(7) . ?
C5 C4 1.375(6) . ?
C2 C1 1.394(7) . ?
C6 C4 1.393(6) . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O3 Tc1 O4 C8 -3.8(6) . . . . ?
O2 Tc1 O4 C8 -132.6(4) . . . . ?
O1 Tc1 O4 C8 121.5(4) . . . . ?
N1 Tc1 O4 C8 -46.6(3) . . . . ?
N2 Tc1 O4 C8 33.1(3) . . . . ?
C5 N4 N2 C6 0.2(5) . . . . ?
C7 N4 N2 C6 -180.0(3) . . . . ?
C5 N4 N2 Tc1 -176.1(3) . . . . ?
C7 N4 N2 Tc1 3.8(4) . . . . ?
O3 Tc1 N2 C6 -48.8(4) . . . . ?
O2 Tc1 N2 C6 -167.7(4) . . . . ?
O1 Tc1 N2 C6 56.0(4) . . . . ?
O4 Tc1 N2 C6 144.5(4) . . . . ?
N1 Tc1 N2 C6 -137.5(4) . . . . ?
O3 Tc1 N2 N4 126.5(3) . . . . ?
O2 Tc1 N2 N4 7.6(6) . . . . ?
O1 Tc1 N2 N4 -128.8(3) . . . . ?
O4 Tc1 N2 N4 -40.2(3) . . . . ?
N1 Tc1 N2 N4 37.8(3) . . . . ?
C5 N4 C7 N3 115.6(4) . . . . ?
N2 N4 C7 N3 -64.2(4) . . . . ?
C5 N4 C7 C8 -124.0(4) . . . . ?
N2 N4 C7 C8 56.2(4) . . . . ?
N4 C7 N3 N1 61.1(4) . . . . ?
C8 C7 N3 N1 -59.1(4) . . . . ?
N4 C7 N3 C3 -124.5(4) . . . . ?
C8 C7 N3 C3 115.2(4) . . . . ?
C3 N3 N1 C1 0.5(5) . . . . ?
C7 N3 N1 C1 175.9(3) . . . . ?
C3 N3 N1 Tc1 -173.5(3) . . . . ?
C7 N3 N1 Tc1 1.9(5) . . . . ?
O3 Tc1 N1 C1 62.3(4) . . . . ?
O2 Tc1 N1 C1 -42.5(4) . . . . ?
O1 Tc1 N1 C1 -169.9(4) . . . . ?
O4 Tc1 N1 C1 -132.7(4) . . . . ?
N2 Tc1 N1 C1 147.2(4) . . . . ?
O3 Tc1 N1 N3 -125.4(3) . . . . ?
O2 Tc1 N1 N3 129.9(3) . . . . ?
O1 Tc1 N1 N3 2.4(6) . . . . ?
O4 Tc1 N1 N3 39.7(3) . . . . ?
N2 Tc1 N1 N3 -40.5(3) . . . . ?
N1 N3 C3 C2 0.1(5) . . . . ?
C7 N3 C3 C2 -174.7(4) . . . . ?
N2 N4 C5 C4 -0.6(5) . . . . ?
C7 N4 C5 C4 179.6(4) . . . . ?
N3 C3 C2 C1 -0.6(5) . . . . ?
N4 N2 C6 C4 0.4(5) . . . . ?
Tc1 N2 C6 C4 176.2(3) . . . . ?
Tc1 O4 C8 O5 -172.4(3) . . . . ?
Tc1 O4 C8 C7 9.3(5) . . . . ?
N3 C7 C8 O5 -123.2(4) . . . . ?
N4 C7 C8 O5 115.8(4) . . . . ?
N3 C7 C8 O4 55.2(4) . . . . ?
N4 C7 C8 O4 -65.7(4) . . . . ?
N4 C5 C4 C6 0.8(5) . . . . ?
N2 C6 C4 C5 -0.7(5) . . . . ?
N3 N1 C1 C2 -0.9(5) . . . . ?
Tc1 N1 C1 C2 172.4(3) . . . . ?
C3 C2 C1 N1 1.0(5) . . . . ?
