Pb2+ Complexes of Small-Cavity Azamacrocyclic Ligands. Thermodynamic and Kinetic Studies
Liberato, Andrea; Aguinaco, Almudena; Clares, Maria Paz; Delgado-Pinar, Estefania; Blasco, Salvador; Pitarch-Jarque, Javier; Basallote, Manuel G.; García-España, Enrique; Verdejo, Begoña; Dalton Trans.  (2017) –; doi:10.1039/C7DT00680B

data_7042741
_publ_section_title
;
 Pb2+ Complexes of Small-Cavity Azamacrocyclic Ligands. Thermodynamic and
 Kinetic Studies
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT00680B
_journal_year                    2017
_chemical_formula_moiety         '2(C27 H34 Cl0.5 N5.5 O2 Pb), 2(Cl), 3(O)'
_chemical_formula_sum            'C54 H68 Cl3 N11 O7 Pb2'
_chemical_formula_weight         1503.92
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_symmetry_space_group_name_Hall  '-P 2n 2ab'
_symmetry_space_group_name_H-M   'P b c n'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2017-01-18
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5289)
;
_audit_update_record
;
2017-01-22 deposited with the CCDC.
2017-04-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1619(4)
_cell_length_b                   13.0751(4)
_cell_length_c                   33.1703(10)
_cell_measurement_reflns_used    1350
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      28.3720
_cell_measurement_theta_min      3.7510
_cell_volume                     5708.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0267
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.996
_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    -36.00   1.00   1.00   46.00    --  -20.96 -19.00 -90.00   37
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0206898000
_diffrn_orient_matrix_UB_12      -0.0056338000
_diffrn_orient_matrix_UB_13      0.0123664000
_diffrn_orient_matrix_UB_21      -0.0049056000
_diffrn_orient_matrix_UB_22      -0.0004117000
_diffrn_orient_matrix_UB_23      0.0527593000
_diffrn_orient_matrix_UB_31      -0.0021361000
_diffrn_orient_matrix_UB_32      -0.0535504000
_diffrn_orient_matrix_UB_33      -0.0017330000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0405
_diffrn_reflns_av_unetI/netI     0.0513
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            13519
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         3.295
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.092
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93098
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            COLORLESS
_exptl_crystal_density_diffrn    1.750
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             2960
_exptl_crystal_preparation       ', Luminescent'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: water'
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.533
_refine_diff_density_min         -1.827
_refine_diff_density_rms         0.166
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.368
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     445
_refine_ls_number_reflns         5006
_refine_ls_number_restraints     104
_refine_ls_restrained_S_all      1.362
_refine_ls_R_factor_all          0.0765
_refine_ls_R_factor_gt           0.0651
_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^)+104.1935P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1313
_refine_ls_wR_factor_ref         0.1350
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4305
_reflns_number_total             5006
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt00680b2.cif
_cod_data_source_block           begopb
_cod_database_code               7042741
_shelx_shelxl_version_number     2016/6
_cell_oxdiff_angle_alpha         90.028(7)
_cell_oxdiff_angle_beta          90.037(9)
_cell_oxdiff_angle_gamma         89.992(3)
_cell_oxdiff_length_a            33.1908(15)
_cell_oxdiff_length_b            13.1724(3)
_cell_oxdiff_length_c            13.083(3)
_cell_oxdiff_measurement_reflns_used 1350
_cell_oxdiff_volume              5720(2)
_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) groups,
  All N(H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 H1d-O2
 1.87 with sigma of 0.01
 H1c-Cl1
 2.27 with sigma of 0.01
 H1c-O4
 1.89 with sigma of 0.01
3. Rigid bond restraints
 O1, Pb01
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C8, C9B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C22, C23
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C21, C22
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O13, C18, C19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Pb01, O13
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C9B \\sim C8: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04
Uanis(N4A) \\sim Ueq, Uanis(N4B) \\sim Ueq, Uanis(C10B) \\sim Ueq, Uanis(C10A)
\\sim Ueq, Uanis(C9B) \\sim Ueq, Uanis(C9A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.1
Uanis(C10B) \\sim Ueq: with sigma of 0.008 and sigma for terminal atoms of 0.08
Uanis(C11A) \\sim Ueq, Uanis(C11B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.1
Uanis(C23) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17)
\\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
of 0.1
Uanis(O13) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C12B) \\sim Ueq, Uanis(C9B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
5. Others
 Fixed Sof: Cl1(0.5) Cl2B(0.5) Cl2A(0.5) H5a(0.5) H5b(0.5) H13c(0.5) H13d(0.5)
 H13a(0.5) H13b(0.5) H14c(0.5) H14d(0.5) H14a(0.5) H14b(0.5) H8bc(0.5)
 H8bd(0.5) H8aa(0.5) H8ab(0.5) O2(0.5) N4B(0.5) H4B(0.5) N4A(0.5) H4A(0.5)
 O3(0.5) C12B(0.5) H12a(0.5) H12b(0.5) C12A(0.5) H12c(0.5) H12d(0.5) C9B(0.5)
 H9Ba(0.5) H9Bb(0.5) C9A(0.5) H9Aa(0.5) H9Ab(0.5) C10A(0.5) H10a(0.5) H10b(0.5)
 C10B(0.5) H10c(0.5) H10d(0.5) O1(0.5) H1c(0.5) H1d(0.5) C11A(0.5) H11a(0.5)
 H11b(0.5) C11B(0.5) H11c(0.5) H11d(0.5) O2AA(0.5) O0AA(0.5) N1AA(0.5) O4(0.5)
 O13(0.5)
6.a Free rotating group:
 O1(H1c,H1d)
6.b Ternary CH refined with riding coordinates:
 N2(H2), N5(H5a), N5(H5b), N4B(H4B), N4A(H4A)
6.c Secondary CH2 refined with riding coordinates:
 C18(H18a,H18b), C13(H13c,H13d), C13(H13a,H13b), C1(H1a,H1b), C14(H14c,H14d),
 C14(H14a,H14b), C7(H7a,H7b), C8(H8bc,H8bd), C8(H8aa,H8ab), C12B(H12a,H12b),
 C12A(H12c,H12d), C9B(H9Ba,H9Bb), C9A(H9Aa,H9Ab), C10A(H10a,H10b), C10B(H10c,
 H10d), C11A(H11a,H11b), C11B(H11c,H11d)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C16(H16), C5(H5), C23(H23), C26(H26), C4(H4), C27(H27), C22(H22),
 C20(H20), C21(H21)
;
_olex2_submission_special_instructions 'No special instructions were received'