#------------------------------------------------------------------------------
#$Date: 2016-03-25 13:40:45 +0200 (Fri, 25 Mar 2016) $
#$Revision: 179857 $
#$URL: svn://www.crystallography.net/cod/cif/7/01/53/7015347.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_7015347
loop_
_publ_author_name
'Kopylovich, Maximilian N.'
'Nunes, Andreia C. C.'
'Mahmudov, Kamran T.'
'Haukka, Matti'
'Mac Leod, Tatiana C. O.'
'Martins, Luísa M D R S'
'Kuznetsov, Maxim L.'
'Pombeiro, Armando J. L.'
_publ_section_title
;
 Complexes of copper(II) with 3-(ortho-substituted
 phenylhydrazo)pentane-2,4-diones: syntheses, properties and catalytic
 activity for cyclohexane oxidation.
;
_journal_issue                   12
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2822
_journal_page_last               2836
_journal_paper_doi               10.1039/c0dt01527j
_journal_volume                  40
_journal_year                    2011
_chemical_formula_moiety
'C4 H16 Cu N8 O4, 2(C11 H11 N2 O5 S), 6(H2 O)'
_chemical_formula_sum            'C26 H50 Cu N12 O20 S2'
_chemical_formula_weight         978.44
_chemical_name_systematic
;
?
;
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                108.578(7)
_cell_angle_beta                 100.618(7)
_cell_angle_gamma                104.892(5)
_cell_formula_units_Z            1
_cell_length_a                   6.9100(6)
_cell_length_b                   12.0491(13)
_cell_length_c                   14.337(2)
_cell_measurement_reflns_used    1556
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.36
_cell_measurement_theta_min      2.89
_cell_volume                     1046.3(2)
_computing_cell_refinement       'SAINT (Bruker AXS, 2009)'
_computing_data_collection       'APEX2 (Bruker AXS, 2009)'
_computing_data_reduction        'SAINT (Bruker AXS, 2009)'
_computing_molecular_graphics    'Diamond v.3.2d (Brandenburg, 2010)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 16
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device
'62mm x 62mm CCD camera on three-circle goniostat'
_diffrn_measurement_device_type  'Bruker SMART APEX II CCD'
_diffrn_measurement_method       'φ scans and ω scans'
_diffrn_radiation_monochromator  'flat graphite crystal'
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0473
_diffrn_reflns_av_sigmaI/netI    0.1218
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            8178
_diffrn_reflns_theta_full        27.50
_diffrn_reflns_theta_max         27.50
_diffrn_reflns_theta_min         1.57
_exptl_absorpt_coefficient_mu    0.713
_exptl_absorpt_correction_T_max  0.9465
_exptl_absorpt_correction_T_min  0.8226
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2008)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.553
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             511
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.454
_refine_diff_density_min         -0.578
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.854
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     279
_refine_ls_number_reflns         4674
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.854
_refine_ls_R_factor_all          0.0878
_refine_ls_R_factor_gt           0.0432
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0208P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0705
_refine_ls_wR_factor_ref         0.0801
_reflns_number_gt                2833
_reflns_number_total             4674
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c0dt01527j.txt
_cod_data_source_block           14
_cod_database_code               7015347
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
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
Cu1 Cu 0.0000 0.5000 0.5000 0.01162(14) Uani 1 2 d S . .
S1 S 0.10174(10) 0.32918(7) 0.75791(6) 0.01337(18) Uani 1 1 d . . .
O1 O -0.0926(3) 0.35538(19) 0.74612(16) 0.0204(5) Uani 1 1 d . . .
O2 O 0.0817(3) 0.20365(18) 0.69674(16) 0.0227(5) Uani 1 1 d . . .
O3 O 0.2674(3) 0.42175(18) 0.74452(16) 0.0173(5) Uani 1 1 d . . .
O4 O 0.3050(3) 0.98815(19) 1.08449(17) 0.0243(6) Uani 1 1 d . . .
O5 O 0.1190(3) 0.66738(19) 0.81701(16) 0.0195(5) Uani 1 1 d . . .
O6 O 0.2512(2) 0.54582(17) 0.61580(15) 0.0172(5) Uani 1 1 d . . .
H6O H 0.3122 0.6205 0.6601 0.026 Uiso 1 1 d R . .
H6P H 0.2285 0.4968 0.6477 0.026 Uiso 1 1 d R . .
O7 O -0.2884(3) 0.75289(17) 0.57523(15) 0.0175(5) Uani 1 1 d . . .
H7O H -0.2857 0.6801 0.5621 0.026 Uiso 1 1 d R . .
H7P H -0.3539 0.7516 0.5145 0.026 Uiso 1 1 d R . .
O8 O -0.1759(3) 0.57407(17) 0.62321(15) 0.0171(5) Uani 1 1 d . . .
H8O H -0.2764 0.5077 0.6061 0.026 Uiso 1 1 d R . .
H8P H -0.0965 0.5953 0.6845 0.026 Uiso 1 1 d R . .
O9 O 0.5181(3) 0.78118(19) 0.73064(18) 0.0356(7) Uani 1 1 d . . .
H9O H 0.5941 0.7871 0.6913 0.053 Uiso 1 1 d R . .
H9P H 0.5634 0.8474 0.7847 0.053 Uiso 1 1 d R . .
O10 O -0.4510(3) 0.36591(17) 0.63445(15) 0.0181(5) Uani 1 1 d . . .
H10O H -0.3576 0.3396 0.6550 0.027 Uiso 1 1 d R . .
H10P H -0.5272 0.3781 0.6724 0.027 Uiso 1 1 d R . .
N1 N 0.2135(3) 0.5662(2) 0.94346(19) 0.0157(6) Uani 1 1 d . . .
H1N H 0.1675 0.5765 0.8855 0.023 Uiso 1 1 d R . .
N2 N 0.2627(3) 0.6762(2) 1.01653(19) 0.0139(6) Uani 1 1 d . . .
N3 N -0.1057(3) 0.3342(2) 0.50184(19) 0.0150(6) Uani 1 1 d . . .
N4 N -0.3004(3) 0.1220(2) 0.48066(19) 0.0155(6) Uani 1 1 d . . .
N5 N -0.0734(3) 0.0433(2) 0.39551(19) 0.0181(6) Uani 1 1 d . . .
H5N H -0.0028 0.1108 0.3883 0.027 Uiso 1 1 d R . .
H5M H -0.0466 -0.0249 0.3654 0.027 Uiso 1 1 d R . .
N6 N -0.3472(3) -0.0853(2) 0.42167(19) 0.0163(6) Uani 1 1 d . . .
H6M H -0.3225 -0.1495 0.3868 0.024 Uiso 1 1 d R . .
H6N H -0.4567 -0.0987 0.4424 0.024 Uiso 1 1 d R . .
C1 C 0.1843(4) 0.3488(3) 0.8885(2) 0.0128(7) Uani 1 1 d . . .
C2 C 0.2017(4) 0.2491(3) 0.9131(2) 0.0156(7) Uani 1 1 d . . .
H2 H 0.1718 0.1708 0.8595 0.019 Uiso 1 1 calc R . .
C3 C 0.2615(4) 0.2610(3) 1.0139(2) 0.0177(7) Uani 1 1 d . . .
H3 H 0.2733 0.1917 1.0294 0.021 Uiso 1 1 calc R . .
C4 C 0.3046(4) 0.3751(3) 1.0927(2) 0.0181(8) Uani 1 1 d . . .
H4 H 0.3458 0.3835 1.1623 0.022 Uiso 1 1 calc R . .
C5 C 0.2878(4) 0.4757(3) 1.0705(2) 0.0166(7) Uani 1 1 d . . .
H5 H 0.3163 0.5532 1.1249 0.020 Uiso 1 1 calc R . .
C6 C 0.2291(4) 0.4651(3) 0.9686(2) 0.0133(7) Uani 1 1 d . . .
C7 C 0.2457(4) 0.7732(3) 0.9957(2) 0.0135(7) Uani 1 1 d . . .
C8 C 0.3125(4) 0.8895(3) 1.0894(2) 0.0166(7) Uani 1 1 d . . .
C9 C 0.3913(4) 0.8825(3) 1.1910(2) 0.0200(8) Uani 1 1 d . . .
H9A H 0.4179 0.9625 1.2463 0.030 Uiso 1 1 calc R . .
H9B H 0.5214 0.8635 1.1942 0.030 Uiso 1 1 calc R . .
H9C H 0.2861 0.8168 1.1991 0.030 Uiso 1 1 calc R . .
C10 C 0.1665(4) 0.7679(3) 0.8912(2) 0.0162(7) Uani 1 1 d . . .
C11 C 0.1376(4) 0.8771(3) 0.8701(3) 0.0243(8) Uani 1 1 d . . .
H11A H 0.0795 0.8525 0.7960 0.036 Uiso 1 1 calc R . .
H11B H 0.2730 0.9441 0.8948 0.036 Uiso 1 1 calc R . .
H11C H 0.0413 0.9063 0.9058 0.036 Uiso 1 1 calc R . .
C12 C -0.1938(4) 0.2336(3) 0.4901(2) 0.0124(7) Uani 1 1 d . . .
C14 C -0.2363(4) 0.0281(3) 0.4327(2) 0.0137(7) Uani 1 1 d . . .
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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 '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
N3 Cu1 N3 180.0 2_566 . ?
N3 Cu1 O6 90.97(9) 2_566 2_566 ?
N3 Cu1 O6 89.03(9) . 2_566 ?
N3 Cu1 O6 89.04(9) 2_566 . ?
N3 Cu1 O6 90.96(9) . . yes
O6 Cu1 O6 180.00(12) 2_566 . ?
N3 Cu1 O8 89.32(8) 2_566 2_566 ?
N3 Cu1 O8 90.68(8) . 2_566 ?
O6 Cu1 O8 88.63(7) 2_566 2_566 ?
O6 Cu1 O8 91.37(7) . 2_566 ?
N3 Cu1 O8 90.68(8) 2_566 . ?
N3 Cu1 O8 89.32(8) . . yes
O6 Cu1 O8 91.37(7) 2_566 . ?
O6 Cu1 O8 88.63(7) . . yes
O8 Cu1 O8 180.000(1) 2_566 . ?
O2 S1 O1 114.56(12) . . ?
O2 S1 O3 112.04(13) . . ?
O1 S1 O3 111.90(13) . . ?
O2 S1 C1 106.82(14) . . ?
O1 S1 C1 105.06(13) . . ?
O3 S1 C1 105.66(12) . . ?
Cu1 O6 H6O 122.1 . . ?
Cu1 O6 H6P 110.0 . . ?
H6O O6 H6P 108.7 . . ?
H7O O7 H7P 104.6 . . ?
Cu1 O8 H8O 98.5 . . ?
Cu1 O8 H8P 109.6 . . ?
H8O O8 H8P 111.1 . . ?
H9O O9 H9P 110.0 . . ?
H10O O10 H10P 114.5 . . ?
N2 N1 C6 120.0(3) . . ?
N2 N1 H1N 104.5 . . ?
C6 N1 H1N 135.3 . . ?
N1 N2 C7 121.7(3) . . ?
C12 N3 Cu1 169.1(2) . . ?
C12 N4 C14 117.1(2) . . ?
C14 N5 H5N 127.3 . . ?
C14 N5 H5M 115.8 . . ?
H5N N5 H5M 116.1 . . ?
C14 N6 H6M 121.4 . . ?
C14 N6 H6N 121.6 . . ?
H6M N6 H6N 116.6 . . ?
C2 C1 C6 119.2(3) . . ?
C2 C1 S1 120.0(2) . . ?
C6 C1 S1 120.8(2) . . ?
C3 C2 C1 121.3(3) . . ?
C3 C2 H2 119.4 . . ?
C1 C2 H2 119.4 . . ?
C2 C3 C4 119.7(3) . . ?
C2 C3 H3 120.2 . . ?
C4 C3 H3 120.2 . . ?
C5 C4 C3 120.3(3) . . ?
C5 C4 H4 119.8 . . ?
C3 C4 H4 119.8 . . ?
C4 C5 C6 120.5(3) . . ?
C4 C5 H5 119.7 . . ?
C6 C5 H5 119.7 . . ?
C5 C6 N1 121.9(3) . . ?
C5 C6 C1 119.0(3) . . ?
N1 C6 C1 119.0(3) . . ?
N2 C7 C10 124.0(3) . . ?
N2 C7 C8 113.1(3) . . ?
C10 C7 C8 122.9(3) . . ?
O4 C8 C7 121.9(3) . . ?
O4 C8 C9 120.5(3) . . ?
C7 C8 C9 117.6(3) . . ?
C8 C9 H9A 109.5 . . ?
C8 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
C8 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
O5 C10 C7 118.6(3) . . ?
O5 C10 C11 118.5(3) . . ?
C7 C10 C11 122.9(3) . . ?
C10 C11 H11A 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C10 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
N3 C12 N4 176.5(3) . . ?
N6 C14 N5 119.4(3) . . ?
N6 C14 N4 116.8(3) . . ?
N5 C14 N4 123.8(3) . . ?
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
Cu1 N3 1.953(2) 2_566 ?
Cu1 N3 1.954(2) . yes
Cu1 O6 1.9838(18) 2_566 ?
Cu1 O6 1.9838(18) . yes
Cu1 O8 2.3956(19) 2_566 ?
Cu1 O8 2.3956(19) . yes
S1 O2 1.442(2) . ?
S1 O1 1.4492(18) . ?
S1 O3 1.467(2) . ?
S1 C1 1.773(3) . ?
O4 C8 1.227(4) . ?
O5 C10 1.246(3) . ?
O6 H6O 0.8563 . ?
O6 H6P 0.8566 . ?
O7 H7O 0.8426 . ?
O7 H7P 0.8974 . ?
O8 H8O 0.8416 . ?
O8 H8P 0.8638 . ?
O9 H9O 0.8450 . ?
O9 H9P 0.8508 . ?
O10 H10O 0.8360 . ?
O10 H10P 0.8308 . ?
N1 N2 1.312(3) . ?
N1 C6 1.400(4) . ?
N1 H1N 0.8912 . ?
N2 C7 1.323(4) . ?
N3 C12 1.150(3) . ?
N4 C12 1.306(4) . ?
N4 C14 1.350(3) . ?
N5 C14 1.328(3) . ?
N5 H5N 0.8828 . ?
N5 H5M 0.8812 . ?
N6 C14 1.326(3) . ?
N6 H6M 0.8541 . ?
N6 H6N 0.8587 . ?
C1 C2 1.382(4) . ?
C1 C6 1.414(4) . ?
C2 C3 1.376(4) . ?
C2 H2 0.9500 . ?
C3 C4 1.389(4) . ?
C3 H3 0.9500 . ?
C4 C5 1.375(4) . ?
C4 H4 0.9500 . ?
C5 C6 1.397(4) . ?
C5 H5 0.9500 . ?
C7 C10 1.473(4) . ?
C7 C8 1.489(4) . ?
C8 C9 1.495(4) . ?
C9 H9A 0.9800 . ?
C9 H9B 0.9800 . ?
C9 H9C 0.9800 . ?
C10 C11 1.492(4) . ?
C11 H11A 0.9800 . ?
C11 H11B 0.9800 . ?
C11 H11C 0.9800 . ?
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
O6 H6O O9 0.86 1.90 2.715(3) 159.2 . yes
O6 H6P O3 0.86 1.90 2.724(3) 161.5 . yes
O6 H6P S1 0.86 3.00 3.848(2) 173.5 . yes
O7 H7O O8 0.84 1.98 2.707(3) 143.2 . yes
O7 H7P O10 0.90 2.10 2.875(3) 143.9 2_466 yes
O7 H7P N6 0.90 2.70 3.409(3) 137.0 1_565 yes
O8 H8O O10 0.84 2.03 2.802(3) 152.9 . yes
O8 H8P O5 0.86 1.95 2.808(3) 169.0 . yes
O9 H9O O7 0.85 1.96 2.778(3) 163.4 1_655 yes
O9 H9P O4 0.85 2.09 2.934(3) 176.0 2_677 yes
O10 H10O O1 0.84 1.97 2.746(3) 154.4 . yes
O10 H10P O3 0.83 1.98 2.803(3) 168.6 1_455 yes
N1 H1N O5 0.89 1.74 2.565(3) 152.6 . yes
N5 H5N O7 0.88 2.09 2.874(3) 146.8 2_566 yes
N5 H5M O2 0.88 1.98 2.825(3) 160.2 2_556 yes
N6 H6M O2 0.85 2.33 3.038(3) 140.7 2_556 yes
N6 H6M O10 0.85 2.56 3.074(3) 119.6 2_456 yes
N6 H6N N4 0.86 2.18 3.031(3) 170.8 2_456 yes
