#------------------------------------------------------------------------------
#$Date: 2016-03-25 10:39:36 +0200 (Fri, 25 Mar 2016) $
#$Revision: 179758 $
#$URL: svn://www.crystallography.net/cod/cif/7/00/54/7005405.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_7005405
loop_
_publ_author_name
'Klingele, Julia'
'Prikhod'ko, Alexander I.'
'Leibeling, Guido'
'Demeshko, Serhiy'
'Dechert, Sebastian'
'Meyer, Franc'
_publ_section_title
;
 Pyrazolate-based copper(II) and nickel(II) [2 x 2] grid complexes:
 protonation-dependent self-assembly, structures and properties.
;
_journal_issue                   20
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2003
_journal_page_last               2013
_journal_paper_doi               10.1039/b701981e
_journal_year                    2007
_chemical_formula_moiety         'C68 H56 Cu4 N24 O8, 8(H2 O)'
_chemical_formula_sum            'C68 H72 Cu4 N24 O16'
_chemical_formula_weight         1735.66
_chemical_name_systematic
;
?
;
_space_group_IT_number           88
_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_Hall  '-I 4ad'
_symmetry_space_group_name_H-M   'I 41/a :2'
_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                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   22.8617(11)
_cell_length_b                   22.8617(11)
_cell_length_c                   13.8078(6)
_cell_measurement_reflns_used    21906
_cell_measurement_temperature    133(2)
_cell_measurement_theta_max      24.79
_cell_measurement_theta_min      1.72
_cell_volume                     7216.7(6)
_computing_cell_refinement       'X-AREA (Stoe & Cie, 2002)'
_computing_data_collection       'X-AREA (Stoe & Cie, 2002)'
_computing_data_reduction        'X-AREA (Stoe & Cie, 2002)'
_computing_molecular_graphics    'DIAMOND (Brandenburg, 2001)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      133(2)
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'STOE IPDS II'
_diffrn_measurement_method       ω
_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  0.0447
_diffrn_reflns_av_sigmaI/netI    0.0226
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            21906
_diffrn_reflns_theta_full        24.79
_diffrn_reflns_theta_max         24.79
_diffrn_reflns_theta_min         1.72
_exptl_absorpt_coefficient_mu    1.249
_exptl_absorpt_correction_T_max  0.7812
_exptl_absorpt_correction_T_min  0.6626
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   'X-RED (STOE & CIE, 2002)'
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.597
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3568
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.314
_refine_diff_density_min         -0.219
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         3101
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0421
_refine_ls_R_factor_gt           0.0319
_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)+(0.0377P)²+11.4388P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0731
_refine_ls_wR_factor_ref         0.0772
_reflns_number_gt                2620
_reflns_number_total             3101
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            b701981e.txt
_cod_data_source_block           Cu4L4
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               7005405
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-y+3/4, x+1/4, z+1/4'
'y+3/4, -x+3/4, z+3/4'
'x+1/2, y+1/2, z+1/2'
'-x+1, -y+1/2, z+1'
'-y+5/4, x+3/4, z+3/4'
'y+5/4, -x+5/4, z+5/4'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'y-3/4, -x-1/4, -z-1/4'
'-y-3/4, x-3/4, -z-3/4'
'-x+1/2, -y+1/2, -z+1/2'
'x, y+1/2, -z'
'y-1/4, -x+1/4, -z+1/4'
'-y-1/4, x-1/4, -z-1/4'
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 0.587283(13) 0.695328(13) 0.53983(2) 0.02476(11) Uani 1 1 d . . .
N1 N 0.50414(9) 0.67651(9) 0.51662(14) 0.0251(4) Uani 1 1 d . . .
N2 N 0.45576(9) 0.66595(9) 0.56883(15) 0.0258(5) Uani 1 1 d . . .
N3 N 0.58937(9) 0.69121(9) 0.40023(15) 0.0281(5) Uani 1 1 d . . .
N4 N 0.67072(9) 0.72046(9) 0.51971(15) 0.0297(5) Uani 1 1 d . . .
N5 N 0.31211(10) 0.62272(11) 0.48855(18) 0.0338(5) Uani 1 1 d . . .
H5 H 0.3178(13) 0.6257(13) 0.435(2) 0.027(8) Uiso 1 1 d . . .
N6 N 0.20106(11) 0.51081(11) 0.53318(19) 0.0456(6) Uani 1 1 d . . .
O1 O 0.53257(8) 0.67798(9) 0.26288(12) 0.0353(4) Uani 1 1 d . . .
O2 O 0.35006(8) 0.63487(8) 0.63896(13) 0.0323(4) Uani 1 1 d . . .
C1 C 0.43309(11) 0.65453(11) 0.41106(18) 0.0280(6) Uani 1 1 d . . .
H1 H 0.4128 0.6472 0.3540 0.034 Uiso 1 1 calc R . .
C2 C 0.49123(11) 0.66988(10) 0.42175(17) 0.0254(5) Uani 1 1 d . . .
C3 C 0.41197(11) 0.65257(11) 0.50571(18) 0.0264(5) Uani 1 1 d . . .
C4 C 0.54044(11) 0.68005(11) 0.35270(18) 0.0278(5) Uani 1 1 d . . .
C5 C 0.64257(12) 0.70834(12) 0.35110(19) 0.0313(6) Uani 1 1 d . . .
H5A H 0.6351 0.7418 0.3098 0.038 Uiso 1 1 calc R . .
H5B H 0.6566 0.6765 0.3110 0.038 Uiso 1 1 calc R . .
C6 C 0.68768(12) 0.72367(11) 0.42639(19) 0.0311(6) Uani 1 1 d . . .
C7 C 0.74467(12) 0.73926(13) 0.4021(2) 0.0384(7) Uani 1 1 d . . .
H7 H 0.7558 0.7418 0.3375 0.046 Uiso 1 1 calc R . .
C8 C 0.78444(13) 0.75099(14) 0.4744(2) 0.0439(7) Uani 1 1 d . . .
H8 H 0.8226 0.7615 0.4591 0.053 Uiso 1 1 calc R . .
C9 C 0.76692(13) 0.74698(14) 0.5705(2) 0.0434(7) Uani 1 1 d . . .
H9 H 0.7932 0.7542 0.6204 0.052 Uiso 1 1 calc R . .
C10 C 0.70985(12) 0.73217(13) 0.5903(2) 0.0378(6) Uani 1 1 d . . .
H10 H 0.6978 0.7302 0.6545 0.045 Uiso 1 1 calc R . .
C11 C 0.35543(11) 0.63655(11) 0.54948(18) 0.0297(6) Uani 1 1 d . . .
C12 C 0.25653(12) 0.59995(13) 0.5223(2) 0.0376(6) Uani 1 1 d . . .
H12A H 0.2260 0.6125 0.4782 0.045 Uiso 1 1 calc R . .
H12B H 0.2481 0.6165 0.5854 0.045 Uiso 1 1 calc R . .
C13 C 0.25498(13) 0.53354(13) 0.5299(2) 0.0389(7) Uani 1 1 d . . .
C14 C 0.30416(15) 0.49887(14) 0.5358(2) 0.0468(7) Uani 1 1 d . . .
H14 H 0.3411 0.5157 0.5332 0.056 Uiso 1 1 calc R . .
C15 C 0.29840(17) 0.43924(15) 0.5455(2) 0.0544(9) Uani 1 1 d . . .
H15 H 0.3312 0.4154 0.5509 0.065 Uiso 1 1 calc R . .
C16 C 0.24371(18) 0.41579(16) 0.5471(2) 0.0570(9) Uani 1 1 d . . .
H16 H 0.2386 0.3755 0.5516 0.068 Uiso 1 1 calc R . .
C17 C 0.19658(17) 0.45199(15) 0.5418(2) 0.0529(9) Uani 1 1 d . . .
H17 H 0.1594 0.4355 0.5442 0.063 Uiso 1 1 calc R . .
O3 O 0.09394(11) 0.56739(11) 0.51851(18) 0.0488(6) Uani 1 1 d . . .
H3B H 0.091(2) 0.596(2) 0.476(3) 0.084(15) Uiso 1 1 d . . .
H3A H 0.1311(19) 0.5544(17) 0.515(3) 0.062(11) Uiso 1 1 d . . .
O4 O 0.58879(12) 0.67308(12) 0.0864(2) 0.0517(6) Uani 1 1 d . . .
H4A H 0.5786(16) 0.6782(16) 0.138(3) 0.055(12) Uiso 1 1 d . . .
H4B H 0.5803(17) 0.6996(17) 0.065(3) 0.052(13) Uiso 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'
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 N2 175.77(9) . 12_767 ?
N3 Cu1 N1 81.44(9) . . ?
N2 Cu1 N1 98.70(8) 12_767 . ?
N3 Cu1 N4 81.53(9) . . ?
N2 Cu1 N4 97.93(9) 12_767 . ?
N1 Cu1 N4 162.27(8) . . ?
N3 Cu1 O2 110.35(8) . 12_767 ?
N2 Cu1 O2 73.86(7) 12_767 12_767 ?
N1 Cu1 O2 96.92(7) . 12_767 ?
N4 Cu1 O2 93.57(8) . 12_767 ?
N2 N1 C2 108.7(2) . . ?
N2 N1 Cu1 138.18(16) . . ?
C2 N1 Cu1 113.07(16) . . ?
N1 N2 C3 107.6(2) . . ?
N1 N2 Cu1 129.74(16) . 15_566 ?
C3 N2 Cu1 122.50(17) . 15_566 ?
C4 N3 C5 122.1(2) . . ?
C4 N3 Cu1 118.97(17) . . ?
C5 N3 Cu1 118.41(16) . . ?
C6 N4 C10 119.3(2) . . ?
C6 N4 Cu1 114.86(17) . . ?
C10 N4 Cu1 125.85(18) . . ?
C11 N5 C12 122.1(2) . . ?
C13 N6 C17 117.3(3) . . ?
C2 C1 C3 103.9(2) . . ?
N1 C2 C1 110.0(2) . . ?
N1 C2 C4 115.9(2) . . ?
C1 C2 C4 134.1(2) . . ?
N2 C3 C1 109.8(2) . . ?
N2 C3 C11 116.0(2) . . ?
C1 C3 C11 134.2(2) . . ?
O1 C4 N3 128.3(2) . . ?
O1 C4 C2 121.2(2) . . ?
N3 C4 C2 110.5(2) . . ?
N3 C5 C6 108.4(2) . . ?
N4 C6 C7 120.9(3) . . ?
N4 C6 C5 116.8(2) . . ?
C7 C6 C5 122.3(2) . . ?
C8 C7 C6 119.6(3) . . ?
C7 C8 C9 119.3(3) . . ?
C10 C9 C8 118.7(3) . . ?
N4 C10 C9 122.3(3) . . ?
O2 C11 N5 123.0(2) . . ?
O2 C11 C3 120.2(2) . . ?
N5 C11 C3 116.8(2) . . ?
N5 C12 C13 113.6(2) . . ?
N6 C13 C14 121.7(3) . . ?
N6 C13 C12 114.3(3) . . ?
C14 C13 C12 124.0(3) . . ?
C15 C14 C13 119.8(3) . . ?
C16 C15 C14 118.7(3) . . ?
C17 C16 C15 119.2(3) . . ?
N6 C17 C16 123.3(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 1.930(2) . ?
Cu1 N2 1.967(2) 12_767 ?
Cu1 N1 1.975(2) . ?
Cu1 N4 2.012(2) . ?
Cu1 O2 2.4730(18) 12_767 ?
Cu1 Cu1 4.0768(4) 12_767 ?
Cu1 Cu1 4.0768(4) 15_566 ?
Cu1 Cu1 4.7091(5) 6_564 ?
N1 N2 1.342(3) . ?
N1 C2 1.351(3) . ?
N2 C3 1.362(3) . ?
N2 Cu1 1.967(2) 15_566 ?
N3 C4 1.322(3) . ?
N3 C5 1.447(3) . ?
N4 C6 1.348(3) . ?
N4 C10 1.349(4) . ?
N5 C11 1.338(3) . ?
N5 C12 1.450(4) . ?
N6 C13 1.338(4) . ?
N6 C17 1.354(4) . ?
O1 C4 1.254(3) . ?
O2 C11 1.242(3) . ?
C1 C2 1.383(4) . ?
C1 C3 1.394(4) . ?
C2 C4 1.493(4) . ?
C3 C11 1.473(4) . ?
C5 C6 1.506(4) . ?
C6 C7 1.392(4) . ?
C7 C8 1.377(4) . ?
C8 C9 1.388(4) . ?
C9 C10 1.375(4) . ?
C12 C13 1.522(4) . ?
C13 C14 1.378(4) . ?
C14 C15 1.376(5) . ?
C15 C16 1.361(5) . ?
C16 C17 1.361(5) . ?
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
N5 H5 O3 0.76(3) 2.40(3) 3.135(4) 165(3) 4_454
O3 H3B O4 0.88(5) 1.97(5) 2.819(4) 163(4) 10_556
O3 H3A N6 0.90(4) 1.90(4) 2.777(4) 163(3) .
O4 H4A O1 0.76(4) 2.02(4) 2.758(3) 164(4) .
O4 H4B O1 0.70(4) 2.19(4) 2.879(3) 168(4) 12_766
