##############################################################################
#                                                                            #
# This CIF contains the data in a paper accepted for publication in          #
# Acta Crystallographica Section E. It conforms to the requirements of       #
# Notes for Authors for Acta Crystallographica Section E, and has been       #
# peer reviewed under the auspices of the IUCr Commission on Journals.       #
#                                                                            #
# Full details of the Crystallographic Information File format               #
# are given in the paper "The Crystallographic Information File (CIF):       #
# a New Standard Archive File for Crystallography" by S. R. Hall, F. H.      #
# Allen and I. D. Brown [Acta Cryst. (1991), A47, 655-685].                  #
#                                                                            #
# The current version of the core CIF dictionary is obtainable from          #
# ftp://ftp.iucr.org/pub/cif_core.dic.                                       #
#                                                                            #
# Software is freely available for graphical display of the structure(s)     #
# in this CIF. For information consult the CIF software page                 #
# http://www.iucr.org/resources/cif/software.                                #
#                                                                            #
# This file may be used for bona fide research purposes within the           #
# scientific community so long as proper attribution is given to the journal # 
# article from which it was obtained.                                        #
#                                                                            #
##############################################################################
data_I
_audit_creation_method     SHELXL-97
_chemical_name_systematic
;
cyclo-Tetrakis(μ-3-acetyl-4-methyl-1H-pyrazole-5-carboxylato-
κ⁴N²,O³:N¹,O⁵)tetrakis[aquacopper(II)]
tetradecahydrate
;
_chemical_name_common     ?
_chemical_formula_moiety     'C28 H32 Cu4 N8 O16, 14(H2 O)'
_chemical_formula_sum     'C28 H60 Cu4 N8 O30'
_chemical_formula_iupac     '[Cu4 (C7 H6 N2 O3)4 (H2 O)4], 14H2 O'
_chemical_formula_weight     1243.00
_chemical_melting_point     ?
_symmetry_cell_setting     tetragonal
_symmetry_space_group_name_H-M     'I 41/a'
_symmetry_space_group_name_Hall     '-I 4ad'
loop_
    _symmetry_equiv_pos_as_xyz
    'x, y, z'
    '-y+3/4, x+1/4, z+1/4'
    '-x, -y+1/2, z'
    'y+1/4, -x+1/4, z+1/4'
    'x+1/2, y+1/2, z+1/2'
    '-y+5/4, x+3/4, z+3/4'
    '-x+1/2, -y+1, z+1/2'
    'y+3/4, -x+3/4, z+3/4'
    '-x, -y, -z'
    'y-3/4, -x-1/4, -z-1/4'
    'x, y-1/2, -z'
    '-y-1/4, x-1/4, -z-1/4'
    '-x+1/2, -y+1/2, -z+1/2'
    'y-1/4, -x+1/4, -z+1/4'
    'x+1/2, y, -z+1/2'
    '-y+1/4, x+1/4, -z+1/4'
_cell_length_a     13.8502(7)
_cell_length_b     13.8502(7)
_cell_length_c     26.280(3)
_cell_angle_alpha     90.00
_cell_angle_beta     90.00
_cell_angle_gamma     90.00
_cell_volume     5041.1(6)
_cell_formula_units_Z     4
_cell_measurement_reflns_used     9905
_cell_measurement_theta_min     2.59
_cell_measurement_theta_max     30.28
_cell_measurement_temperature     100(2)
_exptl_crystal_description     block
_exptl_crystal_colour     blue
_exptl_crystal_size_max     0.35
_exptl_crystal_size_mid     0.25
_exptl_crystal_size_min     0.15
_exptl_crystal_density_diffrn     1.638
_exptl_crystal_density_meas     ?
_exptl_crystal_density_method     'not measured'
_exptl_crystal_F_000     2560
_exptl_absorpt_coefficient_mu     1.762
_exptl_absorpt_correction_type     multi-scan
_exptl_absorpt_process_details     '(SADABS; Sheldrick, 2008)'
_exptl_absorpt_correction_T_min     0.5775
_exptl_absorpt_correction_T_max     0.7780
_exptl_special_details     ?
_diffrn_ambient_temperature     100(2)
_diffrn_radiation_type     MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_source     'fine-focus sealed tube'
_diffrn_radiation_monochromator     'flat graphite crystal'
_diffrn_measurement_device_type     'Bruker SMART APEXII CCD'
_diffrn_measurement_device
                              '62mm x 62mm CCD camera on three-circle goniostat'
_diffrn_measurement_method     'φ scans and ω scans'
_diffrn_detector_area_resol_mean     16
_diffrn_reflns_number     37816
_diffrn_reflns_av_R_equivalents     0.0374
_diffrn_reflns_av_sigmaI/netI     0.0201
_diffrn_reflns_theta_min     1.66
_diffrn_reflns_theta_max     30.93
_diffrn_reflns_theta_full     30.93
_diffrn_measured_fraction_theta_max     0.998
_diffrn_measured_fraction_theta_full     0.998
_diffrn_reflns_limit_h_min     -19
_diffrn_reflns_limit_h_max     19
_diffrn_reflns_limit_k_min     -19
_diffrn_reflns_limit_k_max     19
_diffrn_reflns_limit_l_min     -37
_diffrn_reflns_limit_l_max     38
_diffrn_standards_number     ?
_diffrn_standards_interval_count     ?
_diffrn_standards_interval_time     ?
_diffrn_standards_decay_%     ?
_refine_special_details
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;
_reflns_number_total     3993
_reflns_number_gt     3254
_reflns_threshold_expression     I>2sigma(I)
_refine_ls_structure_factor_coef     Fsqd
_refine_ls_matrix_type     full
_refine_ls_R_factor_all     0.0476
_refine_ls_R_factor_gt     0.0337
_refine_ls_wR_factor_gt     0.0877
_refine_ls_wR_factor_ref     0.0965
_refine_ls_goodness_of_fit_ref     1.056
_refine_ls_restrained_S_all     1.056
_refine_ls_number_reflns     3993
_refine_ls_number_parameters     165
_refine_ls_number_restraints     0
_refine_ls_hydrogen_treatment     constr
_refine_ls_weighting_scheme     calc
_refine_ls_weighting_details
        'calc w=1/[σ²(Fo²)+(0.0463P)²+11.3899P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_hydrogens     geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary     difmap
_refine_ls_shift/su_max     0.000
_refine_ls_shift/su_mean     0.000
_refine_diff_density_max     1.202
_refine_diff_density_min     -0.581
_refine_ls_extinction_method     none
_refine_ls_extinction_coef     ?
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'
_computing_data_collection     'APEX2 (Bruker, 2009)'
_computing_cell_refinement     'SAINT (Bruker, 2009)'
_computing_data_reduction     'SAINT (Bruker, 2009)'
_computing_structure_solution     'SIR2004 (Burla et al., 2005)'
_computing_structure_refinement     'SHELXL97 (Sheldrick, 2008)'
_computing_molecular_graphics     'DIAMOND (Brandenburg, 2009)'
_computing_publication_material     'SHELXL97 (Sheldrick, 2008)'
loop_
    _atom_site_type_symbol
    _atom_site_label
    _atom_site_fract_x
    _atom_site_fract_y
    _atom_site_fract_z
    _atom_site_U_iso_or_equiv
    _atom_site_adp_type
    _atom_site_calc_flag
    _atom_site_refinement_flags
    _atom_site_occupancy
    _atom_site_symmetry_multiplicity
    _atom_site_disorder_assembly
    _atom_site_disorder_group
    Cu Cu1 0.164669(16) 0.330841(17) 0.089037(8) 0.01628(8) Uani d . 1 1 . .
    O O1 0.19490(11) 0.47600(11) 0.13584(6) 0.0220(3) Uani d . 1 1 . .
    O O2 0.18857(10) 0.33808(11) 0.01594(5) 0.0191(3) Uani d . 1 1 . .
    O O3 0.11824(11) 0.36118(11) -0.05924(5) 0.0207(3) Uani d . 1 1 . .
    O O4 0.30114(11) 0.29660(13) 0.09939(6) 0.0290(4) Uani d . 1 1 . .
    H H4O 0.3390 0.2983 0.0745 0.044 Uiso d R 1 1 . .
    H H4P 0.3283 0.3161 0.1259 0.044 Uiso d R 1 1 . .
    O O5 0.42451(14) 0.31765(18) 0.02160(7) 0.0496(6) Uani d . 1 1 . .
    H H5O 0.4877 0.3162 0.0229 0.074 Uiso d R 1 1 . .
    H H5P 0.3994 0.3042 -0.0049 0.074 Uiso d R 1 1 . .
    O O6 0.34700(12) 0.60006(12) 0.10161(6) 0.0300(3) Uani d . 1 1 . .
    H H6O 0.3363 0.6619 0.0904 0.045 Uiso d R 1 1 . .
    H H6P 0.2916 0.5694 0.1089 0.045 Uiso d R 1 1 . .
    O O7 0.32202(12) 0.28601(12) -0.06718(6) 0.0275(3) Uani d . 1 1 . .
    H H7O 0.3430 0.3107 -0.0939 0.041 Uiso d R 1 1 . .
    H H7P 0.2651 0.2997 -0.0606 0.041 Uiso d R 1 1 . .
    O O8 0.4789(2) 0.4970(4) 0.04080(17) 0.0610(16) Uani d P 0.50 1 . .
    H H8O 0.4561 0.4429 0.0310 0.092 Uiso d PR 0.50 1 . .
    H H8P 0.4390 0.5278 0.0564 0.092 Uiso d PR 0.50 1 . .
    N N1 0.13450(12) 0.30012(11) 0.16041(6) 0.0161(3) Uani d . 1 1 . .
    N N2 0.03441(11) 0.36571(11) 0.06776(6) 0.0152(3) Uani d . 1 1 . .
    C C1 0.17729(14) 0.46349(14) 0.18133(8) 0.0191(4) Uani d . 1 1 . .
    C C2 0.18659(19) 0.54292(15) 0.21907(9) 0.0284(5) Uani d . 1 1 . .
    H H2A 0.2408 0.5293 0.2419 0.043 Uiso calc R 1 1 . .
    H H2B 0.1269 0.5478 0.2389 0.043 Uiso calc R 1 1 . .
    H H2C 0.1982 0.6040 0.2012 0.043 Uiso calc R 1 1 . .
    C C3 0.14765(13) 0.36668(13) 0.19793(7) 0.0159(3) Uani d . 1 1 . .
    C C4 -0.07281(13) 0.38673(13) 0.00422(7) 0.0161(3) Uani d . 1 1 . .
    C C5 -0.11564(15) 0.39273(16) -0.04787(7) 0.0218(4) Uani d . 1 1 . .
    H H5A -0.0653 0.3807 -0.0733 0.033 Uiso calc R 1 1 . .
    H H5B -0.1430 0.4572 -0.0531 0.033 Uiso calc R 1 1 . .
    H H5C -0.1667 0.3442 -0.0513 0.033 Uiso calc R 1 1 . .
    C C6 0.02326(13) 0.36773(13) 0.01655(7) 0.0145(3) Uani d . 1 1 . .
    C C7 0.11406(13) 0.35477(13) -0.01228(7) 0.0159(3) Uani d . 1 1 . .
loop_
    _atom_site_aniso_label
    _atom_site_aniso_U_11
    _atom_site_aniso_U_22
    _atom_site_aniso_U_33
    _atom_site_aniso_U_12
    _atom_site_aniso_U_13
    _atom_site_aniso_U_23
    Cu1 0.01545(12) 0.02178(13) 0.01160(11) -0.00004(8) -0.00341(8) 0.00135(8)
    O1 0.0244(7) 0.0211(7) 0.0207(7) -0.0033(5) -0.0084(5) 0.0037(5)
    O2 0.0159(6) 0.0270(7) 0.0145(6) -0.0023(5) -0.0004(5) 0.0028(5)
    O3 0.0246(7) 0.0253(7) 0.0122(6) -0.0018(6) 0.0017(5) 0.0031(5)
    O4 0.0222(7) 0.0459(10) 0.0190(7) 0.0079(7) -0.0080(6) -0.0070(7)
    O5 0.0298(9) 0.0881(17) 0.0307(9) 0.0203(10) -0.0046(8) -0.0200(10)
    O6 0.0302(8) 0.0300(8) 0.0297(8) -0.0047(7) -0.0066(7) 0.0033(7)
    O7 0.0244(7) 0.0294(8) 0.0288(8) -0.0005(6) 0.0089(6) 0.0036(6)
    O8 0.0102(14) 0.102(4) 0.071(3) 0.0179(18) -0.0138(16) -0.068(3)
    N1 0.0212(8) 0.0149(7) 0.0121(7) 0.0011(6) -0.0041(6) -0.0001(5)
    N2 0.0158(7) 0.0197(7) 0.0102(6) -0.0028(5) -0.0003(5) 0.0028(5)
    C1 0.0199(8) 0.0157(8) 0.0216(9) 0.0016(6) -0.0083(7) -0.0002(7)
    C2 0.0416(13) 0.0164(9) 0.0270(10) -0.0008(8) -0.0070(9) -0.0035(8)
    C3 0.0188(8) 0.0150(8) 0.0138(8) 0.0031(6) -0.0046(6) -0.0008(6)
    C4 0.0172(8) 0.0170(8) 0.0140(8) -0.0046(6) -0.0030(6) 0.0045(6)
    C5 0.0218(9) 0.0284(10) 0.0152(8) -0.0034(8) -0.0070(7) 0.0038(7)
    C6 0.0164(8) 0.0158(8) 0.0112(7) -0.0037(6) -0.0017(6) 0.0029(6)
    C7 0.0184(8) 0.0155(8) 0.0138(8) -0.0037(6) 0.0009(6) 0.0025(6)
_geom_special_details
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
    _geom_bond_atom_site_label_1
    _geom_bond_atom_site_label_2
    _geom_bond_site_symmetry_2
    _geom_bond_distance
    _geom_bond_publ_flag
    Cu1 N2 . 1.9495(16) yes
    Cu1 O2 . 1.9519(14) yes
    Cu1 O4 . 1.9676(15) yes
    Cu1 N1 . 1.9682(16) yes
    Cu1 O1 . 2.3938(15) yes
    Cu1 Cu1 14 4.0600(4) yes
    Cu1 Cu1 16 4.0600(4) yes
    Cu1 Cu1 3 5.0814(5) yes
    O1 C1 . 1.232(3) ?
    O2 C7 . 1.292(2) ?
    O3 C7 . 1.239(2) ?
    O4 H4O . 0.8400 ?
    O4 H4P . 0.8355 ?
    O5 H5O . 0.8760 ?
    O5 H5P . 0.7998 ?
    O6 H6O . 0.9174 ?
    O6 H6P . 0.8985 ?
    O7 H7O . 0.8324 ?
    O7 H7P . 0.8289 ?
    O8 H8O . 0.8529 ?
    O8 H8P . 0.8080 ?
    N1 N2 14 1.329(2) ?
    N1 C3 . 1.362(2) ?
    N2 N1 16 1.329(2) ?
    N2 C6 . 1.355(2) ?
    C1 C3 . 1.469(3) ?
    C1 C2 . 1.487(3) ?
    C2 H2A . 0.9800 ?
    C2 H2B . 0.9800 ?
    C2 H2C . 0.9800 ?
    C3 C4 14 1.405(3) ?
    C4 C6 . 1.394(2) ?
    C4 C3 16 1.405(3) ?
    C4 C5 . 1.494(3) ?
    C5 H5A . 0.9800 ?
    C5 H5B . 0.9800 ?
    C5 H5C . 0.9800 ?
    C6 C7 . 1.479(3) ?
loop_
    _geom_angle_atom_site_label_1
    _geom_angle_atom_site_label_2
    _geom_angle_atom_site_label_3
    _geom_angle_site_symmetry_1
    _geom_angle_site_symmetry_3
    _geom_angle
    _geom_angle_publ_flag
    N2 Cu1 O2 . . 82.06(6) yes
    N2 Cu1 O4 . . 171.24(6) ?
    O2 Cu1 O4 . . 89.18(6) yes
    N2 Cu1 N1 . . 97.49(7) yes
    O2 Cu1 N1 . . 170.07(6) ?
    O4 Cu1 N1 . . 91.15(7) yes
    N2 Cu1 O1 . . 95.81(6) ?
    O2 Cu1 O1 . . 115.65(6) ?
    O4 Cu1 O1 . . 87.90(6) ?
    N1 Cu1 O1 . . 74.28(6) yes
    N2 Cu1 Cu1 . 14 94.38(5) ?
    O2 Cu1 Cu1 . 14 123.35(4) ?
    O4 Cu1 Cu1 . 14 90.48(5) ?
    N1 Cu1 Cu1 . 14 46.73(5) ?
    O1 Cu1 Cu1 . 14 120.95(4) ?
    N2 Cu1 Cu1 . 16 44.57(5) ?
    O2 Cu1 Cu1 . 16 125.84(4) ?
    O4 Cu1 Cu1 . 16 144.00(5) ?
    N1 Cu1 Cu1 . 16 55.97(5) ?
    O1 Cu1 Cu1 . 16 70.56(4) ?
    Cu1 Cu1 Cu1 14 16 77.482(5) ?
    N2 Cu1 Cu1 . 3 43.82(5) ?
    O2 Cu1 Cu1 . 3 100.07(4) ?
    O4 Cu1 Cu1 . 3 139.12(6) ?
    N1 Cu1 Cu1 . 3 73.39(5) ?
    O1 Cu1 Cu1 . 3 121.81(4) ?
    Cu1 Cu1 Cu1 14 3 51.259(3) ?
    Cu1 Cu1 Cu1 16 3 51.259(3) ?
    C1 O1 Cu1 . . 110.22(12) ?
    C7 O2 Cu1 . . 116.03(12) ?
    Cu1 O4 H4O . . 119.0 ?
    Cu1 O4 H4P . . 118.0 ?
    H4O O4 H4P . . 111.1 ?
    H5O O5 H5P . . 117.6 ?
    H6O O6 H6P . . 111.8 ?
    H7O O7 H7P . . 114.5 ?
    H8O O8 H8P . . 111.3 ?
    N2 N1 C3 14 . 108.05(15) ?
    N2 N1 Cu1 14 . 130.03(12) ?
    C3 N1 Cu1 . . 121.00(13) ?
    N1 N2 C6 16 . 108.91(15) ?
    N1 N2 Cu1 16 . 137.70(12) ?
    C6 N2 Cu1 . . 113.30(12) ?
    O1 C1 C3 . . 118.16(17) ?
    O1 C1 C2 . . 121.73(18) ?
    C3 C1 C2 . . 120.11(18) ?
    C1 C2 H2A . . 109.5 ?
    C1 C2 H2B . . 109.5 ?
    H2A C2 H2B . . 109.5 ?
    C1 C2 H2C . . 109.5 ?
    H2A C2 H2C . . 109.5 ?
    H2B C2 H2C . . 109.5 ?
    N1 C3 C4 . 14 109.93(16) ?
    N1 C3 C1 . . 116.13(16) ?
    C4 C3 C1 14 . 133.70(17) ?
    C6 C4 C3 . 16 103.01(15) ?
    C6 C4 C5 . . 127.02(18) ?
    C3 C4 C5 16 . 129.97(17) ?
    C4 C5 H5A . . 109.5 ?
    C4 C5 H5B . . 109.5 ?
    H5A C5 H5B . . 109.5 ?
    C4 C5 H5C . . 109.5 ?
    H5A C5 H5C . . 109.5 ?
    H5B C5 H5C . . 109.5 ?
    N2 C6 C4 . . 110.08(16) ?
    N2 C6 C7 . . 114.16(15) ?
    C4 C6 C7 . . 135.66(17) ?
    O3 C7 O2 . . 123.20(17) ?
    O3 C7 C6 . . 122.78(17) ?
    O2 C7 C6 . . 114.02(15) ?
loop_
    _geom_hbond_atom_site_label_D
    _geom_hbond_atom_site_label_H
    _geom_hbond_atom_site_label_A
    _geom_hbond_site_symmetry_A
    _geom_hbond_distance_DH
    _geom_hbond_distance_HA
    _geom_hbond_distance_DA
    _geom_hbond_angle_DHA
    _geom_hbond_publ_flag
    O4 H4O O5 . 0.84 1.84 2.680(3) 173.0 yes
    O4 H4P O3 2 0.84 2.03 2.868(2) 177.2 yes
    O5 H5O O5 3_655 0.88 2.22 2.808(4) 124.4 yes
    O5 H5P O7 . 0.80 1.97 2.766(3) 171.1 yes
    O6 H6O O7 11_565 0.92 1.84 2.752(2) 176.8 yes
    O6 H6P O1 . 0.90 1.99 2.863(2) 163.3 yes
    O7 H7O O6 8_454 0.83 1.92 2.707(2) 156.7 yes
    O7 H7P O3 . 0.83 2.21 3.016(2) 165.5 yes
    O7 H7P O2 . 0.83 2.33 2.951(2) 131.6 yes
    O8 H8O O5 . 0.85 1.81 2.644(5) 167.1 yes
    O8 H8P O6 . 0.81 2.01 2.815(4) 174.1 yes
data_global
_journal_date_recd_electronic     2011-07-26
_journal_date_accepted     2011-08-01
_journal_name_full     'Acta Crystallographica, Section E'
_journal_year     2011
_journal_volume     67
_journal_issue      9
_journal_page_first     m1260
_journal_page_last     m1261
_journal_paper_category     QM
_journal_coeditor_code     JH2318
_publ_contact_author_name     'Sergey Malinkin'
_publ_contact_author_address
;
Kiev National Taras Shevchenko University,
Department of Chemistry,
Volodymyrska Str. 64,
01601 Kiev, Ukraine
;
_publ_contact_author_email     malinachem@mail.ru
_publ_contact_author_fax      380442393393
_publ_contact_author_phone      380442393393
_publ_section_title
;\
cyclo-Tetrakis(μ-3-acetyl-4-methyl-1H-pyrazole-5-carboxylato-\
κ⁴N²,O³:N¹,O⁵)tetrakis[aquacopper(II)]
tetradecahydrate
;
loop_
    _publ_author_name
    _publ_author_footnote
    _publ_author_address
    'Malinkin, Sergey' .
;
Kiev National Taras Shevchenko University,
Department of Chemistry,
Volodymyrska Str. 64,
01601 Kiev, Ukraine
;
    'Golenya, Irina A.' .
;
Kiev National Taras Shevchenko University,
Department of Chemistry,
Volodymyrska Str. 64,
01601 Kiev, Ukraine
;
    'Pavlenko, Vadim A.' .
;
Kiev National Taras Shevchenko University,
Department of Chemistry,
Volodymyrska Str. 64,
01601 Kiev, Ukraine
;
    'Haukka, Matti' .
;
University of Joensuu, Department of Chemistry,
PO Box 111, FI-80101 Joensuu, Finland
;
    'Iskenderov, Turganbay S.' .
;
Kiev National Taras Shevchenko University,
Department of Chemistry,
Volodymyrska Str. 64,
01601 Kiev, Ukraine
;
