#------------------------------------------------------------------------------
#$Date: 2016-02-20 22:30:07 +0200 (Sat, 20 Feb 2016) $
#$Revision: 176789 $
#$URL: svn://www.crystallography.net/cod/cif/2/22/78/2227872.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_2227872
loop_
_publ_author_name
'Zhou, Xin-Hui'
_publ_section_title
;
 Piperazine-1,4-diium bis(2-carboxy-1H-pyrazole-4-carboxylate)
 tetrahydrate
;
_journal_coeditor_code           OM2361
_journal_issue                   10
_journal_name_full               'Acta Crystallographica Section E'
_journal_page_first              o2578
_journal_paper_doi               10.1107/S160053681003655X
_journal_volume                  66
_journal_year                    2010
_chemical_formula_iupac          'C4 H12 N2, 2C5 H3 N2 O4, 4H2 O'
_chemical_formula_moiety         'C4 H12 N2, 2(C5 H3 N2 O4), 4(H2 O)'
_chemical_formula_sum            'C14 H26 N6 O12'
_chemical_formula_weight         470.41
_chemical_name_systematic
;
Piperazine-1,4-diium bis(2-carboxy-1H-pyrazole-4-carboxylate)
tetrahydrate
;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 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                 90.812(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   8.3363(13)
_cell_length_b                   16.246(3)
_cell_length_c                   7.3930(11)
_cell_measurement_reflns_used    1373
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      24.0
_cell_measurement_theta_min      2.7
_cell_volume                     1001.1(3)
_computing_cell_refinement       'SAINT (Bruker, 2000)'
_computing_data_collection       'SMART (Bruker, 2000)'
_computing_data_reduction        'SAINT (Bruker, 2000)'
_computing_molecular_graphics    'DIAMOND (Brandenburg, 2008)'
_computing_publication_material  'SHELXTL (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXTL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXTL (Sheldrick, 2008)'
_diffrn_ambient_temperature      291(2)
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker SMART APEX CCD'
_diffrn_measurement_method       'phi and omega scans'
_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  0.0507
_diffrn_reflns_av_sigmaI/netI    0.0491
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            5265
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         26.00
_diffrn_reflns_theta_min         2.44
_exptl_absorpt_coefficient_mu    0.137
_exptl_absorpt_correction_T_max  0.9838
_exptl_absorpt_correction_T_min  0.9798
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '(SADABS; Bruker, 2000)'
_exptl_crystal_colour            white
_exptl_crystal_density_diffrn    1.560
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             496
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.407
_refine_diff_density_min         -0.230
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     169
_refine_ls_number_reflns         1946
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0773
_refine_ls_R_factor_gt           0.0588
_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)+(0.0729P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1365
_refine_ls_wR_factor_ref         0.1466
_reflns_number_gt                1524
_reflns_number_total             1946
_reflns_threshold_expression     I>2sigma(I)
_cod_data_source_file            om2361.cif
_cod_data_source_block           I
_cod_original_cell_volume        1001.2(3)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               2227872
_cod_database_fobs_code          2227872
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'
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_disorder_assembly
_atom_site_disorder_group
C C1 1.1506(3) 0.78226(15) 0.2962(3) 0.0267(6) Uani d . 1 . .
C C2 0.9861(3) 0.77149(14) 0.2216(3) 0.0233(6) Uani d . 1 . .
C C3 0.8727(3) 0.82885(15) 0.1741(3) 0.0256(6) Uani d . 1 . .
H H3 0.8827 0.8858 0.1785 0.031 Uiso calc R 1 . .
C C4 0.7391(3) 0.78344(14) 0.1178(3) 0.0226(5) Uani d . 1 . .
C C5 0.5785(3) 0.81182(15) 0.0528(3) 0.0246(6) Uani d . 1 . .
C C6 0.6653(4) 0.51108(17) -0.0379(5) 0.0455(8) Uani d . 1 . .
H H6A 0.7149 0.4999 0.0790 0.055 Uiso calc R 1 . .
H H6B 0.7496 0.5242 -0.1223 0.055 Uiso calc R 1 . .
C C7 0.4237(3) 0.56416(16) 0.1024(4) 0.0380(7) Uani d . 1 . .
H H7A 0.3509 0.6107 0.1070 0.046 Uiso calc R 1 . .
H H7B 0.4666 0.5548 0.2233 0.046 Uiso calc R 1 . .
N N1 0.9196(2) 0.69726(13) 0.1933(3) 0.0266(5) Uani d . 1 . .
H H1 0.962(3) 0.6522(18) 0.220(4) 0.032 Uiso d . 1 . .
N N2 0.7696(2) 0.70254(12) 0.1296(3) 0.0262(5) Uani d . 1 . .
N N3 0.5556(3) 0.58226(14) -0.0224(3) 0.0399(7) Uani d . 1 . .
H H3A 0.604(4) 0.6268(19) 0.020(4) 0.048 Uiso d . 1 . .
H H3B 0.514(4) 0.5944(18) -0.130(4) 0.048 Uiso d . 1 . .
O O1 1.2097(2) 0.85001(11) 0.3144(3) 0.0454(6) Uani d . 1 . .
O O2 1.2193(2) 0.71272(11) 0.3390(3) 0.0360(5) Uani d . 1 . .
H H2 1.311(4) 0.7215(17) 0.394(4) 0.043 Uiso d . 1 . .
O O3 0.5431(2) 0.88609(10) 0.0779(3) 0.0360(5) Uani d . 1 . .
O O4 0.4901(2) 0.75870(11) -0.0188(3) 0.0358(5) Uani d . 1 . .
O O5 0.0107(3) 0.53912(14) 0.2765(4) 0.0528(7) Uani d . 1 . .
H H5A -0.077(5) 0.510(2) 0.316(5) 0.063 Uiso d . 1 . .
H H5B 0.093(5) 0.539(2) 0.346(5) 0.063 Uiso d . 1 . .
O O6 0.2621(2) 0.51492(13) 0.5325(3) 0.0476(6) Uani d . 1 . .
H H6C 0.323(4) 0.472(2) 0.486(5) 0.057 Uiso d . 1 . .
H H6D 0.320(4) 0.549(2) 0.556(5) 0.057 Uiso d . 1 . .
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'
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
O1 C1 O2 . . 125.7(2) ?
O1 C1 C2 . . 121.4(2) ?
O2 C1 C2 . . 112.9(2) ?
N1 C2 C3 . . 106.9(2) ?
N1 C2 C1 . . 122.8(2) ?
C3 C2 C1 . . 130.3(2) ?
C2 C3 C4 . . 105.2(2) ?
C2 C3 H3 . . 127.4 ?
C4 C3 H3 . . 127.4 ?
N2 C4 C3 . . 110.4(2) ?
N2 C4 C5 . . 119.6(2) ?
C3 C4 C5 . . 130.0(2) ?
O4 C5 O3 . . 126.1(2) ?
O4 C5 C4 . . 116.5(2) ?
O3 C5 C4 . . 117.5(2) ?
N3 C6 C7 . 3_665 111.0(2) ?
N3 C6 H6A . . 109.4 ?
C7 C6 H6A 3_665 . 109.4 ?
N3 C6 H6B . . 109.4 ?
C7 C6 H6B 3_665 . 109.4 ?
H6A C6 H6B . . 108.0 ?
N3 C7 C6 . 3_665 109.4(2) ?
N3 C7 H7A . . 109.8 ?
C6 C7 H7A 3_665 . 109.8 ?
N3 C7 H7B . . 109.8 ?
C6 C7 H7B 3_665 . 109.8 ?
H7A C7 H7B . . 108.2 ?
N2 N1 C2 . . 112.3(2) ?
N2 N1 H1 . . 122.4(18) ?
C2 N1 H1 . . 125.1(19) ?
N1 N2 C4 . . 105.21(19) ?
C7 N3 C6 . . 111.1(2) ?
C7 N3 H3A . . 106(2) ?
C6 N3 H3A . . 113(2) ?
C7 N3 H3B . . 108(2) ?
C6 N3 H3B . . 110(2) ?
H3A N3 H3B . . 108(3) ?
C1 O2 H2 . . 110.5(18) ?
H5A O5 H5B . . 117(3) ?
H6C O6 H6D . . 107(3) ?
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
C1 O1 . 1.213(3) ?
C1 O2 . 1.304(3) ?
C1 C2 . 1.481(3) ?
C2 N1 . 1.342(3) ?
C2 C3 . 1.369(3) ?
C3 C4 . 1.395(3) ?
C3 H3 . 0.9300 ?
C4 N2 . 1.341(3) ?
C4 C5 . 1.489(3) ?
C5 O4 . 1.248(3) ?
C5 O3 . 1.256(3) ?
C6 N3 . 1.480(4) ?
C6 C7 3_665 1.504(4) ?
C6 H6A . 0.9700 ?
C6 H6B . 0.9700 ?
C7 N3 . 1.476(4) ?
C7 C6 3_665 1.504(4) ?
C7 H7A . 0.9700 ?
C7 H7B . 0.9700 ?
N1 N2 . 1.333(3) ?
N1 H1 . 0.84(3) ?
N3 H3A . 0.88(3) ?
N3 H3B . 0.88(3) ?
O2 H2 . 0.87(3) ?
O5 H5A . 0.92(4) ?
O5 H5B . 0.85(4) ?
O6 H6C . 0.93(3) ?
O6 H6D . 0.76(3) ?
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
N1 H1 O5 1_655 0.84(3) 1.93(3) 2.746(3) 167(3)
O2 H2 O4 4_676 0.87(3) 1.65(3) 2.520(2) 175(3)
N3 H3A O4 . 0.88(3) 2.36(3) 2.918(3) 121(2)
N3 H3A N2 . 0.88(3) 2.01(3) 2.865(3) 162(3)
N3 H3B O3 4_575 0.88(3) 2.20(3) 2.999(3) 150(3)
O5 H5B O6 . 0.85(4) 2.00(4) 2.831(3) 166(3)
O5 H5A O6 3_566 0.92(4) 1.96(4) 2.833(3) 157(3)
O6 H6C O3 2_645 0.93(3) 1.85(3) 2.779(3) 173(3)
O6 H6D O3 4_576 0.76(3) 2.14(3) 2.858(3) 158(4)
C6 H6B O5 3_665 0.97 2.53 3.348(4) 141.7
C7 H7A O1 4_475 0.97 2.53 3.091(3) 116.8
