##############################################################################
#                                                                            #
# 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_global
_audit_creation_method     'from SHELXTL CIF, local template and enCIFer'
_journal_date_recd_electronic     2017-12-08
_journal_date_accepted     2018-02-08
_journal_name_full     'Acta Crystallographica, Section E'
_journal_year     2018
_journal_volume     74
_journal_issue      3
_journal_page_first     357
_journal_page_last     362
_journal_paper_category     GM
_journal_paper_doi     10.1107/S2056989018002359
_journal_coeditor_code     VM2208
_publ_contact_author_name     'Dr. Ian D. Giles'
_publ_contact_author_address
;
CBMSE, Code 6910
Naval Research Laboratory
4555 Overlook Ave, SW
Washington, DC 20375
;
_publ_contact_author_email     'ian.giles@nrl.navy.mil'
_publ_contact_author_fax     '(202)767-1264'
_publ_contact_author_phone     '(202)767-9594'
_publ_section_title
;
Two CuII complexes of 3,4,5-trimethyl-1H-pyrazole
;
_publ_section_title_footnote     .
loop_
    _publ_author_name
    _publ_author_footnote
    _publ_author_address
;
Vincent, Collin J.
;
 ?
;
Department of Chemistry
Washington College
300 Washington Ave.
Chestertown, MD 21620, USA
;
;
Giles, Ian D.
;
 ?
;
CBMSE, Code 6910
U. S. Naval Research Laboratory
4555 Overlook Ave, SW
Washington, DC 20375, USA
;
;
Deschamps, Jeffrey R.
;
 ?
;
CBMSE, Code 6910
U. S. Naval Research Laboratory
4555 Overlook Ave, SW
Washington, DC 20375, USA
;
_publ_section_synopsis
;
The crystal structures of two CuII complexes of
3,4,5-trimethyl-1H-pyrazole,
cis-[{CuCl[3,4,5-(CH₃)₃(C₃H₂N₂)]₂}₂(μ-Cl)₂] and
[Cu{3,4,5-(CH₃)₃(C₃HN₂)}₄(H₂O)](NO₃)₂, are presented and
compared to the 3-methyl-1H-pyrazole and
1H-3,5-dimethylpyrozole analogues.
;
data_1
_database_code_depnum_ccdc_archive 'CCDC 1823017'
_audit_creation_method     'SHELXL-2014/7'
_chemical_name_systematic
;
Di-μ-chlorido-bis[chloridobis(3,4,5-trimethyl-1H-pyrazole-\
κN²)copper(II)]
;
_chemical_name_common     ?
_chemical_formula_moiety     'C24 H40 Cl4 Cu2 N8'
_chemical_formula_sum     'C24 H40 Cl4 Cu2 N8'
_chemical_formula_iupac     '[Cu2 Cl4 (C6 H10 N2)4]'
_chemical_formula_weight     709.52
_chemical_melting_point     ?
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system     triclinic
_space_group_name_H-M_alt     'P -1'
_space_group_name_Hall     '-P 1'
loop_
    _space_group_symop_operation_xyz
    'x, y, z'
    '-x, -y, -z'
_cell_length_a     8.887(3)
_cell_length_b     9.460(3)
_cell_length_c     11.214(3)
_cell_angle_alpha     85.408(4)
_cell_angle_beta     69.978(4)
_cell_angle_gamma     64.097(4)
_cell_volume     794.1(4)
_cell_formula_units_Z     1
_cell_measurement_reflns_used     1932
_cell_measurement_theta_min     5.780
_cell_measurement_theta_max     55.074
_cell_measurement_temperature     150(2)
_exptl_crystal_description     'block'
_exptl_crystal_colour     'green'
_exptl_crystal_size_max     0.065
_exptl_crystal_size_mid     0.049
_exptl_crystal_size_min     0.025
_exptl_crystal_density_diffrn     1.484
_exptl_crystal_density_meas     ?
_exptl_crystal_density_method     'not measured'
_exptl_crystal_F_000     366
_exptl_absorpt_coefficient_mu     1.704
_exptl_absorpt_correction_type     multi-scan
_exptl_absorpt_process_details
;
(SADABS; Bruker, 2014)
;
_shelx_estimated_absorpt_T_min     0.897
_shelx_estimated_absorpt_T_max     0.959
_exptl_absorpt_correction_T_min     0.6603
_exptl_absorpt_correction_T_max     0.7456
_diffrn_ambient_temperature     150(2)
_diffrn_radiation_type     'MoK\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_source     'fine focus sealed tube'
_diffrn_radiation_monochromator     graphite
_diffrn_measurement_device_type     'Bruker SMART APEXII CCD'
_diffrn_measurement_method     'ω scans'
_diffrn_detector_area_resol_mean     ?
_diffrn_reflns_number     7770
_diffrn_reflns_av_R_equivalents     0.0480
_diffrn_reflns_theta_min     3.747
_diffrn_reflns_theta_max     27.604
_diffrn_reflns_theta_full     25.242
_diffrn_measured_fraction_theta_max     0.981
_diffrn_measured_fraction_theta_full     0.983
_diffrn_reflns_limit_h_min     -11
_diffrn_reflns_limit_h_max     11
_diffrn_reflns_limit_k_min     -12
_diffrn_reflns_limit_k_max     12
_diffrn_reflns_limit_l_min     -14
_diffrn_reflns_limit_l_max     14
_refine_special_details
;
Reflections omitted from final refinement on account of beamstop truncation:
(h k l) 1 1 0; 1 0 0; 0 1 0; 0 0 1; 1 1 1
;
_reflns_number_total     3620
_reflns_number_gt     2472
_reflns_threshold_expression     'I > 2σ(I)'
_refine_ls_structure_factor_coef     Fsqd
_refine_ls_matrix_type     full
_refine_ls_R_factor_all     0.0844
_refine_ls_R_factor_gt     0.0457
_refine_ls_wR_factor_gt     0.1188
_refine_ls_wR_factor_ref     0.1378
_refine_ls_goodness_of_fit_ref     0.881
_refine_ls_restrained_S_all     0.881
_refine_ls_number_reflns     3620
_refine_ls_number_parameters     180
_refine_ls_number_restraints     0
_refine_ls_hydrogen_treatment     mixed
_refine_ls_weighting_scheme     calc
_refine_ls_weighting_details
                      'w=1/[σ²(Fo²)+(0.0940P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_hydrogens     mixed
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary     ?
_refine_ls_shift/su_max     0.000
_refine_ls_shift/su_mean     0.000
_refine_diff_density_max     0.874
_refine_diff_density_min     -0.621
_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'
    'Cl' 'Cl' 0.1484 0.1585
                         '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'
    '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'
_computing_data_collection
;
APEX2 (Bruker, 2014)
;
_computing_cell_refinement
;
SAINT (Bruker, 2014)
;
_computing_data_reduction
;
SAINT (Bruker, 2014) and XPREP (Bruker, 2014)
;
_computing_structure_solution
;
SHELXTL (Sheldrick, 2008)
;
_computing_structure_refinement
;
SHELXL2016/6 (Sheldrick, 2015)
;
_computing_molecular_graphics
;
SHELXTL (Sheldrick, 2008) and XSEED (Barbour, 2001)
;
_computing_publication_material
;
SHELXTL (Sheldrick, 2008) and XSEED (Barbour, 2001)
;
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_occupancy
    _atom_site_disorder_assembly
    _atom_site_disorder_group
    Cu Cu1 -0.10296(6) 0.41056(5) 0.43296(5) 0.01719(16) Uani d 1 . .
    Cl Cl1 -0.07621(13) 0.41784(11) 0.63096(9) 0.0204(2) Uani d 1 . .
    Cl Cl2 -0.38433(13) 0.61388(11) 0.50173(10) 0.0216(2) Uani d 1 . .
    N N9 0.2606(5) 0.1725(4) 0.3862(3) 0.0218(8) Uani d 1 . .
    N N2 -0.1329(4) 0.3931(4) 0.2643(3) 0.0197(7) Uani d 1 . .
    N N10 0.0972(4) 0.1950(4) 0.3908(3) 0.0201(7) Uani d 1 . .
    N N1 -0.2889(5) 0.3999(4) 0.2661(4) 0.0201(7) Uani d 1 . .
    C C11 0.1218(5) 0.0584(5) 0.3422(4) 0.0186(8) Uani d 1 . .
    C C13 0.3867(6) 0.0275(5) 0.3368(4) 0.0222(9) Uani d 1 . .
    C C3 -0.0190(6) 0.3394(5) 0.1455(4) 0.0211(9) Uani d 1 . .
    C C5 -0.2781(6) 0.3542(5) 0.1527(4) 0.0224(9) Uani d 1 . .
    C C4 -0.1062(6) 0.3149(5) 0.0708(4) 0.0252(9) Uani d 1 . .
    C C14 -0.0313(6) 0.0362(5) 0.3344(4) 0.0250(9) Uani d 1 . .
    H H14D 0.0120 -0.0703 0.2965 0.037 Uiso calc 0.5 . .
    H H14F -0.1182 0.0502 0.4201 0.037 Uiso calc 0.5 . .
    H H14E -0.0880 0.1141 0.2814 0.037 Uiso calc 0.5 . .
    H H14B -0.1415 0.1330 0.3688 0.037 Uiso calc 0.5 . .
    H H14A -0.0113 0.0125 0.2453 0.037 Uiso calc 0.5 . .
    H H14C -0.0415 -0.0514 0.3840 0.037 Uiso calc 0.5 . .
    C C12 0.3018(6) -0.0507(5) 0.3073(4) 0.0213(9) Uani d 1 . .
    C C16 0.5772(6) -0.0243(5) 0.3215(5) 0.0316(11) Uani d 1 . .
    H H16B 0.6475 -0.1334 0.2839 0.047 Uiso calc 0.5 . .
    H H16A 0.6221 0.0442 0.2656 0.047 Uiso calc 0.5 . .
    H H16C 0.5873 -0.0176 0.4050 0.047 Uiso calc 0.5 . .
    H H16D 0.5904 0.0622 0.3525 0.047 Uiso calc 0.5 . .
    H H16F 0.6158 -0.1154 0.3707 0.047 Uiso calc 0.5 . .
    H H16E 0.6506 -0.0536 0.2313 0.047 Uiso calc 0.5 . .
    C C6 0.1712(6) 0.3110(6) 0.1056(4) 0.0282(10) Uani d 1 . .
    H H6D 0.2313 0.2721 0.0155 0.042 Uiso calc 0.5 . .
    H H6F 0.1766 0.4099 0.1180 0.042 Uiso calc 0.5 . .
    H H6E 0.2305 0.2325 0.1571 0.042 Uiso calc 0.5 . .
    H H6B 0.1942 0.3375 0.1782 0.042 Uiso calc 0.5 . .
    H H6A 0.2490 0.1997 0.0757 0.042 Uiso calc 0.5 . .
    H H6C 0.1951 0.3771 0.0366 0.042 Uiso calc 0.5 . .
    C C8 -0.4341(6) 0.3511(6) 0.1316(5) 0.0308(10) Uani d 1 . .
    H H8B -0.4000 0.3145 0.0428 0.046 Uiso calc 0.5 . .
    H H8A -0.4720 0.2794 0.1881 0.046 Uiso calc 0.5 . .
    H H8C -0.5325 0.4575 0.1500 0.046 Uiso calc 0.5 . .
    H H8D -0.5363 0.3864 0.2111 0.046 Uiso calc 0.5 . .
    H H8F -0.4643 0.4215 0.0658 0.046 Uiso calc 0.5 . .
    H H8E -0.4038 0.2434 0.1040 0.046 Uiso calc 0.5 . .
    C C15 0.3862(7) -0.2166(5) 0.2485(5) 0.0344(11) Uani d 1 . .
    H H15B 0.2947 -0.2410 0.2383 0.052 Uiso calc 0.5 . .
    H H15A 0.4762 -0.2268 0.1650 0.052 Uiso calc 0.5 . .
    H H15C 0.4428 -0.2900 0.3038 0.052 Uiso calc 0.5 . .
    H H15D 0.5144 -0.2642 0.2331 0.052 Uiso calc 0.5 . .
    H H15F 0.3329 -0.2785 0.3065 0.052 Uiso calc 0.5 . .
    H H15E 0.3663 -0.2152 0.1676 0.052 Uiso calc 0.5 . .
    C C7 -0.0263(7) 0.2544(6) -0.0659(4) 0.0376(12) Uani d 1 . .
    H H7B 0.0983 0.2371 -0.0989 0.056 Uiso calc 0.5 . .
    H H7A -0.0321 0.1547 -0.0739 0.056 Uiso calc 0.5 . .
    H H7C -0.0926 0.3318 -0.1146 0.056 Uiso calc 0.5 . .
    H H7D -0.1159 0.2453 -0.0927 0.056 Uiso calc 0.5 . .
    H H7F 0.0145 0.3277 -0.1177 0.056 Uiso calc 0.5 . .
    H H7E 0.0750 0.1506 -0.0771 0.056 Uiso calc 0.5 . .
    H H1 -0.367(5) 0.427(4) 0.328(4) 0.000(10) Uiso d 1 . .
    H H9 0.270(7) 0.251(7) 0.412(5) 0.047(16) Uiso d 1 . .
_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 N10 . 1.988(3) ?
    Cu1 N2 . 2.026(3) ?
    Cu1 Cl2 . 2.2939(12) ?
    Cu1 Cl1 . 2.3220(12) ?
    Cu1 Cl1 2_566 2.6410(12) ?
    Cl1 Cu1 2_566 2.6410(12) ?
    N9 C13 . 1.341(5) ?
    N9 N10 . 1.356(5) ?
    N9 H9 . 0.86(6) ?
    N2 C3 . 1.339(5) ?
    N2 N1 . 1.353(5) ?
    N10 C11 . 1.341(5) ?
    N1 C5 . 1.335(5) ?
    N1 H1 . 0.75(4) ?
    C11 C12 . 1.403(6) ?
    C11 C14 . 1.497(6) ?
    C13 C12 . 1.388(6) ?
    C13 C16 . 1.492(6) ?
    C3 C4 . 1.410(6) ?
    C3 C6 . 1.495(6) ?
    C5 C4 . 1.383(6) ?
    C5 C8 . 1.497(6) ?
    C4 C7 . 1.490(6) ?
    C14 H14D . 0.9800 ?
    C14 H14F . 0.9800 ?
    C14 H14E . 0.9800 ?
    C14 H14B . 0.9800 ?
    C14 H14A . 0.9800 ?
    C14 H14C . 0.9800 ?
    C12 C15 . 1.503(6) ?
    C16 H16B . 0.9800 ?
    C16 H16A . 0.9800 ?
    C16 H16C . 0.9800 ?
    C16 H16D . 0.9800 ?
    C16 H16F . 0.9800 ?
    C16 H16E . 0.9800 ?
    C6 H6D . 0.9800 ?
    C6 H6F . 0.9800 ?
    C6 H6E . 0.9800 ?
    C6 H6B . 0.9800 ?
    C6 H6A . 0.9800 ?
    C6 H6C . 0.9800 ?
    C8 H8B . 0.9800 ?
    C8 H8A . 0.9800 ?
    C8 H8C . 0.9800 ?
    C8 H8D . 0.9800 ?
    C8 H8F . 0.9800 ?
    C8 H8E . 0.9800 ?
    C15 H15B . 0.9800 ?
    C15 H15A . 0.9800 ?
    C15 H15C . 0.9800 ?
    C15 H15D . 0.9800 ?
    C15 H15F . 0.9800 ?
    C15 H15E . 0.9800 ?
    C7 H7B . 0.9800 ?
    C7 H7A . 0.9800 ?
    C7 H7C . 0.9800 ?
    C7 H7D . 0.9800 ?
    C7 H7F . 0.9800 ?
    C7 H7E . 0.9800 ?
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
    N10 Cu1 N2 . . 88.98(14) ?
    N10 Cu1 Cl2 . . 161.92(10) ?
    N2 Cu1 Cl2 . . 88.85(10) ?
    N10 Cu1 Cl1 . . 89.71(10) ?
    N2 Cu1 Cl1 . . 176.07(10) ?
    Cl2 Cu1 Cl1 . . 91.26(4) ?
    N10 Cu1 Cl1 . 2_566 100.25(10) ?
    N2 Cu1 Cl1 . 2_566 99.04(10) ?
    Cl2 Cu1 Cl1 . 2_566 97.81(5) ?
    Cl1 Cu1 Cl1 . 2_566 84.83(4) ?
    Cu1 Cl1 Cu1 . 2_566 95.17(4) ?
    C13 N9 N10 . . 112.5(3) ?
    C13 N9 H9 . . 130(4) ?
    N10 N9 H9 . . 118(4) ?
    C3 N2 N1 . . 105.8(3) ?
    C3 N2 Cu1 . . 133.9(3) ?
    N1 N2 Cu1 . . 118.3(3) ?
    C11 N10 N9 . . 105.3(3) ?
    C11 N10 Cu1 . . 134.0(3) ?
    N9 N10 Cu1 . . 119.6(2) ?
    C5 N1 N2 . . 112.0(4) ?
    C5 N1 H1 . . 129(3) ?
    N2 N1 H1 . . 119(3) ?
    N10 C11 C12 . . 110.4(3) ?
    N10 C11 C14 . . 121.0(4) ?
    C12 C11 C14 . . 128.6(4) ?
    N9 C13 C12 . . 106.5(4) ?
    N9 C13 C16 . . 122.2(4) ?
    C12 C13 C16 . . 131.4(4) ?
    N2 C3 C4 . . 109.8(4) ?
    N2 C3 C6 . . 122.3(4) ?
    C4 C3 C6 . . 127.8(4) ?
    N1 C5 C4 . . 107.2(4) ?
    N1 C5 C8 . . 121.7(4) ?
    C4 C5 C8 . . 131.2(4) ?
    C5 C4 C3 . . 105.2(4) ?
    C5 C4 C7 . . 128.0(4) ?
    C3 C4 C7 . . 126.8(4) ?
    C11 C14 H14D . . 109.5 ?
    C11 C14 H14F . . 109.5 ?
    H14D C14 H14F . . 109.5 ?
    C11 C14 H14E . . 109.5 ?
    H14D C14 H14E . . 109.5 ?
    H14F C14 H14E . . 109.5 ?
    C11 C14 H14B . . 109.5 ?
    H14D C14 H14B . . 141.1 ?
    H14F C14 H14B . . 56.3 ?
    H14E C14 H14B . . 56.3 ?
    C11 C14 H14A . . 109.5 ?
    H14D C14 H14A . . 56.3 ?
    H14F C14 H14A . . 141.1 ?
    H14E C14 H14A . . 56.3 ?
    H14B C14 H14A . . 109.5 ?
    C11 C14 H14C . . 109.5 ?
    H14D C14 H14C . . 56.3 ?
    H14F C14 H14C . . 56.3 ?
    H14E C14 H14C . . 141.1 ?
    H14B C14 H14C . . 109.5 ?
    H14A C14 H14C . . 109.5 ?
    C13 C12 C11 . . 105.5(3) ?
    C13 C12 C15 . . 127.0(4) ?
    C11 C12 C15 . . 127.6(4) ?
    C13 C16 H16B . . 109.5 ?
    C13 C16 H16A . . 109.5 ?
    H16B C16 H16A . . 109.5 ?
    C13 C16 H16C . . 109.5 ?
    H16B C16 H16C . . 109.5 ?
    H16A C16 H16C . . 109.5 ?
    C13 C16 H16D . . 109.5 ?
    H16B C16 H16D . . 141.1 ?
    H16A C16 H16D . . 56.3 ?
    H16C C16 H16D . . 56.3 ?
    C13 C16 H16F . . 109.5 ?
    H16B C16 H16F . . 56.3 ?
    H16A C16 H16F . . 141.1 ?
    H16C C16 H16F . . 56.3 ?
    H16D C16 H16F . . 109.5 ?
    C13 C16 H16E . . 109.5 ?
    H16B C16 H16E . . 56.3 ?
    H16A C16 H16E . . 56.3 ?
    H16C C16 H16E . . 141.1 ?
    H16D C16 H16E . . 109.5 ?
    H16F C16 H16E . . 109.5 ?
    C3 C6 H6D . . 109.5 ?
    C3 C6 H6F . . 109.5 ?
    H6D C6 H6F . . 109.5 ?
    C3 C6 H6E . . 109.5 ?
    H6D C6 H6E . . 109.5 ?
    H6F C6 H6E . . 109.5 ?
    C3 C6 H6B . . 109.5 ?
    H6D C6 H6B . . 141.1 ?
    H6F C6 H6B . . 56.3 ?
    H6E C6 H6B . . 56.3 ?
    C3 C6 H6A . . 109.5 ?
    H6D C6 H6A . . 56.3 ?
    H6F C6 H6A . . 141.1 ?
    H6E C6 H6A . . 56.3 ?
    H6B C6 H6A . . 109.5 ?
    C3 C6 H6C . . 109.5 ?
    H6D C6 H6C . . 56.3 ?
    H6F C6 H6C . . 56.3 ?
    H6E C6 H6C . . 141.1 ?
    H6B C6 H6C . . 109.5 ?
    H6A C6 H6C . . 109.5 ?
    C5 C8 H8B . . 109.5 ?
    C5 C8 H8A . . 109.5 ?
    H8B C8 H8A . . 109.5 ?
    C5 C8 H8C . . 109.5 ?
    H8B C8 H8C . . 109.5 ?
    H8A C8 H8C . . 109.5 ?
    C5 C8 H8D . . 109.5 ?
    H8B C8 H8D . . 141.1 ?
    H8A C8 H8D . . 56.3 ?
    H8C C8 H8D . . 56.3 ?
    C5 C8 H8F . . 109.5 ?
    H8B C8 H8F . . 56.3 ?
    H8A C8 H8F . . 141.1 ?
    H8C C8 H8F . . 56.3 ?
    H8D C8 H8F . . 109.5 ?
    C5 C8 H8E . . 109.5 ?
    H8B C8 H8E . . 56.3 ?
    H8A C8 H8E . . 56.3 ?
    H8C C8 H8E . . 141.1 ?
    H8D C8 H8E . . 109.5 ?
    H8F C8 H8E . . 109.5 ?
    C12 C15 H15B . . 109.5 ?
    C12 C15 H15A . . 109.5 ?
    H15B C15 H15A . . 109.5 ?
    C12 C15 H15C . . 109.5 ?
    H15B C15 H15C . . 109.5 ?
    H15A C15 H15C . . 109.5 ?
    C12 C15 H15D . . 109.5 ?
    H15B C15 H15D . . 141.1 ?
    H15A C15 H15D . . 56.3 ?
    H15C C15 H15D . . 56.3 ?
    C12 C15 H15F . . 109.5 ?
    H15B C15 H15F . . 56.3 ?
    H15A C15 H15F . . 141.1 ?
    H15C C15 H15F . . 56.3 ?
    H15D C15 H15F . . 109.5 ?
    C12 C15 H15E . . 109.5 ?
    H15B C15 H15E . . 56.3 ?
    H15A C15 H15E . . 56.3 ?
    H15C C15 H15E . . 141.1 ?
    H15D C15 H15E . . 109.5 ?
    H15F C15 H15E . . 109.5 ?
    C4 C7 H7B . . 109.5 ?
    C4 C7 H7A . . 109.5 ?
    H7B C7 H7A . . 109.5 ?
    C4 C7 H7C . . 109.5 ?
    H7B C7 H7C . . 109.5 ?
    H7A C7 H7C . . 109.5 ?
    C4 C7 H7D . . 109.5 ?
    H7B C7 H7D . . 141.1 ?
    H7A C7 H7D . . 56.3 ?
    H7C C7 H7D . . 56.3 ?
    C4 C7 H7F . . 109.5 ?
    H7B C7 H7F . . 56.3 ?
    H7A C7 H7F . . 141.1 ?
    H7C C7 H7F . . 56.3 ?
    H7D C7 H7F . . 109.5 ?
    C4 C7 H7E . . 109.5 ?
    H7B C7 H7E . . 56.3 ?
    H7A C7 H7E . . 56.3 ?
    H7C C7 H7E . . 141.1 ?
    H7D C7 H7E . . 109.5 ?
    H7F C7 H7E . . 109.5 ?
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
    C14 H14E N2 . 0.98 2.49 3.199(5) 128.7
    C14 H14E N1 . 0.98 2.54 3.401(6) 146.6
    C14 H14E N2 . 0.98 2.49 3.199(5) 128.7
    C14 H14E N1 . 0.98 2.54 3.401(6) 146.6
    C16 H16F Cl2 1_645 0.98 2.85 3.776(5) 158.2
    C6 H6E N9 . 0.98 2.67 3.521(6) 146.0
    C6 H6E N10 . 0.98 2.55 3.240(6) 127.6
    C6 H6B Cl1 2_566 0.98 2.86 3.692(5) 143.5
    N1 H1 Cl2 . 0.75(4) 2.66(4) 3.102(4) 120(3)
    N1 H1 Cl2 2_466 0.75(4) 2.54(4) 3.214(4) 151(3)
    N9 H9 Cl1 2_566 0.86(6) 2.94(6) 3.506(4) 125(5)
    N9 H9 Cl2 2_566 0.86(6) 2.37(6) 3.188(4) 159(5)
data_2
_database_code_depnum_ccdc_archive 'CCDC 1823018'
_audit_creation_method     'SHELXL-2014/7'
_chemical_name_systematic
;\
Aquatetrakis(3,4,5-trimethyl-1H-pyrazole-\
κN²)copper(II) dinitrate
;
_chemical_name_common     ?
_chemical_formula_moiety     'C24 H42 Cu N8 O, 2(N O3)'
_chemical_formula_sum     'C24 H42 Cu N10 O7'
_chemical_formula_iupac     '[Cu (C6 H10 N2)4 (H2 O)] (N O3)2'
_chemical_formula_weight     646.21
_chemical_melting_point     ?
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system     monoclinic
_space_group_name_H-M_alt     'I 2/a'
_space_group_name_Hall     '-I 2ya'
loop_
    _space_group_symop_operation_xyz
    'x, y, z'
    '-x+1/2, y, -z'
    'x+1/2, y+1/2, z+1/2'
    '-x+1, y+1/2, -z+1/2'
    '-x, -y, -z'
    'x-1/2, -y, z'
    '-x+1/2, -y+1/2, -z+1/2'
    'x, -y+1/2, z+1/2'
_cell_length_a     20.107(7)
_cell_length_b     7.8939(16)
_cell_length_c     20.472(4)
_cell_angle_alpha     90
_cell_angle_beta     102.651(2)
_cell_angle_gamma     90
_cell_volume     3170.5(14)
_cell_formula_units_Z     4
_cell_measurement_reflns_used     4118
_cell_measurement_theta_min     5.549
_cell_measurement_theta_max     54.806
_cell_measurement_temperature     150(2)
_exptl_crystal_description     'plate'
_exptl_crystal_colour     'blue'
_exptl_crystal_size_max     0.164
_exptl_crystal_size_mid     0.104
_exptl_crystal_size_min     0.034
_exptl_crystal_density_diffrn     1.354
_exptl_crystal_density_meas     ?
_exptl_crystal_density_method     'not measured'
_exptl_crystal_F_000     1364
_exptl_absorpt_coefficient_mu     0.745
_exptl_absorpt_correction_type     multi-scan
_exptl_absorpt_process_details
;
(SADABS; Bruker, 2014)
;
_shelx_estimated_absorpt_T_min     0.888
_shelx_estimated_absorpt_T_max     0.975
_exptl_absorpt_correction_T_min     0.6540
_exptl_absorpt_correction_T_max     0.7456
_diffrn_ambient_temperature     150(2)
_diffrn_radiation_type     'MoK\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_source     'fine focus sealed tube'
_diffrn_radiation_monochromator     graphite
_diffrn_measurement_device_type     'Bruker SMART APEXII CCD'
_diffrn_measurement_method     'ω scans'
_diffrn_detector_area_resol_mean     ?
_diffrn_reflns_number     13530
_diffrn_reflns_av_R_equivalents     0.0568
_diffrn_reflns_theta_min     3.214
_diffrn_reflns_theta_max     27.531
_diffrn_reflns_theta_full     25.242
_diffrn_measured_fraction_theta_max     0.992
_diffrn_measured_fraction_theta_full     0.998
_diffrn_reflns_limit_h_min     -26
_diffrn_reflns_limit_h_max     26
_diffrn_reflns_limit_k_min     -10
_diffrn_reflns_limit_k_max     9
_diffrn_reflns_limit_l_min     -26
_diffrn_reflns_limit_l_max     26
_refine_special_details
;
Reflections omitted from final refinement on account of beamstop truncation:
(h k l) 1 1 0; 2 0 0; 0 1 1; -2 0 2; 0 0 2
;
_reflns_number_total     3636
_reflns_number_gt     2719
_reflns_threshold_expression     'I > 2σ(I)'
_refine_ls_structure_factor_coef     Fsqd
_refine_ls_matrix_type     full
_refine_ls_R_factor_all     0.0690
_refine_ls_R_factor_gt     0.0445
_refine_ls_wR_factor_gt     0.1209
_refine_ls_wR_factor_ref     0.1353
_refine_ls_goodness_of_fit_ref     0.906
_refine_ls_restrained_S_all     0.906
_refine_ls_number_reflns     3636
_refine_ls_number_parameters     203
_refine_ls_number_restraints     0
_refine_ls_hydrogen_treatment     mixed
_refine_ls_weighting_scheme     calc
_refine_ls_weighting_details
                      'w=1/[σ²(Fo²)+(0.1000P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_hydrogens     mixed
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary     ?
_refine_ls_shift/su_max     0.000
_refine_ls_shift/su_mean     0.000
_refine_diff_density_max     0.776
_refine_diff_density_min     -0.612
_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'
    'Cu' 'Cu' 0.3201 1.2651
                         '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'
_computing_data_collection
;
APEX2 (Bruker, 2014)
;
_computing_cell_refinement
;
SAINT (Bruker, 2014)
;
_computing_data_reduction
;
SAINT (Bruker, 2014) and XPREP (Bruker, 2014)
;
_computing_structure_solution
;
SHELXTL (Sheldrick, 2008)
;
_computing_structure_refinement
;
SHELXL2016/6 (Sheldrick, 2015)
;
_computing_molecular_graphics
;
SHELXTL (Sheldrick, 2008) and XSEED (Barbour, 2001)
;
_computing_publication_material
;
SHELXTL (Sheldrick, 2008) and XSEED (Barbour, 2001)
;
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_occupancy
    _atom_site_disorder_assembly
    _atom_site_disorder_group
    Cu Cu1 0.2500 0.50985(5) 0.5000 0.01754(15) Uani d 1 . .
    O O17 0.2500 0.2345(3) 0.5000 0.0297(6) Uani d 1 . .
    N N2 0.20222(9) 0.5683(3) 0.40597(10) 0.0207(4) Uani d 1 . .
    N N9 0.11241(10) 0.6406(3) 0.50436(11) 0.0224(5) Uani d 1 . .
    N N10 0.15931(9) 0.5173(3) 0.52824(10) 0.0203(4) Uani d 1 . .
    N N1 0.15514(11) 0.4676(3) 0.36661(12) 0.0234(5) Uani d 1 . .
    C C5 0.13309(13) 0.5350(4) 0.30513(13) 0.0271(6) Uani d 1 . .
    C C11 0.13728(12) 0.4445(3) 0.57851(13) 0.0222(5) Uani d 1 . .
    C C12 0.07613(12) 0.5194(3) 0.58642(14) 0.0241(5) Uani d 1 . .
    C C15 0.03256(14) 0.4712(4) 0.63443(16) 0.0355(7) Uani d 1 . .
    H H15B 0.0540 0.3773 0.6627 0.053 Uiso calc 0.5 . .
    H H15A 0.0278 0.5688 0.6627 0.053 Uiso calc 0.5 . .
    H H15C -0.0126 0.4361 0.6093 0.053 Uiso calc 0.5 . .
    H H15D -0.0078 0.5442 0.6271 0.053 Uiso calc 0.5 . .
    H H15F 0.0184 0.3527 0.6271 0.053 Uiso calc 0.5 . .
    H H15E 0.0587 0.4854 0.6805 0.053 Uiso calc 0.5 . .
    C C13 0.06302(12) 0.6451(3) 0.53899(13) 0.0236(5) Uani d 1 . .
    C C3 0.21029(12) 0.7012(3) 0.36840(12) 0.0226(5) Uani d 1 . .
    C C6 0.25867(14) 0.8425(4) 0.39353(15) 0.0321(6) Uani d 1 . .
    H H6D 0.2567 0.9269 0.3580 0.048 Uiso calc 0.5 . .
    H H6F 0.2460 0.8958 0.4323 0.048 Uiso calc 0.5 . .
    H H6E 0.3051 0.7975 0.4068 0.048 Uiso calc 0.5 . .
    H H6B 0.2818 0.8199 0.4400 0.048 Uiso calc 0.5 . .
    H H6A 0.2925 0.8510 0.3658 0.048 Uiso calc 0.5 . .
    H H6C 0.2334 0.9493 0.3913 0.048 Uiso calc 0.5 . .
    C C4 0.16753(13) 0.6859(4) 0.30470(13) 0.0277(6) Uani d 1 . .
    C C14 0.17411(14) 0.3017(4) 0.61920(15) 0.0326(6) Uani d 1 . .
    H H14D 0.1492 0.2678 0.6532 0.049 Uiso calc 0.5 . .
    H H14F 0.1771 0.2052 0.5899 0.049 Uiso calc 0.5 . .
    H H14E 0.2201 0.3387 0.6412 0.049 Uiso calc 0.5 . .
    H H14B 0.2151 0.2733 0.6029 0.049 Uiso calc 0.5 . .
    H H14A 0.1872 0.3359 0.6663 0.049 Uiso calc 0.5 . .
    H H14C 0.1442 0.2025 0.6150 0.049 Uiso calc 0.5 . .
    C C16 0.00746(13) 0.7757(4) 0.52520(16) 0.0336(6) Uani d 1 . .
    H H16B -0.0235 0.7581 0.5555 0.050 Uiso calc 0.5 . .
    H H16A 0.0276 0.8891 0.5324 0.050 Uiso calc 0.5 . .
    H H16C -0.0180 0.7652 0.4787 0.050 Uiso calc 0.5 . .
    H H16D 0.0142 0.8501 0.4889 0.050 Uiso calc 0.5 . .
    H H16F -0.0369 0.7191 0.5120 0.050 Uiso calc 0.5 . .
    H H16E 0.0087 0.8430 0.5657 0.050 Uiso calc 0.5 . .
    C C8 0.08068(15) 0.4500(5) 0.25270(15) 0.0398(7) Uani d 1 . .
    H H8B 0.0717 0.5188 0.2119 0.060 Uiso calc 0.5 . .
    H H8A 0.0973 0.3381 0.2430 0.060 Uiso calc 0.5 . .
    H H8C 0.0385 0.4369 0.2688 0.060 Uiso calc 0.5 . .
    H H8D 0.0666 0.3438 0.2705 0.060 Uiso calc 0.5 . .
    H H8F 0.0410 0.5245 0.2394 0.060 Uiso calc 0.5 . .
    H H8E 0.0999 0.4257 0.2136 0.060 Uiso calc 0.5 . .
    C C7 0.15739(18) 0.8152(5) 0.24974(16) 0.0456(8) Uani d 1 . .
    H H7B 0.1890 0.9098 0.2633 0.068 Uiso calc 0.5 . .
    H H7A 0.1662 0.7632 0.2090 0.068 Uiso calc 0.5 . .
    H H7C 0.1104 0.8572 0.2411 0.068 Uiso calc 0.5 . .
    H H7D 0.1214 0.7770 0.2123 0.068 Uiso calc 0.5 . .
    H H7F 0.1442 0.9236 0.2666 0.068 Uiso calc 0.5 . .
    H H7E 0.2000 0.8296 0.2345 0.068 Uiso calc 0.5 . .
    O O20 0.10612(12) 0.1364(3) 0.37019(11) 0.0430(6) Uani d 1 . .
    O O21 0.07101(11) -0.1135(3) 0.38872(12) 0.0459(6) Uani d 1 . .
    O O19 0.14070(10) 0.0169(3) 0.46693(12) 0.0411(5) Uani d 1 . .
    N N18 0.10557(11) 0.0134(3) 0.40797(13) 0.0297(5) Uani d 1 . .
    H H1 0.1460(14) 0.383(4) 0.3781(14) 0.021(8) Uiso d 1 . .
    H H9 0.1192(14) 0.702(4) 0.4685(15) 0.031(8) Uiso d 1 . .
    H H17 0.2176(14) 0.176(4) 0.4879(15) 0.029(8) Uiso d 1 . .
_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 . 2.008(2) ?
    Cu1 N2 2_556 2.008(2) ?
    Cu1 N10 . 2.031(2) ?
    Cu1 N10 2_556 2.031(2) ?
    Cu1 O17 . 2.174(3) ?
    O17 H17 . 0.79(3) ?
    N2 C3 . 1.332(3) ?
    N2 N1 . 1.358(3) ?
    N9 C13 . 1.341(3) ?
    N9 N10 . 1.369(3) ?
    N9 H9 . 0.92(3) ?
    N10 C11 . 1.336(3) ?
    N1 C5 . 1.349(4) ?
    N1 H1 . 0.75(3) ?
    C5 C4 . 1.379(4) ?
    C5 C8 . 1.489(4) ?
    C11 C12 . 1.405(4) ?
    C11 C14 . 1.497(4) ?
    C12 C13 . 1.373(4) ?
    C12 C15 . 1.502(4) ?
    C15 H15B . 0.9800 ?
    C15 H15A . 0.9800 ?
    C15 H15C . 0.9800 ?
    C15 H15D . 0.9800 ?
    C15 H15F . 0.9800 ?
    C15 H15E . 0.9800 ?
    C13 C16 . 1.501(3) ?
    C3 C4 . 1.401(4) ?
    C3 C6 . 1.495(4) ?
    C6 H6D . 0.9800 ?
    C6 H6F . 0.9800 ?
    C6 H6E . 0.9800 ?
    C6 H6B . 0.9800 ?
    C6 H6A . 0.9800 ?
    C6 H6C . 0.9800 ?
    C4 C7 . 1.499(4) ?
    C14 H14D . 0.9800 ?
    C14 H14F . 0.9800 ?
    C14 H14E . 0.9800 ?
    C14 H14B . 0.9800 ?
    C14 H14A . 0.9800 ?
    C14 H14C . 0.9800 ?
    C16 H16B . 0.9800 ?
    C16 H16A . 0.9800 ?
    C16 H16C . 0.9800 ?
    C16 H16D . 0.9800 ?
    C16 H16F . 0.9800 ?
    C16 H16E . 0.9800 ?
    C8 H8B . 0.9800 ?
    C8 H8A . 0.9800 ?
    C8 H8C . 0.9800 ?
    C8 H8D . 0.9800 ?
    C8 H8F . 0.9800 ?
    C8 H8E . 0.9800 ?
    C7 H7B . 0.9800 ?
    C7 H7A . 0.9800 ?
    C7 H7C . 0.9800 ?
    C7 H7D . 0.9800 ?
    C7 H7F . 0.9800 ?
    C7 H7E . 0.9800 ?
    O20 N18 . 1.243(3) ?
    O21 N18 . 1.234(3) ?
    O19 N18 . 1.258(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 N2 . 2_556 153.41(13) ?
    N2 Cu1 N10 . . 89.73(8) ?
    N2 Cu1 N10 2_556 . 89.51(8) ?
    N2 Cu1 N10 . 2_556 89.50(8) ?
    N2 Cu1 N10 2_556 2_556 89.73(8) ?
    N10 Cu1 N10 . 2_556 176.69(12) ?
    N2 Cu1 O17 . . 103.30(6) ?
    N2 Cu1 O17 2_556 . 103.29(6) ?
    N10 Cu1 O17 . . 91.66(6) ?
    N10 Cu1 O17 2_556 . 91.66(6) ?
    Cu1 O17 H17 . . 126(2) ?
    C3 N2 N1 . . 106.0(2) ?
    C3 N2 Cu1 . . 129.93(17) ?
    N1 N2 Cu1 . . 124.01(17) ?
    C13 N9 N10 . . 111.2(2) ?
    C13 N9 H9 . . 131.9(18) ?
    N10 N9 H9 . . 116.9(18) ?
    C11 N10 N9 . . 105.21(19) ?
    C11 N10 Cu1 . . 132.58(16) ?
    N9 N10 Cu1 . . 120.67(16) ?
    C5 N1 N2 . . 111.5(2) ?
    C5 N1 H1 . . 126(2) ?
    N2 N1 H1 . . 122(2) ?
    N1 C5 C4 . . 106.5(2) ?
    N1 C5 C8 . . 122.1(3) ?
    C4 C5 C8 . . 131.4(3) ?
    N10 C11 C12 . . 110.7(2) ?
    N10 C11 C14 . . 123.0(2) ?
    C12 C11 C14 . . 126.2(2) ?
    C13 C12 C11 . . 105.1(2) ?
    C13 C12 C15 . . 126.6(2) ?
    C11 C12 C15 . . 128.3(3) ?
    C12 C15 H15B . . 109.5 ?
    C12 C15 H15A . . 109.5 ?
    H15B C15 H15A . . 109.5 ?
    C12 C15 H15C . . 109.5 ?
    H15B C15 H15C . . 109.5 ?
    H15A C15 H15C . . 109.5 ?
    C12 C15 H15D . . 109.5 ?
    H15B C15 H15D . . 141.1 ?
    H15A C15 H15D . . 56.3 ?
    H15C C15 H15D . . 56.3 ?
    C12 C15 H15F . . 109.5 ?
    H15B C15 H15F . . 56.3 ?
    H15A C15 H15F . . 141.1 ?
    H15C C15 H15F . . 56.3 ?
    H15D C15 H15F . . 109.5 ?
    C12 C15 H15E . . 109.5 ?
    H15B C15 H15E . . 56.3 ?
    H15A C15 H15E . . 56.3 ?
    H15C C15 H15E . . 141.1 ?
    H15D C15 H15E . . 109.5 ?
    H15F C15 H15E . . 109.5 ?
    N9 C13 C12 . . 107.7(2) ?
    N9 C13 C16 . . 121.7(2) ?
    C12 C13 C16 . . 130.5(2) ?
    N2 C3 C4 . . 110.0(2) ?
    N2 C3 C6 . . 122.8(2) ?
    C4 C3 C6 . . 127.2(2) ?
    C3 C6 H6D . . 109.5 ?
    C3 C6 H6F . . 109.5 ?
    H6D C6 H6F . . 109.5 ?
    C3 C6 H6E . . 109.5 ?
    H6D C6 H6E . . 109.5 ?
    H6F C6 H6E . . 109.5 ?
    C3 C6 H6B . . 109.5 ?
    H6D C6 H6B . . 141.1 ?
    H6F C6 H6B . . 56.3 ?
    H6E C6 H6B . . 56.3 ?
    C3 C6 H6A . . 109.5 ?
    H6D C6 H6A . . 56.3 ?
    H6F C6 H6A . . 141.1 ?
    H6E C6 H6A . . 56.3 ?
    H6B C6 H6A . . 109.5 ?
    C3 C6 H6C . . 109.5 ?
    H6D C6 H6C . . 56.3 ?
    H6F C6 H6C . . 56.3 ?
    H6E C6 H6C . . 141.1 ?
    H6B C6 H6C . . 109.5 ?
    H6A C6 H6C . . 109.5 ?
    C5 C4 C3 . . 106.0(2) ?
    C5 C4 C7 . . 127.4(3) ?
    C3 C4 C7 . . 126.5(3) ?
    C11 C14 H14D . . 109.5 ?
    C11 C14 H14F . . 109.5 ?
    H14D C14 H14F . . 109.5 ?
    C11 C14 H14E . . 109.5 ?
    H14D C14 H14E . . 109.5 ?
    H14F C14 H14E . . 109.5 ?
    C11 C14 H14B . . 109.5 ?
    H14D C14 H14B . . 141.1 ?
    H14F C14 H14B . . 56.3 ?
    H14E C14 H14B . . 56.3 ?
    C11 C14 H14A . . 109.5 ?
    H14D C14 H14A . . 56.3 ?
    H14F C14 H14A . . 141.1 ?
    H14E C14 H14A . . 56.3 ?
    H14B C14 H14A . . 109.5 ?
    C11 C14 H14C . . 109.5 ?
    H14D C14 H14C . . 56.3 ?
    H14F C14 H14C . . 56.3 ?
    H14E C14 H14C . . 141.1 ?
    H14B C14 H14C . . 109.5 ?
    H14A C14 H14C . . 109.5 ?
    C13 C16 H16B . . 109.5 ?
    C13 C16 H16A . . 109.5 ?
    H16B C16 H16A . . 109.5 ?
    C13 C16 H16C . . 109.5 ?
    H16B C16 H16C . . 109.5 ?
    H16A C16 H16C . . 109.5 ?
    C13 C16 H16D . . 109.5 ?
    H16B C16 H16D . . 141.1 ?
    H16A C16 H16D . . 56.3 ?
    H16C C16 H16D . . 56.3 ?
    C13 C16 H16F . . 109.5 ?
    H16B C16 H16F . . 56.3 ?
    H16A C16 H16F . . 141.1 ?
    H16C C16 H16F . . 56.3 ?
    H16D C16 H16F . . 109.5 ?
    C13 C16 H16E . . 109.5 ?
    H16B C16 H16E . . 56.3 ?
    H16A C16 H16E . . 56.3 ?
    H16C C16 H16E . . 141.1 ?
    H16D C16 H16E . . 109.5 ?
    H16F C16 H16E . . 109.5 ?
    C5 C8 H8B . . 109.5 ?
    C5 C8 H8A . . 109.5 ?
    H8B C8 H8A . . 109.5 ?
    C5 C8 H8C . . 109.5 ?
    H8B C8 H8C . . 109.5 ?
    H8A C8 H8C . . 109.5 ?
    C5 C8 H8D . . 109.5 ?
    H8B C8 H8D . . 141.1 ?
    H8A C8 H8D . . 56.3 ?
    H8C C8 H8D . . 56.3 ?
    C5 C8 H8F . . 109.5 ?
    H8B C8 H8F . . 56.3 ?
    H8A C8 H8F . . 141.1 ?
    H8C C8 H8F . . 56.3 ?
    H8D C8 H8F . . 109.5 ?
    C5 C8 H8E . . 109.5 ?
    H8B C8 H8E . . 56.3 ?
    H8A C8 H8E . . 56.3 ?
    H8C C8 H8E . . 141.1 ?
    H8D C8 H8E . . 109.5 ?
    H8F C8 H8E . . 109.5 ?
    C4 C7 H7B . . 109.5 ?
    C4 C7 H7A . . 109.5 ?
    H7B C7 H7A . . 109.5 ?
    C4 C7 H7C . . 109.5 ?
    H7B C7 H7C . . 109.5 ?
    H7A C7 H7C . . 109.5 ?
    C4 C7 H7D . . 109.5 ?
    H7B C7 H7D . . 141.1 ?
    H7A C7 H7D . . 56.3 ?
    H7C C7 H7D . . 56.3 ?
    C4 C7 H7F . . 109.5 ?
    H7B C7 H7F . . 56.3 ?
    H7A C7 H7F . . 141.1 ?
    H7C C7 H7F . . 56.3 ?
    H7D C7 H7F . . 109.5 ?
    C4 C7 H7E . . 109.5 ?
    H7B C7 H7E . . 56.3 ?
    H7A C7 H7E . . 56.3 ?
    H7C C7 H7E . . 141.1 ?
    H7D C7 H7E . . 109.5 ?
    H7F C7 H7E . . 109.5 ?
    O21 N18 O20 . . 121.1(3) ?
    O21 N18 O19 . . 118.8(2) ?
    O20 N18 O19 . . 120.0(2) ?
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
    C6 H6E N9 2_556 0.98 2.50 3.355(4) 145.0
    C6 H6E N10 2_556 0.98 2.60 3.274(4) 126.1
    C6 H6F O19 1_565 0.98 2.56 3.367(4) 139.7
    C6 H6E N9 2_556 0.98 2.50 3.355(4) 145.0
    C6 H6E N10 2_556 0.98 2.60 3.274(4) 126.1
    C14 H14B O17 . 0.98 2.38 3.193(3) 139.7
    C16 H16B O20 5_566 0.98 2.62 3.525(4) 153.2
    C16 H16B N18 5_566 0.98 2.66 3.342(4) 126.9
    C16 H16D O21 1_565 0.98 2.57 3.430(4) 146.2
    C8 H8D O20 . 0.98 2.60 3.411(4) 140.1
    N1 H1 O20 . 0.75(3) 2.10(3) 2.801(3) 158(3)
    N9 H9 N2 . 0.92(3) 2.54(3) 3.039(3) 114(2)
    N9 H9 O21 1_565 0.92(3) 2.24(3) 3.033(3) 144(2)
    N9 H9 O19 1_565 0.92(3) 2.52(3) 3.150(3) 126(2)
    O17 H17 O19 . 0.79(3) 1.97(3) 2.755(3) 174(3)
    C6 H6F O19 1_565 0.98 2.56 3.367(4) 139.7
    C6 H6E N9 2_556 0.98 2.50 3.355(4) 145.0
    C6 H6E N10 2_556 0.98 2.60 3.274(4) 126.1
    C6 H6E N9 2_556 0.98 2.50 3.355(4) 145.0
    C6 H6E N10 2_556 0.98 2.60 3.274(4) 126.1
    C14 H14B O17 . 0.98 2.38 3.193(3) 139.7
    C16 H16B O20 5_566 0.98 2.62 3.525(4) 153.2
    C16 H16B N18 5_566 0.98 2.66 3.342(4) 126.9
    C16 H16D O21 1_565 0.98 2.57 3.430(4) 146.2
    C8 H8D O20 . 0.98 2.60 3.411(4) 140.1
    N1 H1 O20 . 0.75(3) 2.10(3) 2.801(3) 158(3)
    N9 H9 N2 . 0.92(3) 2.54(3) 3.039(3) 114(2)
    N9 H9 O21 1_565 0.92(3) 2.24(3) 3.033(3) 144(2)
    N9 H9 O19 1_565 0.92(3) 2.52(3) 3.150(3) 126(2)
    O17 H17 O19 . 0.79(3) 1.97(3) 2.755(3) 174(3)
