#------------------------------------------------------------------------------
#$Date: 2017-03-21 19:55:39 +0200 (Tue, 21 Mar 2017) $
#$Revision: 194389 $
#$URL: file:///home/coder/svn-repositories/cod/cif/2/24/16/2241604.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/. The original data for this entry
# were provided by IUCr Journals, http://journals.iucr.org/.
#
# The file may be used within the scientific community so long as
# proper attribution is given to the journal article from which the
# data were obtained.
#
data_2241604
loop_
_publ_author_name
'Mathivathanan, Logesh'
'Cruz, Raquel'
'Raptis, Raphael G.'
_publ_section_title
;
 A [Cu₃(μ₃-O)]--pyrazolate metallacycle with terminal nitrate ligands
 exhibiting point group symmetry 3
;
_journal_coeditor_code           WM4004
_journal_issue                   4
_journal_name_full               'Acta Crystallographica Section E'
_journal_page_first              492
_journal_page_last               494
_journal_paper_doi               10.1107/S2056989016003741
_journal_volume                  72
_journal_year                    2016
_chemical_formula_iupac
'(C36 H30 P2 N) [Cu3 (C3 H2 Cl1 N2)3 (N O3)3 O]  N O3, H2 O1'
_chemical_formula_moiety
'3(C36 H30 P2 N +), C9 H6 Cl3 Cu3 N9 O10 2-. N O3 -, H2 O1'
_chemical_formula_sum            'C117 H98 Cl3 Cu3 N13 O14 P6'
_chemical_formula_weight         2390.85
_chemical_name_systematic
;Tris[bis(triphenylphosphoranylidene)ammonium]
tris(μ₂-4-chloropyrazolato-κ²N:N')-μ₃-oxido-tris[(nitrato-κ²O,O')cuprate(II)] nitrate monohydrate
;
_space_group_crystal_system      trigonal
_space_group_IT_number           146
_space_group_name_Hall           'R 3'
_space_group_name_H-M_alt        'R 3'
_symmetry_space_group_name_Hall  'R 3'
_symmetry_space_group_name_H-M   'R 3 :H'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   23.038(2)
_cell_length_b                   23.038(2)
_cell_length_c                   18.4214(17)
_cell_measurement_reflns_used    9882
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      26.04
_cell_measurement_theta_min      2.32
_cod_depositor_comments
;
 Marking attached hydrogen atoms.

 Antanas Vaitkus,
 2017-03-21
;
_cell_volume                     8467.3(13)
_computing_cell_refinement
;
SAINT (Bruker, 2005)
;
_computing_data_collection
;
APEX2 (Bruker, 2005)
;
_computing_data_reduction
;
SAINT (Bruker, 2005)
;
_computing_molecular_graphics
;
Mercury (Macrae et al., 2006)
;
_computing_publication_material
;
publCIF (Westrip, 2010)
;
_computing_structure_refinement
;
SHELXL2014 (Sheldrick, 2015)
;
_computing_structure_solution
;
SHELXS97 (Sheldrick, 2008)
;
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEXII CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0329
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            30414
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.358
_diffrn_reflns_theta_min         2.322
_exptl_absorpt_coefficient_mu    0.785
_exptl_absorpt_correction_T_max  0.9049
_exptl_absorpt_correction_T_min  0.8401
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
(SADABS; Bruker, 2005)
;
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.407
_exptl_crystal_description       polygon
_exptl_crystal_F_000             3687
_exptl_crystal_size_max          0.230
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.130
_refine_diff_density_max         0.406
_refine_diff_density_min         -0.289
_refine_ls_abs_structure_details
;
Flack x determined using 2750 quotients
[(I⁺)-(I⁻)]/[(I⁺)+(I⁻)]
(Parsons et al., 2013)
;
_refine_ls_abs_structure_Flack   0.004(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     468
_refine_ls_number_reflns         7675
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0466
_refine_ls_R_factor_gt           0.0340
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[σ²(Fo²)+(0.0468P)²+0.1352P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0811
_refine_ls_wR_factor_ref         0.0882
_reflns_number_gt                6428
_reflns_number_total             7675
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            wm4004sup1.cif
_cod_data_source_block           I
_cod_original_cell_volume        8466.9(17)
_cod_database_code               2241604
_cod_database_fobs_code          2241604
#BEGIN Tags that were not found in dictionaries:
_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.
;
_shelx_estimated_absorpt_t_min   0.840
_shelx_estimated_absorpt_t_max   0.905
#END Tags that were not found in dictionaries
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
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_attached_hydrogens
O O1W 0.0000 1.0000 0.3698(7) 0.141(4) Uiso d 1 2
Cu Cu1 0.57819(3) 0.31688(3) 0.88140(3) 0.04893(15) Uani d 1 0
O O1 0.6667 0.3333 0.8748(4) 0.0691(18) Uani d 1 0
O O2 0.48058(17) 0.29648(18) 0.8736(2) 0.0619(9) Uani d 1 0
N N1 0.54504(18) 0.22155(19) 0.8997(2) 0.0504(9) Uani d 1 0
N N2 0.61014(18) 0.41208(18) 0.8960(2) 0.0493(9) Uani d 1 0
N N3 0.4670(2) 0.28251(19) 0.8087(3) 0.0582(10) Uani d 1 0
C C1 0.4851(2) 0.1710(2) 0.9186(3) 0.0590(12) Uani d 1 0
H H1 0.4465 0.1738 0.9249 0.071 Uiso calc 1 0
C C2 0.4893(3) 0.1144(2) 0.9272(3) 0.0570(12) Uani d 1 0
C C3 0.5783(3) 0.4455(3) 0.9126(3) 0.0582(12) Uani d 1 0
H H3 0.5321 0.4274 0.9141 0.070 Uiso calc 1 0
Cl Cl1 0.42537(8) 0.03570(7) 0.95132(10) 0.0859(5) Uani d 1 0
O O3 0.5141(2) 0.2937(2) 0.7664(2) 0.0753(10) Uani d 1 0
O O4 0.4095(2) 0.2572(3) 0.7874(3) 0.1105(17) Uani d 1 0
P P1 0.81315(5) 0.23893(5) 0.23155(5) 0.0379(2) Uani d 1 0
P P2 0.78221(5) 0.16748(5) 0.37198(5) 0.0392(2) Uani d 1 0
N N4 0.78666(18) 0.21790(18) 0.31150(18) 0.0461(8) Uani d 1 0
C C4 0.7627(2) 0.1937(2) 0.4558(2) 0.0440(10) Uani d 1 0
C C5 0.7353(2) 0.2344(2) 0.4544(2) 0.0487(11) Uani d 1 0
H H5 0.7293 0.2500 0.4101 0.058 Uiso calc 1 0
C C6 0.7165(3) 0.2526(3) 0.5183(3) 0.0625(13) Uani d 1 0
H H6 0.6978 0.2803 0.5167 0.075 Uiso calc 1 0
C C7 0.7254(3) 0.2299(3) 0.5829(3) 0.0754(17) Uani d 1 0
H H7 0.7129 0.2424 0.6256 0.090 Uiso calc 1 0
C C8 0.7527(3) 0.1887(3) 0.5860(3) 0.0788(17) Uani d 1 0
H H8 0.7584 0.1732 0.6305 0.095 Uiso calc 1 0
C C9 0.7717(3) 0.1703(3) 0.5224(3) 0.0615(13) Uani d 1 0
H H9 0.7904 0.1427 0.5242 0.074 Uiso calc 1 0
C C10 0.8593(2) 0.1669(2) 0.3837(2) 0.0463(10) Uani d 1 0
C C11 0.9135(2) 0.2251(3) 0.4090(3) 0.0610(12) Uani d 1 0
H H11 0.9081 0.2606 0.4241 0.073 Uiso calc 1 0
C C12 0.9761(3) 0.2304(4) 0.4120(3) 0.0801(18) Uani d 1 0
H H12 1.0128 0.2696 0.4289 0.096 Uiso calc 1 0
C C13 0.9836(3) 0.1783(4) 0.3899(3) 0.0796(18) Uani d 1 0
H H13 1.0257 0.1819 0.3922 0.095 Uiso calc 1 0
C C14 0.9302(3) 0.1205(4) 0.3645(4) 0.0833(18) Uani d 1 0
H H14 0.9363 0.0855 0.3490 0.100 Uiso calc 1 0
C C15 0.8679(3) 0.1139(3) 0.3617(3) 0.0629(13) Uani d 1 0
H H15 0.8315 0.0743 0.3451 0.075 Uiso calc 1 0
C C16 0.7162(2) 0.0829(2) 0.3546(2) 0.0467(10) Uani d 1 0
C C17 0.6790(2) 0.0681(3) 0.2917(3) 0.0569(12) Uani d 1 0
H H17 0.6875 0.1021 0.2589 0.068 Uiso calc 1 0
C C18 0.6291(3) 0.0032(3) 0.2771(3) 0.0732(15) Uani d 1 0
H H18 0.6053 -0.0064 0.2338 0.088 Uiso calc 1 0
C C19 0.6146(3) -0.0466(3) 0.3259(4) 0.0771(17) Uani d 1 0
H H19 0.5810 -0.0902 0.3158 0.093 Uiso calc 1 0
C C20 0.6493(3) -0.0327(3) 0.3896(4) 0.0807(18) Uani d 1 0
H H20 0.6381 -0.0665 0.4236 0.097 Uiso calc 1 0
C C21 0.7012(3) 0.0315(3) 0.4039(3) 0.0737(16) Uani d 1 0
H H21 0.7260 0.0403 0.4465 0.088 Uiso calc 1 0
C C22 0.8529(2) 0.1956(2) 0.1928(2) 0.0414(9) Uani d 1 0
C C23 0.8160(2) 0.1331(2) 0.1628(3) 0.0532(11) Uani d 1 0
H H23 0.7698 0.1141 0.1578 0.064 Uiso calc 1 0
C C24 0.8467(3) 0.0979(3) 0.1398(3) 0.0678(14) Uani d 1 0
H H24 0.8214 0.0559 0.1185 0.081 Uiso calc 1 0
C C25 0.9149(3) 0.1251(3) 0.1483(3) 0.0666(14) Uani d 1 0
H H25 0.9355 0.1010 0.1339 0.080 Uiso calc 1 0
C C26 0.9520(3) 0.1870(3) 0.1778(3) 0.0630(13) Uani d 1 0
H H26 0.9980 0.2055 0.1828 0.076 Uiso calc 1 0
C C27 0.9219(2) 0.2228(2) 0.2003(3) 0.0505(10) Uani d 1 0
H H27 0.9477 0.2652 0.2204 0.061 Uiso calc 1 0
C C28 0.7444(2) 0.2268(2) 0.1749(2) 0.0415(9) Uani d 1 0
C C29 0.6909(2) 0.2287(2) 0.2075(3) 0.0526(11) Uani d 1 0
H H29 0.6902 0.2334 0.2575 0.063 Uiso calc 1 0
C C30 0.6394(2) 0.2237(3) 0.1659(3) 0.0674(14) Uani d 1 0
H H30 0.6037 0.2250 0.1880 0.081 Uiso calc 1 0
C C31 0.6397(3) 0.2167(3) 0.0916(3) 0.0738(16) Uani d 1 0
H H31 0.6048 0.2140 0.0636 0.089 Uiso calc 1 0
C C32 0.6910(3) 0.2138(3) 0.0599(3) 0.0698(15) Uani d 1 0
H H32 0.6906 0.2081 0.0098 0.084 Uiso calc 1 0
C C33 0.7439(3) 0.2192(3) 0.1000(2) 0.0578(12) Uani d 1 0
H H33 0.7791 0.2176 0.0772 0.069 Uiso calc 1 0
C C34 0.8736(2) 0.3267(2) 0.2287(3) 0.0468(10) Uani d 1 0
C C35 0.8897(3) 0.3652(3) 0.2894(4) 0.0845(19) Uani d 1 0
H H35 0.8686 0.3462 0.3331 0.101 Uiso calc 1 0
C C36 0.9372(5) 0.4322(3) 0.2866(5) 0.123(3) Uani d 1 0
H H36 0.9495 0.4580 0.3287 0.147 Uiso calc 1 0
C C37 0.9664(4) 0.4611(3) 0.2211(5) 0.106(3) Uani d 1 0
H H37 0.9980 0.5065 0.2190 0.127 Uiso calc 1 0
C C38 0.9497(3) 0.4245(3) 0.1612(4) 0.0813(18) Uani d 1 0
H H38 0.9697 0.4445 0.1173 0.098 Uiso calc 1 0
C C39 0.9028(3) 0.3568(2) 0.1633(3) 0.0632(13) Uani d 1 0
H H39 0.8908 0.3316 0.1208 0.076 Uiso calc 1 0
N N5 0.6667 0.3333 0.3566(5) 0.069(2) Uani d 1 0
O O5 0.6275(3) 0.2721(2) 0.3545(3) 0.1083(16) Uani d 1 0
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'
P P 0.1023 0.0942 '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'
Cl Cl 0.1484 0.1585 '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
O1 Cu1 N2 . . 91.18(12)
O1 Cu1 N1 . . 90.73(12)
N2 Cu1 N1 . . 162.20(16)
O1 Cu1 O2 . . 172.2(2)
N2 Cu1 O2 . . 91.22(15)
N1 Cu1 O2 . . 89.25(14)
Cu1 O1 Cu1 . 2_655 119.59(5)
Cu1 O1 Cu1 . 3_665 119.59(5)
Cu1 O1 Cu1 2_655 3_665 119.59(5)
N3 O2 Cu1 . . 103.4(3)
C1 N1 N2 . 2_655 108.1(4)
C1 N1 Cu1 . . 132.6(3)
N2 N1 Cu1 2_655 . 119.3(3)
C3 N2 N1 . 3_665 108.3(4)
C3 N2 Cu1 . . 132.1(3)
N1 N2 Cu1 3_665 . 118.9(3)
O4 N3 O2 . . 120.7(5)
O4 N3 O3 . . 121.5(5)
O2 N3 O3 . . 117.9(4)
N1 C1 C2 . . 109.1(4)
C1 C2 C3 . 2_655 105.8(4)
C1 C2 Cl1 . . 127.0(4)
C3 C2 Cl1 2_655 . 127.2(4)
N2 C3 C2 . 3_665 108.6(4)
N4 P1 C34 . . 109.7(2)
N4 P1 C28 . . 108.61(19)
C34 P1 C28 . . 106.6(2)
N4 P1 C22 . . 115.14(19)
C34 P1 C22 . . 106.8(2)
C28 P1 C22 . . 109.62(19)
N4 P2 C10 . . 113.0(2)
N4 P2 C4 . . 107.2(2)
C10 P2 C4 . . 108.3(2)
N4 P2 C16 . . 112.4(2)
C10 P2 C16 . . 108.4(2)
C4 P2 C16 . . 107.4(2)
P1 N4 P2 . . 139.5(2)
C5 C4 C9 . . 119.3(4)
C5 C4 P2 . . 119.6(3)
C9 C4 P2 . . 121.0(4)
C4 C5 C6 . . 120.8(5)
C7 C6 C5 . . 119.7(5)
C6 C7 C8 . . 120.7(5)
C7 C8 C9 . . 119.8(5)
C8 C9 C4 . . 119.5(5)
C11 C10 C15 . . 119.6(4)
C11 C10 P2 . . 117.0(4)
C15 C10 P2 . . 123.2(4)
C10 C11 C12 . . 119.8(5)
C13 C12 C11 . . 119.8(6)
C12 C13 C14 . . 120.8(5)
C13 C14 C15 . . 120.4(6)
C14 C15 C10 . . 119.6(6)
C17 C16 C21 . . 118.6(4)
C17 C16 P2 . . 120.0(4)
C21 C16 P2 . . 121.4(4)
C16 C17 C18 . . 120.6(5)
C19 C18 C17 . . 120.3(5)
C18 C19 C20 . . 120.1(5)
C19 C20 C21 . . 120.4(6)
C20 C21 C16 . . 119.9(5)
C23 C22 C27 . . 118.8(4)
C23 C22 P1 . . 121.4(3)
C27 C22 P1 . . 119.4(3)
C22 C23 C24 . . 120.6(4)
C25 C24 C23 . . 120.0(5)
C26 C25 C24 . . 119.9(5)
C25 C26 C27 . . 120.6(5)
C26 C27 C22 . . 120.1(5)
C33 C28 C29 . . 118.8(4)
C33 C28 P1 . . 123.1(3)
C29 C28 P1 . . 118.1(3)
C30 C29 C28 . . 120.1(5)
C29 C30 C31 . . 120.6(5)
C32 C31 C30 . . 119.5(5)
C31 C32 C33 . . 121.3(5)
C32 C33 C28 . . 119.7(5)
C35 C34 C39 . . 118.9(5)
C35 C34 P1 . . 121.2(4)
C39 C34 P1 . . 119.9(4)
C34 C35 C36 . . 120.4(6)
C35 C36 C37 . . 119.7(7)
C38 C37 C36 . . 120.5(6)
C37 C38 C39 . . 120.6(6)
C38 C39 C34 . . 119.8(5)
O5 N5 O5 2_655 . 119.91(5)
O5 N5 O5 2_655 3_665 119.90(6)
O5 N5 O5 . 3_665 119.91(5)
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 O1 . 1.8816(7) y
Cu1 N2 . 1.952(4) y
Cu1 N1 . 1.960(4) y
Cu1 O2 . 2.059(3) y
Cu1 O3 . 2.483(4) y
O1 Cu1 2_655 1.8816(7) ?
O1 Cu1 3_665 1.8816(7) ?
O2 N3 . 1.237(5) ?
N1 C1 . 1.334(6) ?
N1 N2 2_655 1.345(5) ?
N2 C3 . 1.337(6) ?
N2 N1 3_665 1.345(5) ?
N3 O4 . 1.215(6) ?
N3 O3 . 1.253(6) ?
C1 C2 . 1.364(7) ?
C2 C3 2_655 1.368(7) ?
C2 Cl1 . 1.727(5) ?
C3 C2 3_665 1.368(7) ?
P1 N4 . 1.575(4) ?
P1 C34 . 1.794(4) ?
P1 C28 . 1.799(4) ?
P1 C22 . 1.805(4) ?
P2 N4 . 1.576(4) ?
P2 C10 . 1.795(4) ?
P2 C4 . 1.795(4) ?
P2 C16 . 1.802(4) ?
C4 C5 . 1.366(6) ?
C4 C9 . 1.397(6) ?
C5 C6 . 1.391(7) ?
C6 C7 . 1.356(8) ?
C7 C8 . 1.379(9) ?
C8 C9 . 1.388(8) ?
C10 C11 . 1.378(7) ?
C10 C15 . 1.393(7) ?
C11 C12 . 1.385(8) ?
C12 C13 . 1.360(9) ?
C13 C14 . 1.366(9) ?
C14 C15 . 1.367(8) ?
C16 C17 . 1.379(6) ?
C16 C21 . 1.391(7) ?
C17 C18 . 1.382(7) ?
C18 C19 . 1.362(9) ?
C19 C20 . 1.365(9) ?
C20 C21 . 1.386(8) ?
C22 C23 . 1.371(6) ?
C22 C27 . 1.393(6) ?
C23 C24 . 1.382(7) ?
C24 C25 . 1.379(8) ?
C25 C26 . 1.356(8) ?
C26 C27 . 1.381(6) ?
C28 C33 . 1.389(6) ?
C28 C29 . 1.391(6) ?
C29 C30 . 1.368(7) ?
C30 C31 . 1.379(8) ?
C31 C32 . 1.350(8) ?
C32 C33 . 1.378(7) ?
C34 C35 . 1.358(7) ?
C34 C39 . 1.386(7) ?
C35 C36 . 1.376(9) ?
C36 C37 . 1.379(11) ?
C37 C38 . 1.323(10) ?
C38 C39 . 1.384(8) ?
N5 O5 2_655 1.238(5) ?
N5 O5 . 1.238(5) ?
N5 O5 3_665 1.238(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
C13 H13 O3 9_654 0.93 2.53 3.410(11) 157
