research communications
N,N′-ethylenebis{3-[2-(3-nitrophenyl)hydrazin-1-ylidene]-4-oxopentan-2-iminato})copper(II)–3-[2-(3-nitrophenyl)hydrazin-1-ylidene]pentane-2,4-dione (1/1)
of (aTU Bergakademie Freiberg, Leipziger Str. 29, D-09596 Freiberg/Sachsen, Germany
*Correspondence e-mail: edwin.weber@chemie.tu-freiberg.de
In the title 1:1 24H24N8O6)]·C11H11N3O4, each of the crystal components forms undulating layers which stack alternately along the b-axis direction. Molecules of the CuII complex are connected via C—H⋯O hydrogen bonds involving the nitro and keto oxygen atoms, thus forming supramolecular networks. Molecules of the arylhydrazone component are linked by C—H⋯O interactions into zigzag strands showing no interstrand association.
[Cu(CKeywords: crystal structure; arylhydrazone; CuII chelate; two-component crystal; molecular layer formation; C—H⋯O hydrogen bonding.
CCDC reference: 1912679
1. Chemical context
Hydrazone β-diketones and aryldiazonium salts using a Japp–Klingemann route (Phillips, 1959) have attracted considerable interest as precursors of potential antidiabetic drugs (Garg & Prakash, 1971; Küçükgüzel et al., 1999) as well as regarding their particular property of hydrogen bonding (Marten et al., 2007; Sethukumar & Arul Prakasam, 2010) and their remarkable behavior in the formation of metal complexes. Transition-metal chelates of the respective hydrazine have been described in great numbers (Albert et al., 1997; Mishra et al., 2000; Marten et al., 2005). Preferentially, the chelates with CuII, CoII and NiII show a tetrahedrally distorted square N2O2 coordination environment. In the presence of a diamine and NiII, related bis(hydrazonoimine) complexes are formed displaying an unusual behavior of the effective at low temperature (Khudina et al., 2007). A corresponding chelate complex, formed of 3-[2-(3-nitrophenyl)hydrazin-1-ylidene]pentane-2,4-dione (Marten et al., 2018) and bis(ethylenediamine)copper(II) chloride yielded a consisting of N,N′-ethylenebis{3-[2-(3-nitrophenyl)hydrazine-1-ylidene]-4-oxopentane-2-iminato}copper(II) and 3-[2-(3-nitrophenyl)hydrazine-1-ylidene]pentane-2,4-dione in a 1:1 stoichiometric composition (the title compound), whose is reported on herein.
derived from2. Structural commentary
The title Pbca) with one molecule of the CuII complex and one molecule of the arylhydrazone in the A perspective view is shown in Fig. 1. The metal center of the complex adopts a tetrahedrally distorted square coordination environment formed by four nitrogen atoms (N2, N4, N7, N8) of the ligand. As a result of the tetradentate coordination mode and the steric interaction between the terminal aromatic rings of the ligand, the complex molecule adopts a helical geometry with a distance of 3.384 (4) Å between the benzene ring centroids and a dihedral angle of 10.43 (4)° between the benzene ring planes. The Cu—N distances are 1.940 (2), 1.943 (2), 1.953 (2) and 1.957 (2) Å, the bond angles N7—Cu—N8, N7—Cu—N2, N8—Cu—N5 and N2—Cu—N5 are 86.3 (1), 88.4 (1), 89.1 (1) and 100.4 (1)°, respectively. The nitro groups deviate slightly from the planes of the respective benzene rings, with plane N3/O2/O3 being inclined to benzene ring C6–C11 of 3.8 (1)° and plane N6/O5/O6 being inclined to benzene ring C17–C22 by 5.1 (2)° between the nitro groups and the respective benzene rings. The conformation of the arylhydrazone component is nearly identical with that found in the reported structure of this compound (Marten et al., 2018). The molecule features an intramolecular N—H⋯O=C interaction that yields a six-membered hydrogen-bonded ring. The dihedral angle between the mean plane of this ring and the aromatic ring is 7.8 (2)°. The nitro group is tilted at an angle of 5.8 (2)° with respect to the benzene ring.
possesses orthorhombic symmetry (space group3. Supramolecular features
In the crystal, the CuII complexes as well as the arylhydrazone molecules form undulating layers extending parallel to the ac plane and arranged in an alternating order along the b-axis direction (Fig. 2). Within a layer of complexes, one carbonyl oxygen and one nitro group per molecule interact via Carene—H⋯O hydrogen bonding (Desiraju & Steiner, 1999), thus generating a supramolecular network (Table 1, Fig. 3). The arylhydrazone molecules are connected by means of Caryl—H⋯Onitro interactions to form zigzag-like strands that run along the a-axis direction (Table 1, Fig. 4). No directed non-covalent bonds are observed between the supramolecular strands. In the stacking direction, the molecules are linked by C—H⋯O interactions involving a nitro oxygen atom of the arylhydrazone molecule and a methyl hydrogen of the coordinated ligand.
4. Database survey
A search in the Cambridge Structural Database (CSD, Version 5.38, update February 2017; Groom et al., 2016) revealed one hit for a of a transition-metal complex containing a structurally related ligand species. The complex N,N′-ethylene-bis[3-(4-methylphenyl)hydrazono-4-oxo-5,5,6,6,7,7,8,8-octafluorooctane-2-iminato]nickel(II) (JIXQAJ; Khudina et al., 2007) adopts a helical geometry that resembles that of the title complex. As a result of the presence of two extended fluoroalkyl moieties, the pattern of intermolecular non-covalent bonding is dominated by C—H⋯F and F⋯F interactions (Reichenbächer et al., 2005), creating a three-dimensional supramolecular architecture. Unlike the title structure, in the reported of 3-[2-(3-nitrophenyl)hydrazine-1-ylidene]pentane-2,4-dione (Marten et al., 2018) the molecules are connected via Carene—H⋯Onitro and Carene—H⋯Oketo interactions giving rise to supramolecular sheets.
5. Synthesis and crystallization
A solution containing 3-[2-(3-nitrophenyl)hydrazine-1-ylidene]pentane-2,4-dione and bis(ethylenediamine)copper(II) chloride in n-butanol was heated for several hours. After cooling and storing the reaction solution, blue-colored crystals could be isolated which turned out to consist of the title compound.
6. Refinement
Crystal data, data collection and structure . The NH H atom of 3-[2-(3-nitrophenyl)-hydrazine-1-ylidene]pentane-2,4-dione was located in a difference-Fourier map and freely refined. The C-bound and N-bound H atoms were included in the model in calculated positions and refined as riding atoms: C—H = 0.95–0.99 Å with Uiso(H) = 1.5Ueq(C) for methyl and Uiso(H) = 1.2Ueq(C) for other H atoms.
details are summarized in Table 2
|
Supporting information
CCDC reference: 1912679
https://doi.org/10.1107/S2056989019005838/yk2120sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019005838/yk2120Isup2.hkl
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Cu(C24H24N8O6)]·C11H11N3O4 | Dx = 1.520 Mg m−3 |
Mr = 833.28 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 8051 reflections |
a = 15.5820 (5) Å | θ = 2.2–28.2° |
b = 20.0517 (7) Å | µ = 0.68 mm−1 |
c = 23.3082 (8) Å | T = 153 K |
V = 7282.5 (4) Å3 | Plate, blue |
Z = 8 | 0.54 × 0.44 × 0.07 mm |
F(000) = 3448 |
Bruker SMART APEXII diffractometer | 6112 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.106 |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | θmax = 29.3°, θmin = 2.2° |
Tmin = 0.712, Tmax = 0.954 | h = −20→21 |
86372 measured reflections | k = −27→25 |
9862 independent reflections | l = −31→28 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: mixed |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0736P)2 + 0.2354P] where P = (Fo2 + 2Fc2)/3 |
9862 reflections | (Δ/σ)max = 0.001 |
524 parameters | Δρmax = 1.00 e Å−3 |
1 restraint | Δρmin = −0.67 e Å−3 |
Geometry. 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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.23540 (2) | 0.01555 (2) | 0.46535 (2) | 0.01874 (9) | |
O1 | −0.07371 (10) | −0.09037 (9) | 0.50519 (7) | 0.0288 (4) | |
O2 | 0.46419 (12) | −0.03799 (13) | 0.31472 (9) | 0.0542 (6) | |
O3 | 0.43989 (13) | −0.02538 (13) | 0.22515 (9) | 0.0543 (6) | |
O4 | 0.56630 (10) | 0.08866 (10) | 0.47203 (8) | 0.0357 (4) | |
O5 | 0.23463 (12) | 0.16123 (9) | 0.16939 (7) | 0.0348 (4) | |
O6 | 0.35277 (12) | 0.13307 (11) | 0.21053 (8) | 0.0419 (5) | |
N1 | 0.10026 (11) | −0.06399 (9) | 0.41500 (7) | 0.0171 (4) | |
N2 | 0.17823 (11) | −0.04081 (9) | 0.40872 (7) | 0.0181 (4) | |
N3 | 0.41581 (13) | −0.03341 (11) | 0.27448 (9) | 0.0293 (5) | |
N4 | 0.36211 (11) | 0.10044 (9) | 0.41302 (8) | 0.0197 (4) | |
N5 | 0.27979 (11) | 0.08627 (9) | 0.41566 (7) | 0.0180 (4) | |
N6 | 0.27544 (13) | 0.14372 (10) | 0.21161 (8) | 0.0244 (4) | |
N7 | 0.18147 (11) | −0.03715 (10) | 0.52509 (7) | 0.0200 (4) | |
N8 | 0.31978 (12) | 0.04022 (10) | 0.52296 (8) | 0.0208 (4) | |
C1 | 0.07728 (15) | −0.11055 (13) | 0.57134 (10) | 0.0282 (5) | |
H1A | 0.1254 | −0.1339 | 0.5895 | 0.042* | |
H1B | 0.0352 | −0.1432 | 0.5576 | 0.042* | |
H1C | 0.0500 | −0.0809 | 0.5994 | 0.042* | |
C2 | 0.10993 (14) | −0.06983 (11) | 0.52124 (9) | 0.0188 (4) | |
C3 | 0.06458 (13) | −0.07253 (11) | 0.46652 (9) | 0.0176 (4) | |
C4 | −0.02728 (13) | −0.09027 (11) | 0.46301 (10) | 0.0203 (5) | |
C5 | −0.06491 (15) | −0.10480 (14) | 0.40497 (10) | 0.0315 (6) | |
H5A | −0.1214 | −0.1256 | 0.4096 | 0.047* | |
H5B | −0.0269 | −0.1352 | 0.3840 | 0.047* | |
H5C | −0.0710 | −0.0631 | 0.3834 | 0.047* | |
C6 | 0.20627 (13) | −0.04200 (11) | 0.35057 (9) | 0.0175 (4) | |
C7 | 0.29434 (13) | −0.04252 (11) | 0.34078 (9) | 0.0191 (4) | |
H7 | 0.3338 | −0.0463 | 0.3717 | 0.023* | |
C8 | 0.32268 (14) | −0.03731 (12) | 0.28491 (10) | 0.0214 (5) | |
C9 | 0.26778 (15) | −0.03286 (11) | 0.23830 (10) | 0.0224 (5) | |
H9 | 0.2895 | −0.0283 | 0.2004 | 0.027* | |
C10 | 0.18059 (15) | −0.03522 (11) | 0.24867 (10) | 0.0227 (5) | |
H10 | 0.1415 | −0.0339 | 0.2174 | 0.027* | |
C11 | 0.14957 (14) | −0.03950 (11) | 0.30421 (9) | 0.0204 (5) | |
H11 | 0.0894 | −0.0407 | 0.3108 | 0.025* | |
C12 | 0.44975 (16) | 0.08755 (14) | 0.56354 (11) | 0.0351 (6) | |
H12A | 0.4146 | 0.1030 | 0.5958 | 0.053* | |
H12B | 0.4891 | 0.1232 | 0.5518 | 0.053* | |
H12C | 0.4829 | 0.0483 | 0.5753 | 0.053* | |
C13 | 0.39251 (14) | 0.06942 (11) | 0.51413 (10) | 0.0213 (5) | |
C14 | 0.41621 (13) | 0.08968 (11) | 0.45596 (9) | 0.0204 (5) | |
C15 | 0.50662 (15) | 0.10235 (12) | 0.43992 (11) | 0.0257 (5) | |
C16 | 0.52487 (15) | 0.12956 (15) | 0.38115 (11) | 0.0377 (7) | |
H16A | 0.5842 | 0.1457 | 0.3795 | 0.057* | |
H16B | 0.4856 | 0.1665 | 0.3730 | 0.057* | |
H16C | 0.5168 | 0.0943 | 0.3526 | 0.057* | |
C17 | 0.23544 (13) | 0.10738 (10) | 0.36559 (9) | 0.0172 (4) | |
C18 | 0.27775 (13) | 0.11919 (11) | 0.31372 (9) | 0.0191 (4) | |
H18 | 0.3385 | 0.1164 | 0.3114 | 0.023* | |
C19 | 0.22975 (14) | 0.13491 (11) | 0.26627 (9) | 0.0200 (5) | |
C20 | 0.14114 (14) | 0.14071 (11) | 0.26706 (10) | 0.0228 (5) | |
H20 | 0.1098 | 0.1516 | 0.2334 | 0.027* | |
C21 | 0.10001 (14) | 0.12994 (11) | 0.31900 (10) | 0.0238 (5) | |
H21 | 0.0393 | 0.1339 | 0.3212 | 0.029* | |
C22 | 0.14640 (13) | 0.11353 (11) | 0.36762 (9) | 0.0204 (5) | |
H22 | 0.1172 | 0.1064 | 0.4029 | 0.025* | |
C23 | 0.23529 (15) | −0.04049 (13) | 0.57677 (10) | 0.0249 (5) | |
H23A | 0.2720 | −0.0808 | 0.5752 | 0.030* | |
H23B | 0.1984 | −0.0437 | 0.6112 | 0.030* | |
C24 | 0.29118 (15) | 0.02124 (13) | 0.58082 (10) | 0.0260 (5) | |
H24A | 0.2582 | 0.0583 | 0.5982 | 0.031* | |
H24B | 0.3416 | 0.0120 | 0.6055 | 0.031* | |
O1A | 0.46165 (13) | 0.22072 (15) | 0.78627 (10) | 0.0664 (7) | |
O2A | 0.28475 (13) | 0.17207 (10) | 0.66034 (9) | 0.0457 (5) | |
O3A | 0.04080 (11) | 0.24229 (10) | 0.94118 (10) | 0.0469 (5) | |
O4A | 0.06525 (13) | 0.25224 (11) | 1.03186 (10) | 0.0499 (6) | |
N1A | 0.28478 (13) | 0.20901 (10) | 0.80646 (10) | 0.0296 (5) | |
N2A | 0.33228 (13) | 0.21815 (11) | 0.85192 (10) | 0.0332 (5) | |
H2A | 0.3888 (7) | 0.2245 (15) | 0.8469 (13) | 0.051 (9)* | |
N3A | 0.08951 (14) | 0.24565 (11) | 0.98228 (12) | 0.0370 (6) | |
C1A | 0.45036 (19) | 0.21587 (17) | 0.68630 (13) | 0.0501 (8) | |
H1A1 | 0.5084 | 0.2346 | 0.6880 | 0.075* | |
H1A2 | 0.4142 | 0.2441 | 0.6619 | 0.075* | |
H1A3 | 0.4527 | 0.1707 | 0.6703 | 0.075* | |
C2A | 0.41369 (17) | 0.21322 (14) | 0.74488 (13) | 0.0386 (7) | |
C3A | 0.32060 (16) | 0.20372 (12) | 0.75493 (11) | 0.0295 (6) | |
C4A | 0.25922 (17) | 0.18854 (13) | 0.70795 (13) | 0.0341 (6) | |
C5A | 0.16462 (17) | 0.19307 (15) | 0.71948 (13) | 0.0423 (7) | |
H5A1 | 0.1413 | 0.2328 | 0.7006 | 0.063* | |
H5A2 | 0.1548 | 0.1962 | 0.7609 | 0.063* | |
H5A3 | 0.1360 | 0.1532 | 0.7045 | 0.063* | |
C6A | 0.29704 (16) | 0.22805 (12) | 0.90680 (11) | 0.0277 (5) | |
C7A | 0.20906 (16) | 0.22976 (12) | 0.91655 (12) | 0.0291 (6) | |
H7A | 0.1691 | 0.2227 | 0.8864 | 0.035* | |
C8A | 0.18222 (15) | 0.24215 (12) | 0.97171 (12) | 0.0310 (6) | |
C9A | 0.23753 (18) | 0.25281 (14) | 1.01735 (14) | 0.0367 (6) | |
H9A | 0.2164 | 0.2613 | 1.0549 | 0.044* | |
C10A | 0.32440 (17) | 0.25058 (13) | 1.00628 (13) | 0.0369 (6) | |
H10A | 0.3642 | 0.2577 | 1.0366 | 0.044* | |
C11A | 0.35401 (16) | 0.23805 (13) | 0.95142 (12) | 0.0330 (6) | |
H11A | 0.4140 | 0.2363 | 0.9443 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01805 (14) | 0.02554 (15) | 0.01264 (15) | −0.00435 (10) | −0.00054 (11) | 0.00152 (11) |
O1 | 0.0193 (8) | 0.0433 (10) | 0.0237 (10) | −0.0008 (7) | 0.0055 (7) | 0.0031 (8) |
O2 | 0.0194 (10) | 0.1091 (19) | 0.0342 (12) | 0.0037 (10) | −0.0026 (9) | 0.0060 (12) |
O3 | 0.0299 (11) | 0.1047 (19) | 0.0285 (12) | −0.0084 (11) | 0.0138 (9) | −0.0071 (11) |
O4 | 0.0180 (8) | 0.0470 (11) | 0.0420 (12) | −0.0009 (7) | −0.0038 (8) | 0.0096 (9) |
O5 | 0.0451 (11) | 0.0437 (11) | 0.0155 (9) | 0.0029 (8) | −0.0008 (8) | 0.0026 (8) |
O6 | 0.0291 (10) | 0.0713 (14) | 0.0254 (11) | 0.0017 (9) | 0.0110 (8) | 0.0074 (9) |
N1 | 0.0152 (9) | 0.0209 (9) | 0.0152 (10) | −0.0009 (7) | 0.0019 (7) | 0.0002 (7) |
N2 | 0.0149 (9) | 0.0263 (10) | 0.0132 (10) | −0.0015 (7) | 0.0019 (7) | −0.0010 (7) |
N3 | 0.0193 (10) | 0.0425 (13) | 0.0261 (12) | 0.0009 (8) | 0.0057 (9) | −0.0055 (9) |
N4 | 0.0166 (9) | 0.0229 (10) | 0.0197 (10) | −0.0026 (7) | 0.0023 (7) | −0.0014 (7) |
N5 | 0.0160 (9) | 0.0259 (10) | 0.0122 (9) | −0.0009 (7) | 0.0000 (7) | −0.0001 (7) |
N6 | 0.0328 (12) | 0.0263 (10) | 0.0140 (11) | −0.0034 (8) | 0.0029 (9) | −0.0022 (8) |
N7 | 0.0187 (9) | 0.0287 (10) | 0.0125 (10) | −0.0021 (7) | −0.0001 (7) | 0.0017 (7) |
N8 | 0.0201 (9) | 0.0283 (10) | 0.0139 (10) | −0.0030 (8) | −0.0017 (7) | 0.0000 (8) |
C1 | 0.0287 (13) | 0.0370 (14) | 0.0189 (13) | −0.0090 (10) | 0.0002 (10) | 0.0064 (10) |
C2 | 0.0189 (11) | 0.0234 (11) | 0.0142 (11) | 0.0018 (8) | 0.0021 (8) | 0.0008 (8) |
C3 | 0.0165 (10) | 0.0212 (11) | 0.0151 (11) | −0.0001 (8) | 0.0018 (9) | 0.0005 (9) |
C4 | 0.0176 (11) | 0.0249 (12) | 0.0184 (12) | −0.0002 (8) | 0.0006 (9) | 0.0036 (9) |
C5 | 0.0186 (12) | 0.0507 (16) | 0.0251 (14) | −0.0082 (11) | −0.0044 (10) | 0.0038 (11) |
C6 | 0.0196 (10) | 0.0191 (10) | 0.0138 (11) | −0.0022 (8) | 0.0021 (9) | −0.0005 (8) |
C7 | 0.0177 (10) | 0.0251 (11) | 0.0144 (11) | 0.0009 (9) | −0.0019 (9) | −0.0019 (9) |
C8 | 0.0162 (10) | 0.0283 (12) | 0.0196 (12) | −0.0002 (9) | 0.0032 (9) | −0.0038 (9) |
C9 | 0.0269 (12) | 0.0280 (12) | 0.0124 (11) | −0.0011 (9) | 0.0047 (9) | −0.0022 (9) |
C10 | 0.0253 (12) | 0.0276 (12) | 0.0150 (12) | 0.0004 (9) | −0.0023 (9) | −0.0012 (9) |
C11 | 0.0170 (11) | 0.0245 (11) | 0.0197 (12) | −0.0009 (8) | −0.0009 (9) | −0.0009 (9) |
C12 | 0.0307 (14) | 0.0470 (16) | 0.0275 (15) | −0.0145 (12) | −0.0082 (11) | 0.0006 (12) |
C13 | 0.0202 (11) | 0.0237 (12) | 0.0200 (12) | −0.0013 (8) | −0.0007 (9) | 0.0009 (9) |
C14 | 0.0166 (10) | 0.0246 (12) | 0.0201 (13) | −0.0016 (8) | −0.0011 (9) | −0.0011 (9) |
C15 | 0.0211 (12) | 0.0276 (13) | 0.0284 (14) | −0.0041 (9) | 0.0002 (10) | −0.0010 (10) |
C16 | 0.0212 (12) | 0.0599 (19) | 0.0320 (16) | −0.0085 (12) | 0.0048 (11) | 0.0052 (13) |
C17 | 0.0181 (10) | 0.0183 (10) | 0.0152 (11) | −0.0027 (8) | −0.0004 (9) | −0.0016 (8) |
C18 | 0.0179 (11) | 0.0203 (11) | 0.0191 (12) | −0.0031 (8) | 0.0020 (9) | −0.0006 (9) |
C19 | 0.0273 (12) | 0.0196 (11) | 0.0132 (11) | −0.0037 (9) | 0.0043 (9) | 0.0001 (8) |
C20 | 0.0242 (12) | 0.0240 (11) | 0.0202 (13) | 0.0011 (9) | −0.0042 (9) | 0.0025 (9) |
C21 | 0.0189 (11) | 0.0285 (13) | 0.0240 (13) | 0.0024 (9) | 0.0014 (9) | 0.0015 (10) |
C22 | 0.0200 (11) | 0.0245 (11) | 0.0168 (12) | −0.0001 (8) | 0.0051 (9) | 0.0020 (9) |
C23 | 0.0241 (11) | 0.0348 (13) | 0.0157 (12) | −0.0046 (10) | −0.0034 (10) | 0.0058 (10) |
C24 | 0.0232 (11) | 0.0399 (14) | 0.0148 (12) | −0.0082 (10) | −0.0012 (10) | −0.0009 (10) |
O1A | 0.0253 (11) | 0.125 (2) | 0.0487 (15) | −0.0036 (13) | 0.0007 (10) | −0.0065 (14) |
O2A | 0.0480 (12) | 0.0499 (13) | 0.0391 (13) | −0.0020 (9) | −0.0019 (10) | −0.0082 (10) |
O3A | 0.0217 (10) | 0.0523 (13) | 0.0666 (16) | 0.0003 (8) | −0.0052 (10) | −0.0050 (11) |
O4A | 0.0394 (12) | 0.0507 (13) | 0.0598 (16) | −0.0008 (9) | 0.0198 (11) | −0.0019 (10) |
N1A | 0.0268 (11) | 0.0212 (10) | 0.0408 (14) | 0.0010 (8) | −0.0017 (10) | 0.0022 (9) |
N2A | 0.0194 (11) | 0.0390 (13) | 0.0413 (15) | 0.0025 (9) | −0.0025 (10) | 0.0045 (10) |
N3A | 0.0273 (12) | 0.0277 (12) | 0.0561 (17) | −0.0010 (9) | 0.0066 (12) | −0.0004 (11) |
C1A | 0.0426 (17) | 0.058 (2) | 0.050 (2) | −0.0103 (14) | 0.0105 (15) | −0.0140 (15) |
C2A | 0.0309 (15) | 0.0421 (16) | 0.0430 (18) | 0.0001 (12) | 0.0060 (13) | −0.0037 (13) |
C3A | 0.0293 (13) | 0.0230 (12) | 0.0363 (16) | 0.0030 (9) | 0.0015 (11) | −0.0006 (10) |
C4A | 0.0338 (15) | 0.0234 (13) | 0.0451 (18) | 0.0008 (10) | −0.0033 (13) | 0.0007 (11) |
C5A | 0.0324 (15) | 0.0404 (16) | 0.054 (2) | −0.0016 (11) | −0.0050 (13) | −0.0117 (14) |
C6A | 0.0250 (12) | 0.0260 (13) | 0.0321 (15) | 0.0032 (9) | 0.0007 (11) | 0.0049 (10) |
C7A | 0.0235 (12) | 0.0246 (12) | 0.0392 (16) | 0.0001 (9) | −0.0047 (11) | 0.0025 (10) |
C8A | 0.0193 (12) | 0.0253 (13) | 0.0483 (18) | 0.0015 (9) | 0.0018 (12) | 0.0050 (11) |
C9A | 0.0367 (15) | 0.0365 (15) | 0.0369 (16) | 0.0031 (11) | 0.0011 (12) | 0.0034 (12) |
C10A | 0.0309 (14) | 0.0410 (15) | 0.0388 (17) | 0.0013 (11) | −0.0111 (13) | 0.0055 (12) |
C11A | 0.0218 (12) | 0.0347 (14) | 0.0426 (18) | 0.0023 (10) | −0.0012 (11) | 0.0072 (11) |
Cu1—N7 | 1.9395 (18) | C15—C16 | 1.502 (3) |
Cu1—N8 | 1.9434 (18) | C16—H16A | 0.9800 |
Cu1—N2 | 1.9527 (18) | C16—H16B | 0.9800 |
Cu1—N5 | 1.9573 (18) | C16—H16C | 0.9800 |
O1—C4 | 1.221 (3) | C17—C22 | 1.394 (3) |
O2—N3 | 1.207 (3) | C17—C18 | 1.397 (3) |
O3—N3 | 1.220 (3) | C18—C19 | 1.372 (3) |
O4—C15 | 1.225 (3) | C18—H18 | 0.9500 |
O5—N6 | 1.223 (2) | C19—C20 | 1.386 (3) |
O6—N6 | 1.224 (3) | C20—C21 | 1.387 (3) |
N1—N2 | 1.309 (2) | C20—H20 | 0.9500 |
N1—C3 | 1.334 (3) | C21—C22 | 1.384 (3) |
N2—C6 | 1.424 (3) | C21—H21 | 0.9500 |
N3—C8 | 1.473 (3) | C22—H22 | 0.9500 |
N4—N5 | 1.315 (2) | C23—C24 | 1.516 (3) |
N4—C14 | 1.326 (3) | C23—H23A | 0.9900 |
N5—C17 | 1.421 (3) | C23—H23B | 0.9900 |
N6—C19 | 1.470 (3) | C24—H24A | 0.9900 |
N7—C2 | 1.296 (3) | C24—H24B | 0.9900 |
N7—C23 | 1.469 (3) | O1A—C2A | 1.230 (3) |
N8—C13 | 1.292 (3) | O2A—C4A | 1.224 (3) |
N8—C24 | 1.471 (3) | O3A—N3A | 1.224 (3) |
C1—C2 | 1.513 (3) | O4A—N3A | 1.223 (3) |
C1—H1A | 0.9800 | N1A—N2A | 1.305 (3) |
C1—H1B | 0.9800 | N1A—C3A | 1.329 (3) |
C1—H1C | 0.9800 | N2A—C6A | 1.406 (3) |
C2—C3 | 1.459 (3) | N2A—H2A | 0.898 (10) |
C3—C4 | 1.477 (3) | N3A—C8A | 1.467 (3) |
C4—C5 | 1.503 (3) | C1A—C2A | 1.481 (4) |
C5—H5A | 0.9800 | C1A—H1A1 | 0.9800 |
C5—H5B | 0.9800 | C1A—H1A2 | 0.9800 |
C5—H5C | 0.9800 | C1A—H1A3 | 0.9800 |
C6—C7 | 1.391 (3) | C2A—C3A | 1.482 (4) |
C6—C11 | 1.397 (3) | C3A—C4A | 1.485 (4) |
C7—C8 | 1.379 (3) | C4A—C5A | 1.501 (4) |
C7—H7 | 0.9500 | C5A—H5A1 | 0.9800 |
C8—C9 | 1.386 (3) | C5A—H5A2 | 0.9800 |
C9—C10 | 1.381 (3) | C5A—H5A3 | 0.9800 |
C9—H9 | 0.9500 | C6A—C11A | 1.382 (4) |
C10—C11 | 1.385 (3) | C6A—C7A | 1.390 (4) |
C10—H10 | 0.9500 | C7A—C8A | 1.375 (4) |
C11—H11 | 0.9500 | C7A—H7A | 0.9500 |
C12—C13 | 1.501 (3) | C8A—C9A | 1.386 (4) |
C12—H12A | 0.9800 | C9A—C10A | 1.379 (4) |
C12—H12B | 0.9800 | C9A—H9A | 0.9500 |
C12—H12C | 0.9800 | C10A—C11A | 1.382 (4) |
C13—C14 | 1.463 (3) | C10A—H10A | 0.9500 |
C14—C15 | 1.479 (3) | C11A—H11A | 0.9500 |
N7—Cu1—N8 | 86.32 (8) | C15—C16—H16B | 109.5 |
N7—Cu1—N2 | 88.42 (8) | H16A—C16—H16B | 109.5 |
N8—Cu1—N2 | 157.38 (8) | C15—C16—H16C | 109.5 |
N7—Cu1—N5 | 166.59 (8) | H16A—C16—H16C | 109.5 |
N8—Cu1—N5 | 89.16 (7) | H16B—C16—H16C | 109.5 |
N2—Cu1—N5 | 100.40 (7) | C22—C17—C18 | 119.0 (2) |
N2—N1—C3 | 122.21 (18) | C22—C17—N5 | 118.85 (18) |
N1—N2—C6 | 112.66 (17) | C18—C17—N5 | 122.12 (18) |
N1—N2—Cu1 | 123.59 (14) | C19—C18—C17 | 118.63 (19) |
C6—N2—Cu1 | 120.87 (13) | C19—C18—H18 | 120.7 |
O2—N3—O3 | 123.4 (2) | C17—C18—H18 | 120.7 |
O2—N3—C8 | 118.9 (2) | C18—C19—C20 | 123.5 (2) |
O3—N3—C8 | 117.7 (2) | C18—C19—N6 | 117.53 (19) |
N5—N4—C14 | 123.34 (18) | C20—C19—N6 | 118.9 (2) |
N4—N5—C17 | 111.82 (17) | C19—C20—C21 | 117.3 (2) |
N4—N5—Cu1 | 121.92 (14) | C19—C20—H20 | 121.3 |
C17—N5—Cu1 | 122.01 (13) | C21—C20—H20 | 121.3 |
O5—N6—O6 | 123.0 (2) | C22—C21—C20 | 120.7 (2) |
O5—N6—C19 | 118.68 (19) | C22—C21—H21 | 119.6 |
O6—N6—C19 | 118.27 (19) | C20—C21—H21 | 119.6 |
C2—N7—C23 | 121.64 (18) | C21—C22—C17 | 120.9 (2) |
C2—N7—Cu1 | 126.75 (15) | C21—C22—H22 | 119.6 |
C23—N7—Cu1 | 111.48 (13) | C17—C22—H22 | 119.6 |
C13—N8—C24 | 121.95 (19) | N7—C23—C24 | 109.98 (19) |
C13—N8—Cu1 | 126.78 (16) | N7—C23—H23A | 109.7 |
C24—N8—Cu1 | 111.27 (13) | C24—C23—H23A | 109.7 |
C2—C1—H1A | 109.5 | N7—C23—H23B | 109.7 |
C2—C1—H1B | 109.5 | C24—C23—H23B | 109.7 |
H1A—C1—H1B | 109.5 | H23A—C23—H23B | 108.2 |
C2—C1—H1C | 109.5 | N8—C24—C23 | 109.15 (18) |
H1A—C1—H1C | 109.5 | N8—C24—H24A | 109.8 |
H1B—C1—H1C | 109.5 | C23—C24—H24A | 109.8 |
N7—C2—C3 | 119.72 (19) | N8—C24—H24B | 109.8 |
N7—C2—C1 | 120.57 (19) | C23—C24—H24B | 109.8 |
C3—C2—C1 | 119.46 (19) | H24A—C24—H24B | 108.3 |
N1—C3—C2 | 125.46 (19) | N2A—N1A—C3A | 120.5 (2) |
N1—C3—C4 | 112.64 (18) | N1A—N2A—C6A | 122.5 (2) |
C2—C3—C4 | 121.77 (19) | N1A—N2A—H2A | 118 (2) |
O1—C4—C3 | 122.0 (2) | C6A—N2A—H2A | 119 (2) |
O1—C4—C5 | 119.6 (2) | O4A—N3A—O3A | 123.6 (2) |
C3—C4—C5 | 118.32 (19) | O4A—N3A—C8A | 117.9 (2) |
C4—C5—H5A | 109.5 | O3A—N3A—C8A | 118.5 (2) |
C4—C5—H5B | 109.5 | C2A—C1A—H1A1 | 109.5 |
H5A—C5—H5B | 109.5 | C2A—C1A—H1A2 | 109.5 |
C4—C5—H5C | 109.5 | H1A1—C1A—H1A2 | 109.5 |
H5A—C5—H5C | 109.5 | C2A—C1A—H1A3 | 109.5 |
H5B—C5—H5C | 109.5 | H1A1—C1A—H1A3 | 109.5 |
C7—C6—C11 | 119.83 (19) | H1A2—C1A—H1A3 | 109.5 |
C7—C6—N2 | 117.31 (18) | O1A—C2A—C1A | 119.0 (3) |
C11—C6—N2 | 122.79 (19) | O1A—C2A—C3A | 119.1 (3) |
C8—C7—C6 | 118.0 (2) | C1A—C2A—C3A | 121.9 (3) |
C8—C7—H7 | 121.0 | N1A—C3A—C2A | 122.9 (2) |
C6—C7—H7 | 121.0 | N1A—C3A—C4A | 114.4 (2) |
C7—C8—C9 | 123.2 (2) | C2A—C3A—C4A | 122.7 (2) |
C7—C8—N3 | 118.4 (2) | O2A—C4A—C3A | 121.0 (2) |
C9—C8—N3 | 118.4 (2) | O2A—C4A—C5A | 119.8 (2) |
C10—C9—C8 | 117.9 (2) | C3A—C4A—C5A | 119.2 (2) |
C10—C9—H9 | 121.0 | C4A—C5A—H5A1 | 109.5 |
C8—C9—H9 | 121.0 | C4A—C5A—H5A2 | 109.5 |
C9—C10—C11 | 120.6 (2) | H5A1—C5A—H5A2 | 109.5 |
C9—C10—H10 | 119.7 | C4A—C5A—H5A3 | 109.5 |
C11—C10—H10 | 119.7 | H5A1—C5A—H5A3 | 109.5 |
C10—C11—C6 | 120.3 (2) | H5A2—C5A—H5A3 | 109.5 |
C10—C11—H11 | 119.8 | C11A—C6A—C7A | 120.5 (2) |
C6—C11—H11 | 119.8 | C11A—C6A—N2A | 117.0 (2) |
C13—C12—H12A | 109.5 | C7A—C6A—N2A | 122.5 (2) |
C13—C12—H12B | 109.5 | C8A—C7A—C6A | 117.2 (2) |
H12A—C12—H12B | 109.5 | C8A—C7A—H7A | 121.4 |
C13—C12—H12C | 109.5 | C6A—C7A—H7A | 121.4 |
H12A—C12—H12C | 109.5 | C7A—C8A—C9A | 123.8 (2) |
H12B—C12—H12C | 109.5 | C7A—C8A—N3A | 117.7 (2) |
N8—C13—C14 | 119.7 (2) | C9A—C8A—N3A | 118.4 (2) |
N8—C13—C12 | 120.6 (2) | C10A—C9A—C8A | 117.5 (3) |
C14—C13—C12 | 119.6 (2) | C10A—C9A—H9A | 121.2 |
N4—C14—C13 | 125.75 (19) | C8A—C9A—H9A | 121.2 |
N4—C14—C15 | 112.74 (19) | C9A—C10A—C11A | 120.4 (3) |
C13—C14—C15 | 121.5 (2) | C9A—C10A—H10A | 119.8 |
O4—C15—C14 | 122.0 (2) | C11A—C10A—H10A | 119.8 |
O4—C15—C16 | 119.7 (2) | C6A—C11A—C10A | 120.5 (2) |
C14—C15—C16 | 118.2 (2) | C6A—C11A—H11A | 119.7 |
C15—C16—H16A | 109.5 | C10A—C11A—H11A | 119.7 |
C3—N1—N2—C6 | 174.16 (18) | N4—N5—C17—C22 | −162.16 (19) |
C3—N1—N2—Cu1 | −25.0 (3) | Cu1—N5—C17—C22 | 40.6 (3) |
C14—N4—N5—C17 | 175.52 (19) | N4—N5—C17—C18 | 20.8 (3) |
C14—N4—N5—Cu1 | −27.2 (3) | Cu1—N5—C17—C18 | −136.36 (17) |
C23—N7—C2—C3 | −171.5 (2) | C22—C17—C18—C19 | −1.5 (3) |
Cu1—N7—C2—C3 | 4.0 (3) | N5—C17—C18—C19 | 175.48 (19) |
C23—N7—C2—C1 | 2.7 (3) | C17—C18—C19—C20 | 1.0 (3) |
Cu1—N7—C2—C1 | 178.17 (17) | C17—C18—C19—N6 | −176.94 (18) |
N2—N1—C3—C2 | −12.0 (3) | O5—N6—C19—C18 | −176.2 (2) |
N2—N1—C3—C4 | 172.09 (19) | O6—N6—C19—C18 | 3.9 (3) |
N7—C2—C3—N1 | 23.5 (3) | O5—N6—C19—C20 | 5.9 (3) |
C1—C2—C3—N1 | −150.7 (2) | O6—N6—C19—C20 | −174.1 (2) |
N7—C2—C3—C4 | −161.0 (2) | C18—C19—C20—C21 | 0.1 (3) |
C1—C2—C3—C4 | 24.8 (3) | N6—C19—C20—C21 | 177.9 (2) |
N1—C3—C4—O1 | −168.9 (2) | C19—C20—C21—C22 | −0.5 (3) |
C2—C3—C4—O1 | 15.1 (3) | C20—C21—C22—C17 | 0.0 (3) |
N1—C3—C4—C5 | 7.6 (3) | C18—C17—C22—C21 | 1.1 (3) |
C2—C3—C4—C5 | −168.4 (2) | N5—C17—C22—C21 | −176.0 (2) |
N1—N2—C6—C7 | −156.94 (19) | C2—N7—C23—C24 | −156.1 (2) |
Cu1—N2—C6—C7 | 41.6 (2) | Cu1—N7—C23—C24 | 27.8 (2) |
N1—N2—C6—C11 | 26.1 (3) | C13—N8—C24—C23 | −149.4 (2) |
Cu1—N2—C6—C11 | −135.30 (18) | Cu1—N8—C24—C23 | 30.5 (2) |
C11—C6—C7—C8 | 3.0 (3) | N7—C23—C24—N8 | −37.7 (3) |
N2—C6—C7—C8 | −173.99 (19) | C3A—N1A—N2A—C6A | 176.1 (2) |
C6—C7—C8—C9 | −1.2 (3) | N2A—N1A—C3A—C2A | −5.2 (4) |
C6—C7—C8—N3 | 176.08 (19) | N2A—N1A—C3A—C4A | 175.8 (2) |
O2—N3—C8—C7 | 3.4 (3) | O1A—C2A—C3A—N1A | 6.4 (4) |
O3—N3—C8—C7 | −176.3 (2) | C1A—C2A—C3A—N1A | −171.8 (2) |
O2—N3—C8—C9 | −179.2 (2) | O1A—C2A—C3A—C4A | −174.6 (3) |
O3—N3—C8—C9 | 1.1 (3) | C1A—C2A—C3A—C4A | 7.2 (4) |
C7—C8—C9—C10 | −1.4 (3) | N1A—C3A—C4A—O2A | −168.4 (2) |
N3—C8—C9—C10 | −178.7 (2) | C2A—C3A—C4A—O2A | 12.5 (4) |
C8—C9—C10—C11 | 2.3 (3) | N1A—C3A—C4A—C5A | 11.1 (3) |
C9—C10—C11—C6 | −0.5 (3) | C2A—C3A—C4A—C5A | −167.9 (2) |
C7—C6—C11—C10 | −2.2 (3) | N1A—N2A—C6A—C11A | −179.2 (2) |
N2—C6—C11—C10 | 174.6 (2) | N1A—N2A—C6A—C7A | −0.9 (4) |
C24—N8—C13—C14 | −177.5 (2) | C11A—C6A—C7A—C8A | 0.5 (3) |
Cu1—N8—C13—C14 | 2.6 (3) | N2A—C6A—C7A—C8A | −177.7 (2) |
C24—N8—C13—C12 | −2.3 (3) | C6A—C7A—C8A—C9A | 0.0 (4) |
Cu1—N8—C13—C12 | 177.78 (18) | C6A—C7A—C8A—N3A | 178.6 (2) |
N5—N4—C14—C13 | −8.6 (3) | O4A—N3A—C8A—C7A | 175.2 (2) |
N5—N4—C14—C15 | 173.19 (19) | O3A—N3A—C8A—C7A | −5.2 (3) |
N8—C13—C14—N4 | 22.3 (4) | O4A—N3A—C8A—C9A | −6.1 (3) |
C12—C13—C14—N4 | −153.0 (2) | O3A—N3A—C8A—C9A | 173.5 (2) |
N8—C13—C14—C15 | −159.6 (2) | C7A—C8A—C9A—C10A | −0.2 (4) |
C12—C13—C14—C15 | 25.1 (3) | N3A—C8A—C9A—C10A | −178.8 (2) |
N4—C14—C15—O4 | −172.4 (2) | C8A—C9A—C10A—C11A | −0.1 (4) |
C13—C14—C15—O4 | 9.2 (4) | C7A—C6A—C11A—C10A | −0.7 (4) |
N4—C14—C15—C16 | 4.4 (3) | N2A—C6A—C11A—C10A | 177.6 (2) |
C13—C14—C15—C16 | −174.0 (2) | C9A—C10A—C11A—C6A | 0.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11A—H11A···O4Ai | 0.95 | 2.43 | 3.320 (3) | 156 |
N2A—H2A···O1A | 0.90 (1) | 1.81 (2) | 2.531 (3) | 135 (3) |
C22—H22···O1ii | 0.95 | 2.27 | 3.207 (3) | 169 |
C16—H16A···O5iii | 0.98 | 2.63 | 3.532 (3) | 154 |
C12—H12B···O3Aiv | 0.98 | 2.53 | 3.413 (3) | 151 |
C11—H11···O3v | 0.95 | 2.50 | 3.350 (3) | 150 |
C5—H5C···O3v | 0.98 | 2.65 | 3.426 (3) | 137 |
C1—H1B···O3Avi | 0.98 | 2.58 | 3.490 (3) | 154 |
C1—H1B···O1 | 0.98 | 2.34 | 2.842 (3) | 111 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+2; (ii) −x, −y, −z+1; (iii) x+1/2, y, −z+1/2; (iv) x+1/2, y, −z+3/2; (v) x−1/2, y, −z+1/2; (vi) −x, y−1/2, −z+3/2. |
References
Albert, J., González, A., Granell, J., Moragas, R., Puerta, C. & Valerga, P. (1997). Organometallics, 16, 3775–3778. CSD CrossRef CAS Google Scholar
Bruker (2008). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2014). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond. Oxford University Press. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Garg, H. G. & Prakash, C. (1971). J. Pharm. Sci. 60, 323–325. CrossRef CAS PubMed Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Khudina, O. G., Shchegol'kov, E. V., Burgart, V., Saloutin, V. I., Bukhvalov, D. V., Starichenko, D. V., Shvachko, Yu. N., Korolev, A. V., Ustinov, V. V., Aleksandrov, G. G., Eremenko, I. L., Kazheva, O. N., Shilov, G. V., D'yachenko, O. A. & Chupakhin, O. N. (2007). Russ. Chem. Bull. 56, 108–114. CrossRef CAS Google Scholar
Küçükgüzel, G., Rollas, S., Küçükgüzel, I. & Kiraz, M. (1999). Eur. J. Med. Chem. 34, 1093–1100. Google Scholar
Marten, J., Seichter, W. & Weber, E. (2005). Z. Anorg. Allg. Chem. 631, 869–877. Web of Science CSD CrossRef CAS Google Scholar
Marten, J., Seichter, W. & Weber, E. (2018). IUCrData, 3, x181344. Google Scholar
Marten, J., Seichter, W., Weber, E. & Böhme, U. (2007). J. Phys. Org. Chem. 20, 716–731. Web of Science CSD CrossRef CAS Google Scholar
Mishra, L., Yadaw, A. K., Srivastava, S. & Bahadur Patel, A. (2000). New J. Chem. 24, 505–510. CrossRef CAS Google Scholar
Phillips, R. R. (1959). Org. React. 10, 143–178. CAS Google Scholar
Reichenbächer, K., Süss, H. I. & Hulliger, J. (2005). Chem. Soc. Rev. 34, 22–30. Web of Science CrossRef PubMed Google Scholar
Sethukumar, A. & Arul Prakasam, B. (2010). J. Mol. Struct. 963, 250–257. CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.