supplementary materials


fk2070 scheme

Acta Cryst. (2013). E69, o765-o766    [ doi:10.1107/S1600536813009628 ]

A second monoclinic polymorph of 2-(3,5-dimethyl-1H-pyrazol-1-yl)-2-hydroxyimino-N'-[1-(pyridin-2-yl)ethylidene]acetohydrazide

M. O. Plutenko, R. D. Lampeka, M. Haukka and E. Nordlander

Abstract top

The title compound, C14H16N6O2, is a second monoclinic polymorph of 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyimino-N'-[1-(2-pyridyl)ethylidene] acetohydrazide, with two crystallographically independent molecules per asymmetric unit. The non-planar molecules are chemically equal having similar geometric parameters. The previously reported polymorph [Plutenko et al. (2012). Acta Cryst. E68, o3281] was described in space group Cc (Z = 4). The oxime group and the O atom of the amide group are anti with respect to the C-C bond. In the crystal, molecules are connected by N-H...N hydrogen bonds into zigzag chains extending along the b axis.

Comment top

Oximes are one of the most efficient bridging ligands class. Polydentate ligands containing both oxime and other donor functions are of special interest due to their potential for the bridging coordination modes and mediation of strong magnetic superexchange between metal ions (Penkova et al., 2009; Kanderal et al., 2005; Moroz et al., 2010). Oxime ligands having the pyridyl groups in the molecule have been used in the preparation of complexes with a variety of transition metals, binding to metals in different modes most commonly as chelates or serving as bridge to metals, and the resulting species have been employed in molecular magnetism and supramolecular chemistry (Moroz et al., 2010, 2012). Herein we report a second polymorph of 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyimino-N'-[1-(2-pyridyl)ethylidene] acetohydrazide (II) (Fig. 1). In comparison, the first polymorph I described previously (Plutenko et al., 2012), crystallized in monoclinic space group Cc, Z = 4, while the title compound II crystallized in space group P21/n with Z = 8 (Fig. 1).

Bond lengths N-N', N-C and C-O of the amide group are 1.3693 (10), 1.3589 (11) and 1.2162 (11) respectively for molecule A and 1.3705 (11), 1.3603 (11) and 1.2156 (11) respectively for molecule B. Such bond lengths are typical for the protonated amide groups (Kanderal et al., 2005). The oxime group is situated in anti- position to the amide group which was shown earlier in the structures of the amide derivatives of 2-hydroxyiminopropanoic acid (Onindo et al., 1995; Sliva et al., 1997; Fritsky et al., 2006). The NC(=NOH)C(O)NH fragment deviates from planarity because of a twist between the oxime and the amide groups about the C(8)-C9 and C(22)-C(23) bonds; the O(1)-C(8)-C(9)-N(3) and O(22)-C(23)-C(9)-N(8) torsion angles are -175.953 (2)° and 164.073 (2)°. The bond lengths N-O and C-N of the oxime group are 1.3615 (9) and 1.2836 (11) Å respectively for A and 1.3645 (10) and 1.2819 (11) Å respectively for B. The bond lengths and angles within the oxime groups are normal and comparable to those in the related structures (Świątek-Kozłowska et al., 2000; Mokhir et al., 2002; Fritsky et al., 1998). The C=N and N—O bond lengths in the oxime moiety of the molecule clearly indicates that the oxime group exists in the nitroso rather than in the isonitroso form (Duda et al., 1997; Kanderal et al., 2005; Fritsky et al., 2004).

The C-C, C-N and N-N' (1,331 (0) – 1,409 (0) Å) bond lengths in the pyrazole ring exhibit normal values (Penkova et al., 2010). The angles C-C'-C'', C-N-C', N-C-C' and N-N'-C are near 108°. The pyrazole ring deviates from the plane formed by other atoms of ligand molecule. The N(4)-C(9)-N(5)-N(6) and torsion angles are -103.589 (2) and 105.359 (2)° respectively. The C-N and C-C bond lengths in the pyridine rings are normal for 2-substituted pyridine derivatives (Fritsky et al., 2000; Krämer et al., 2000; Strotmeyer et al., 2003).

In the crystal packing both molecules A and B are each connected by N-H···N hydrogen bonds, where the oxime nitrogen acts as donor and the pyrazole nitrogen atom acts as acceptor (Table 1). Thus, zig-zag supramolecular chains along b-axis are formed.

Related literature top

For uses of oxime ligands, see: Penkova et al. (2009); Kanderal et al. (2005). For uses of oximes having additional donor functions as versatile ligands, see: Fritsky et al. (1998, 2004, 2006), Kanderal et al. (2005), Onindo et al. (1995); Sliva et al. (1997). For related structures, see: Duda et al. (1997); Kanderal et al. (2005); Krämer & Fritsky (2000); Moroz et al. (2010, 2012); Sliva et al. (1997); Świątek-Kozłowska et al. (2000); Mokhir et al. (2002); Penkova et al. (2010); Strotmeyer et al. (2003); Fritsky et al. (2000). For structure of the first polymorph, see Plutenko et al. (2012). For the synthesis, see: Kozikowski & Adamczyk (1983).

Experimental top

The present compound was synthesized according to Plutenko et al. (2012):

Synthesis of ethyl 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyiminoacetate: A mixture of ethyl 2-chloro-2-hydroxyiminoacetate synthesized according to Kozikowski et al. (1983) (0.906g, 6 mmol) and 3,5-dimethylpyrazol (1.152g, 12 mmol) in 10 ml of chloroform was left for evaporation in the air overnight. The resulting precipitate was crystallized from water. Yield: 1.12g (88 %).

Synthesis of 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyiminoacetohydrazide: A solution of hydrazine hydrate (0.57 ml, 60%, 10.6 mmol) in water was added to a solution of ethyl 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyiminoacetate (1.12g, 5.3 mmol) in methanol (30 ml). The resulting mixture was heating under reflux for 1.5 hours. After that solvent was evaporated and product was crystallized from methanol. Yield 0.5g (48 %).

Synthesis of 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyimino-N'-[1-(2-pyridyl)ethylidene]acetohydrazide: A solution of 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyiminoacetohydrazide (0.5g, 2.54 mmol) in methanol (30 ml) was treated with 2-acetylpyridine (0.307g, 2.54 mmol) and the mixture was heated under reflux for 3 hours. After that the solvent was evaporated in vacuum and the product was crystallized from methanol. Yield 0.65g (85 %).

Refinement top

OH, NH and CH3 hydrogen atoms were located from difference Fourier maps, other hydrogen atoms were positioned geometrically and all but H(N) and H(O) were refined at idealized positions riding on the parent atoms, with C—H = 0.95–0.98 Å, and Uiso = 1.2–1.5 Ueq(parent atom). H(N) and H(O) atoms were refined freely with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O). All CH3 hydrogen atoms were allowed to rotate but not to tip. The highest peak is located 0.74 Å from atom C9 and the deepest hole is located 1.03 Å from atom N4.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of molecules A and B of the title compound, with displacement ellipsoids shown at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.
[Figure 2] Fig. 2. Crystal packing viewed along b-axis. Hydrogen bonds are indicated by dashed lines. H atoms not involved in H-bonds are omitted for clarity.
2-(3,5-Dimethyl-1H-pyrazol-1-yl)-2-hydroxyimino-N'-[1-(pyridin-2-yl)ethylidene]acetohydrazide top
Crystal data top
C14H16N6O2F(000) = 1264
Mr = 300.33Dx = 1.343 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 9866 reflections
a = 19.4734 (4) Åθ = 2.8–31.6°
b = 7.7679 (2) ŵ = 0.10 mm1
c = 19.8042 (4) ÅT = 100 K
β = 97.552 (1)°Block, colourless
V = 2969.74 (11) Å30.39 × 0.33 × 0.28 mm
Z = 8
Data collection top
Bruker Kappa APEXII DUO CCD
diffractometer
9973 independent reflections
Radiation source: fine-focus sealed tube8213 reflections with I > 2σ(I)
Curved graphite crystal monochromatorRint = 0.027
Detector resolution: 16 pixels mm-1θmax = 31.7°, θmin = 1.6°
φ scans and ω scans with κ offseth = 2828
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)
k = 1111
Tmin = 0.964, Tmax = 0.974l = 2929
64574 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: difference Fourier map
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0555P)2 + 0.8835P]
where P = (Fo2 + 2Fc2)/3
9973 reflections(Δ/σ)max = 0.001
419 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C14H16N6O2V = 2969.74 (11) Å3
Mr = 300.33Z = 8
Monoclinic, P21/nMo Kα radiation
a = 19.4734 (4) ŵ = 0.10 mm1
b = 7.7679 (2) ÅT = 100 K
c = 19.8042 (4) Å0.39 × 0.33 × 0.28 mm
β = 97.552 (1)°
Data collection top
Bruker Kappa APEXII DUO CCD
diffractometer
9973 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)
8213 reflections with I > 2σ(I)
Tmin = 0.964, Tmax = 0.974Rint = 0.027
64574 measured reflectionsθmax = 31.7°
Refinement top
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106Δρmax = 0.49 e Å3
S = 1.03Δρmin = 0.25 e Å3
9973 reflectionsAbsolute structure: ?
419 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.23337 (4)0.28795 (10)0.54568 (4)0.02361 (15)
O20.24501 (3)0.03509 (9)0.75693 (3)0.01915 (13)
H2O0.2117 (9)0.025 (2)0.7803 (8)0.046 (4)*
O30.45992 (4)0.18904 (10)0.25984 (4)0.02138 (14)
O40.24039 (3)0.02793 (9)0.25464 (3)0.01929 (13)
H4O0.2170 (9)0.087 (2)0.2888 (9)0.052 (5)*
N10.09028 (4)0.25022 (10)0.52885 (4)0.01688 (14)
H2N0.1179 (7)0.1554 (19)0.6202 (7)0.030 (4)*
N20.13341 (4)0.20263 (11)0.58605 (4)0.01772 (15)
N30.20653 (4)0.08553 (10)0.69785 (4)0.01612 (14)
N40.31385 (4)0.18287 (9)0.66691 (4)0.01408 (13)
N50.34090 (4)0.34130 (10)0.68560 (4)0.01503 (14)
N60.47175 (4)0.22400 (11)0.40050 (4)0.01828 (15)
H7N0.3769 (8)0.131 (2)0.3781 (7)0.033 (4)*
N70.41368 (4)0.16597 (11)0.36033 (4)0.01910 (15)
N80.30122 (4)0.02189 (10)0.29165 (4)0.01648 (14)
N90.33140 (4)0.11492 (9)0.18502 (4)0.01428 (13)
N100.31523 (4)0.27505 (9)0.15885 (4)0.01431 (13)
N110.08655 (4)0.22180 (11)0.46263 (4)0.01968 (15)
N160.53482 (4)0.25441 (12)0.57576 (4)0.02314 (17)
C10.00368 (5)0.38205 (12)0.41941 (4)0.01765 (16)
H10.05000.42350.42600.021*
C20.04025 (5)0.42371 (13)0.36098 (5)0.02003 (17)
H20.02420.49110.32620.024*
C30.10829 (5)0.36503 (14)0.35412 (5)0.02119 (18)
H30.13990.39150.31470.025*
C40.12863 (5)0.26698 (14)0.40633 (5)0.02197 (18)
H40.17540.22920.40200.026*
C50.02103 (4)0.27821 (12)0.46846 (4)0.01566 (15)
C60.02508 (4)0.22338 (12)0.53059 (4)0.01642 (16)
C70.00595 (5)0.14381 (14)0.58873 (5)0.02139 (18)
H7A0.00140.22040.62840.032*
H7B0.01630.03260.60040.032*
H7C0.05570.12660.57540.032*
C80.20300 (4)0.22472 (11)0.58951 (4)0.01588 (15)
C90.24134 (4)0.16000 (11)0.65548 (4)0.01431 (15)
C100.40910 (4)0.31716 (12)0.69744 (4)0.01572 (15)
C110.45625 (5)0.46298 (13)0.72087 (5)0.02263 (18)
H11A0.42900.55860.73570.034*
H11B0.48070.50120.68330.034*
H11C0.49000.42490.75900.034*
C120.42576 (4)0.14436 (12)0.68606 (4)0.01676 (16)
H120.47080.09520.69040.020*
C130.36410 (5)0.06078 (11)0.66743 (4)0.01532 (15)
C140.34846 (6)0.12230 (12)0.64969 (5)0.02392 (19)
H14A0.32540.12960.60270.036*
H14B0.31800.16970.68070.036*
H14C0.39170.18840.65400.036*
C150.58299 (5)0.37652 (12)0.48087 (5)0.01906 (17)
H150.57860.39910.43340.023*
C160.64057 (5)0.43270 (14)0.52371 (5)0.02242 (18)
H160.67680.49240.50590.027*
C170.64462 (5)0.40039 (15)0.59324 (5)0.0246 (2)
H170.68340.43780.62390.030*
C180.59051 (5)0.31215 (15)0.61631 (5)0.0256 (2)
H180.59300.29130.66380.031*
C190.53144 (5)0.28602 (12)0.50876 (5)0.01802 (16)
C200.46937 (5)0.21770 (12)0.46535 (5)0.01815 (16)
C210.41019 (5)0.14593 (15)0.49801 (5)0.02440 (19)
H21A0.36830.21320.48360.037*
H21B0.42130.15200.54770.037*
H21C0.40230.02570.48410.037*
C220.41232 (5)0.15523 (11)0.29161 (4)0.01576 (15)
C230.34393 (4)0.09303 (11)0.25621 (4)0.01461 (15)
C240.30610 (4)0.25375 (12)0.09149 (4)0.01495 (15)
C250.28426 (5)0.40217 (13)0.04578 (5)0.02124 (18)
H25A0.26840.49660.07270.032*
H25B0.24640.36620.01110.032*
H25C0.32360.44110.02360.032*
C260.31770 (5)0.08076 (12)0.07453 (4)0.01728 (16)
H260.31550.03330.03010.021*
C270.33293 (5)0.00536 (11)0.13529 (4)0.01654 (16)
C280.34777 (6)0.18986 (13)0.15142 (6)0.0263 (2)
H28A0.39180.19950.18150.039*
H28B0.35090.25330.10920.039*
H28C0.31040.23830.17420.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0180 (3)0.0324 (4)0.0200 (3)0.0017 (3)0.0009 (2)0.0084 (3)
O20.0143 (3)0.0255 (3)0.0163 (3)0.0025 (2)0.0030 (2)0.0069 (2)
O30.0169 (3)0.0272 (3)0.0204 (3)0.0039 (3)0.0040 (2)0.0007 (3)
O40.0160 (3)0.0253 (3)0.0161 (3)0.0069 (2)0.0004 (2)0.0022 (2)
N10.0141 (3)0.0204 (3)0.0149 (3)0.0017 (3)0.0026 (2)0.0008 (3)
N20.0129 (3)0.0239 (4)0.0154 (3)0.0002 (3)0.0019 (3)0.0040 (3)
N30.0140 (3)0.0177 (3)0.0155 (3)0.0008 (3)0.0022 (2)0.0023 (3)
N40.0114 (3)0.0138 (3)0.0166 (3)0.0002 (2)0.0003 (2)0.0001 (3)
N50.0129 (3)0.0145 (3)0.0173 (3)0.0012 (2)0.0005 (2)0.0010 (3)
N60.0155 (3)0.0217 (4)0.0167 (3)0.0014 (3)0.0011 (3)0.0006 (3)
N70.0158 (3)0.0260 (4)0.0152 (3)0.0046 (3)0.0007 (3)0.0001 (3)
N80.0152 (3)0.0177 (3)0.0161 (3)0.0020 (3)0.0005 (3)0.0012 (3)
N90.0167 (3)0.0135 (3)0.0129 (3)0.0001 (2)0.0025 (2)0.0001 (2)
N100.0146 (3)0.0148 (3)0.0135 (3)0.0014 (2)0.0016 (2)0.0007 (2)
N110.0137 (3)0.0266 (4)0.0181 (3)0.0003 (3)0.0002 (3)0.0005 (3)
N160.0203 (4)0.0316 (4)0.0172 (3)0.0015 (3)0.0009 (3)0.0005 (3)
C10.0149 (4)0.0220 (4)0.0155 (4)0.0001 (3)0.0001 (3)0.0009 (3)
C20.0201 (4)0.0246 (4)0.0148 (4)0.0016 (3)0.0001 (3)0.0002 (3)
C30.0176 (4)0.0294 (5)0.0152 (4)0.0043 (3)0.0031 (3)0.0027 (3)
C40.0132 (4)0.0321 (5)0.0195 (4)0.0000 (3)0.0020 (3)0.0028 (4)
C50.0132 (4)0.0186 (4)0.0146 (3)0.0022 (3)0.0002 (3)0.0022 (3)
C60.0146 (4)0.0194 (4)0.0147 (4)0.0015 (3)0.0001 (3)0.0006 (3)
C70.0169 (4)0.0288 (5)0.0184 (4)0.0009 (3)0.0021 (3)0.0037 (3)
C80.0141 (4)0.0171 (4)0.0155 (3)0.0003 (3)0.0014 (3)0.0007 (3)
C90.0118 (3)0.0148 (3)0.0155 (3)0.0005 (3)0.0010 (3)0.0002 (3)
C100.0126 (4)0.0201 (4)0.0142 (3)0.0009 (3)0.0009 (3)0.0011 (3)
C110.0165 (4)0.0241 (4)0.0263 (4)0.0054 (3)0.0005 (3)0.0009 (4)
C120.0130 (4)0.0218 (4)0.0155 (4)0.0033 (3)0.0019 (3)0.0017 (3)
C130.0161 (4)0.0164 (4)0.0135 (3)0.0030 (3)0.0021 (3)0.0006 (3)
C140.0264 (5)0.0166 (4)0.0287 (5)0.0028 (3)0.0034 (4)0.0036 (3)
C150.0176 (4)0.0210 (4)0.0185 (4)0.0024 (3)0.0019 (3)0.0019 (3)
C160.0162 (4)0.0257 (4)0.0249 (4)0.0021 (3)0.0010 (3)0.0042 (4)
C170.0165 (4)0.0332 (5)0.0229 (4)0.0050 (4)0.0021 (3)0.0070 (4)
C180.0216 (4)0.0367 (5)0.0175 (4)0.0052 (4)0.0005 (3)0.0023 (4)
C190.0167 (4)0.0204 (4)0.0164 (4)0.0030 (3)0.0004 (3)0.0018 (3)
C200.0165 (4)0.0205 (4)0.0172 (4)0.0007 (3)0.0015 (3)0.0002 (3)
C210.0223 (4)0.0314 (5)0.0197 (4)0.0058 (4)0.0034 (3)0.0005 (4)
C220.0156 (4)0.0151 (4)0.0161 (4)0.0001 (3)0.0004 (3)0.0005 (3)
C230.0154 (4)0.0145 (3)0.0138 (3)0.0001 (3)0.0012 (3)0.0008 (3)
C240.0116 (3)0.0198 (4)0.0134 (3)0.0001 (3)0.0015 (3)0.0001 (3)
C250.0212 (4)0.0259 (4)0.0162 (4)0.0049 (3)0.0012 (3)0.0030 (3)
C260.0159 (4)0.0212 (4)0.0149 (4)0.0013 (3)0.0027 (3)0.0037 (3)
C270.0158 (4)0.0162 (4)0.0183 (4)0.0019 (3)0.0048 (3)0.0031 (3)
C280.0349 (5)0.0151 (4)0.0311 (5)0.0007 (4)0.0126 (4)0.0015 (4)
Geometric parameters (Å, º) top
O1—C81.2162 (11)C7—H7B0.9800
O2—N31.3615 (9)C7—H7C0.9800
O2—H2O0.964 (17)C8—C91.5035 (12)
O3—C221.2156 (11)C10—C121.4061 (13)
O4—N81.3645 (10)C10—C111.4931 (13)
O4—H4O0.978 (18)C11—H11A0.9800
N1—C61.2915 (11)C11—H11B0.9800
N1—N21.3693 (10)C11—H11C0.9800
N2—C81.3589 (11)C12—C131.3721 (12)
N2—H2N0.859 (15)C12—H120.9500
N3—C91.2836 (11)C13—C141.4868 (13)
N4—C131.3619 (11)C14—H14A0.9800
N4—N51.3703 (10)C14—H14B0.9800
N4—C91.4115 (11)C14—H14C0.9800
N5—C101.3313 (11)C15—C161.3846 (13)
N6—C201.2921 (12)C15—C191.3974 (13)
N6—N71.3705 (11)C15—H150.9500
N7—C221.3603 (11)C16—C171.3916 (14)
N7—H7N0.882 (15)C16—H160.9500
N8—C231.2819 (11)C17—C181.3840 (15)
N9—C271.3607 (11)C17—H170.9500
N9—N101.3683 (10)C18—H180.9500
N9—C231.4090 (11)C19—C201.4862 (13)
N10—C241.3327 (11)C20—C211.5010 (13)
N11—C51.3396 (11)C21—H21A0.9800
N11—C41.3408 (12)C21—H21B0.9800
N16—C181.3391 (13)C21—H21C0.9800
N16—C191.3425 (12)C22—C231.5010 (12)
C1—C21.3841 (12)C24—C261.4105 (13)
C1—C51.3959 (12)C24—C251.4927 (13)
C1—H10.9500C25—H25A0.9800
C2—C31.3909 (14)C25—H25B0.9800
C2—H20.9500C25—H25C0.9800
C3—C41.3834 (14)C26—C271.3747 (13)
C3—H30.9500C26—H260.9500
C4—H40.9500C27—C281.4884 (13)
C5—C61.4872 (12)C28—H28A0.9800
C6—C71.5019 (13)C28—H28B0.9800
C7—H7A0.9800C28—H28C0.9800
N3—O2—H2O102.8 (10)C13—C12—H12126.8
N8—O4—H4O102.3 (10)C10—C12—H12126.8
C6—N1—N2115.63 (8)N4—C13—C12105.97 (8)
C8—N2—N1120.46 (8)N4—C13—C14122.66 (8)
C8—N2—H2N117.7 (10)C12—C13—C14131.37 (8)
N1—N2—H2N121.8 (10)C13—C14—H14A109.5
C9—N3—O2114.41 (7)C13—C14—H14B109.5
C13—N4—N5111.90 (7)H14A—C14—H14B109.5
C13—N4—C9128.04 (8)C13—C14—H14C109.5
N5—N4—C9119.83 (7)H14A—C14—H14C109.5
C10—N5—N4105.09 (7)H14B—C14—H14C109.5
C20—N6—N7115.45 (8)C16—C15—C19118.83 (9)
C22—N7—N6120.46 (8)C16—C15—H15120.6
C22—N7—H7N118.1 (10)C19—C15—H15120.6
N6—N7—H7N121.4 (10)C15—C16—C17119.05 (9)
C23—N8—O4114.08 (7)C15—C16—H16120.5
C27—N9—N10112.07 (7)C17—C16—H16120.5
C27—N9—C23128.60 (8)C18—C17—C16117.99 (9)
N10—N9—C23119.32 (7)C18—C17—H17121.0
C24—N10—N9105.08 (7)C16—C17—H17121.0
C5—N11—C4117.20 (8)N16—C18—C17124.04 (9)
C18—N16—C19117.51 (9)N16—C18—H18118.0
C2—C1—C5119.02 (8)C17—C18—H18118.0
C2—C1—H1120.5N16—C19—C15122.57 (9)
C5—C1—H1120.5N16—C19—C20115.91 (8)
C1—C2—C3118.76 (9)C15—C19—C20121.53 (8)
C1—C2—H2120.6N6—C20—C19115.39 (8)
C3—C2—H2120.6N6—C20—C21124.91 (8)
C4—C3—C2118.04 (8)C19—C20—C21119.70 (8)
C4—C3—H3121.0C20—C21—H21A109.5
C2—C3—H3121.0C20—C21—H21B109.5
N11—C4—C3124.19 (9)H21A—C21—H21B109.5
N11—C4—H4117.9C20—C21—H21C109.5
C3—C4—H4117.9H21A—C21—H21C109.5
N11—C5—C1122.73 (8)H21B—C21—H21C109.5
N11—C5—C6116.25 (8)O3—C22—N7126.06 (8)
C1—C5—C6121.02 (8)O3—C22—C23121.19 (8)
N1—C6—C5114.87 (8)N7—C22—C23112.74 (7)
N1—C6—C7125.65 (8)N8—C23—N9124.08 (8)
C5—C6—C7119.48 (8)N8—C23—C22118.86 (8)
C6—C7—H7A109.5N9—C23—C22117.06 (7)
C6—C7—H7B109.5N10—C24—C26110.62 (8)
H7A—C7—H7B109.5N10—C24—C25120.07 (8)
C6—C7—H7C109.5C26—C24—C25129.28 (8)
H7A—C7—H7C109.5C24—C25—H25A109.5
H7B—C7—H7C109.5C24—C25—H25B109.5
O1—C8—N2126.18 (8)H25A—C25—H25B109.5
O1—C8—C9121.51 (8)C24—C25—H25C109.5
N2—C8—C9112.31 (7)H25A—C25—H25C109.5
N3—C9—N4123.70 (8)H25B—C25—H25C109.5
N3—C9—C8118.31 (8)C27—C26—C24106.14 (8)
N4—C9—C8117.99 (7)C27—C26—H26126.9
N5—C10—C12110.61 (8)C24—C26—H26126.9
N5—C10—C11120.42 (8)N9—C27—C26106.07 (8)
C12—C10—C11128.96 (8)N9—C27—C28121.87 (8)
C10—C11—H11A109.5C26—C27—C28132.05 (9)
C10—C11—H11B109.5C27—C28—H28A109.5
H11A—C11—H11B109.5C27—C28—H28B109.5
C10—C11—H11C109.5H28A—C28—H28B109.5
H11A—C11—H11C109.5C27—C28—H28C109.5
H11B—C11—H11C109.5H28A—C28—H28C109.5
C13—C12—C10106.42 (8)H28B—C28—H28C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···N5i0.964 (17)1.664 (17)2.6193 (10)170.1 (16)
O4—H4O···N10ii0.978 (18)1.670 (18)2.6341 (10)167.8 (17)
Symmetry codes: (i) x+1/2, y1/2, z+3/2; (ii) x+1/2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···N5i0.964 (17)1.664 (17)2.6193 (10)170.1 (16)
O4—H4O···N10ii0.978 (18)1.670 (18)2.6341 (10)167.8 (17)
Symmetry codes: (i) x+1/2, y1/2, z+3/2; (ii) x+1/2, y1/2, z+1/2.
Acknowledgements top

Financial support from the State Fund for Fundamental Research of Ukraine (grant No. F40.3/041) and the Swedish Institute (Visby Program) is gratefully acknowledged.

references
References top

Brandenburg, K. (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Bruker (2009). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2010). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Duda, A. M., Karaczyn, A., Kozłowski, H., Fritsky, I. O., Głowiak, T., Prisyazhnaya, E. V., Sliva, T. Yu. & Świątek-Kozłowska, J. (1997). J. Chem. Soc. Dalton Trans. pp. 3853–3859.

Fritsky, I. O., Kozłowski, H., Kanderal, O. M. M., Świątek-Kozłowska, J., Gumienna-Kontecka, E. & Meyer, F. (2006). Chem. Commun. pp. 4125–4127.

Fritsky, I. O., Kozłowski, H., Sadler, P. J., Yefetova, O. P., Świątek-Kozłowska, J., Kalibabchuk, V. A. & Głowiak, T. (1998). J. Chem. Soc. Dalton Trans. pp. 3269–3274.

Fritsky, I. O., Ott, R. & Krämer, R. (2000). Angew. Chem. Int. Ed. 39, 3255–3258.

Fritsky, I. O., Świątek-Kozłowska, J., Dobosz, A., Sliva, T. Y. & Dudarenko, N. M. (2004). Inorg. Chim. Acta, 357, 3746–3752.

Kanderal, O. M., Kozłowski, H., Dobosz, A., Świątek-Kozłowska, J., Meyer, F. & Fritsky, I. O. (2005). Dalton Trans. pp. 1428–1437.

Kozikowski, A. P. & Adamczyk, M. (1983). J. Org. Chem. 48, 366–372.

Krämer, R. & Fritsky, I. O. (2000). Eur. J. Org. Chem. pp. 3505–3510.

Mokhir, A. A., Gumienna-Kontecka, E., Świątek-Kozłowska, J., Petkova, E. G., Fritsky, I. O., Jerzykiewicz, L., Kapshuk, A. A. & Sliva, T. Y. (2002). Inorg. Chim. Acta, 329, 113–121.

Moroz, Y. S., Demeshko, S., Haukka, M., Mokhir, A., Mitra, U., Stocker, M., Müller, P., Meyer, F. & Fritsky, I. O. (2012). Inorg. Chem. 51, 7445–7447.

Moroz, Y. S., Szyrweil, L., Demeshko, S., Kozłowski, H., Meyer, F. & Fritsky, I. O. (2010). Inorg. Chem. 49, 4750–4752.

Onindo, C. O., Sliva, T. Yu., Kowalik-Jankowska, T., Fritsky, I. O., Buglyo, P., Pettit, L. D., Kozłowski, H. & Kiss, T. (1995). J. Chem. Soc. Dalton Trans. pp. 3911–3915.

Penkova, L. V., Demeshko, S., Pavlenko, V. A., Dechert, S., Meyer, F. & Fritsky, I. O. (2010). Inorg. Chim. Acta, 363, 3036–3040.

Penkova, L. V., Maciag, A., Rybak-Akimova, E. V., Haukka, M., Pavlenko, V. A., Iskenderov, T. S., Kozłowski, H., Meyer, F. & Fritsky, I. O. (2009). Inorg. Chem. 48, 6960–6971.

Plutenko, M. O., Lampeka, R. D., Haukka, M. & Nordlander, E. (2012). Acta Cryst. E68, o3381.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Sliva, T. Yu., Kowalik-Jankowska, T., Amirkhanov, V. M., Głowiak, T., Onindo, C. O., Fritsky, I. O. & Kozłowski, H. (1997). J. Inorg. Biochem. 65, 287–294.

Strotmeyer, K. P., Fritsky, I. O., Ott, R., Pritzkow, H. & Krämer, R. (2003). Supramol. Chem. 15, 529–547.

Świątek-Kozłowska, J., Fritsky, I. O., Dobosz, A., Karaczyn, A., Dudarenko, N. M., Sliva, T. Yu., Gumienna-Kontecka, E. & Jerzykiewicz, L. (2000). J. Chem. Soc. Dalton Trans. pp. 4064–4068.