organic compounds

Acta Crystallographica Section C substitituents can play an important role in their activity (Du
Crystal Structure et al., 2002; Hall et al., 2009).
Communications The advantageous fact that SC and TSC Schiff bases can
ISSN 0108-2701 easily be modified by variation of the parent aldehyde or
ketone has been used for the synthesis of derivatives incor-
porating biologically important substrates such as pyridoxal,
(E)-4-[(2-Carbamoylhydrazinylidene)- which is one of the forms of vitamin B6 (Casas et al., 2012). In
methyl]-3-hydroxy-5-hydroxymethyl- the last few decades, pyridoxal thiosemicarbazone (PLTSC)
complexes with a variety of metals have attracted particular
2-methylpyridin-1-ium nitrate interest due to their evident antitumor activity (Belicchi-
Ferrari et al., 1992, 2004, 2005). Investigations into the struc-
Sladjana B. Novaković,a* Goran A. Bogdanović,a tural and biological properties of the analogous pyridoxal
Vukadin M. Leovac,b Marko V. Rodić,b Ljiljana S.
Vojinović-Ješićb and Sonja Ivkovićc
a
‘Vinča’ Institute of Nuclear Sciences, Laboratory of Theoretical Physics and
Condensed Matter Physics, University of Belgrade, PO Box 522, 11001 Belgrade,
Serbia, bFaculty of Sciences, University of Novi Sad, Trg Dositeja Obradovića 3,
21000 Novi Sad, Serbia, and cFaculty of Environmental Protection, University
EDUCONS, V. Putnika bb, 1202 Sremska Kamenica, Serbia
Correspondence e-mail: snovak@vin.bg.ac.rs

Received 30 April 2013

Accepted 20 May 2013

The title compound, C9H13N4O3+NO3, is the first structu-

rally characterized Schiff base derived from semicarbazide
and pyridoxal. Unusually for an unsubstituted semicarbazone,
the compound adopts a syn conformation, in which the
carbonyl O atom is in a cis disposition relative to the
azomethine N atom. This arrangement is supported by a pair
of hydrogen bonds between the organic cation and the nitrate semicarbazone (PLSC) complexes are also becoming more
anion. The cation is essentially planar, with only a hydroxy- frequent (Leovac et al., 2005, 2007a,b; Vidović et al., 2011;
methyl O atom deviating significantly from the mean plane of Jevtović, et al., 2011). Surprisingly, the Cambridge Structural
the remaining atoms (r.m.s. deviation of the remaining non-H Database (CSD, Release 5.33, August 2012; Allen, 2002) does
atoms = 0.01 Å). The molecules are linked into flat layers by not contain structural data for any corresponding PLSC
N—H  O and C—H  O hydrogen bonds. O—H  O ligands; by comparison, five crystal structures of the analogous
hydrogen bonds involving the hydroxymethyl group as a
donor interconnect the layers into a three-dimensional
structure.

Comment
Semicarbazones (SC) and the analogous thiosemicarbazones
(TSC) are extensively investigated Schiff bases [see (I) and
(II) in the Scheme] with interesting structural, physicochem-
ical and pharmacological properties (Lobana et al., 2009;
Casas et al., 2000; Gómez Quiroga & Navarro Ranninger,
2004). The broad biological activity of SC (antiprotozoal and
anticonvulsant) and TSC (antibacterial, antiviral and anti-
tumor), as well as of their metal complexes, has been reviewed,
together with proposed mechanisms of action (Beraldo &
Gambino, 2004). The biological relevance of these compounds
is usually related to their ability to form stable chelates with
metal ions in vivo (Kalinowski & Richardson, 2005); there are,
Figure 1
however, examples in which the structure and conformational The molecular structure of (III), showing the atom-numbering scheme.
flexibility of SC or TSC cores or the size of the attached Displacement ellipsoids are drawn at the 50% probability level.

Acta Cryst. (2013). C69, 761–764 doi:10.1107/S0108270113013929 # 2013 International Union of Crystallography 761
organic compounds
Figure 2
N—H  O hydrogen bonds linking the components of (III) into ribbons,
which further interact by C—H  O interactions to give flat layers.
[Symmetry codes: (ii) x + 1, y, z + 2; (v) x, y  1, z + 1; (vi) x + 2,
y + 1, z + 3.]
sulfur-containing PLTSC ligands have been reported
(Belicchi-Ferrari et al., 1986, 2002; Vrdoljak et al., 2009;
Abram et al., 2000). The present work describes the synthesis
and the first crystal structure determination of a Schiff base
derived from semicarbazide and pyridoxal, namely (E)-4-[(2-
carbamoylhydrazinylidene)methyl]-3-hydroxy-5-hydroxymethyl-
2-methylpyridin-1-ium nitrate, (III).
The molecular structure of (III), together with the atom-
labelling scheme and the hydrogen bonding within the asym-
metric unit, is shown in Fig. 1. The asymmetric unit contains
the PLSC fragment, protonated at the pyridine N atom, and a
nitrate anion. In a review of the general structural properties
of both SC and TSC (Casas et al., 2000), it was noted that the
azomethine N and the O (or S) atom usually adopt relative
trans positions, i.e. they are in an anti conformation [see (I) in
the Scheme] with respect to the N1—C1 bond in the unsub-
stituted ligands. The present case is an exception to this rule,
displaying a syn conformation [see (II) in the Scheme], with an
N2—N1—C1—O1 torsion angle of 0.1 (2) . This is probably
due to the complementary hydrogen bonding formed between
what is thus a suitably oriented pair of N—H donors at atoms
N1 and N3 of the PLSC cation and two of the nitrate O atoms
(Fig. 1). It should be mentioned that in two crystal structures
of unsubstitued PLTSC ligands [CSD refcodes FADBOB
762 Novaković et al.  C9H13N4O3+NO3
(Belicchi-Ferrari et al., 1986) and NUKFOP (Vrdoljak et al.,
2009)], the molecules remain in the usual E configuration
(average N2—N1—C1—O1 torsion angle = 179 ), which is
stabilized by the expected intramolecular hydrogen bond
between the amine N3—H group and azomethine atom N2.
The structure of (III) is stabilized by an intramolecular
O2—H2  N2 hydrogen bond (Table 1). The significance of
this interaction can be appreciated by comparison with the two
PLTSC analogues, viz. FADBOB and NUKFOP. These
PLTSC were isolated as zwitterions, with phenol atom O2
deprotonated, thus obviating the formation of the intra-
molecular O2—H2  N2 interaction. The orientation of the
C2—N2—N1—C1( S)—N3 fragment relative to the pyri-
doxal moiety can change by rotation around the C2—C3 bond;
the average N2—C2—C3—C4 torsion angle in the PLTSC
analogues is 174 , while in (III) this angle is 1.49 (19) . This
comparison demonstrates the great flexibility of these Schiff
bases and the importance of intra- and intermolecular inter-
actions in establishing their configurations.
The bond lengths and angles listed in Table 2 are compar-
able to those found for similar semicarbazones derived from
aromatic carbonyls (CSD; Allen, 2002). In PLSC, as in
previous cases, the N2—N1, N1—C1, C1—N3 and C1—O1
bonds have partial double-bond character, which suggests that
there is electron delocalization within the SC fragment. Closer
inspection shows that N2—N1 [1.3491 (16) Å] is noticeably
shorter than N1—C1 [1.3906 (17) Å], which is opposite to
what is usually found in similar SC structures (average values
for N2—N1 and N1—C1 = 1.38 and 1.36 Å, respectively).
Another difference can be observed in the N1—C1—N3 angle
[113.07 (13) ], which is considerably smaller than in previously
reported structures (average value = 117.8 ). The PLSC
fragment as a whole is essentially planar, with a near-zero
dihedral angle [0.86 (5) ] between the best planes of the
pyridine and SC moieties. Among the non-H atoms of the
ligand, the only significant deviation from planarity is
observed for hydroxymethyl atom O3 whose orientation is
apparently influenced by hydrogen bonding. Atom O3 devi-
ates from the mean plane formed by all of the other non-H
atoms of PLSC (r.m.s deviation = 0.01 Å) by 1.23 (1) Å.
The crystal packing in (III) is mediated by four N—H  O
and one O—H  O hydrogen bonds (Table 1) with nearly
linear geometries (all D—H  O > 170 ). The strongest
interaction is, as expected, formed between the charged parts
of the molecules, the protonated pyridine N4 and nitrate O5iii
atoms [symmetry code: (iii) x  1, y  1, z  1]. In addition to
this interaction, the inversion-related pair of hydrogen bonds
based on N3—H3B  O1ii [symmetry code: (ii) x + 1, y,
z + 2], linking centrosymmetrically related molecules,
together with the complementary hydrogen bonds N1—
H1  O4 and N3—H3A  O5, leads to the formation of
discrete molecular ribbons, approximately 15 Å wide. Ribbons
in the same plane are connected by two weak C—H  O
interactions (Table 1) to form flat two-dimensional layers
(Fig. 2). This structure therefore contains three types of
hydrogen-bonded rings which can all be assigned the graph-set
notation R22 (8) (Etter, 1991). The nitrate anions which are
Acta Cryst. (2013). C69, 761–764
 organic compounds
Table 1
Hydrogen-bond geometry (Å,  ).

D—H  A D—H H  A D  A D—H  A

O2—H2  N2 0.85 (3) 1.87 (3) 2.5968 (16) 143 (2)
O3—H3  O1i 0.84 (3) 2.03 (3) 2.8534 (16) 170 (2)
N1—H1  O4 0.863 (19) 2.00 (2) 2.8647 (18) 177.8 (16)
N3—H3A  O5 0.88 (2) 1.98 (2) 2.8542 (19) 177.2 (19)
N3—H3B  O1ii 0.87 (2) 2.09 (2) 2.9497 (17) 173.7 (18)
N4—H4  O5iii 0.87 (3) 1.85 (3) 2.7124 (18) 173 (2)
C9—H9A  O4iv 0.97 2.41 3.206 (2) 140
C7—H7  O6iv 0.93 2.50 3.384 (3) 160
Figure 3 Symmetry codes: (i) x þ 1; y; z þ 1; (ii) x þ 1; y; z þ 2; (iii) x  1; y  1,
The three-dimensional crystal structure of (III). Layers (shown in Fig. 2) z  1; (iv) x þ 1; y þ 1; z þ 1.
are interconnected by O3—H3  O1i and symmetry-related hydrogen
bonds. [Symmetry code: (i) x + 1, y, z + 1.]
Table 2
Selected geometric parameters (Å,  ).
lodged in these two-dimensional frameworks deviate only
slightly from the plane of the cation [the dihedral angle O1—C1 1.2261 (18) N3—C1 1.3311 (19)
between the best planes of the anion and the cation = O2—C4 1.3375 (16) O4—N5 1.2386 (18)
N1—N2 1.3491 (16) O5—N5 1.2369 (18)
5.50 (9) ]. In agreement with the strengths of the nonbonded N1—C1 1.3906 (17) O6—N5 1.2185 (18)
interactions, we observe that N5—O6, whose hydrogen-bond N2—C2 1.2842 (17)
acceptor atom O6 is involved in a weak C7—H7  O6iv N2—N1—C1 118.03 (12) O1—C1—N1 121.78 (12)
contact only [symmetry code: (iv) x + 1, y + 1, z + 1], is C2—N2—N1 118.84 (12) N3—C1—N1 113.07 (13)
shorter than the other two N—O bonds (Table 2). The
hydroxymethyl O3—H groups of the pyridoxal units are the
only fragments that deviate significantly from the corre-
Refinement
sponding layers. They are oriented toward the O1 acceptors of
R[F 2 > 2(F 2)] = 0.042 H atoms treated by a mixture of
neighbouring layers in order to form an O3—H3  O1i wR(F 2) = 0.123 independent and constrained
hydrogen bond [symmetry code: (i) x + 1, y, z + 1] which S = 1.06 refinement
connects the layers into a three-dimensional structure (Fig. 3). 2410 reflections
max = 0.31 e Å3
207 parameters
min = 0.20 e Å3
The average orthogonal separation between neighbouring
layers is 3.3 Å.
H atoms bonded to C atoms were placed at calculated positions,
with C—H distances fixed at 0.93 Å for aromatic Csp2 atoms and at
Experimental 0.96 and 0.97 Å for methyl and methylene Csp3 atoms, respectively.
Pyridoxal semicarbazone dihydrate (PLSC2H2O, 50 mg), which was The corresponding Uiso values of the H atoms were set at 1.5Ueq for
prepared according to a known procedure (Knežević et al., 2003), was the methyl group and at 1.2Ueq otherwise. H atoms attached to N and
mixed with warm H2O (10 ml) and two drops of concentrated HNO3 O atoms were located in a difference Fourier map and refined
were added to the mixture. The resulting clear solution was left at isotropically.
room temperature to evaporate to a small volume, from which yellow Data collection: CrysAlis PRO (Agilent, 2013); cell refinement:
prismatic single crystals were filtered and washed with H2O (yield: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to
51 mg, 92%; m.p. 505 K). Analysis calculated for C9H13N5O6: C 37.63, solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to
H 4.56, N 24.38%; found: C 37.55, H 4.48, N 24.13%. Molar refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
conductivity, M (S cm2 mol1): 138 (H2O), 60 (dimethylformamide). ORTEP-3 (Farrugia, 2012); software used to prepare material for
The title compound is quite soluble in H2O, dimethylformamide and publication: WinGX (Farrugia, 2012), PLATON (Spek, 2009) and
MeOH, less so in EtOH and insoluble in Et2O. PARST (Nardelli, 1995).

Crystal data This work was supported by the Ministry of Education,

C9H13N4O3+NO3  = 104.589 (4) Science and Technological Development of the Republic of
Mr = 287.24 V = 608.09 (5) Å3 Serbia (grant No. 172014).
Triclinic, P1 Z=2
a = 7.1093 (3) Å Cu K radiation
b = 8.1905 (4) Å  = 1.15 mm1 Supplementary data for this paper are available from the IUCr electronic
c = 11.6494 (6) Å T = 294 K archives (Reference: FA3317). Services for accessing these data are
 = 110.117 (5) 0.49  0.33  0.18 mm described at the back of the journal.
 = 93.566 (4)

Data collection References

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Tmin = 0.648, Tmax = 0.831 Rint = 0.022 England.

Acta Cryst. (2013). C69, 761–764 Novaković et al.  C9H13N4O3+NO3 763

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Acta Cryst. (2013). C69, 761–764
 supplementary materials

supplementary materials

Acta Cryst. (2013). C69, 761-764 [doi:10.1107/S0108270113013929]

(E)-4-[(2-Carbamoylhydrazinylidene)methyl]-3-hydroxy-5-hydroxymethyl-2-
methylpyridin-1-ium nitrate
Sladjana B. Novaković, Goran A. Bogdanović, Vukadin M. Leovac, Marko V. Rodić, Ljiljana S.
Vojinović-Ješić and Sonja Ivković

Computing details
Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis
PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare
material for publication: WinGX (Farrugia, 2012), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

(E)-4-[(2-Carbamoylhydrazinylidene)methyl]-3-hydroxy-5-hydroxymethyl-2-methylpyridin-1-ium nitrate

Crystal data
C9H13N4O3+·NO3− Dx = 1.569 Mg m−3
Mr = 287.24 Dm = 1.57 Mg m−3
Triclinic, P1 Dm measured by flotation in bromoform –
Hall symbol: -P 1 diethylether mixture
a = 7.1093 (3) Å Melting point: 505 K
b = 8.1905 (4) Å Cu Kα radiation, λ = 1.54180 Å
c = 11.6494 (6) Å Cell parameters from 5840 reflections
α = 110.117 (5)° θ = 5.9–72.7°
β = 93.566 (4)° µ = 1.15 mm−1
γ = 104.589 (4)° T = 294 K
V = 608.09 (5) Å3 Block, translucent pale yellow
Z=2 0.49 × 0.33 × 0.18 mm
F(000) = 300

Data collection
Agilent Gemini S 9478 measured reflections
diffractometer 2410 independent reflections
Radiation source: fine-focus sealed tube 2299 reflections with I > 2σ(I)
Graphite monochromator Rint = 0.022
Detector resolution: 16.3280 pixels mm-1 θmax = 72.7°, θmin = 4.1°
ω scans h = −8→8
Absorption correction: gaussian k = −10→10
(CrysAlis PRO; Agilent, 2013) l = −14→14
Tmin = 0.648, Tmax = 0.831

Acta Cryst. (2013). C69, 761-764 sup-1

 supplementary materials
Refinement
Refinement on F2 Hydrogen site location: inferred from
Least-squares matrix: full neighbouring sites
R[F2 > 2σ(F2)] = 0.042 H atoms treated by a mixture of independent
wR(F2) = 0.123 and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0712P)2 + 0.1565P]
2410 reflections where P = (Fo2 + 2Fc2)/3
207 parameters (Δ/σ)max < 0.001
0 restraints Δρmax = 0.31 e Å−3
Primary atom site location: structure-invariant Δρmin = −0.20 e Å−3
direct methods Extinction correction: SHELXL97 (Sheldrick,
Secondary atom site location: difference Fourier 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
map Extinction coefficient: 0.034 (3)

Special details
Experimental. Absorption correction: numerical absorption correction based on gaussian integration over a multifaceted
crystal model CrysAlisPro, Agilent Technologies (2013).
Selected FTIR data (KBr, ν, cm–1): 3331s, 3190vs, 3021–2655br, 1717vs, 1648m, 1551vs, 1428s, 1384vs, 1338s, 1305s,
1253m, 1181s, 1049s, 930m, 819w, 728m, 604m;
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)

x y z Uiso*/Ueq
O1 0.39375 (18) −0.08434 (14) 0.82584 (9) 0.0458 (3)
O2 0.13596 (17) −0.26177 (15) 0.49673 (10) 0.0452 (3)
O3 0.50461 (16) 0.32306 (15) 0.38814 (10) 0.0453 (3)
N1 0.46254 (18) 0.15784 (16) 0.76394 (10) 0.0367 (3)
N2 0.35489 (17) 0.05302 (16) 0.65103 (10) 0.0331 (3)
N3 0.5881 (2) 0.19177 (19) 0.95758 (12) 0.0479 (4)
N4 0.00310 (18) −0.20154 (17) 0.21980 (11) 0.0369 (3)
C1 0.4760 (2) 0.07714 (19) 0.85024 (12) 0.0353 (3)
C2 0.34297 (19) 0.12480 (18) 0.56968 (12) 0.0324 (3)
H2A 0.4082 0.2466 0.5878 0.039*
C3 0.22443 (18) 0.01055 (18) 0.44781 (11) 0.0300 (3)
C4 0.12876 (19) −0.17534 (18) 0.41856 (12) 0.0322 (3)
C5 0.01570 (19) −0.28178 (19) 0.30141 (13) 0.0345 (3)
C6 −0.0933 (2) −0.4782 (2) 0.26578 (15) 0.0464 (4)
H6A −0.0787 −0.5449 0.1828 0.070*
H6B −0.2305 −0.4911 0.2699 0.070*
H6C −0.0409 −0.5248 0.3217 0.070*
C7 0.0897 (2) −0.0249 (2) 0.24367 (13) 0.0368 (3)
H7 0.0743 0.0226 0.1829 0.044*
C8 0.20127 (19) 0.08639 (18) 0.35781 (12) 0.0322 (3)
C9 0.2981 (2) 0.28364 (19) 0.38026 (13) 0.0381 (3)

Acta Cryst. (2013). C69, 761-764 sup-2

 supplementary materials
H9A 0.2452 0.3124 0.3133 0.046*
H9B 0.2671 0.3596 0.4567 0.046*
H1 0.518 (3) 0.272 (3) 0.7815 (16) 0.035 (4)*
H3 0.526 (3) 0.257 (3) 0.320 (2) 0.067 (6)*
H2 0.219 (4) −0.192 (4) 0.561 (3) 0.085 (8)*
H4 −0.065 (3) −0.270 (3) 0.147 (2) 0.066 (6)*
H3A 0.641 (3) 0.307 (3) 0.9725 (19) 0.051 (5)*
H3B 0.603 (3) 0.161 (3) 1.021 (2) 0.054 (5)*
O4 0.6370 (2) 0.53928 (18) 0.82584 (12) 0.0692 (4)
O5 0.7716 (3) 0.56532 (18) 1.00199 (13) 0.0812 (6)
O6 0.8425 (3) 0.79232 (18) 0.94813 (14) 0.0766 (5)
N5 0.7513 (2) 0.63406 (18) 0.92440 (11) 0.0454 (3)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

O1 0.0670 (7) 0.0327 (5) 0.0291 (5) 0.0033 (5) −0.0002 (4) 0.0104 (4)
O2 0.0520 (6) 0.0396 (6) 0.0396 (6) 0.0012 (5) −0.0066 (5) 0.0204 (5)
O3 0.0445 (6) 0.0396 (6) 0.0384 (6) 0.0003 (4) 0.0024 (4) 0.0076 (5)
N1 0.0470 (7) 0.0304 (6) 0.0248 (6) 0.0034 (5) −0.0035 (5) 0.0080 (4)
N2 0.0362 (6) 0.0357 (6) 0.0232 (5) 0.0083 (5) 0.0011 (4) 0.0080 (4)
N3 0.0693 (9) 0.0360 (7) 0.0271 (6) −0.0007 (6) −0.0089 (6) 0.0125 (5)
N4 0.0374 (6) 0.0383 (6) 0.0265 (6) 0.0051 (5) −0.0032 (4) 0.0072 (5)
C1 0.0432 (7) 0.0344 (7) 0.0250 (6) 0.0087 (6) 0.0028 (5) 0.0095 (5)
C2 0.0348 (6) 0.0321 (6) 0.0266 (6) 0.0069 (5) 0.0017 (5) 0.0089 (5)
C3 0.0284 (6) 0.0342 (7) 0.0256 (6) 0.0083 (5) 0.0035 (5) 0.0095 (5)
C4 0.0309 (6) 0.0350 (7) 0.0300 (6) 0.0078 (5) 0.0030 (5) 0.0127 (5)
C5 0.0320 (6) 0.0342 (7) 0.0324 (7) 0.0070 (5) 0.0026 (5) 0.0087 (5)
C6 0.0484 (8) 0.0354 (7) 0.0445 (8) 0.0022 (6) −0.0023 (6) 0.0104 (6)
C7 0.0402 (7) 0.0395 (7) 0.0289 (6) 0.0076 (6) 0.0000 (5) 0.0145 (5)
C8 0.0324 (6) 0.0347 (7) 0.0281 (6) 0.0083 (5) 0.0025 (5) 0.0114 (5)
C9 0.0451 (8) 0.0344 (7) 0.0330 (7) 0.0076 (6) 0.0003 (5) 0.0144 (5)
O4 0.0939 (10) 0.0542 (7) 0.0376 (6) −0.0122 (7) −0.0184 (6) 0.0197 (6)
O5 0.1186 (13) 0.0452 (7) 0.0539 (8) −0.0165 (7) −0.0412 (8) 0.0252 (6)
O6 0.1034 (12) 0.0441 (7) 0.0596 (8) −0.0171 (7) −0.0072 (7) 0.0230 (6)
N5 0.0552 (8) 0.0384 (7) 0.0328 (6) 0.0000 (6) 0.0005 (5) 0.0122 (5)

Geometric parameters (Å, º)

O1—C1 1.2261 (18) C2—H2A 0.9300

O2—C4 1.3375 (16) C3—C4 1.4105 (19)
O2—H2 0.85 (3) C3—C8 1.4108 (17)
O3—C9 1.4117 (18) C4—C5 1.4002 (19)
O3—H3 0.84 (3) C5—C6 1.4948 (19)
N1—N2 1.3491 (16) C6—H6A 0.9600
N1—C1 1.3906 (17) C6—H6B 0.9600
N1—H1 0.863 (19) C6—H6C 0.9600
N2—C2 1.2842 (17) C7—C8 1.3779 (19)
N3—C1 1.3311 (19) C7—H7 0.9300
N3—H3A 0.88 (2) C8—C9 1.5096 (19)

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 supplementary materials
N3—H3B 0.87 (2) C9—H9A 0.9700
N4—C5 1.3389 (18) C9—H9B 0.9700
N4—C7 1.3428 (19) O4—N5 1.2386 (18)
N4—H4 0.87 (3) O5—N5 1.2369 (18)
C2—C3 1.4634 (17) O6—N5 1.2185 (18)

C4—O2—H2 109.3 (18) N4—C5—C4 117.93 (12)

C9—O3—H3 106.6 (16) N4—C5—C6 119.38 (13)
N2—N1—C1 118.03 (12) C4—C5—C6 122.68 (13)
N2—N1—H1 120.0 (11) C5—C6—H6A 109.5
C1—N1—H1 122.0 (12) C5—C6—H6B 109.5
C2—N2—N1 118.84 (12) H6A—C6—H6B 109.5
C1—N3—H3A 122.5 (13) C5—C6—H6C 109.5
C1—N3—H3B 122.6 (14) H6A—C6—H6C 109.5
H3A—N3—H3B 114.5 (19) H6B—C6—H6C 109.5
C5—N4—C7 124.19 (12) N4—C7—C8 120.28 (13)
C5—N4—H4 116.4 (15) N4—C7—H7 119.9
C7—N4—H4 119.4 (15) C8—C7—H7 119.9
O1—C1—N3 125.14 (13) C7—C8—C3 118.74 (13)
O1—C1—N1 121.78 (12) C7—C8—C9 118.57 (12)
N3—C1—N1 113.07 (13) C3—C8—C9 122.67 (12)
N2—C2—C3 118.49 (12) O3—C9—C8 111.90 (11)
N2—C2—H2A 120.8 O3—C9—H9A 109.2
C3—C2—H2A 120.8 C8—C9—H9A 109.2
C4—C3—C8 118.76 (12) O3—C9—H9B 109.2
C4—C3—C2 121.13 (12) C8—C9—H9B 109.2
C8—C3—C2 120.10 (12) H9A—C9—H9B 107.9
O2—C4—C5 115.57 (12) O6—N5—O5 118.96 (14)
O2—C4—C3 124.35 (12) O6—N5—O4 122.57 (14)
C5—C4—C3 120.08 (12) O5—N5—O4 118.46 (13)

C1—N1—N2—C2 −179.11 (12) C3—C4—C5—N4 0.25 (19)

N2—N1—C1—O1 0.1 (2) O2—C4—C5—C6 1.1 (2)
N2—N1—C1—N3 178.94 (12) C3—C4—C5—C6 −178.43 (13)
N1—N2—C2—C3 −179.45 (11) C5—N4—C7—C8 0.4 (2)
N2—C2—C3—C4 −1.49 (19) N4—C7—C8—C3 0.8 (2)
N2—C2—C3—C8 177.40 (11) N4—C7—C8—C9 179.28 (12)
C8—C3—C4—O2 −178.53 (11) C4—C3—C8—C7 −1.46 (19)
C2—C3—C4—O2 0.4 (2) C2—C3—C8—C7 179.63 (12)
C8—C3—C4—C5 0.93 (19) C4—C3—C8—C9 −179.84 (12)
C2—C3—C4—C5 179.83 (11) C2—C3—C8—C9 1.24 (19)
C7—N4—C5—C4 −1.0 (2) C7—C8—C9—O3 −109.53 (14)
C7—N4—C5—C6 177.76 (14) C3—C8—C9—O3 68.85 (16)
O2—C4—C5—N4 179.76 (11)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O2—H2···N2 0.85 (3) 1.87 (3) 2.5968 (16) 143 (2)
O3—H3···O1i 0.84 (3) 2.03 (3) 2.8534 (16) 170 (2)

Acta Cryst. (2013). C69, 761-764 sup-4

 supplementary materials
N1—H1···O4 0.863 (19) 2.00 (2) 2.8647 (18) 177.8 (16)
N3—H3A···O5 0.88 (2) 1.98 (2) 2.8542 (19) 177.2 (19)
N3—H3B···O1ii 0.87 (2) 2.09 (2) 2.9497 (17) 173.7 (18)
N4—H4···O5iii 0.87 (3) 1.85 (3) 2.7124 (18) 173 (2)
C9—H9A···O4iv 0.97 2.41 3.206 (2) 140
C7—H7···O6iv 0.93 2.50 3.384 (3) 160
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z+2; (iii) x−1, y−1, z−1; (iv) −x+1, −y+1, −z+1.

Acta Cryst. (2013). C69, 761-764 sup-5