(E)-2-(4-Hy­droxy-3-meth­oxy­benzyl­idene)hydrazinecarboxamide

Fun, H.-K.; Yeap, C.S.; Malladi, S.; Isloor, A.M.

doi:10.1107/S1600536811024068

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1786

doi:10.1107/S1600536811024068

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(E)-2-(4-Hydroxy-3-methoxybenzylidene)hydrazinecarboxamide

Hoong-Kun Fun,^a ^*‡ Chin Sing Yeap,^a § Shridhar Malladi ^b and Arun M. Isloor ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bOrganic Chemistry Division, Department of Chemistry, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India
^*Correspondence e-mail: hkfun@usm.my

(Received 17 June 2011; accepted 20 June 2011; online 25 June 2011)

The asymmetric unit of the title compound, C₉H₁₁N₃O₃, consists of two crystallographically independent molecules. Both molecules are almost planar, with r.m.s. deviations of 0.107 and 0.099 Å. In the crystal, the two independent molecules form a dimer with an R₂²(8) ring motif via N—H⋯O hydrogen bonds. The dimers are further linked into a three-dimensional network by O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For applications of semicarbazone derivatives, see: Warren et al. (1977 ); Chandra & Gupta (2005 ); Jain et al. (2002 ); Pilgram (1978 ); Yogeeswari et al. (2004 ). For the synthesis, see: Vogel et al. (1978 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₁₁N₃O₃
M_r = 209.21
Orthorhombic, P c a 2₁
a = 13.8568 (3) Å
b = 5.0379 (1) Å
c = 26.8582 (5) Å
V = 1874.95 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.56 × 0.21 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.939, T_max = 0.992
27088 measured reflections
3785 independent reflections
3477 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.098
S = 1.05
3785 reflections
305 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2A—H2OA⋯O2Bⁱ	0.86 (3)	2.22 (3)	2.9924 (18)	149 (3)
N2A—H2NA⋯O3B	0.88 (3)	2.03 (3)	2.8966 (19)	171 (3)
N3A—H3NB⋯O3Bⁱⁱ	0.89 (3)	2.10 (3)	2.961 (2)	165 (2)
N2B—H2NB⋯O3A	0.90 (3)	2.00 (3)	2.8812 (18)	169 (2)
N3B—H3ND⋯O3Aⁱⁱⁱ	0.86 (3)	2.09 (3)	2.9415 (19)	172 (3)
Symmetry codes: (i) $[-x+1, -y+2, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+2, z]$ ; (iii) $[x-{\script{1\over 2}}, -y+1, z]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811024068/is2735sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024068/is2735Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811024068/is2735Isup3.cml

checkCIF report

Comment top

In organic chemistry, semicarbazone is a derivative of an aldehyde or ketone formed by condensation between a ketone or aldehyde and a semicarbazide. Semicarbazones find a large number of applications in the field of synthetic chemistry, such as in medicinal chemistry (Warren et al., 1977), organometallics (Chandra & Gupta, 2005), polymers (Jain et al., 2002), and herbicides (Pilgram, 1978). 4-Sulphamoylphenyl semicarbazones were found to possess anti-convulsant activity (Yogeeswari et al., 2004). Prompted by the diverse activities of semicarbazones, we have synthesized the title compound to study its crystal structure.

The asymmetric unit of title compound consists of two crystallographically independent molecules, A and B (Fig. 1). Both molecules are almost planar with the maximum deviation of 0.3177 (16) Å at N3A for molecule A whereas 0.1729 (12) Å at O3B for molecule B. The two independent molecules are interconnected by N2A—H2NA···O3B and N2B—H2NB···O3A hydrogen bonds (Fig. 1, Table 1) generating an R²₂(8) ring motif (Bernstein et al., 1995). In the crystal structure, the molecules are further linked into a three-dimensional network (Fig. 2) by O2A—H2OA···O2B, N3A—H3NB···O3B and N3B—H3ND···O3A hydrogen bonds (Table 1).

Related literature top

For applications of semicarbazone derivatives, see: Warren et al. (1977); Chandra & Gupta (2005); Jain et al. (2002); Pilgram (1978); Yogeeswari et al. (2004). For the synthesis, see: Vogel et al. (1978). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

Semicarbazide hydrochloride (0.86 g, 7.70 mmol) and freshly re-crystallized sodium acetate (0.77 g, 9.40 mmol) were dissolved in water (10 ml) following a literature procedure (Vogel et al., 1978). The reaction mixture was stirred at room temperature for 10 minutes. To this, vanillin (1.1 g, 7.23 mmol) was added and the mixture was shaken well. A little alcohol was added to dissolve the turbidity. The mixture was shaken for a further 10 minutes and allowed to stand. The title compound crystallizes on standing for 6 h. The separated crystals were filtered, washed with cold water and re-crystallized from ethanol. Yield: 1.34 g, 88.74%. M.p.: 502–504 K (Vogel et al., 1978).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 50% probability ellipsoids for non-H atoms. Hydrogen bonds (dashed lines) are shown.
	Fig. 2. A packing diagram of the title compound viewed along the b axis, showing molecules linked into a three-dimensional network. Hydrogen bonds (dashed lines) are shown.

(E)-2-(4-Hydroxy-3-methoxybenzylidene)hydrazinecarboxamide top

Crystal data top

C₉H₁₁N₃O₃	F(000) = 880
M_r = 209.21	D_x = 1.482 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 8792 reflections
a = 13.8568 (3) Å	θ = 3.0–33.7°
b = 5.0379 (1) Å	µ = 0.11 mm⁻¹
c = 26.8582 (5) Å	T = 100 K
V = 1874.95 (7) Å³	Plate, colourless
Z = 8	0.56 × 0.21 × 0.08 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3785 independent reflections
Radiation source: fine-focus sealed tube	3477 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 33.8°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −21→21
T_min = 0.939, T_max = 0.992	k = −7→7
27088 measured reflections	l = −42→34

Refinement top

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0558P)² + 0.2848P] where P = (F_o² + 2F_c²)/3
3785 reflections	(Δ/σ)_max < 0.001
305 parameters	Δρ_max = 0.38 e Å⁻³
1 restraint	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₉H₁₁N₃O₃	V = 1874.95 (7) Å³
M_r = 209.21	Z = 8
Orthorhombic, Pca2₁	Mo Kα radiation
a = 13.8568 (3) Å	µ = 0.11 mm⁻¹
b = 5.0379 (1) Å	T = 100 K
c = 26.8582 (5) Å	0.56 × 0.21 × 0.08 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3785 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3477 reflections with I > 2σ(I)
T_min = 0.939, T_max = 0.992	R_int = 0.034
27088 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	1 restraint
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.38 e Å⁻³
3785 reflections	Δρ_min = −0.20 e Å⁻³
305 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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

	x	y	z	U_iso*/U_eq
O1A	0.36344 (8)	1.9545 (3)	0.42045 (5)	0.0210 (2)
O2A	0.17592 (9)	1.9564 (2)	0.43391 (5)	0.0184 (2)
H2OA	0.220 (2)	2.071 (6)	0.4406 (12)	0.039 (8)*
O3A	0.56955 (8)	0.7961 (2)	0.21626 (5)	0.0197 (2)
N1A	0.42454 (10)	1.2040 (3)	0.29115 (5)	0.0167 (2)
N2A	0.45328 (10)	0.9953 (3)	0.26135 (6)	0.0176 (3)
H2NA	0.411 (2)	0.885 (6)	0.2484 (11)	0.034 (7)*
N3A	0.60407 (11)	1.1886 (3)	0.25456 (6)	0.0203 (3)
H3NA	0.581 (2)	1.323 (6)	0.2682 (12)	0.041 (8)*
H3NB	0.6599 (18)	1.207 (5)	0.2389 (10)	0.025 (6)*
C1A	0.35450 (11)	1.5891 (3)	0.36049 (6)	0.0156 (3)
H1A	0.4220	1.5897	0.3544	0.019*
C2A	0.31448 (10)	1.7697 (3)	0.39336 (6)	0.0144 (3)
C3A	0.21404 (11)	1.7756 (3)	0.40168 (6)	0.0148 (3)
C4A	0.15552 (11)	1.5929 (3)	0.37808 (6)	0.0173 (3)
H4A	0.0879	1.5941	0.3839	0.021*
C5A	0.19573 (11)	1.4062 (3)	0.34560 (6)	0.0170 (3)
H5A	0.1553	1.2793	0.3298	0.020*
C6A	0.29452 (11)	1.4047 (3)	0.33624 (6)	0.0152 (3)
C7A	0.33449 (12)	1.2052 (3)	0.30250 (6)	0.0165 (3)
H7A	0.2931	1.0740	0.2887	0.020*
C8A	0.54501 (11)	0.9882 (3)	0.24256 (6)	0.0156 (3)
C9A	0.46611 (11)	1.9590 (4)	0.41561 (7)	0.0213 (3)
H9AA	0.4930	2.0937	0.4380	0.032*
H9AB	0.4834	2.0020	0.3812	0.032*
H9AC	0.4923	1.7845	0.4244	0.032*
O1B	0.53465 (8)	−0.4555 (2)	0.01033 (5)	0.0185 (2)
O2B	0.72055 (9)	−0.3736 (3)	−0.00747 (5)	0.0207 (2)
H1OB	0.6814 (19)	−0.481 (5)	−0.0197 (11)	0.031 (7)*
O3B	0.29971 (9)	0.6842 (2)	0.21721 (5)	0.0191 (2)
N1B	0.44745 (10)	0.2792 (3)	0.14260 (5)	0.0161 (2)
N2B	0.41711 (10)	0.4832 (3)	0.17293 (5)	0.0177 (3)
H2NB	0.4597 (19)	0.600 (5)	0.1853 (10)	0.029 (6)*
N3B	0.26476 (11)	0.2964 (3)	0.17689 (6)	0.0203 (3)
H3ND	0.2088 (18)	0.283 (5)	0.1902 (10)	0.026 (6)*
H3NC	0.288 (2)	0.162 (6)	0.1622 (11)	0.038 (8)*
C1B	0.53046 (11)	−0.0990 (3)	0.07266 (6)	0.0154 (3)
H1B	0.4640	−0.1245	0.0799	0.019*
C2B	0.57608 (10)	−0.2581 (3)	0.03781 (6)	0.0144 (3)
C3B	0.67512 (11)	−0.2216 (3)	0.02783 (6)	0.0156 (3)
C4B	0.72711 (11)	−0.0285 (3)	0.05253 (6)	0.0174 (3)
H4B	0.7940	−0.0062	0.0459	0.021*
C5B	0.68118 (11)	0.1338 (3)	0.08729 (6)	0.0169 (3)
H5B	0.7168	0.2673	0.1042	0.020*
C6B	0.58328 (11)	0.1011 (3)	0.09736 (6)	0.0148 (3)
C7B	0.53818 (11)	0.2863 (3)	0.13190 (6)	0.0157 (3)
H7B	0.5773	0.4180	0.1472	0.019*
C8B	0.32466 (11)	0.4926 (3)	0.19051 (6)	0.0152 (3)
C9B	0.43242 (11)	−0.4943 (3)	0.01562 (7)	0.0192 (3)
H9BA	0.4123	−0.6471	−0.0044	0.029*
H9BB	0.3983	−0.3351	0.0042	0.029*
H9BC	0.4170	−0.5272	0.0507	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.0126 (5)	0.0269 (6)	0.0234 (6)	−0.0001 (4)	−0.0005 (4)	−0.0095 (5)
O2A	0.0139 (5)	0.0211 (5)	0.0201 (6)	0.0010 (4)	0.0028 (4)	−0.0038 (4)
O3A	0.0163 (5)	0.0177 (5)	0.0250 (6)	−0.0002 (4)	0.0041 (4)	−0.0053 (5)
N1A	0.0182 (6)	0.0160 (5)	0.0160 (6)	0.0016 (4)	0.0019 (5)	−0.0029 (4)
N2A	0.0147 (6)	0.0173 (6)	0.0209 (6)	−0.0013 (4)	0.0041 (5)	−0.0056 (5)
N3A	0.0161 (6)	0.0185 (6)	0.0261 (7)	−0.0022 (5)	0.0036 (5)	−0.0058 (5)
C1A	0.0130 (6)	0.0177 (6)	0.0161 (6)	0.0014 (5)	0.0011 (5)	−0.0006 (5)
C2A	0.0117 (6)	0.0178 (6)	0.0137 (6)	−0.0003 (5)	−0.0007 (5)	0.0001 (5)
C3A	0.0133 (6)	0.0167 (6)	0.0144 (6)	0.0022 (5)	0.0013 (5)	0.0010 (5)
C4A	0.0122 (6)	0.0198 (6)	0.0199 (7)	0.0001 (5)	0.0015 (5)	0.0000 (5)
C5A	0.0141 (6)	0.0180 (6)	0.0188 (7)	−0.0004 (5)	−0.0001 (5)	−0.0012 (5)
C6A	0.0148 (6)	0.0161 (6)	0.0146 (6)	0.0008 (5)	0.0005 (5)	0.0000 (5)
C7A	0.0167 (6)	0.0172 (6)	0.0154 (6)	0.0011 (5)	0.0001 (5)	−0.0012 (5)
C8A	0.0150 (6)	0.0161 (6)	0.0155 (6)	0.0014 (5)	0.0000 (5)	0.0009 (5)
C9A	0.0135 (6)	0.0280 (7)	0.0223 (7)	−0.0024 (5)	0.0004 (6)	−0.0044 (6)
O1B	0.0143 (5)	0.0201 (5)	0.0212 (6)	−0.0006 (4)	0.0002 (4)	−0.0053 (4)
O2B	0.0160 (5)	0.0247 (5)	0.0213 (6)	0.0017 (4)	0.0021 (4)	−0.0074 (5)
O3B	0.0166 (5)	0.0170 (5)	0.0236 (6)	0.0011 (4)	0.0038 (4)	−0.0046 (4)
N1B	0.0168 (6)	0.0162 (5)	0.0154 (6)	0.0010 (4)	0.0024 (5)	−0.0027 (4)
N2B	0.0144 (6)	0.0181 (5)	0.0206 (6)	−0.0011 (4)	0.0038 (5)	−0.0059 (5)
N3B	0.0166 (6)	0.0186 (6)	0.0258 (7)	−0.0018 (5)	0.0032 (5)	−0.0055 (5)
C1B	0.0135 (6)	0.0177 (6)	0.0151 (6)	0.0006 (5)	0.0007 (5)	−0.0005 (5)
C2B	0.0126 (6)	0.0156 (6)	0.0151 (6)	0.0007 (5)	0.0001 (5)	−0.0004 (5)
C3B	0.0149 (6)	0.0174 (6)	0.0145 (6)	0.0028 (5)	0.0017 (5)	−0.0013 (5)
C4B	0.0135 (6)	0.0206 (6)	0.0181 (7)	0.0013 (5)	0.0012 (5)	−0.0010 (5)
C5B	0.0151 (6)	0.0190 (6)	0.0167 (7)	−0.0002 (5)	0.0002 (5)	−0.0005 (5)
C6B	0.0154 (6)	0.0160 (6)	0.0131 (6)	0.0016 (5)	0.0009 (5)	−0.0002 (5)
C7B	0.0164 (6)	0.0166 (6)	0.0140 (6)	0.0000 (5)	0.0005 (5)	−0.0008 (5)
C8B	0.0151 (6)	0.0153 (6)	0.0152 (6)	0.0011 (5)	0.0014 (5)	0.0000 (5)
C9B	0.0139 (6)	0.0232 (7)	0.0206 (7)	−0.0019 (5)	−0.0013 (5)	−0.0009 (5)

Geometric parameters (Å, º) top

O1A—C2A	1.3626 (19)	O1B—C2B	1.3651 (18)
O1A—C9A	1.429 (2)	O1B—C9B	1.4370 (19)
O2A—C3A	1.3630 (19)	O2B—C3B	1.3717 (19)
O2A—H2OA	0.86 (3)	O2B—H1OB	0.83 (3)
O3A—C8A	1.2458 (19)	O3B—C8B	1.2511 (18)
N1A—C7A	1.285 (2)	N1B—C7B	1.290 (2)
N1A—N2A	1.3801 (19)	N1B—N2B	1.3772 (18)
N2A—C8A	1.368 (2)	N2B—C8B	1.3661 (19)
N2A—H2NA	0.88 (3)	N2B—H2NB	0.90 (3)
N3A—C8A	1.339 (2)	N3B—C8B	1.341 (2)
N3A—H3NA	0.83 (3)	N3B—H3ND	0.86 (3)
N3A—H3NB	0.89 (3)	N3B—H3NC	0.85 (3)
C1A—C2A	1.384 (2)	C1B—C2B	1.385 (2)
C1A—C6A	1.406 (2)	C1B—C6B	1.411 (2)
C1A—H1A	0.9500	C1B—H1B	0.9500
C2A—C3A	1.410 (2)	C2B—C3B	1.410 (2)
C3A—C4A	1.381 (2)	C3B—C4B	1.380 (2)
C4A—C5A	1.399 (2)	C4B—C5B	1.395 (2)
C4A—H4A	0.9500	C4B—H4B	0.9500
C5A—C6A	1.392 (2)	C5B—C6B	1.393 (2)
C5A—H5A	0.9500	C5B—H5B	0.9500
C6A—C7A	1.462 (2)	C6B—C7B	1.457 (2)
C7A—H7A	0.9500	C7B—H7B	0.9500
C9A—H9AA	0.9800	C9B—H9BA	0.9800
C9A—H9AB	0.9800	C9B—H9BB	0.9800
C9A—H9AC	0.9800	C9B—H9BC	0.9800

C2A—O1A—C9A	117.26 (12)	C2B—O1B—C9B	117.40 (12)
C3A—O2A—H2OA	108 (2)	C3B—O2B—H1OB	109.6 (19)
C7A—N1A—N2A	114.92 (13)	C7B—N1B—N2B	114.11 (13)
C8A—N2A—N1A	120.12 (13)	C8B—N2B—N1B	121.10 (13)
C8A—N2A—H2NA	117.1 (19)	C8B—N2B—H2NB	117.9 (17)
N1A—N2A—H2NA	121.3 (18)	N1B—N2B—H2NB	120.4 (17)
C8A—N3A—H3NA	119 (2)	C8B—N3B—H3ND	120.2 (17)
C8A—N3A—H3NB	119.9 (17)	C8B—N3B—H3NC	118.5 (19)
H3NA—N3A—H3NB	117 (3)	H3ND—N3B—H3NC	119 (2)
C2A—C1A—C6A	119.54 (14)	C2B—C1B—C6B	119.62 (13)
C2A—C1A—H1A	120.2	C2B—C1B—H1B	120.2
C6A—C1A—H1A	120.2	C6B—C1B—H1B	120.2
O1A—C2A—C1A	126.19 (13)	O1B—C2B—C1B	126.52 (13)
O1A—C2A—C3A	113.11 (13)	O1B—C2B—C3B	113.67 (13)
C1A—C2A—C3A	120.70 (14)	C1B—C2B—C3B	119.82 (13)
O2A—C3A—C4A	120.61 (14)	O2B—C3B—C4B	119.08 (13)
O2A—C3A—C2A	119.82 (14)	O2B—C3B—C2B	120.34 (13)
C4A—C3A—C2A	119.54 (14)	C4B—C3B—C2B	120.56 (14)
C3A—C4A—C5A	120.05 (14)	C3B—C4B—C5B	119.78 (14)
C3A—C4A—H4A	120.0	C3B—C4B—H4B	120.1
C5A—C4A—H4A	120.0	C5B—C4B—H4B	120.1
C6A—C5A—C4A	120.52 (14)	C6B—C5B—C4B	120.33 (14)
C6A—C5A—H5A	119.7	C6B—C5B—H5B	119.8
C4A—C5A—H5A	119.7	C4B—C5B—H5B	119.8
C5A—C6A—C1A	119.62 (14)	C5B—C6B—C1B	119.88 (14)
C5A—C6A—C7A	119.20 (14)	C5B—C6B—C7B	117.75 (14)
C1A—C6A—C7A	121.15 (14)	C1B—C6B—C7B	122.30 (14)
N1A—C7A—C6A	121.20 (14)	N1B—C7B—C6B	122.82 (14)
N1A—C7A—H7A	119.4	N1B—C7B—H7B	118.6
C6A—C7A—H7A	119.4	C6B—C7B—H7B	118.6
O3A—C8A—N3A	123.75 (15)	O3B—C8B—N3B	123.62 (15)
O3A—C8A—N2A	118.88 (14)	O3B—C8B—N2B	118.94 (14)
N3A—C8A—N2A	117.36 (14)	N3B—C8B—N2B	117.42 (14)
O1A—C9A—H9AA	109.5	O1B—C9B—H9BA	109.5
O1A—C9A—H9AB	109.5	O1B—C9B—H9BB	109.5
H9AA—C9A—H9AB	109.5	H9BA—C9B—H9BB	109.5
O1A—C9A—H9AC	109.5	O1B—C9B—H9BC	109.5
H9AA—C9A—H9AC	109.5	H9BA—C9B—H9BC	109.5
H9AB—C9A—H9AC	109.5	H9BB—C9B—H9BC	109.5

C7A—N1A—N2A—C8A	173.09 (15)	C7B—N1B—N2B—C8B	−175.20 (15)
C9A—O1A—C2A—C1A	−1.7 (2)	C9B—O1B—C2B—C1B	3.9 (2)
C9A—O1A—C2A—C3A	178.26 (14)	C9B—O1B—C2B—C3B	−175.85 (14)
C6A—C1A—C2A—O1A	178.16 (15)	C6B—C1B—C2B—O1B	−178.73 (14)
C6A—C1A—C2A—C3A	−1.8 (2)	C6B—C1B—C2B—C3B	1.0 (2)
O1A—C2A—C3A—O2A	0.6 (2)	O1B—C2B—C3B—O2B	1.3 (2)
C1A—C2A—C3A—O2A	−179.49 (14)	C1B—C2B—C3B—O2B	−178.42 (14)
O1A—C2A—C3A—C4A	−177.67 (14)	O1B—C2B—C3B—C4B	179.73 (14)
C1A—C2A—C3A—C4A	2.3 (2)	C1B—C2B—C3B—C4B	0.0 (2)
O2A—C3A—C4A—C5A	−179.16 (15)	O2B—C3B—C4B—C5B	177.80 (14)
C2A—C3A—C4A—C5A	−0.9 (2)	C2B—C3B—C4B—C5B	−0.6 (2)
C3A—C4A—C5A—C6A	−0.9 (2)	C3B—C4B—C5B—C6B	0.3 (2)
C4A—C5A—C6A—C1A	1.3 (2)	C4B—C5B—C6B—C1B	0.7 (2)
C4A—C5A—C6A—C7A	179.36 (15)	C4B—C5B—C6B—C7B	−176.57 (14)
C2A—C1A—C6A—C5A	0.0 (2)	C2B—C1B—C6B—C5B	−1.3 (2)
C2A—C1A—C6A—C7A	−177.99 (15)	C2B—C1B—C6B—C7B	175.81 (14)
N2A—N1A—C7A—C6A	176.29 (14)	N2B—N1B—C7B—C6B	−175.18 (14)
C5A—C6A—C7A—N1A	176.93 (15)	C5B—C6B—C7B—N1B	177.73 (15)
C1A—C6A—C7A—N1A	−5.1 (2)	C1B—C6B—C7B—N1B	0.6 (2)
N1A—N2A—C8A—O3A	179.13 (15)	N1B—N2B—C8B—O3B	−178.70 (15)
N1A—N2A—C8A—N3A	0.4 (2)	N1B—N2B—C8B—N3B	−0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2OA···O2Bⁱ	0.86 (3)	2.22 (3)	2.9924 (18)	149 (3)
N2A—H2NA···O3B	0.88 (3)	2.03 (3)	2.8966 (19)	171 (3)
N3A—H3NB···O3Bⁱⁱ	0.89 (3)	2.10 (3)	2.961 (2)	165 (2)
N2B—H2NB···O3A	0.90 (3)	2.00 (3)	2.8812 (18)	169 (2)
N3B—H3ND···O3Aⁱⁱⁱ	0.86 (3)	2.09 (3)	2.9415 (19)	172 (3)

Symmetry codes: (i) −x+1, −y+2, z+1/2; (ii) x+1/2, −y+2, z; (iii) x−1/2, −y+1, z.

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O₃
M_r	209.21
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	100
a, b, c (Å)	13.8568 (3), 5.0379 (1), 26.8582 (5)
V (Å³)	1874.95 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.56 × 0.21 × 0.08

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.939, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	27088, 3785, 3477
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.783

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.098, 1.05
No. of reflections	3785
No. of parameters	305
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.20

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2OA···O2Bⁱ	0.86 (3)	2.22 (3)	2.9924 (18)	149 (3)
N2A—H2NA···O3B	0.88 (3)	2.03 (3)	2.8966 (19)	171 (3)
N3A—H3NB···O3Bⁱⁱ	0.89 (3)	2.10 (3)	2.961 (2)	165 (2)
N2B—H2NB···O3A	0.90 (3)	2.00 (3)	2.8812 (18)	169 (2)
N3B—H3ND···O3Aⁱⁱⁱ	0.86 (3)	2.09 (3)	2.9415 (19)	172 (3)

Symmetry codes: (i) −x+1, −y+2, z+1/2; (ii) x+1/2, −y+2, z; (iii) x−1/2, −y+1, z.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5523-2009.

Acknowledgements

HKF and CSY thank Universiti Sains Malaysia for the Research University Grant 1001/PFIZIK/811160. AMI thanks the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India for a Young Scientist award. AMI also thanks the Defence Research and Development Organization, New Delhi, India, for financial support.

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