2-Hy-droxy-N'-methyl-5-nitro-benzohydrazide.

In the title compound, C8H9N3O4, there are two mol-ecules in the asymmetric unit, one of which is in the zwitterionic form. The zwitterion contains an intra-molecular N-H⋯O hydrogen bond and the other mol-ecule contains both an intra-molecular N-H⋯O and an intra-molecular O-H⋯O hydrogen bond. In the crystal, N-H⋯O and N-H⋯N hydrogen bonds link the mol-ecules, formimg a two-dimensional network parallel to (10-1).

Related literature

For the biological activities of salicylhydrazide derivatives, see: Bagchi et al. (2004 ▶); Thompson et al. (2004 ▶); Al-Mawsawi et al. (2007 ▶). For metal complexes involving derivatives of the title compound, see: Jin et al. (2006a ▶,b ▶). For related crystal structures, see: Liu et al. (2006 ▶); Luo et al. (2007 ▶); Xu & Liu (2006 ▶); Zhang (2012 ▶).

Experimental

Crystal data

C8H9N3O4

M = 211.18

Monoclinic,

a = 7.3818 (15) Å

b = 13.106 (3) Å

c = 18.719 (4) Å

β = 95.25 (3)°

V = 1803.4 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.13 mm−1

T = 293 K

0.26 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.968, T max = 0.987

11293 measured reflections

3536 independent reflections

2356 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.142

S = 1.06

3536 reflections

291 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813019776/lh5633sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813019776/lh5633Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813019776/lh5633Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C8H9N3O4	F(000) = 880
Mr = 211.18	Dx = 1.556 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1664 reflections
a = 7.3818 (15) Å	θ = 2.9–21.8°
b = 13.106 (3) Å	µ = 0.13 mm−1
c = 18.719 (4) Å	T = 293 K
β = 95.25 (3)°	Block, yellow
V = 1803.4 (6) Å3	0.26 × 0.20 × 0.10 mm
Z = 8

Bruker SMART CCD diffractometer	3536 independent reflections
Radiation source: fine-focus sealed tube	2356 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
φ and ω scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.968, Tmax = 0.987	k = −15→16
11293 measured reflections	l = −23→16

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0565P)2 + 0.5317P] where P = (Fo2 + 2Fc2)/3
3536 reflections	(Δ/σ)max = 0.026
291 parameters	Δρmax = 0.22 e Å−3
5 restraints	Δρmin = −0.18 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.5851 (3)	0.42908 (18)	0.18014 (13)	0.0339 (6)
C2	0.5537 (4)	0.53339 (19)	0.15979 (15)	0.0422 (7)
C3	0.5864 (4)	0.6078 (2)	0.21338 (15)	0.0472 (7)
H3	0.5608	0.6757	0.2021	0.057*
C4	0.6544 (4)	0.5839 (2)	0.28124 (15)	0.0445 (7)
H4	0.6754	0.6347	0.3157	0.053*
C5	0.6921 (3)	0.4822 (2)	0.29859 (14)	0.0377 (6)
C6	0.6547 (3)	0.40610 (19)	0.24911 (13)	0.0358 (6)
H6	0.6766	0.3385	0.2622	0.043*
C7	0.5512 (3)	0.34258 (18)	0.12929 (13)	0.0336 (6)
C8	0.6571 (4)	0.2470 (2)	−0.00925 (16)	0.0549 (8)
H8A	0.7340	0.3000	−0.0249	0.082*
H8B	0.6334	0.1979	−0.0471	0.082*
H8C	0.7167	0.2139	0.0322	0.082*
C9	0.3376 (3)	−0.01241 (18)	0.22768 (14)	0.0341 (6)
C10	0.3287 (4)	−0.1136 (2)	0.25337 (15)	0.0427 (7)
C11	0.3917 (4)	−0.1365 (2)	0.32380 (17)	0.0559 (8)
H11	0.3873	−0.2034	0.3400	0.067*
C12	0.4595 (4)	−0.0621 (2)	0.36920 (17)	0.0557 (8)
H12	0.5013	−0.0778	0.4163	0.067*
C13	0.4657 (4)	0.0376 (2)	0.34444 (14)	0.0421 (7)
C14	0.4053 (3)	0.06248 (19)	0.27498 (14)	0.0382 (6)
H14	0.4099	0.1299	0.2597	0.046*
C15	0.2762 (3)	0.00751 (19)	0.15166 (14)	0.0363 (6)
C16	0.0855 (4)	0.1430 (2)	0.03122 (17)	0.0601 (9)
H16A	0.0122	0.0904	0.0497	0.090*
H16B	0.0630	0.1455	−0.0201	0.090*
H16C	0.0550	0.2076	0.0511	0.090*
N1	0.5069 (3)	0.37013 (16)	0.06155 (12)	0.0432 (6)
H1	0.489 (4)	0.4367 (15)	0.0517 (16)	0.072*
N2	0.4833 (3)	0.29164 (17)	0.00913 (12)	0.0400 (5)
H2A	0.420 (4)	0.321 (2)	−0.0313 (12)	0.072*
H2B	0.409 (4)	0.233 (2)	0.0275 (16)	0.072*
N3	0.7769 (3)	0.45572 (19)	0.36861 (12)	0.0463 (6)
N4	0.3109 (3)	0.09987 (16)	0.12471 (12)	0.0422 (6)
H4A	0.393 (3)	0.143 (2)	0.1470 (15)	0.072*
N5	0.2755 (3)	0.12117 (16)	0.05067 (12)	0.0421 (6)
H5A	0.306 (4)	0.0673 (17)	0.0315 (16)	0.072*
N6	0.5389 (3)	0.1169 (2)	0.39330 (13)	0.0570 (7)
O1	0.4975 (3)	0.55896 (14)	0.09395 (10)	0.0593 (6)
O2	0.5657 (3)	0.25254 (12)	0.14945 (10)	0.0452 (5)
O3	0.8350 (3)	0.36913 (18)	0.37959 (11)	0.0684 (7)
O4	0.7919 (3)	0.52224 (16)	0.41560 (11)	0.0664 (6)
O5	0.2604 (3)	−0.19058 (14)	0.21215 (12)	0.0598 (6)
H5	0.223 (5)	−0.159 (3)	0.1736 (14)	0.090*
O6	0.1955 (3)	−0.05861 (14)	0.11305 (10)	0.0507 (5)
O7	0.5987 (4)	0.0933 (2)	0.45398 (13)	0.0933 (9)
O8	0.5409 (4)	0.20419 (19)	0.37205 (13)	0.0902 (9)

	U11	U22	U33	U12	U13	U23
C1	0.0403 (14)	0.0276 (13)	0.0339 (15)	0.0005 (10)	0.0036 (11)	0.0025 (11)
C2	0.0498 (16)	0.0315 (15)	0.0446 (17)	0.0026 (12)	0.0010 (13)	0.0023 (13)
C3	0.0621 (19)	0.0282 (15)	0.0507 (19)	0.0000 (12)	0.0016 (15)	−0.0019 (13)
C4	0.0556 (17)	0.0333 (15)	0.0443 (17)	−0.0073 (12)	0.0033 (14)	−0.0107 (13)
C5	0.0383 (14)	0.0418 (15)	0.0327 (15)	−0.0069 (11)	0.0009 (11)	−0.0009 (12)
C6	0.0388 (14)	0.0310 (14)	0.0373 (15)	−0.0015 (11)	0.0013 (12)	0.0036 (12)
C7	0.0423 (15)	0.0271 (14)	0.0309 (15)	0.0015 (10)	0.0013 (11)	0.0042 (11)
C8	0.067 (2)	0.0474 (17)	0.0516 (19)	0.0106 (15)	0.0131 (16)	0.0002 (15)
C9	0.0372 (14)	0.0276 (13)	0.0379 (15)	0.0025 (10)	0.0056 (11)	0.0001 (12)
C10	0.0430 (15)	0.0366 (15)	0.0483 (18)	−0.0012 (12)	0.0033 (13)	0.0046 (13)
C11	0.064 (2)	0.0409 (17)	0.062 (2)	−0.0032 (14)	0.0016 (16)	0.0222 (16)
C12	0.0602 (19)	0.060 (2)	0.0470 (19)	0.0040 (15)	0.0020 (15)	0.0199 (16)
C13	0.0446 (16)	0.0467 (17)	0.0349 (16)	0.0002 (12)	0.0030 (12)	0.0007 (13)
C14	0.0461 (15)	0.0346 (14)	0.0341 (15)	0.0024 (11)	0.0046 (12)	0.0029 (12)
C15	0.0430 (15)	0.0285 (14)	0.0374 (16)	0.0007 (11)	0.0030 (12)	−0.0033 (12)
C16	0.067 (2)	0.057 (2)	0.054 (2)	−0.0022 (16)	−0.0081 (16)	−0.0028 (16)
N1	0.0739 (16)	0.0235 (11)	0.0315 (13)	0.0052 (11)	0.0010 (11)	0.0010 (10)
N2	0.0568 (15)	0.0314 (12)	0.0304 (13)	0.0039 (10)	−0.0032 (11)	0.0032 (10)
N3	0.0541 (15)	0.0462 (15)	0.0379 (15)	−0.0087 (12)	0.0004 (11)	−0.0008 (12)
N4	0.0580 (15)	0.0364 (13)	0.0305 (13)	−0.0075 (10)	−0.0048 (11)	0.0004 (10)
N5	0.0590 (15)	0.0362 (13)	0.0297 (13)	−0.0020 (11)	−0.0023 (11)	−0.0008 (10)
N6	0.0685 (17)	0.0639 (19)	0.0370 (16)	−0.0011 (14)	−0.0036 (13)	−0.0037 (14)
O1	0.1027 (17)	0.0323 (10)	0.0399 (12)	0.0062 (10)	−0.0102 (11)	0.0077 (9)
O2	0.0681 (13)	0.0256 (10)	0.0391 (11)	−0.0029 (8)	−0.0099 (9)	0.0051 (8)
O3	0.0945 (17)	0.0608 (15)	0.0451 (13)	0.0100 (13)	−0.0185 (12)	0.0041 (11)
O4	0.0981 (17)	0.0579 (14)	0.0412 (13)	−0.0164 (12)	−0.0037 (12)	−0.0104 (11)
O5	0.0765 (15)	0.0308 (11)	0.0702 (16)	−0.0083 (10)	−0.0033 (12)	0.0015 (11)
O6	0.0681 (13)	0.0373 (11)	0.0454 (12)	−0.0088 (9)	−0.0029 (10)	−0.0066 (9)
O7	0.131 (2)	0.102 (2)	0.0402 (14)	−0.0151 (17)	−0.0271 (14)	0.0047 (14)
O8	0.155 (3)	0.0508 (15)	0.0583 (16)	−0.0083 (15)	−0.0239 (16)	−0.0097 (13)

C1—C6	1.379 (3)	C11—H11	0.9300
C1—C2	1.432 (3)	C12—C13	1.389 (4)
C1—C7	1.487 (3)	C12—H12	0.9300
C2—O1	1.308 (3)	C13—C14	1.375 (4)
C2—C3	1.404 (4)	C13—N6	1.455 (4)
C3—C4	1.359 (4)	C14—H14	0.9300
C3—H3	0.9300	C15—O6	1.245 (3)
C4—C5	1.394 (4)	C15—N4	1.345 (3)
C4—H4	0.9300	C16—N5	1.445 (4)
C5—C6	1.372 (3)	C16—H16A	0.9600
C5—N3	1.443 (3)	C16—H16B	0.9600
C6—H6	0.9300	C16—H16C	0.9600
C7—O2	1.240 (3)	N1—N2	1.421 (3)
C7—N1	1.330 (3)	N1—H1	0.899 (17)
C8—N2	1.479 (3)	N2—H2A	0.937 (17)
C8—H8A	0.9600	N2—H2B	1.02 (3)
C8—H8B	0.9600	N3—O3	1.224 (3)
C8—H8C	0.9600	N3—O4	1.236 (3)
C9—C14	1.384 (3)	N4—N5	1.415 (3)
C9—C10	1.414 (3)	N4—H4A	0.903 (18)
C9—C15	1.477 (3)	N5—H5A	0.832 (17)
C10—O5	1.340 (3)	N6—O8	1.212 (3)
C10—C11	1.390 (4)	N6—O7	1.220 (3)
C11—C12	1.359 (4)	O5—H5	0.854 (18)
C6—C1—C2	119.7 (2)	C13—C12—H12	120.4
C6—C1—C7	117.3 (2)	C14—C13—C12	121.4 (3)
C2—C1—C7	123.0 (2)	C14—C13—N6	119.7 (2)
O1—C2—C3	121.0 (2)	C12—C13—N6	118.9 (3)
O1—C2—C1	121.7 (2)	C13—C14—C9	120.3 (2)
C3—C2—C1	117.4 (2)	C13—C14—H14	119.9
C4—C3—C2	122.2 (3)	C9—C14—H14	119.9
C4—C3—H3	118.9	O6—C15—N4	120.4 (2)
C2—C3—H3	118.9	O6—C15—C9	121.7 (2)
C3—C4—C5	119.2 (2)	N4—C15—C9	117.9 (2)
C3—C4—H4	120.4	N5—C16—H16A	109.5
C5—C4—H4	120.4	N5—C16—H16B	109.5
C6—C5—C4	121.0 (2)	H16A—C16—H16B	109.5
C6—C5—N3	118.8 (2)	N5—C16—H16C	109.5
C4—C5—N3	120.2 (2)	H16A—C16—H16C	109.5
C5—C6—C1	120.5 (2)	H16B—C16—H16C	109.5
C5—C6—H6	119.7	C7—N1—N2	117.7 (2)
C1—C6—H6	119.7	C7—N1—H1	119 (2)
O2—C7—N1	123.7 (2)	N2—N1—H1	124 (2)
O2—C7—C1	121.7 (2)	N1—N2—C8	113.2 (2)
N1—C7—C1	114.6 (2)	N1—N2—H2A	106.1 (19)
N2—C8—H8A	109.5	C8—N2—H2A	110.8 (19)
N2—C8—H8B	109.5	N1—N2—H2B	110.2 (17)
H8A—C8—H8B	109.5	C8—N2—H2B	106.7 (17)
N2—C8—H8C	109.5	H2A—N2—H2B	110 (3)
H8A—C8—H8C	109.5	O3—N3—O4	121.8 (2)
H8B—C8—H8C	109.5	O3—N3—C5	119.5 (2)
C14—C9—C10	118.2 (2)	O4—N3—C5	118.7 (2)
C14—C9—C15	123.5 (2)	C15—N4—N5	121.4 (2)
C10—C9—C15	118.3 (2)	C15—N4—H4A	122 (2)
O5—C10—C11	117.3 (2)	N5—N4—H4A	113 (2)
O5—C10—C9	122.5 (2)	N4—N5—C16	111.9 (2)
C11—C10—C9	120.2 (3)	N4—N5—H5A	103 (2)
C12—C11—C10	120.7 (3)	C16—N5—H5A	111 (2)
C12—C11—H11	119.6	O8—N6—O7	122.1 (3)
C10—C11—H11	119.6	O8—N6—C13	118.9 (2)
C11—C12—C13	119.2 (3)	O7—N6—C13	119.1 (3)
C11—C12—H12	120.4	C10—O5—H5	102 (3)
C6—C1—C2—O1	176.1 (2)	C11—C12—C13—C14	−0.2 (4)
C7—C1—C2—O1	−1.9 (4)	C11—C12—C13—N6	−179.9 (3)
C6—C1—C2—C3	−3.7 (4)	C12—C13—C14—C9	−0.5 (4)
C7—C1—C2—C3	178.3 (2)	N6—C13—C14—C9	179.1 (2)
O1—C2—C3—C4	−176.3 (3)	C10—C9—C14—C13	1.5 (4)
C1—C2—C3—C4	3.5 (4)	C15—C9—C14—C13	−177.8 (2)
C2—C3—C4—C5	−0.4 (4)	C14—C9—C15—O6	−170.9 (2)
C3—C4—C5—C6	−2.7 (4)	C10—C9—C15—O6	9.8 (4)
C3—C4—C5—N3	175.3 (2)	C14—C9—C15—N4	9.4 (4)
C4—C5—C6—C1	2.4 (4)	C10—C9—C15—N4	−169.9 (2)
N3—C5—C6—C1	−175.6 (2)	O2—C7—N1—N2	−3.0 (4)
C2—C1—C6—C5	0.8 (4)	C1—C7—N1—N2	176.3 (2)
C7—C1—C6—C5	179.0 (2)	C7—N1—N2—C8	−75.0 (3)
C6—C1—C7—O2	7.7 (4)	C6—C5—N3—O3	9.4 (4)
C2—C1—C7—O2	−174.2 (2)	C4—C5—N3—O3	−168.7 (3)
C6—C1—C7—N1	−171.6 (2)	C6—C5—N3—O4	−172.0 (2)
C2—C1—C7—N1	6.5 (3)	C4—C5—N3—O4	10.0 (4)
C14—C9—C10—O5	178.0 (2)	O6—C15—N4—N5	−7.0 (4)
C15—C9—C10—O5	−2.7 (4)	C9—C15—N4—N5	172.7 (2)
C14—C9—C10—C11	−1.8 (4)	C15—N4—N5—C16	80.1 (3)
C15—C9—C10—C11	177.5 (2)	C14—C13—N6—O8	1.8 (4)
O5—C10—C11—C12	−178.7 (3)	C12—C13—N6—O8	−178.5 (3)
C9—C10—C11—C12	1.1 (4)	C14—C13—N6—O7	−177.2 (3)
C10—C11—C12—C13	−0.1 (4)	C12—C13—N6—O7	2.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O2	0.90 (2)	1.92 (2)	2.756 (3)	154 (3)
N1—H1···O1	0.90 (2)	1.78 (2)	2.550 (3)	141 (3)
N2—H2B···N5	1.02 (3)	1.84 (3)	2.858 (3)	174 (3)
O5—H5···O6	0.85 (2)	1.74 (2)	2.549 (3)	158 (4)
N5—H5A···O6	0.83 (2)	2.44 (3)	2.719 (3)	101 (2)
N5—H5A···O4i	0.83 (2)	2.46 (2)	3.162 (3)	143 (3)
N2—H2A···O7i	0.94 (2)	2.61 (3)	3.296 (3)	130 (2)
N2—H2A···O1ii	0.94 (2)	2.08 (3)	2.762 (3)	128 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O2	0.90 (2)	1.92 (2)	2.756 (3)	154 (3)
N1—H1⋯O1	0.90 (2)	1.78 (2)	2.550 (3)	141 (3)
N2—H2B⋯N5	1.02 (3)	1.84 (3)	2.858 (3)	174 (3)
O5—H5⋯O6	0.85 (2)	1.74 (2)	2.549 (3)	158 (4)
N5—H5A⋯O6	0.83 (2)	2.44 (3)	2.719 (3)	101 (2)
N5—H5A⋯O4i	0.83 (2)	2.46 (2)	3.162 (3)	143 (3)
N2—H2A⋯O1ii	0.94 (2)	2.08 (3)	2.762 (3)	128 (2)

Symmetry codes: (i) ; (ii) .