(E)-2-[(2-Hydr-oxy-5-nitro-phen-yl)iminiometh-yl]phenolate.

In the title mol-ecule, C(13)H(10)N(2)O(4), the dihedral angle between the mean planes of the benzene and phenolate rings is 21.6 (4)°. The nitro O atoms are twisted slightly out of the plane of the ring to which the nitro group is attached [dihedral angle 8.4 (3)°]. The amine group forms an intra-molecular hydrogen bond with both nearby O atoms. An extended π delocalization throughout the entire mol-ecule exists producing a zwitterionic effect in this region of the mol-ecule. The shortened C-O bond [1.2997 (15) Å] in concert with the slightly longer C-OH bond [1.3310 (16) Å] provide evidence for this effect. The crystal packing is influenced by strong inter-molecular O-H⋯O hydrogen bonding. As a result, mol-ecules are linked into an infinite zigzag chain running along the b axis. A MOPAC PM3 calculation provides support to these observations.

Related literature

For related structures, see: Ersanlı et al. (2003 ▶); Odabaşoğlu et al. (2006 ▶); Jasinski et al. (2007 ▶); Elerman et al. (1995 ▶); Hijji et al. (2008 ▶, 2009 ▶). For the application of Schiff bases in organic synthesis, see: Barba et al. (2001 ▶); Rodriguez et al. (2005 ▶). For details of the MOPAC PM3 calculation, see: Schmidt & Polik (2007 ▶).

Experimental

Crystal data

C13H10N2O4

M = 258.23

Monoclinic,

a = 7.3949 (3) Å

b = 9.1058 (4) Å

c = 17.2734 (6) Å

β = 96.387 (4)°

V = 1155.91 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 296 (2) K

0.45 × 0.36 × 0.21 mm

Data collection

Oxford Diffraction Gemini R diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T min = 0.950, T max = 0.977

16362 measured reflections

3889 independent reflections

2071 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.161

S = 1.01

3889 reflections

173 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.23 e Å−3

Data collection: CrysAlisPro (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlisPro; data reduction: CrysAlisRed (Oxford Diffraction, 2007 ▶); 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001007/bt2849sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001007/bt2849Isup2.hkl

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

C13H10N2O4	F(000) = 536
Mr = 258.23	Dx = 1.484 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5321 reflections
a = 7.3949 (3) Å	θ = 4.6–32.6°
b = 9.1058 (4) Å	µ = 0.11 mm−1
c = 17.2734 (6) Å	T = 296 K
β = 96.387 (4)°	Prism, yellow
V = 1155.91 (8) Å3	0.45 × 0.36 × 0.21 mm
Z = 4

Oxford Diffraction Gemini R diffractometer	3889 independent reflections
Radiation source: fine-focus sealed tube	2071 reflections with I > 2σ(I)
graphite	Rint = 0.045
Detector resolution: 10.5081 pixels mm-1	θmax = 32.5°, θmin = 4.6°
φ and ω scans	h = −10→11
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −12→13
Tmin = 0.950, Tmax = 0.977	l = −25→24
16362 measured reflections

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0893P)2] where P = (Fo2 + 2Fc2)/3
3889 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.23 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
O1	0.07674 (16)	0.78106 (11)	0.74658 (6)	0.0506 (3)
H1O	0.0213	0.8253	0.7779	0.061*
O2	0.56661 (19)	1.27359 (14)	0.63179 (8)	0.0696 (4)
O3	0.64896 (19)	1.09097 (16)	0.56567 (8)	0.0797 (5)
O4	0.10989 (15)	0.42056 (11)	0.66269 (5)	0.0475 (3)
N1	0.56076 (17)	1.14379 (16)	0.61491 (7)	0.0494 (3)
N2	0.25299 (15)	0.67241 (13)	0.63378 (6)	0.0367 (3)
H2B	0.2098	0.6146	0.6665	0.044*
C7	0.27637 (17)	0.61689 (15)	0.56560 (7)	0.0353 (3)
H7A	0.3301	0.6755	0.5304	0.042*
C1	0.19513 (18)	0.87143 (15)	0.71860 (7)	0.0372 (3)
C2	0.2271 (2)	1.01473 (16)	0.74472 (8)	0.0433 (4)
H2A	0.1653	1.0508	0.7847	0.052*
C3	0.3485 (2)	1.10366 (16)	0.71228 (8)	0.0430 (4)
H3A	0.3688	1.1995	0.7297	0.052*
C4	0.44018 (19)	1.04784 (16)	0.65308 (8)	0.0383 (3)
C5	0.41405 (19)	0.90591 (15)	0.62591 (8)	0.0382 (3)
H5A	0.4778	0.8706	0.5863	0.046*
C6	0.29168 (18)	0.81772 (15)	0.65867 (7)	0.0346 (3)
C8	0.22475 (18)	0.47420 (15)	0.54298 (7)	0.0330 (3)
C9	0.13664 (18)	0.37863 (15)	0.59295 (7)	0.0357 (3)
C10	0.0795 (2)	0.23976 (16)	0.56283 (8)	0.0430 (4)
H10A	0.0199	0.1758	0.5934	0.052*
C11	0.1105 (2)	0.19794 (16)	0.48953 (9)	0.0464 (4)
H11A	0.0724	0.1056	0.4714	0.056*
C12	0.1984 (2)	0.29107 (17)	0.44103 (8)	0.0443 (4)
H12A	0.2196	0.2601	0.3915	0.053*
C13	0.25243 (19)	0.42681 (15)	0.46681 (8)	0.0380 (3)
H13A	0.3082	0.4895	0.4342	0.046*

	U11	U22	U33	U12	U13	U23
O1	0.0648 (7)	0.0424 (6)	0.0510 (6)	−0.0085 (5)	0.0346 (5)	−0.0106 (5)
O2	0.0823 (9)	0.0445 (8)	0.0842 (9)	−0.0225 (7)	0.0183 (7)	−0.0007 (6)
O3	0.0888 (10)	0.0751 (10)	0.0847 (9)	−0.0308 (8)	0.0520 (8)	−0.0116 (7)
O4	0.0642 (7)	0.0413 (6)	0.0418 (5)	−0.0029 (5)	0.0272 (5)	0.0021 (4)
N1	0.0507 (8)	0.0468 (8)	0.0520 (7)	−0.0143 (6)	0.0115 (6)	0.0001 (6)
N2	0.0446 (6)	0.0301 (6)	0.0385 (6)	−0.0019 (5)	0.0180 (5)	−0.0009 (5)
C7	0.0367 (7)	0.0335 (7)	0.0383 (7)	−0.0011 (6)	0.0153 (5)	0.0007 (5)
C1	0.0465 (8)	0.0325 (7)	0.0348 (6)	−0.0015 (6)	0.0140 (6)	0.0004 (5)
C2	0.0530 (9)	0.0387 (8)	0.0407 (7)	0.0013 (7)	0.0159 (6)	−0.0064 (6)
C3	0.0518 (9)	0.0337 (8)	0.0439 (7)	−0.0056 (6)	0.0068 (6)	−0.0033 (6)
C4	0.0412 (7)	0.0361 (8)	0.0383 (7)	−0.0059 (6)	0.0075 (6)	0.0018 (6)
C5	0.0422 (8)	0.0354 (8)	0.0390 (7)	−0.0021 (6)	0.0138 (6)	−0.0021 (6)
C6	0.0407 (7)	0.0298 (7)	0.0346 (6)	0.0003 (6)	0.0091 (5)	−0.0021 (5)
C8	0.0347 (6)	0.0303 (7)	0.0360 (6)	0.0010 (5)	0.0133 (5)	0.0007 (5)
C9	0.0378 (7)	0.0324 (7)	0.0390 (7)	0.0034 (6)	0.0138 (5)	0.0035 (5)
C10	0.0466 (8)	0.0327 (8)	0.0509 (8)	−0.0040 (6)	0.0109 (6)	0.0070 (6)
C11	0.0552 (9)	0.0316 (8)	0.0522 (8)	−0.0028 (7)	0.0050 (7)	−0.0038 (6)
C12	0.0551 (9)	0.0401 (9)	0.0390 (7)	0.0018 (7)	0.0113 (6)	−0.0043 (6)
C13	0.0434 (7)	0.0347 (8)	0.0382 (7)	0.0007 (6)	0.0156 (6)	0.0002 (5)

O1—C1	1.3310 (16)	C3—C4	1.3847 (19)
O1—H1O	0.8200	C3—H3A	0.9300
O2—N1	1.2170 (18)	C4—C5	1.3813 (19)
O3—N1	1.2262 (16)	C5—C6	1.3776 (19)
O4—C9	1.2997 (15)	C5—H5A	0.9300
N1—C4	1.4574 (18)	C8—C13	1.4210 (17)
N2—C7	1.3105 (16)	C8—C9	1.4325 (18)
N2—C6	1.4107 (17)	C9—C10	1.414 (2)
N2—H2B	0.8600	C10—C11	1.366 (2)
C7—C8	1.3977 (19)	C10—H10A	0.9300
C7—H7A	0.9300	C11—C12	1.402 (2)
C1—C2	1.392 (2)	C11—H11A	0.9300
C1—C6	1.4089 (18)	C12—C13	1.359 (2)
C2—C3	1.374 (2)	C12—H12A	0.9300
C2—H2A	0.9300	C13—H13A	0.9300
C1—O1—H1O	109.5	C6—C5—H5A	120.7
O2—N1—O3	122.66 (14)	C4—C5—H5A	120.7
O2—N1—C4	118.75 (13)	C5—C6—C1	120.61 (12)
O3—N1—C4	118.56 (14)	C5—C6—N2	122.80 (12)
C7—N2—C6	126.38 (12)	C1—C6—N2	116.58 (12)
C7—N2—H2B	116.8	C7—C8—C13	118.57 (12)
C6—N2—H2B	116.8	C7—C8—C9	121.65 (11)
N2—C7—C8	123.41 (12)	C13—C8—C9	119.70 (12)
N2—C7—H7A	118.3	O4—C9—C10	122.26 (12)
C8—C7—H7A	118.3	O4—C9—C8	120.42 (12)
O1—C1—C2	123.82 (12)	C10—C9—C8	117.32 (12)
O1—C1—C6	117.37 (12)	C11—C10—C9	121.09 (13)
C2—C1—C6	118.80 (12)	C11—C10—H10A	119.5
C3—C2—C1	121.01 (13)	C9—C10—H10A	119.5
C3—C2—H2A	119.5	C10—C11—C12	121.48 (14)
C1—C2—H2A	119.5	C10—C11—H11A	119.3
C2—C3—C4	118.72 (14)	C12—C11—H11A	119.3
C2—C3—H3A	120.6	C13—C12—C11	119.57 (13)
C4—C3—H3A	120.6	C13—C12—H12A	120.2
C5—C4—C3	122.21 (13)	C11—C12—H12A	120.2
C5—C4—N1	118.47 (13)	C12—C13—C8	120.82 (13)
C3—C4—N1	119.23 (13)	C12—C13—H13A	119.6
C6—C5—C4	118.64 (12)	C8—C13—H13A	119.6
C6—N2—C7—C8	−175.95 (12)	C2—C1—C6—N2	−179.38 (12)
O1—C1—C2—C3	−178.63 (14)	C7—N2—C6—C5	−22.8 (2)
C6—C1—C2—C3	0.9 (2)	C7—N2—C6—C1	155.85 (13)
C1—C2—C3—C4	−0.4 (2)	N2—C7—C8—C13	178.40 (13)
C2—C3—C4—C5	−0.3 (2)	N2—C7—C8—C9	1.8 (2)
C2—C3—C4—N1	176.22 (13)	C7—C8—C9—O4	−3.2 (2)
O2—N1—C4—C5	170.80 (13)	C13—C8—C9—O4	−179.81 (12)
O3—N1—C4—C5	−7.5 (2)	C7—C8—C9—C10	176.10 (12)
O2—N1—C4—C3	−5.8 (2)	C13—C8—C9—C10	−0.49 (19)
O3—N1—C4—C3	175.92 (14)	O4—C9—C10—C11	−179.51 (13)
C3—C4—C5—C6	0.4 (2)	C8—C9—C10—C11	1.2 (2)
N1—C4—C5—C6	−176.08 (12)	C9—C10—C11—C12	−0.6 (2)
C4—C5—C6—C1	0.1 (2)	C10—C11—C12—C13	−0.8 (2)
C4—C5—C6—N2	178.66 (12)	C11—C12—C13—C8	1.5 (2)
O1—C1—C6—C5	178.83 (12)	C7—C8—C13—C12	−177.54 (13)
C2—C1—C6—C5	−0.7 (2)	C9—C8—C13—C12	−0.8 (2)
O1—C1—C6—N2	0.15 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O4i	0.82	1.72	2.5407 (13)	175
N2—H2B···O4	0.86	1.91	2.5973 (15)	135
N2—H2B···O1	0.86	2.34	2.6532 (14)	102
C2—H2A···O4i	0.93	2.60	3.2233 (18)	125
C13—H13A···O2ii	0.93	2.65	3.5555 (19)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O4i	0.82	1.72	2.5407 (13)	175
N2—H2B⋯O4	0.86	1.91	2.5973 (15)	135
N2—H2B⋯O1	0.86	2.34	2.6532 (14)	102
C2—H2A⋯O4i	0.93	2.60	3.2233 (18)	125
C13—H13A⋯O2ii	0.93	2.65	3.5555 (19)	163

Symmetry codes: (i) ; (ii) .