(E)-2-[(2-Hydr-oxy-5-nitro-phen-yl)iminiometh-yl]-4-nitro-phenolate.

The title mol-ecule, C(13)H(9)N(3)O(6), consists of a 2-hydr-oxy-5-nitro-phenyl-iminio group and a 4-nitro-phenolate group bonded to a methyl-ene C atom with both of the planar six-membered rings nearly in the plane of the mol-ecule [dihedral angle = 1.3 (4)°]. Each of the nitro O atoms is twisted slightly out of the plane of the mol-ecule. The amine group forms an intra-molecular hydrogen bond with both nearby O atoms, each of which has partial occupancy of attached H atoms [0.36 (3) and 0.64 (3)]. An extended π-delocalization throughout the entire mol-ecule exists producing a zwitterionic effect in this region of the mol-ecule. The shortened phenolate C-O bond [1.2749 (19)°], in concert with the slightly longer phenol C-O bond [1.3316 (19) Å], provides evidence for this effect. The crystal packing is influenced by extensive strong inter-molecular O-H⋯O hydrogen bonding between the depicted phenolate and hydr-oxy O atoms and their respective H atoms within the π-delocalized region of the mol-ecule. As a result, mol-ecules are linked into an infinite polymeric chain diagonally along the [110] plane of the unit cell in an alternate inverted pattern. A MOPAC AM1 calculation provides support for these observations.

Related literature

For related structures, see: Butcher et al. (2007 ▶); Ersanlı et al. (2003 ▶); Gül et al. (2007 ▶); Hijji et al. (2008 ▶); Odabaşoğlu et al. (2006 ▶); Jasinski et al. (2007 ▶). For related literature, see: Schmidt & Polik (2007 ▶).

Experimental

Crystal data

C13H9N3O6

M = 303.23

Monoclinic,

a = 7.9649 (1) Å

b = 8.6110 (1) Å

c = 19.1190 (3) Å

β = 98.433 (2)°

V = 1297.11 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 296 (2) K

0.37 × 0.27 × 0.18 mm

Data collection

Oxford Diffraction Gemini R diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T min = 0.954, T max = 0.978

6432 measured reflections

2495 independent reflections

1819 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.129

S = 1.05

2495 reflections

202 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.17 e Å−3

Data collection: CrysAlisPro (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlisPro; data reduction: CrysAlisPro 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/S1600536809000543/hg2463sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000543/hg2463Isup2.hkl

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

C13H9N3O6	F(000) = 624
Mr = 303.23	Dx = 1.553 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3209 reflections
a = 7.9649 (1) Å	θ = 3.9–73.2°
b = 8.6110 (1) Å	µ = 0.13 mm−1
c = 19.1190 (3) Å	T = 296 K
β = 98.433 (2)°	Prism, orange-brown
V = 1297.11 (3) Å3	0.37 × 0.27 × 0.18 mm
Z = 4

Oxford Diffraction Gemini R diffractometer	2495 independent reflections
Radiation source: fine-focus sealed tube	1819 reflections with I > 2σ(I)
graphite	Rint = 0.023
Detector resolution: 10.5081 pixels mm-1	θmax = 26.2°, θmin = 2.6°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −8→10
Tmin = 0.954, Tmax = 0.978	l = −23→23
6432 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0833P)2] where P = (Fo2 + 2Fc2)/3
2495 reflections	(Δ/σ)max < 0.001
202 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.17 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	Occ. (<1)
O1	0.03590 (18)	0.47993 (15)	0.16546 (7)	0.0582 (4)
H1O	0.0038	0.5417	0.1934	0.070*	0.36 (3)
O2	0.11482 (19)	0.12327 (15)	0.24445 (7)	0.0600 (4)
H2O	0.0821	0.0752	0.2769	0.072*	0.64 (3)
O3	0.1437 (2)	0.91245 (18)	−0.08314 (9)	0.0810 (5)
O4	0.32836 (18)	0.73565 (16)	−0.09586 (7)	0.0624 (4)
O5	0.57970 (19)	−0.17153 (18)	0.04796 (7)	0.0688 (4)
O6	0.5900 (2)	−0.35343 (18)	0.12493 (8)	0.0745 (5)
N1	0.22628 (18)	0.25045 (16)	0.13638 (7)	0.0452 (4)
H1N	0.1589	0.2915	0.1624	0.054*
N2	0.2182 (2)	0.79148 (18)	−0.06471 (8)	0.0518 (4)
N3	0.54401 (19)	−0.22526 (18)	0.10334 (8)	0.0515 (4)
C1	0.0787 (2)	0.5537 (2)	0.11302 (9)	0.0448 (4)
C2	0.0151 (2)	0.7055 (2)	0.09352 (10)	0.0496 (4)
H2A	−0.0587	0.7535	0.1202	0.060*
C3	0.0605 (2)	0.7798 (2)	0.03718 (9)	0.0480 (4)
H3A	0.0173	0.8782	0.0253	0.058*
C4	0.1732 (2)	0.70949 (19)	−0.00398 (9)	0.0440 (4)
C5	0.2393 (2)	0.56601 (19)	0.01239 (9)	0.0432 (4)
H5A	0.3139	0.5216	−0.0150	0.052*
C6	0.1948 (2)	0.48596 (18)	0.07028 (8)	0.0413 (4)
C7	0.2629 (2)	0.3352 (2)	0.08516 (9)	0.0451 (4)
H7A	0.3376	0.2956	0.0565	0.054*
C8	0.2832 (2)	0.09769 (19)	0.15516 (8)	0.0423 (4)
C9	0.2213 (2)	0.0350 (2)	0.21425 (8)	0.0468 (4)
C10	0.2737 (3)	−0.1128 (2)	0.23769 (9)	0.0552 (5)
H10A	0.2348	−0.1551	0.2771	0.066*
C11	0.3830 (2)	−0.1967 (2)	0.20269 (9)	0.0521 (5)
H11A	0.4196	−0.2947	0.2187	0.062*
C12	0.4378 (2)	−0.1335 (2)	0.14340 (8)	0.0443 (4)
C13	0.3896 (2)	0.01318 (19)	0.11899 (8)	0.0434 (4)
H13A	0.4281	0.0539	0.0792	0.052*

	U11	U22	U33	U12	U13	U23
O1	0.0756 (9)	0.0495 (7)	0.0590 (8)	0.0052 (7)	0.0411 (7)	0.0022 (6)
O2	0.0794 (9)	0.0546 (8)	0.0554 (8)	0.0097 (7)	0.0411 (7)	0.0059 (6)
O3	0.1039 (12)	0.0618 (9)	0.0839 (11)	0.0172 (9)	0.0357 (9)	0.0286 (8)
O4	0.0727 (9)	0.0637 (8)	0.0571 (8)	−0.0062 (7)	0.0302 (7)	0.0013 (7)
O5	0.0802 (10)	0.0740 (10)	0.0606 (8)	0.0124 (8)	0.0375 (7)	−0.0015 (7)
O6	0.0804 (10)	0.0618 (9)	0.0859 (11)	0.0272 (8)	0.0270 (8)	0.0051 (8)
N1	0.0526 (8)	0.0419 (7)	0.0464 (8)	0.0009 (6)	0.0247 (6)	−0.0008 (6)
N2	0.0598 (9)	0.0486 (9)	0.0496 (8)	−0.0094 (7)	0.0163 (7)	−0.0001 (7)
N3	0.0475 (8)	0.0537 (9)	0.0547 (9)	0.0054 (7)	0.0127 (7)	−0.0049 (7)
C1	0.0481 (9)	0.0434 (9)	0.0467 (9)	−0.0053 (8)	0.0193 (7)	−0.0017 (7)
C2	0.0519 (10)	0.0444 (9)	0.0572 (10)	0.0024 (8)	0.0233 (8)	−0.0053 (8)
C3	0.0513 (10)	0.0380 (9)	0.0566 (10)	0.0011 (7)	0.0146 (8)	−0.0003 (8)
C4	0.0470 (9)	0.0397 (9)	0.0469 (9)	−0.0046 (7)	0.0121 (7)	−0.0017 (7)
C5	0.0442 (9)	0.0413 (9)	0.0473 (9)	−0.0035 (7)	0.0171 (7)	−0.0056 (7)
C6	0.0436 (9)	0.0372 (8)	0.0459 (9)	−0.0030 (7)	0.0159 (7)	−0.0041 (7)
C7	0.0480 (9)	0.0462 (9)	0.0459 (9)	−0.0011 (8)	0.0228 (7)	−0.0025 (7)
C8	0.0490 (9)	0.0393 (8)	0.0407 (8)	−0.0009 (7)	0.0139 (7)	0.0008 (7)
C9	0.0552 (10)	0.0489 (10)	0.0405 (8)	0.0009 (8)	0.0207 (8)	−0.0001 (7)
C10	0.0739 (13)	0.0542 (10)	0.0420 (9)	0.0033 (9)	0.0237 (9)	0.0097 (8)
C11	0.0639 (12)	0.0459 (9)	0.0483 (9)	0.0081 (8)	0.0145 (8)	0.0081 (8)
C12	0.0437 (9)	0.0476 (9)	0.0437 (8)	0.0022 (7)	0.0127 (7)	−0.0030 (7)
C13	0.0475 (9)	0.0447 (9)	0.0411 (8)	−0.0049 (7)	0.0167 (7)	0.0017 (7)

O1—C1	1.2749 (19)	C3—C4	1.414 (2)
O1—H1O	0.8200	C3—H3A	0.9300
O2—C9	1.3316 (19)	C4—C5	1.361 (2)
O2—H2O	0.8200	C5—C6	1.393 (2)
O3—N2	1.225 (2)	C5—H5A	0.9300
O4—N2	1.2283 (19)	C6—C7	1.420 (2)
O5—N3	1.2264 (19)	C7—H7A	0.9300
O6—N3	1.216 (2)	C8—C13	1.378 (2)
N1—C7	1.288 (2)	C8—C9	1.405 (2)
N1—C8	1.420 (2)	C9—C10	1.393 (3)
N1—H1N	0.8600	C10—C11	1.378 (2)
N2—C4	1.448 (2)	C10—H10A	0.9300
N3—C12	1.455 (2)	C11—C12	1.384 (2)
C1—C2	1.431 (2)	C11—H11A	0.9300
C1—C6	1.444 (2)	C12—C13	1.381 (2)
C2—C3	1.347 (2)	C13—H13A	0.9300
C2—H2A	0.9300
C1—O1—H1O	109.5	C6—C5—H5A	120.1
C9—O2—H2O	109.5	C5—C6—C7	118.51 (14)
C7—N1—C8	128.10 (14)	C5—C6—C1	120.56 (15)
C7—N1—H1N	116.0	C7—C6—C1	120.92 (14)
C8—N1—H1N	116.0	N1—C7—C6	123.19 (15)
O3—N2—O4	122.95 (15)	N1—C7—H7A	118.4
O3—N2—C4	118.60 (15)	C6—C7—H7A	118.4
O4—N2—C4	118.45 (15)	C13—C8—C9	121.00 (15)
O6—N3—O5	122.63 (16)	C13—C8—N1	124.02 (14)
O6—N3—C12	118.91 (15)	C9—C8—N1	114.98 (14)
O5—N3—C12	118.43 (15)	O2—C9—C10	124.19 (15)
O1—C1—C2	122.32 (15)	O2—C9—C8	116.76 (15)
O1—C1—C6	120.74 (15)	C10—C9—C8	119.05 (15)
C2—C1—C6	116.94 (14)	C11—C10—C9	120.25 (15)
C3—C2—C1	121.08 (15)	C11—C10—H10A	119.9
C3—C2—H2A	119.5	C9—C10—H10A	119.9
C1—C2—H2A	119.5	C10—C11—C12	119.28 (16)
C2—C3—C4	120.53 (16)	C10—C11—H11A	120.4
C2—C3—H3A	119.7	C12—C11—H11A	120.4
C4—C3—H3A	119.7	C13—C12—C11	122.07 (16)
C5—C4—C3	121.09 (15)	C13—C12—N3	118.20 (14)
C5—C4—N2	119.60 (14)	C11—C12—N3	119.68 (16)
C3—C4—N2	119.31 (15)	C8—C13—C12	118.30 (14)
C4—C5—C6	119.79 (15)	C8—C13—H13A	120.8
C4—C5—H5A	120.1	C12—C13—H13A	120.8
O1—C1—C2—C3	−178.96 (18)	C7—N1—C8—C13	−0.8 (3)
C6—C1—C2—C3	0.9 (3)	C7—N1—C8—C9	179.85 (17)
C1—C2—C3—C4	−0.3 (3)	C13—C8—C9—O2	−177.90 (15)
C2—C3—C4—C5	−0.4 (3)	N1—C8—C9—O2	1.5 (2)
C2—C3—C4—N2	179.32 (16)	C13—C8—C9—C10	2.3 (3)
O3—N2—C4—C5	172.16 (17)	N1—C8—C9—C10	−178.38 (16)
O4—N2—C4—C5	−7.1 (2)	O2—C9—C10—C11	179.31 (18)
O3—N2—C4—C3	−7.6 (3)	C8—C9—C10—C11	−0.9 (3)
O4—N2—C4—C3	173.17 (15)	C9—C10—C11—C12	−1.0 (3)
C3—C4—C5—C6	0.5 (3)	C10—C11—C12—C13	1.6 (3)
N2—C4—C5—C6	−179.26 (15)	C10—C11—C12—N3	−175.91 (16)
C4—C5—C6—C7	178.68 (15)	O6—N3—C12—C13	178.63 (16)
C4—C5—C6—C1	0.2 (3)	O5—N3—C12—C13	−3.4 (3)
O1—C1—C6—C5	179.03 (16)	O6—N3—C12—C11	−3.7 (3)
C2—C1—C6—C5	−0.8 (2)	O5—N3—C12—C11	174.28 (18)
O1—C1—C6—C7	0.5 (3)	C9—C8—C13—C12	−1.7 (2)
C2—C1—C6—C7	−179.29 (16)	N1—C8—C13—C12	179.01 (16)
C8—N1—C7—C6	178.42 (16)	C11—C12—C13—C8	−0.3 (3)
C5—C6—C7—N1	−178.28 (16)	N3—C12—C13—C8	177.31 (15)
C1—C6—C7—N1	0.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2i	0.82	1.77	2.5570 (16)	161
O2—H2O···O1ii	0.82	1.75	2.5570 (16)	166
N1—H1N···O1	0.86	1.90	2.6001 (19)	138
C3—H3A···O3iii	0.93	2.56	3.295 (2)	137
C7—H7A···O4iv	0.93	2.67	3.289 (2)	125
C7—H7A···O5v	0.93	2.44	3.312 (2)	156
C10—H10A···O4vi	0.93	2.53	3.321 (2)	143
C13—H13A···O4iv	0.93	2.64	3.195 (2)	119
C13—H13A···O5v	0.93	2.63	3.512 (2)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O2i	0.82	1.77	2.5570 (16)	161
O2—H2O⋯O1ii	0.82	1.75	2.5570 (16)	166
N1—H1N⋯O1	0.86	1.90	2.6001 (19)	138
C3—H3A⋯O3iii	0.93	2.56	3.295 (2)	137
C7—H7A⋯O4iv	0.93	2.67	3.289 (2)	125
C7—H7A⋯O5v	0.93	2.44	3.312 (2)	156
C10—H10A⋯O4vi	0.93	2.53	3.321 (2)	143
C13—H13A⋯O4iv	0.93	2.64	3.195 (2)	119
C13—H13A⋯O5v	0.93	2.63	3.512 (2)	160

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .