(E)-2-[(2-Hydr­oxy-5-nitro­phen­yl)iminiometh­yl]-4-nitro­phenolate

Hijji, Y.M.; Barare, B.; Butcher, R.J.; Jasinski, J.P.

doi:10.1107/S1600536809000543

Volume 65
Part 2
Pages o291-o292
February 2009

Received 23 December 2008
Accepted 6 January 2009
Online 14 January 2009

Key indicators
Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.002 Å
R = 0.041
wR = 0.129
Data-to-parameter ratio = 12.4
Details

(E)-2-[(2-Hydroxy-5-nitrophenyl)iminiomethyl]-4-nitrophenolate

Yousef M. Hijji,^a Belygona Barare,^a Ray J. Butcher ^b ^* and Jerry P. Jasinski ^c

^aDepartment of Chemistry, Morgan State University, Baltimore, MD 21251, USA,^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington DC 20059, USA, and ^cDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
Correspondence e-mail: rbutcher99@yahoo.com

The title molecule, C₁₃H₉N₃O₆, consists of a 2-hydroxy-5-nitrophenyliminio group and a 4-nitrophenolate group bonded to a methylene C atom with both of the planar six-membered rings nearly in the plane of the molecule [dihedral angle = 1.3 (4)°]. Each of the nitro O atoms is twisted slightly out of the plane of the molecule. The amine group forms an intramolecular 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 [pi] -delocalization throughout the entire molecule exists producing a zwitterionic effect in this region of the molecule. 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 intermolecular O-HO hydrogen bonding between the depicted phenolate and hydroxy O atoms and their respective H atoms within the [pi] -delocalized region of the molecule. As a result, molecules 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); Ersanli et al. (2003); Gül et al. (2007); Hijji et al. (2008); Odabasoglu et al. (2006); Jasinski et al. (2007). For related literature, see: Schmidt & Polik (2007).

Experimental

Crystal data

C₁₃H₉N₃O₆
M_r = 303.23
Monoclinic, P 2₁ /c
a = 7.9649 (1) Å
b = 8.6110 (1) Å
c = 19.1190 (3) Å
= 98.433 (2)°
V = 1297.11 (3) Å³
Z = 4
Mo K radiation
= 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 $[Oxford Diffraction (2007). CrysAlisPro and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.954, T_max = 0.978
6432 measured reflections
2495 independent reflections
1819 reflections with I > 2(I)
R_int = 0.023

Refinement

R[F² > 2(F²)] = 0.041
wR(F²) = 0.129
S = 1.05
2495 reflections
202 parameters
H-atom parameters constrained
_max = 0.22 e Å^-3
_min = -0.17 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
O1-H1OO2ⁱ	0.82	1.77	2.5570 (16)	161
O2-H2OO1ⁱⁱ	0.82	1.75	2.5570 (16)	166
N1-H1NO1	0.86	1.90	2.6001 (19)	138
C3-H3AO3ⁱⁱⁱ	0.93	2.56	3.295 (2)	137
C7-H7AO4^iv	0.93	2.67	3.289 (2)	125
C7-H7AO5^v	0.93	2.44	3.312 (2)	156
C10-H10AO4^vi	0.93	2.53	3.321 (2)	143
C13-H13AO4^iv	0.93	2.64	3.195 (2)	119
C13-H13AO5^v	0.93	2.63	3.512 (2)	160
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x, -y+2, -z; (iv) -x+1, -y+1, -z; (v) -x+1, -y, -z; (vi) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlisPro (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlisPro and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); 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.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2463 ).

Acknowledgements

Support to YMH and BB was provided by DOE-CETBR grant No. DE-FG02-03ER63580 and NSF-RISE Award No. HRD-0627276. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

References

Butcher, R. J., Jasinski, J. P., Yathirajan, H. S., Vijesh, A. M. & Narayana, B. (2007). Acta Cryst. E63, o3748.
Ersanli, C. C., Albayrak, Ç., Odabasoglu, M. & Erdönmez, A. (2003). Acta Cryst. C59, o601-o602.
Gül, Z. S., Agar, A. A. & Isik, S. (2007). Acta Cryst. E63, o4564.
Hijji, Y. M., Barare, B., Kennedy, A. P. & Butcher, R. (2008). Sensors and Actuators B: Che., doi:10.1016/j.SnB.2008.11.045.
Jasinski, J. P., Butcher, R. J., Narayana, B., Swamy, M. T. & Yathirajan, H. S. (2007). Acta Cryst. E63, o4566-o4567.
Odabasoglu, M., Albayrak, C. & Büyükgüngör, O. (2006). Acta Cryst. E62, o1094-o1096.
Oxford Diffraction (2007). CrysAlisPro and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.
Schmidt, J. R. & Polik, W. F. (2007). WebMO Pro. WebMO, LLC: Holland, MI, USA; URL: http://www.webmo.net.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.

organic compounds