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Volume 69 
Part 3 
Page o425  
March 2013  

Received 25 January 2013
Accepted 15 February 2013
Online 23 February 2013

Key indicators
Single-crystal X-ray study
T = 90 K
Mean [sigma](C-C) = 0.002 Å
R = 0.027
wR = 0.072
Data-to-parameter ratio = 9.5
Details
Open access

A polymorph of 2,4-dinitrophenylhydrazine

aDepartment of Science Education, Graduate School of Education, Hiroshima University, 1-1-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, Japan
Correspondence e-mail: kamimo@hiroshima-u.ac.jp

The crystal structure of a previously unreported polymorph (form II) of 2,4-dinitrophenylhydrazine (DNPH), C6H6N4O4, was determined at 90 K. The first polymorph (form I) is described in the monoclinic space group P21/c [Okabe et al. (1993[Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678-1680.]). Acta Cryst. C49, 1678-1680; Wardell et al. (2006[Wardell, J. L., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o318-o320.]). Acta Cryst. C62, o318-320], whereas form II is in the monoclinic space group Cc. The molecular structures in forms I and II are closely similar, with the nitro groups at the 2- and 4-positions being almost coplanar with the benzene ring [dihedral angles of 3.54 (1) and 3.38 (1)°, respectively in II]. However, their packing arrangements are completely different. Form I exhibits a herringbone packing motif, whereas form II displays a coplanar chain structure. Each chain in form II is connected to adjacent chains by the intermolecular interaction between hydrazine NH2 and 2-nitro groups, forming a sheet normal to (101). The sheet is stabilized by N-H...[pi] interactions.

Related literature

For the use of DNPH for the identification of a carbonyl group, see: Brady & Elsmie (1926[Brady, O. L. & Elsmie, G. V. (1926). Analyst, 51, 77-78.]); Williamson et al. (2006[Williamson, K. L., Minard, R. & Masters, K. M. (2006). Macroscale and Microscale Organic Experiments, 5th ed., ch. 29, pp. 436-450. Boston: Houghton Mifflin.]). For the crystal structure of the first polymorph of DNPH, see: Okabe et al. (1993[Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678-1680.]); Wardell et al. (2006[Wardell, J. L., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o318-o320.]).

[Scheme 1]

Experimental

Crystal data
  • C6H6N4O4

  • Mr = 198.15

  • Monoclinic, C c

  • a = 12.697 (5) Å

  • b = 9.179 (5) Å

  • c = 7.662 (5) Å

  • [beta] = 123.315 (5)°

  • V = 746.2 (7) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 0.15 mm-1

  • T = 90 K

  • 0.3 × 0.2 × 0.15 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • 1878 measured reflections

  • 1433 independent reflections

  • 1424 reflections with I > 2[sigma](I)

  • Rint = 0.019

Refinement
  • R[F2 > 2[sigma](F2)] = 0.027

  • wR(F2) = 0.072

  • S = 1.06

  • 1433 reflections

  • 151 parameters

  • 2 restraints

  • All H-atom parameters refined

  • [Delta][rho]max = 0.25 e Å-3

  • [Delta][rho]min = -0.17 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1-C6 ring.

D-H...A D-H H...A D...A D-H...A
N3-H3N...O4i 0.81 (3) 2.47 (3) 2.919 (3) 116 (2)
N4-H4NA...O1ii 0.90 (3) 2.43 (3) 3.215 (3) 145.1 (17)
N4-H4NA...O3iii 0.90 (3) 2.35 (3) 3.052 (3) 135.0 (15)
N4-H4NB...O4i 1.01 (3) 2.31 (3) 2.981 (3) 123 (2)
N4-H4NB...O2iv 1.01 (3) 2.34 (3) 3.163 (3) 138 (3)
N4-H4NB...Cgv 1.01 (3) 2.91 (4) 3.306 (3) 104 (2)
Symmetry codes: (i) x, y-1, z; (ii) [x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]; (iii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (iv) [x-{\script{1\over 2}}, y-{\script{1\over 2}}, z-1]; (v) [x, -y, z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2 and SAINT, Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2 and SAINT, Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]) and ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DS2226 ).


Acknowledgements

This work was partially supported by a Grant-in-Aid for Young Scientists (B) (23700956) and a Grant-in-Aid for Scientific Research (C) (22300272) from the Japan Society for the Promotion of Science (JSPS). The data collection was performed at the Natural Science Center for Basic Research and Development (N-BARD), Hiroshima University.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.  [CrossRef] [details]
Brady, O. L. & Elsmie, G. V. (1926). Analyst, 51, 77-78.  [CrossRef] [ChemPort]
Bruker (2009). APEX2 and SAINT, Bruker AXS Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.  [ISI] [CrossRef] [ChemPort] [details]
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.  [ISI] [CrossRef] [ChemPort] [details]
Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678-1680.  [CrossRef] [details]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Wardell, J. L., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o318-o320.  [CSD] [CrossRef] [details]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.  [ISI] [CrossRef] [ChemPort] [details]
Williamson, K. L., Minard, R. & Masters, K. M. (2006). Macroscale and Microscale Organic Experiments, 5th ed., ch. 29, pp. 436-450. Boston: Houghton Mifflin.


Acta Cryst (2013). E69, o425  [ doi:10.1107/S1600536813004571 ]

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