A polymorph of 2,4-dinitro­phenyl­hydrazine

Amimoto, K.; Nishiguchi, H.

doi:10.1107/S1600536813004571

organic compounds

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doi:10.1107/S1600536813004571

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A polymorph of 2,4-dinitrophenylhydrazine

Kiichi Amimoto ^a ^* and Hiromitsu Nishiguchi ^a

^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

(Received 25 January 2013; accepted 15 February 2013; online 23 February 2013)

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 ). Acta Cryst. C49, 1678–1680; Wardell et al. (2006 ). 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⋯π interactions.

Related literature

For the use of DNPH for the identification of a carbonyl group, see: Brady & Elsmie (1926 ); Williamson et al. (2006 ). For the crystal structure of the first polymorph of DNPH, see: Okabe et al. (1993); Wardell et al. (2006).

Experimental

Crystal data

C₆H₆N₄O₄
M_r = 198.15
Monoclinic, C c
a = 12.697 (5) Å
b = 9.179 (5) Å
c = 7.662 (5) Å
β = 123.315 (5)°
V = 746.2 (7) Å³
Z = 4
Mo Kα radiation
μ = 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 > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.072
S = 1.06
1433 reflections
151 parameters
2 restraints
All H-atom parameters refined
Δρ_max = 0.25 e Å⁻³
Δρ_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⋯O2^iv	1.01 (3)	2.34 (3)	3.163 (3)	138 (3)
N4—H4NB⋯Cg^v	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 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: Mercury (Macrae et al., 2008 ) and ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813004571/ds2226sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813004571/ds2226Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813004571/ds2226Isup3.cml

checkCIF report

Comment top

The nature and reactivity of carbonyl group is one of the most important topics in organic chemistry. 2,4-Dinitrophenylhydrazine (DNPH) is often used as qualitative test for carbonyl groups in the field of chemical education (Brady & Elsmie 1926; Williamson et al., 2006). DNPH also produces the 2,4-dinitrophenylhydrazone derivatives, which offer a variety of functional organic dye crystals. The crystal structure (I) of DNPH at room temperature and 120 K were reported (Okabe et al. 1993; Wardell et al., 2006). In the course of our studies on the development of teaching materials for organic chemistry and novel crystalline materials of organic dyes, we have found the new polymorph (II) of DNPH. The molecular structure in II is almost the same to that in I. The molecular structure in II adapts the planar conformation: the dihedral angles of nitro groups at the 2- and 4-positions to the benzene ring are 3.54 (1)° and 3.38 (1)°, respectively. In both I and II, there is an intermolecular interaction between hydrazine NH₂ and 4-nitro group, forming a chain structure. The distinguished difference between I and II originates their molecular arrangements in the chain structure. In I a benzene ring is inclined at 54.86 ° to the adjacent one, forming a herringbone packing motif. On the other hand, all benzene rings on a chain structure in II lie on the same plane. The interatomic distances in II between hydrazine moiety and 4-nitro group are N(3)—O(4) = 2.919 (3) Å and N(4)—O(4) = 2.981 (3) Å, respectively. Each chain is connected to adjacent ones in the same direction by the additional interaction between hydrazine NH₂ and 2-nitro group, forming a 2-D sheet normal to [1 0 1] plane [N(4)—O(2) = 3.163 (3) Å]. And the 2-D sheets are built up by the offset stacking. The face-to-face stacking of 3.306 (3) Å between centroid of benzene rings and hydrazine N(4) indicates the existence of π–NH₂ interaction between electron-deficient aromatic ring connected to electron-withdrawing nitro group and electron-donating hydrazine moiety.

Related literature top

For the use of DNPH for the identification of a carbonyl group, see: Brady & Elsmie (1926); Williamson et al. (2006). For the crystal structure of the first polymorph of DNPH, see: Okabe et al. (1993); Wardell et al. (2006).

Experimental top

Crystals of title polymorph II were obtained by slow evaporation with commercially available DNPH using 1,4-dioxane as solvent.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title polymorph II, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. The crystal packing of the title polymorph II showing the 2-D sheet arrangement.

2,4-Dinitrophenylhydrazine top

Crystal data top

C₆H₆N₄O₄	F(000) = 408
M_r = 198.15	D_x = 1.764 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: C -2yc	Cell parameters from 1986 reflections
a = 12.697 (5) Å	θ = 2.9–28.8°
b = 9.179 (5) Å	µ = 0.15 mm⁻¹
c = 7.662 (5) Å	T = 90 K
β = 123.315 (5)°	Block, red
V = 746.2 (7) Å³	0.3 × 0.2 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1424 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 28.9°, θ_min = 2.9°
Detector resolution: 8.333 pixels mm^-1	h = −17→10
phi and ω scan	k = −10→11
1878 measured reflections	l = −9→9
1433 independent reflections

Refinement top

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	All H-atom parameters refined
S = 1.06	w = 1/[σ²(F_o²) + (0.0446P)² + 0.1782P] where P = (F_o² + 2F_c²)/3
1433 reflections	(Δ/σ)_max < 0.001
151 parameters	Δρ_max = 0.25 e Å⁻³
2 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₆H₆N₄O₄	V = 746.2 (7) Å³
M_r = 198.15	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 12.697 (5) Å	µ = 0.15 mm⁻¹
b = 9.179 (5) Å	T = 90 K
c = 7.662 (5) Å	0.3 × 0.2 × 0.15 mm
β = 123.315 (5)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1424 reflections with I > 2σ(I)
1878 measured reflections	R_int = 0.019
1433 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	2 restraints
wR(F²) = 0.072	All H-atom parameters refined
S = 1.06	Δρ_max = 0.25 e Å⁻³
1433 reflections	Δρ_min = −0.17 e Å⁻³
151 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.22967 (12)	0.03156 (15)	0.6894 (2)	0.0099 (3)
C2	0.33423 (13)	0.08580 (17)	0.8822 (2)	0.0111 (3)
C3	0.35605 (13)	0.23444 (16)	0.9232 (2)	0.0113 (3)
C4	0.27641 (14)	0.33162 (17)	0.7701 (2)	0.0121 (3)
C5	0.17463 (14)	0.28510 (15)	0.5739 (2)	0.0126 (3)
C6	0.15142 (14)	0.13877 (16)	0.5363 (2)	0.0126 (3)
N1	0.42299 (11)	−0.00982 (14)	1.04810 (18)	0.0107 (2)
N2	0.30055 (12)	0.48633 (14)	0.8159 (2)	0.0127 (3)
N3	0.20280 (12)	−0.11032 (13)	0.6487 (2)	0.0125 (2)
N4	0.09528 (12)	−0.15491 (14)	0.4547 (2)	0.0145 (3)
O1	0.41196 (11)	−0.14375 (11)	1.01911 (17)	0.0148 (2)
O2	0.50714 (11)	0.04357 (13)	1.21641 (18)	0.0167 (2)
O3	0.38720 (12)	0.52367 (12)	0.99101 (19)	0.0191 (3)
O4	0.23265 (12)	0.57352 (12)	0.67622 (19)	0.0212 (3)
H3	0.431 (2)	0.268 (2)	1.060 (3)	0.008 (4)*
H3N	0.252 (3)	−0.162 (3)	0.746 (4)	0.019 (5)*
H5	0.118 (2)	0.350 (2)	0.464 (4)	0.020 (5)*
H4NA	0.033 (2)	−0.171 (2)	0.476 (4)	0.028 (5)*
H4NB	0.116 (3)	−0.253 (3)	0.422 (5)	0.037 (7)*
H6	0.082 (2)	0.110 (3)	0.414 (4)	0.020 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0112 (7)	0.0085 (7)	0.0118 (7)	0.0013 (4)	0.0074 (6)	0.0009 (5)
C2	0.0126 (7)	0.0085 (7)	0.0138 (6)	0.0015 (5)	0.0082 (6)	0.0013 (5)
C3	0.0122 (7)	0.0096 (6)	0.0133 (7)	0.0002 (5)	0.0078 (6)	0.0002 (5)
C4	0.0144 (8)	0.0070 (7)	0.0169 (7)	0.0009 (5)	0.0100 (6)	0.0011 (5)
C5	0.0147 (7)	0.0090 (6)	0.0149 (7)	0.0041 (5)	0.0087 (6)	0.0045 (5)
C6	0.0139 (7)	0.0103 (7)	0.0147 (6)	0.0005 (5)	0.0085 (6)	0.0005 (5)
N1	0.0114 (6)	0.0086 (5)	0.0111 (6)	0.0013 (4)	0.0057 (5)	0.0016 (4)
N2	0.0137 (6)	0.0072 (5)	0.0178 (6)	0.0008 (5)	0.0089 (5)	0.0008 (5)
N3	0.0138 (6)	0.0086 (5)	0.0134 (6)	0.0000 (5)	0.0064 (5)	0.0005 (5)
N4	0.0137 (6)	0.0108 (5)	0.0141 (6)	−0.0013 (4)	0.0047 (5)	−0.0028 (4)
O1	0.0171 (5)	0.0067 (4)	0.0201 (6)	0.0020 (4)	0.0099 (5)	0.0019 (4)
O2	0.0174 (5)	0.0111 (5)	0.0149 (5)	0.0001 (4)	0.0046 (4)	0.0012 (4)
O3	0.0208 (6)	0.0101 (6)	0.0228 (7)	−0.0019 (4)	0.0098 (5)	−0.0013 (4)
O4	0.0255 (7)	0.0078 (5)	0.0233 (7)	0.0026 (4)	0.0089 (6)	0.0033 (4)

Geometric parameters (Å, º) top

C1—N3	1.3389 (18)	C5—H5	0.96 (2)
C1—C2	1.428 (2)	C6—H6	0.90 (2)
C1—C6	1.4320 (19)	N1—O2	1.2374 (17)
C2—C3	1.393 (2)	N1—O1	1.2434 (17)
C2—N1	1.4430 (19)	N2—O3	1.2273 (19)
C3—C4	1.3753 (19)	N2—O4	1.2312 (18)
C3—H3	1.01 (2)	N3—N4	1.4181 (18)
C4—C5	1.407 (2)	N3—H3N	0.81 (3)
C4—N2	1.4545 (18)	N4—H4NA	0.91 (2)
C5—C6	1.371 (2)	N4—H4NB	1.01 (3)

N3—C1—C2	123.59 (13)	C5—C6—C1	121.93 (14)
N3—C1—C6	120.28 (13)	C5—C6—H6	118.7 (15)
C2—C1—C6	116.12 (13)	C1—C6—H6	119.3 (15)
C3—C2—C1	122.10 (13)	O2—N1—O1	121.72 (12)
C3—C2—N1	115.77 (13)	O2—N1—C2	119.11 (13)
C1—C2—N1	122.12 (13)	O1—N1—C2	119.16 (12)
C4—C3—C2	118.74 (14)	O3—N2—O4	123.23 (13)
C4—C3—H3	121.4 (12)	O3—N2—C4	118.69 (11)
C2—C3—H3	119.8 (12)	O4—N2—C4	118.08 (12)
C3—C4—C5	121.90 (14)	C1—N3—N4	120.02 (12)
C3—C4—N2	117.94 (13)	C1—N3—H3N	113.0 (17)
C5—C4—N2	120.16 (12)	N4—N3—H3N	126.9 (17)
C6—C5—C4	119.14 (13)	N3—N4—H4NA	106.8 (15)
C6—C5—H5	117.0 (14)	N3—N4—H4NB	106.4 (17)
C4—C5—H5	123.8 (14)	H4NA—N4—H4NB	106 (2)

Hydrogen-bond geometry (Å, º) top

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···O2^iv	1.01 (3)	2.34 (3)	3.163 (3)	138 (3)
N4—H4NB···Cg^v	1.01 (3)	2.91 (4)	3.306 (3)	104 (2)

Symmetry codes: (i) x, y−1, z; (ii) x−1/2, −y−1/2, z−1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1/2, y−1/2, z−1; (v) x, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₆N₄O₄
M_r	198.15
Crystal system, space group	Monoclinic, Cc
Temperature (K)	90
a, b, c (Å)	12.697 (5), 9.179 (5), 7.662 (5)
β (°)	123.315 (5)
V (Å³)	746.2 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.3 × 0.2 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	1878, 1433, 1424
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.680

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.072, 1.06
No. of reflections	1433
No. of parameters	151
No. of restraints	2
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.17

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008) and ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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···O2^iv	1.01 (3)	2.34 (3)	3.163 (3)	138 (3)
N4—H4NB···Cg^v	1.01 (3)	2.91 (4)	3.306 (3)	104 (2)

Symmetry codes: (i) x, y−1, z; (ii) x−1/2, −y−1/2, z−1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1/2, y−1/2, z−1; (v) x, −y, z+1/2.

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.

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