2,4-Dinitro­phenyl­hydrazine, redetermined at 120 K: a three-dimensional framework built from N—H⋯O, N—H⋯(O)2, N—H⋯π(arene) and C—H⋯O hydrogen bonds

Wardell, J.L.; Low, J.N.; Glidewell, C.

doi:10.1107/S0108270106013114

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 6| June 2006| Pages o318-o320

doi:10.1107/S0108270106013114

2,4-Dinitrophenylhydrazine, redetermined at 120 K: a three-dimensional framework built from N—H⋯O, N—H⋯(O)₂, N—H⋯π(arene) and C—H⋯O hydrogen bonds

James L. Wardell,^a John N. Low ^b and Christopher Glidewell ^c ^*

^aInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 10 April 2006; accepted 11 April 2006; online 16 May 2006)

In the title compound, C₆H₆N₄O₄, the bond distances indicate significant bond fixation, consistent with charge-separated polar forms. The molecules are almost planar and there is an intramolecular N—H⋯O hydrogen bond. The molecules are linked into a complex three-dimensional framework structure by a combination of N—H⋯O, N—H⋯(O)₂, N—H⋯π(arene) and C—H⋯O hydrogen bonds.

Comment

The structure of 2,4-dintrophenylhydrazine, (I), was reported some years ago from diffraction data collected at ambient temperature (Okabe et al., 1993 ). Although only a fairly small data set was available, the H-atom parameters were all refined, giving a data-to-parameter ratio of only 3.85. The bond distances and angles were reported without comment or discussion, and no description or discussion of the supramolecular aggregation was provided beyond a comment that the three-dimensional arrangement of the molecules is held together by hydrogen bonds. We have now taken the opportunity to redetermine this structure using diffraction data collected at 120 K, leading to a data-to-parameter ratio of 14.0, and we report here a full description of the molecular and supramolecular structures.

With the exception of the H atoms bonded to atom N11, the molecule of compound (I) is nearly planar, as shown by the key torsion angles (Table 1). The coordination of N1 is exactly planar, but that at N11 is markedly pyramidal, and the conformation is such that the lone-pair orbitals on atoms N1 and N11 are approximately orthogonal. The bond distances provide evidence for significant bond fixation. For example, the C3—C4 and C5—C6 bonds are both very short compared with the remaining C—C bonds, the exocyclic bonds C4—N4 and, in particular, C2—N2 are shorter than the mean value for bonds of this type (1.468 Å; Allen et al., 1987 ), and all of the N—O bonds are long for their type. Taken together, these observations point to a significant contribution of the charge-separated o-quinonoid form, (Ia), to the overall molecular electronic structure, with a lesser contribution for the p-quinonoid form, (Ib).

Each of the three independent N—H bonds acts as a hydrogen-bond donor, two in three-centre N—H⋯(O)₂ systems and the third in an N—H⋯π(arene) interaction (Table 2). Together with a C—H⋯O hydrogen bond, these interactions link the molecules into a three-dimensional framework of some complexity whose formation is, however, readily analysed in terms of two independent two-dimensional substructures.

In the first substructure, atom N11 in the molecule at (x, y, z) acts a hydrogen-bond donor, via atom H11A, to atoms O21 and O22 in the molecules at (2 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z) and (1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z), respectively, in a planar three-centre N—H⋯(O)₂ system, so forming two independent C(7) (Bernstein et al., 1995 ) chains running parallel to the [010] direction and generated by the 2₁ screw axes along (1, y, $[{1 \over 4}]$ ) and ( $[{1\over 2}]$ , y, $[{1\over 4}]$ ), respectively. The combination of these two chains then generates an (001) sheet. This sheet is reinforced by an N—H⋯π(arene) hydrogen bond, where atom N11 at (x, y, z) acts as donor, via atom H11B, to the aryl ring of the molecule at (1 + x, y, z) (Fig. 2).

The planar atom N1 forms a short intramolecular N—H⋯O contact with the nitro atom O21, and this interaction can be regarded as one component of a second three-centre N—H⋯(O)₂ system. In the second component, atom N1 at (x, y, z) acts as hydrogen-bond donor to atom O42 in the molecule at (1 + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z), so forming a C(8) chain along [20 $[\overline{1}]$ ] generated by the c-glide plane at y = $[{1\over 4}]$ . At the same time, atom C5 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O21 in the molecule at (x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z), so forming a C(7) chain along [001] generated by the same c-glide plane at y = $[{1\over 4}]$ . The combination of these two chains then generates an (010) sheet of R₄⁴(24) rings (Fig. 3). The combination of the (010) and (001) sheets suffices to generate the three-dimensional framework structure.

Figure 1
The molecule of compound (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 2
A stereoview of part of the crystal structure of (I)

, showing the formation of an (001) sheet built from a three-centre N—H⋯(O)₂ hydrogen bond and an N—H⋯π(arene) hydrogen bond. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Figure 3
A stereoview of part of the crystal structure of (I)

, showing the formation of an (010) sheet built from N—H⋯O and C—H⋯O hydrogen bonds. For the sake of clarity, the intramolecular N—H⋯O contact and H atoms not involved in the motifs shown have been omitted.

Experimental

A commercial sample of (I) (Aldrich) was crystallized from ethanol.

Crystal data

C₆H₆N₄O₄
M_r = 198.15
Monoclinic, P 2₁ /c
a = 4.7917 (2) Å
b = 11.5905 (6) Å
c = 14.0496 (5) Å
β = 98.372 (3)°
V = 771.97 (6) Å³
Z = 4
D_x = 1.705 Mg m⁻³
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 120 (2) K
Plate, orange
0.46 × 0.30 × 0.05 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.961, T_max = 0.993
12045 measured reflections
1775 independent reflections
1165 reflections with I > 2σ(I)
R_int = 0.031
θ_max = 27.6°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.143
S = 1.04
1775 reflections
127 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.084P)² + 0.0429P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—C2	1.426 (3)
C2—C3	1.390 (3)
C3—C4	1.374 (3)
C4—C5	1.402 (3)
C5—C6	1.361 (3)
C6—C1	1.425 (3)
C1—N1	1.346 (2)
C2—N2	1.436 (2)
N2—O21	1.241 (2)
N2—O22	1.237 (2)
C4—N4	1.450 (2)
N4—O41	1.228 (2)
N4—O42	1.238 (2)
N1—N11	1.415 (2)

C2—C1—N1—N11	−176.64 (18)
C1—C2—N2—O21	−8.3 (3)
C3—C4—N4—O41	8.9 (3)

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O21	0.88	1.98	2.612 (2)	127
N1—H1⋯O42ⁱ	0.88	2.23	2.961 (2)	140
N11—H11A⋯O21ⁱⁱ	0.96	2.45	2.948 (2)	112
N11—H11A⋯O22ⁱⁱⁱ	0.96	2.15	3.038 (2)	154
N11—H11B⋯Cg1^iv	0.98	2.80	3.509 (2)	129
C5—H5⋯O21^v	0.95	2.48	3.193 (2)	132
Symmetry codes: (i) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, $[y-{\script{1\over 2}}]$ , $[-z+{\script{1\over 2}}]$ ; (iv) x+1, y, z; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

The space group P2₁/c was uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms; the H atoms bonded to C atoms were assigned C—H distances of 0.95 Å, with U_iso(H) = 1.2U_eq(C), while the H atoms bonded to N atoms were allowed to ride at the N—H distances determined from the difference maps (0.88 Å for N1, and 0.96 and 0.98 Å for N11), with U_iso(H) = 1.2U_eq(N).

Data collection: COLLECT (Nonius, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270106013114/sk3017sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106013114/sk3017Isup2.hkl

Comment top

The structure of 2,4-dintrophenylhydrazine, (I), was reported some years ago, from diffraction data collected at ambient temperature (Okabe et al., 1993). Although only a fairly small data set was available, the H-atom parameters were all refined, giving a data-to-parameter ratio of only 3.85. The bond distances and angles were reported without comment or discussion, and no description or discussion of the supramolecular aggregation was provided beyond a comment that the three-dimensional arrangement of the molecules is held together by hydrogen bonds. We have now taken the opportunity to redetermine this structure using diffraction data collected at 120 K, leading to a data-to-parameter ratio of 14.0, and we report here a full description of the molecular and supramolecular structures.

With the exception of the H atoms bonded to atom N11, the molecule of compound (I) is nearly planar, as shown by the key torsion angles (Table 1). The coordination of N1 is exactly planar, but that at N11 is markedly pyramidal, and the conformation is such that the lone-pair orbitals on atoms N1 and N1 are approximately orthogonal. The bond distances provide evidence for significant bond fixation. For example, the C3—C4 and C5—C6 bonds are both very short compared with the remaining C—C bonds, the exocyclic bonds C4—N4 and in particular C2—N2 are shorter than the mean value for bonds of this type (1.468 Å; Allen et al., 1987), and all of the N—O bonds are long for their type. Taken together, these observations point to a significant contribution of the charge-separated o-quinonoid form, (Ia), to the overall molecular electronic structure, with a lesser contribution for the p-quinonoid form, (Ib).

Each of the three independent N—H bonds acts as a hydrogen-bond donor, two in three-centre N—H···(O)₂ systems and the third in an N—H···π(arene) interaction (Table 2). Together with a C—H···O hydrogen bond, these interactions link the molecules into a three-dimensional framework of some complexity whose formation is, however, readily analysed in terms of two independent two-dimensional sub-structures.

In the first sub-structure, atom N11 in the molecule at (x, y, z) acts a hydrogen-bond donor, via atom H11A, to atoms O21 and O22 in the molecules at (2 − x, −1/2 + y, 1/2 − z) and (1 − x, −1/2 + y, 1/2 − z), respectively, in a planar three-centre N—H···(O)₂ system, so forming two independent C(7) (Bernstein et al., 1995) chains running parallel to the [010] direction and generated by the 2₁ screw axes along (1, y, 1/4) and (1/2, y, 1/4), respectively. The combination of these two chains then generates an (001) sheet. This sheet is reinforced by the N—H···π(arene) hydrogen bond, where atom N11 at (x, y, z) acts as donor, via atom H11B, to the aryl ring of the molecule at (1 + x, y, z) (Fig. 2).

The planar atom N1 forms a short intramolecular N—H···O contact with the nitro atom O21, and this interaction can be regarded as one component of a second three-centre N—H···(O)₂ system. In the second component, atom N1 at (x, y, z) acts as hydrogen-bond donor to atom O42 in the molecule at (1 + x, 1/2 − y, −1/2 + z), so forming a C(8) chain along [201] generated by the c-glide plane at y = 1/4. A t the same time, atom C5 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O21 in the molecule at (x, 1/2 − y, 1/2 + z), so forming a C(7) chain along [001] generated by the same c-glide plane at y = 1/4. The combination of these two chains then generates an (010) sheet of R⁴₄(24) rings (Fig. 3). The combination of the (010) and (001) sheets suffices to generate the three-dimensional framework structure.

Experimental top

A commercial sample of (I) (Aldrich) was crystallized from ethanol.

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT); data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecule of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of an (001) sheet built from a three-centre N—H···(O)₂ hydrogen bond and an N—H···π(arene) hydrogen bond. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
	Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of an (010) sheet built from N—H···O and C—H···O hydrogen bonds. For the sake of clarity, the intramolecular N—H···O contact and H atoms not involved in the motifs shown have been omitted.

2,4-Dinitrophenylhydrazine top

Crystal data top

C₆H₆N₄O₄	F(000) = 408
M_r = 198.15	D_x = 1.705 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1775 reflections
a = 4.7917 (2) Å	θ = 2.9–27.6°
b = 11.5905 (6) Å	µ = 0.15 mm⁻¹
c = 14.0496 (5) Å	T = 120 K
β = 98.372 (3)°	Plate, orange
V = 771.97 (6) Å³	0.46 × 0.30 × 0.05 mm
Z = 4

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	1775 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1165 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 2.9°
ϕ and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→15
T_min = 0.961, T_max = 0.993	l = −18→17
12045 measured 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.084P)² + 0.0429P] where P = (F_o² + 2F_c²)/3
1775 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₆H₆N₄O₄	V = 771.97 (6) Å³
M_r = 198.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.7917 (2) Å	µ = 0.15 mm⁻¹
b = 11.5905 (6) Å	T = 120 K
c = 14.0496 (5) Å	0.46 × 0.30 × 0.05 mm
β = 98.372 (3)°

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	1775 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1165 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.993	R_int = 0.031
12045 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.04	Δρ_max = 0.30 e Å⁻³
1775 reflections	Δρ_min = −0.32 e Å⁻³
127 parameters

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

	x	y	z	U_iso*/U_eq
O21	0.7714 (3)	0.38510 (13)	0.26608 (10)	0.0294 (4)
O22	0.4354 (3)	0.48759 (13)	0.31092 (11)	0.0312 (4)
O41	0.0413 (3)	0.39687 (14)	0.59366 (11)	0.0322 (4)
O42	0.2072 (3)	0.25219 (14)	0.68243 (10)	0.0348 (4)
N1	0.8872 (4)	0.18027 (15)	0.33876 (11)	0.0223 (4)
N2	0.5923 (4)	0.40231 (15)	0.32000 (11)	0.0240 (5)
N4	0.1951 (4)	0.31214 (16)	0.60898 (12)	0.0249 (4)
N11	1.0180 (4)	0.07058 (15)	0.34824 (12)	0.0268 (4)
C1	0.7212 (4)	0.21498 (17)	0.40275 (13)	0.0187 (4)
C2	0.5699 (4)	0.32132 (17)	0.39589 (13)	0.0190 (5)
C3	0.3937 (4)	0.35209 (18)	0.46204 (13)	0.0213 (5)
C4	0.3720 (4)	0.27957 (17)	0.53799 (13)	0.0208 (5)
C5	0.5205 (4)	0.17504 (18)	0.54867 (13)	0.0237 (5)
C6	0.6891 (5)	0.14360 (18)	0.48299 (14)	0.0237 (5)
H1	0.9143	0.2259	0.2909	0.027*
H3	0.2900	0.4222	0.4549	0.026*
H5	0.5036	0.1261	0.6018	0.028*
H6	0.7876	0.0723	0.4909	0.028*
H11A	0.9208	0.0275	0.2950	0.032*
H11B	1.2186	0.0905	0.3511	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0172 (10)	0.0211 (11)	0.0176 (9)	−0.0039 (8)	0.0019 (8)	−0.0033 (7)
N1	0.0257 (10)	0.0223 (9)	0.0201 (8)	0.0001 (8)	0.0069 (7)	−0.0004 (7)
N11	0.0268 (10)	0.0270 (10)	0.0267 (9)	0.0036 (8)	0.0044 (7)	−0.0042 (7)
C2	0.0206 (11)	0.0203 (10)	0.0158 (9)	−0.0019 (9)	0.0018 (8)	0.0002 (7)
N2	0.0251 (10)	0.0238 (10)	0.0231 (9)	−0.0041 (8)	0.0031 (8)	0.0000 (7)
O21	0.0355 (9)	0.0293 (9)	0.0265 (8)	−0.0033 (7)	0.0147 (7)	0.0014 (6)
O22	0.0330 (9)	0.0267 (9)	0.0333 (9)	0.0042 (7)	0.0025 (7)	0.0063 (7)
C3	0.0176 (11)	0.0227 (11)	0.0227 (10)	−0.0007 (8)	−0.0002 (8)	−0.0025 (8)
C4	0.0196 (11)	0.0241 (11)	0.0197 (10)	−0.0017 (9)	0.0063 (8)	−0.0035 (8)
N4	0.0220 (10)	0.0307 (10)	0.0228 (9)	−0.0007 (8)	0.0058 (7)	−0.0047 (7)
O41	0.0250 (9)	0.0380 (10)	0.0350 (9)	0.0077 (7)	0.0083 (7)	−0.0059 (7)
O42	0.0382 (10)	0.0446 (10)	0.0250 (8)	0.0038 (8)	0.0159 (7)	0.0036 (7)
C5	0.0286 (12)	0.0237 (11)	0.0194 (10)	−0.0026 (9)	0.0052 (9)	0.0002 (8)
C6	0.0277 (12)	0.0207 (11)	0.0233 (10)	0.0022 (9)	0.0060 (9)	0.0005 (8)

Geometric parameters (Å, º) top

C1—C2	1.426 (3)	C4—N4	1.450 (2)
C2—C3	1.390 (3)	N4—O41	1.228 (2)
C3—C4	1.374 (3)	N4—O42	1.238 (2)
C4—C5	1.402 (3)	N1—N11	1.415 (2)
C5—C6	1.361 (3)	N1—H1	0.88
C6—C1	1.425 (3)	N11—H11A	0.96
C1—N1	1.346 (2)	N11—H11B	0.98
C2—N2	1.436 (2)	C3—H3	0.95
N2—O21	1.241 (2)	C5—H5	0.95
N2—O22	1.237 (2)	C6—H6	0.95

N1—C1—C6	119.84 (18)	C4—C3—C2	118.97 (19)
N1—C1—C2	123.87 (17)	C4—C3—H3	120.5
C6—C1—C2	116.28 (18)	C2—C3—H3	120.5
C1—N1—N11	120.17 (16)	C3—C4—C5	121.13 (18)
C1—N1—H1	119.9	C3—C4—N4	119.53 (18)
N11—N1—H1	119.9	C5—C4—N4	119.33 (17)
N1—N11—H11A	103.6	O41—N4—O42	123.30 (17)
N1—N11—H11B	102.1	O41—N4—C4	118.93 (17)
H11A—N11—H11B	120.9	O42—N4—C4	117.78 (17)
C3—C2—C1	121.93 (18)	C6—C5—C4	120.05 (19)
C3—C2—N2	116.55 (18)	C6—C5—H5	120.0
C1—C2—N2	121.52 (17)	C4—C5—H5	120.0
O22—N2—O21	121.96 (16)	C5—C6—C1	121.61 (19)
O22—N2—C2	119.27 (16)	C5—C6—H6	119.2
O21—N2—C2	118.76 (17)	C1—C6—H6	119.2

C6—C1—N1—N11	3.2 (3)	C2—C3—C4—C5	−1.0 (3)
C2—C1—N1—N11	−176.64 (18)	C2—C3—C4—N4	178.29 (17)
N1—C1—C2—C3	177.92 (18)	C3—C4—N4—O41	8.9 (3)
C6—C1—C2—C3	−2.0 (3)	C5—C4—N4—O41	−171.84 (18)
N1—C1—C2—N2	−2.1 (3)	C3—C4—N4—O42	−171.26 (18)
C6—C1—C2—N2	177.98 (17)	C5—C4—N4—O42	8.0 (3)
C3—C2—N2—O22	−7.6 (3)	C3—C4—C5—C6	−0.3 (3)
C1—C2—N2—O22	172.50 (17)	N4—C4—C5—C6	−179.54 (18)
C3—C2—N2—O21	171.62 (17)	C4—C5—C6—C1	0.4 (3)
C1—C2—N2—O21	−8.3 (3)	N1—C1—C6—C5	−179.21 (19)
C1—C2—C3—C4	2.1 (3)	C2—C1—C6—C5	0.7 (3)
N2—C2—C3—C4	−177.81 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O21	0.88	1.98	2.612 (2)	127
N1—H1···O42ⁱ	0.88	2.23	2.961 (2)	140
N11—H11A···O21ⁱⁱ	0.96	2.45	2.948 (2)	112
N11—H11A···O22ⁱⁱⁱ	0.96	2.15	3.038 (2)	154
N11—H11B···Cg1^iv	0.98	2.80	3.509 (2)	129
C5—H5···O21^v	0.95	2.48	3.193 (2)	132

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

Experimental details

Crystal data
Chemical formula	C₆H₆N₄O₄
M_r	198.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	4.7917 (2), 11.5905 (6), 14.0496 (5)
β (°)	98.372 (3)
V (Å³)	771.97 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.46 × 0.30 × 0.05

Data collection
Diffractometer	Bruker Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.961, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	12045, 1775, 1165
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.143, 1.04
No. of reflections	1775
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.32

Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT), DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top

C1—C2	1.426 (3)	C2—N2	1.436 (2)
C2—C3	1.390 (3)	N2—O21	1.241 (2)
C3—C4	1.374 (3)	N2—O22	1.237 (2)
C4—C5	1.402 (3)	C4—N4	1.450 (2)
C5—C6	1.361 (3)	N4—O41	1.228 (2)
C6—C1	1.425 (3)	N4—O42	1.238 (2)
C1—N1	1.346 (2)	N1—N11	1.415 (2)

C2—C1—N1—N11	−176.64 (18)	C3—C4—N4—O41	8.9 (3)
C1—C2—N2—O21	−8.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O21	0.88	1.98	2.612 (2)	127
N1—H1···O42ⁱ	0.88	2.23	2.961 (2)	140
N11—H11A···O21ⁱⁱ	0.96	2.45	2.948 (2)	112
N11—H11A···O22ⁱⁱⁱ	0.96	2.15	3.038 (2)	154
N11—H11B···Cg1^iv	0.98	2.80	3.509 (2)	129
C5—H5···O21^v	0.95	2.48	3.193 (2)	132

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

Acknowledgements

The X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff of the Service for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678–1680. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 6| June 2006| Pages o318-o320

doi:10.1107/S0108270106013114

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search term		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)