N-(3,5-Dinitro­benzo­yl)-N′-phenyl­hydrazine: sheets built from N—H⋯O and C—H⋯O hydrogen bonds

Wardell, S.M.S.V.; Souza, M.V.N. de; Wardell, J.L.; Low, J.N.; Glidewell, C.

doi:10.1107/S1600536806020228

organic compounds

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ISSN: 2056-9890

Volume 62| Part 7| July 2006| Pages o2589-o2591

https://doi.org/10.1107/S1600536806020228

N-(3,5-Dinitrobenzoyl)-N′-phenylhydrazine: sheets built from N—H⋯O and C—H⋯O hydrogen bonds

Solange M. S. V. Wardell,^a Marcus V. N. de Souza,^a James L. Wardell,^b John N. Low ^c and Christopher Glidewell ^d ^*

^aInstituto de Tecnologia em Fármacos, Far-Manguinhos, FIOCRUZ, 21041-250 Rio de Janeiro, RJ, Brazil, ^bInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, ^cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 26 May 2006; accepted 29 May 2006; online 9 June 2006)

Molecules of the title compound, C₁₃H₁₀N₄O₅, are linked into sheets by a combination of two N—H⋯O hydrogen bonds and one C—H⋯O hydrogen bond.

Comment

We report here the molecular and supramolecular structure of the title compound, (I) (Fig. 1). The coordination of atom N1 is exactly planar, while that of N2 is markedly pyramidal. The overall molecular conformation is defined by six torsion angles (Table 1), which show that the –C(=O)—NH– portion adopts the usual trans-planar conformation. While the nitrated aryl ring is nearly coplanar with the central amide unit, the torsion angle of nearly 90° around the N—N bond is a reflection of the mutually orthogonal orientation of the lone pairs on the two hydrazine N atoms. The molecules thus have no internal symmetry in the solid state and hence are chiral, but the centrosymmetric space group accommodates equal numbers of the two enantiomeric forms.

The molecules of (I) are linked into sheets by a combination of two N—H⋯O hydrogen bonds and one C—H⋯O hydrogen bond (Table 2), and the formation of the sheet is readily analysed in terms of two one-dimensional substructures. Atom N2 in the molecule at (x, y, z) acts as a hydrogen-bond donor to nitro atom O31 in the molecule at (x, y, 1 + z), so generating by translation a C(9) (Bernstein et al., 1995 ) chain running parallel to the [001] direction (Fig. 2). Atoms N1 and C2 in the molecule at (x, y, z) both act as hydrogen-bond donors to carbonyl atom O7 in the molecule at (− $[{1\over 2}]$ + x, $[3\over2]$ − y, − $[{1\over 2}]$ + z), so forming a C(4)C(5)[R₂¹(7)] chain of rings along [101] and generated by the n-glide plane at y = $[3\over4]$ (Fig. 3). The combination of the [001] and [101] chains then generates a sheet parallel to (010) (Fig. 4). Two such sheets, generated by the n-glide planes at y = $[1\over4]$ and y = $[3\over4]$ , pass through each unit cell, but there are no direction-specific interactions between adjacent sheets.

Figure 1
The molecular structure of (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
Part of the crystal structure of (I)

, showing the formation of a C(9) chain parallel to [001]. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, y, 1 + z) and (x, y, −1 + z), respectively.

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

, showing the formation of a C(4)C(5)[R₂¹(7)] chain of rings parallel to [101]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Figure 4
A stereoview of part of the crystal structure of (I)

, showing the formation of a hydrogen-bonded (010) sheet. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Experimental

A mixture of equimolar quantities (10 mmol of each component) of 3,5-dinitrobenzoyl chloride and phenylhydrazine in tetrahydrofuran (20 ml) was heated under reflux for 24 h in a dinitrogen atmosphere. The reaction mixture was cooled, and the solvent was removed under reduced pressure. The solid product was washed successively with cold ethanol and diethyl ether, and then recrystallized from ethanol (m.p. 473–475 K; GC/MS m/z 302 [M]⁺. IR (KBr disk, χm⁻¹) 3330 and 3280 (NH), 1648 (CO), 1540 and 1344 (NO₂).

Crystal data

C₁₃H₁₀N₄O₅
M_r = 302.25
Monoclinic, P 2₁ /n
a = 7.5696 (3) Å
b = 22.176 (2) Å
c = 8.4099 (4) Å
β = 110.802 (3)°
V = 1319.69 (15) Å³
Z = 4
D_x = 1.521 Mg m⁻³
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 120 (2) K
Lath, yellow
0.44 × 0.08 × 0.02 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.961, T_max = 0.997
14875 measured reflections
3022 independent reflections
1961 reflections with I > 2σ(I)
R_int = 0.067
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.144
S = 1.05
3022 reflections
199 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0578P)² + 0.6665P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Selected torsion angles (°)

C1—C7—N1—N2	174.32 (18)
C7—N1—N2—C21	84.2 (2)
N1—N2—C21—C22	50.8 (3)
N1—C7—C1—C2	19.8 (3)
C2—C3—N3—O31	7.0 (3)
C4—C5—N5—O51	−13.6 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O7ⁱ	0.88	1.97	2.806 (2)	157
N2—H2A⋯O31ⁱⁱ	0.88	2.16	3.020 (3)	165
C2—H2⋯O7ⁱ	0.95	2.47	3.355 (3)	155
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y, z+1.

All H atoms were located in difference maps and then treated as riding atoms with distances C—H = 0.95 Å and N—H = 0.88 Å, and with U_iso(H) = 1.2U_eq(C,N).

Data collection: COLLECT (Hooft, 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: https://doi.org/10.1107/S1600536806020228/lh2091sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806020228/lh2091Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 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).

N-(3,5-Dinitrobenzoyl)-N'-phenylhydrazine top

Crystal data top

C₁₃H₁₀N₄O₅	F(000) = 624
M_r = 302.25	D_x = 1.521 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3022 reflections
a = 7.5696 (3) Å	θ = 3.0–27.5°
b = 22.176 (2) Å	µ = 0.12 mm⁻¹
c = 8.4099 (4) Å	T = 120 K
β = 110.802 (3)°	Lath, yellow
V = 1319.69 (15) Å³	0.44 × 0.08 × 0.02 mm
Z = 4

Data collection top

Bruker–Nonius KappaCCD diffractometer	3022 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1961 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −28→28
T_min = 0.961, T_max = 0.997	l = −10→10
14875 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) = 0.144	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0578P)² + 0.6665P] where P = (F_o² + 2F_c²)/3
3022 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Special details top

Experimental. NMR (DMSO-d₆): δ(H) 11.08 (1H, s, NH), 9.12 (2H, d, J = 2.0 Hz), 9.01 (1H, d, 2.0), 7.18 (2H, dd, J = 7.5 and 8.0 Hz), 6.84 (2H, d, J = 7.5 Hz), 6.76 (1H, dd, J = 7.0 and 7.5 Hz); δ(C) 162.3, 148.7, 148.2, 135.4, 128.7, 127.6, 121.1, 119.0, 112.4.

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

	x	y	z	U_iso*/U_eq
C1	0.3507 (3)	0.66944 (9)	0.3671 (3)	0.0219 (5)
C2	0.2617 (3)	0.68260 (10)	0.1953 (3)	0.0238 (5)
C3	0.2731 (3)	0.64172 (10)	0.0765 (3)	0.0246 (5)
N3	0.1766 (3)	0.65608 (9)	−0.1038 (2)	0.0343 (5)
O31	0.1060 (3)	0.70687 (8)	−0.1391 (2)	0.0398 (5)
O32	0.1661 (3)	0.61737 (9)	−0.2088 (2)	0.0568 (6)
C4	0.3710 (3)	0.58807 (10)	0.1178 (3)	0.0257 (5)
C5	0.4630 (3)	0.57717 (9)	0.2893 (3)	0.0231 (5)
N5	0.5719 (3)	0.52110 (8)	0.3400 (2)	0.0277 (5)
O51	0.5481 (2)	0.48150 (7)	0.2329 (2)	0.0390 (5)
O52	0.6815 (2)	0.51683 (7)	0.4883 (2)	0.0332 (4)
C6	0.4550 (3)	0.61626 (9)	0.4147 (3)	0.0236 (5)
C7	0.3390 (3)	0.70940 (10)	0.5064 (3)	0.0234 (5)
O7	0.4536 (2)	0.70439 (7)	0.65282 (19)	0.0306 (4)
N1	0.1957 (3)	0.74860 (8)	0.4635 (2)	0.0244 (4)
N2	0.1620 (3)	0.78444 (8)	0.5875 (2)	0.0271 (5)
C21	0.2694 (3)	0.83829 (10)	0.6312 (3)	0.0242 (5)
C22	0.2748 (3)	0.87735 (10)	0.5041 (3)	0.0283 (5)
C23	0.3666 (3)	0.93227 (11)	0.5482 (3)	0.0321 (6)
C24	0.4539 (3)	0.94840 (11)	0.7171 (3)	0.0344 (6)
C25	0.4493 (3)	0.90925 (11)	0.8429 (3)	0.0334 (6)
C26	0.3579 (3)	0.85433 (11)	0.8015 (3)	0.0288 (5)
H2	0.1942	0.7193	0.1607	0.029*
H4	0.3750	0.5602	0.0332	0.031*
H6	0.5195	0.6071	0.5314	0.028*
H1	0.1121	0.7528	0.3601	0.029*
H2A	0.1693	0.7622	0.6762	0.033*
H22	0.2160	0.8665	0.3878	0.034*
H23	0.3697	0.9592	0.4613	0.039*
H24	0.5164	0.9862	0.7461	0.041*
H25	0.5096	0.9201	0.9590	0.040*
H26	0.3553	0.8276	0.8889	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0203 (11)	0.0199 (11)	0.0258 (11)	−0.0031 (9)	0.0085 (9)	0.0011 (9)
C2	0.0211 (11)	0.0218 (11)	0.0269 (12)	−0.0009 (9)	0.0066 (9)	0.0035 (9)
C3	0.0260 (12)	0.0259 (12)	0.0237 (11)	−0.0033 (9)	0.0112 (10)	0.0020 (9)
N3	0.0436 (13)	0.0337 (12)	0.0276 (11)	0.0061 (10)	0.0152 (9)	0.0031 (9)
O31	0.0574 (12)	0.0348 (10)	0.0305 (9)	0.0131 (9)	0.0196 (9)	0.0109 (8)
O32	0.0876 (16)	0.0517 (12)	0.0266 (10)	0.0251 (11)	0.0146 (10)	−0.0054 (9)
C4	0.0278 (12)	0.0237 (12)	0.0277 (12)	−0.0037 (9)	0.0125 (10)	−0.0018 (9)
C5	0.0194 (11)	0.0180 (10)	0.0335 (12)	−0.0012 (9)	0.0113 (9)	0.0033 (9)
N5	0.0264 (10)	0.0252 (10)	0.0333 (11)	0.0009 (8)	0.0128 (9)	0.0038 (9)
O51	0.0480 (11)	0.0246 (9)	0.0440 (10)	0.0065 (8)	0.0157 (9)	−0.0047 (8)
O52	0.0293 (9)	0.0328 (9)	0.0352 (9)	0.0046 (7)	0.0087 (8)	0.0087 (8)
C6	0.0211 (11)	0.0234 (11)	0.0247 (11)	−0.0047 (9)	0.0061 (9)	0.0007 (9)
C7	0.0242 (12)	0.0209 (11)	0.0220 (11)	−0.0033 (9)	0.0044 (9)	0.0001 (9)
O7	0.0319 (9)	0.0277 (9)	0.0251 (9)	0.0014 (7)	0.0014 (7)	−0.0022 (7)
N1	0.0257 (10)	0.0241 (9)	0.0210 (9)	0.0017 (8)	0.0052 (8)	−0.0012 (8)
N2	0.0339 (11)	0.0252 (10)	0.0239 (10)	0.0021 (8)	0.0123 (9)	0.0003 (8)
C21	0.0227 (12)	0.0241 (11)	0.0245 (11)	0.0066 (9)	0.0069 (9)	−0.0006 (9)
C22	0.0335 (13)	0.0262 (12)	0.0224 (11)	0.0014 (10)	0.0066 (10)	−0.0021 (10)
C23	0.0300 (13)	0.0265 (12)	0.0374 (14)	0.0020 (10)	0.0088 (11)	0.0015 (11)
C24	0.0269 (13)	0.0292 (13)	0.0427 (15)	0.0025 (10)	0.0070 (11)	−0.0102 (12)
C25	0.0245 (13)	0.0402 (14)	0.0299 (13)	0.0073 (11)	0.0028 (10)	−0.0131 (11)
C26	0.0241 (12)	0.0351 (13)	0.0258 (12)	0.0106 (10)	0.0072 (10)	0.0007 (10)

Geometric parameters (Å, º) top

C1—C2	1.391 (3)	C7—N1	1.336 (3)
C1—C6	1.396 (3)	N1—N2	1.405 (2)
C1—C7	1.496 (3)	N1—H1	0.88
C2—C3	1.374 (3)	N2—C21	1.418 (3)
C2—H2	0.95	N2—H2A	0.88
C3—C4	1.379 (3)	C21—C22	1.388 (3)
C3—N3	1.465 (3)	C21—C26	1.395 (3)
N3—O32	1.214 (3)	C22—C23	1.386 (3)
N3—O31	1.237 (2)	C22—H22	0.95
C4—C5	1.382 (3)	C23—C24	1.385 (3)
C4—H4	0.95	C23—H23	0.95
C5—C6	1.383 (3)	C24—C25	1.378 (3)
C5—N5	1.469 (3)	C24—H24	0.95
N5—O51	1.225 (2)	C25—C26	1.383 (3)
N5—O52	1.232 (2)	C25—H25	0.95
C6—H6	0.95	C26—H26	0.95
C7—O7	1.234 (2)

C2—C1—C6	119.4 (2)	N1—C7—C1	116.21 (18)
C2—C1—C7	123.19 (19)	C7—N1—N2	120.76 (18)
C6—C1—C7	117.43 (19)	C7—N1—H1	124.5
C3—C2—C1	119.0 (2)	N2—N1—H1	114.7
C3—C2—H2	120.5	N1—N2—C21	115.50 (18)
C1—C2—H2	120.5	N1—N2—H2A	109.8
C2—C3—C4	123.6 (2)	C21—N2—H2A	113.3
C2—C3—N3	118.16 (19)	C22—C21—C26	119.8 (2)
C4—C3—N3	118.3 (2)	C22—C21—N2	119.80 (19)
O32—N3—O31	123.9 (2)	C26—C21—N2	120.2 (2)
O32—N3—C3	118.6 (2)	C23—C22—C21	119.4 (2)
O31—N3—C3	117.42 (19)	C23—C22—H22	120.3
C3—C4—C5	116.1 (2)	C21—C22—H22	120.3
C3—C4—H4	122.0	C24—C23—C22	120.9 (2)
C5—C4—H4	122.0	C24—C23—H23	119.6
C4—C5—C6	123.0 (2)	C22—C23—H23	119.6
C4—C5—N5	118.3 (2)	C25—C24—C23	119.5 (2)
C6—C5—N5	118.74 (19)	C25—C24—H24	120.3
O51—N5—O52	124.02 (19)	C23—C24—H24	120.3
O51—N5—C5	118.21 (18)	C24—C25—C26	120.5 (2)
O52—N5—C5	117.78 (18)	C24—C25—H25	119.7
C5—C6—C1	119.0 (2)	C26—C25—H25	119.7
C5—C6—H6	120.5	C25—C26—C21	119.9 (2)
C1—C6—H6	120.5	C25—C26—H26	120.1
O7—C7—N1	123.0 (2)	C21—C26—H26	120.1
O7—C7—C1	120.8 (2)

C1—C7—N1—N2	174.32 (18)	C6—C5—N5—O52	−14.4 (3)
C7—N1—N2—C21	84.2 (2)	C4—C5—C6—C1	−0.4 (3)
N1—N2—C21—C22	50.8 (3)	N5—C5—C6—C1	−179.55 (18)
N1—C7—C1—C2	19.8 (3)	C2—C1—C6—C5	−1.7 (3)
C6—C1—C2—C3	2.4 (3)	C7—C1—C6—C5	177.64 (19)
C7—C1—C2—C3	−176.9 (2)	C2—C1—C7—O7	−162.2 (2)
C1—C2—C3—C4	−1.0 (3)	C6—C1—C7—O7	18.4 (3)
C1—C2—C3—N3	179.3 (2)	C6—C1—C7—N1	−159.5 (2)
C2—C3—N3—O32	−171.1 (2)	O7—C7—N1—N2	−3.6 (3)
C4—C3—N3—O32	9.1 (3)	N1—N2—C21—C26	−134.1 (2)
C2—C3—N3—O31	7.0 (3)	C26—C21—C22—C23	−0.7 (3)
C4—C3—N3—O31	−172.8 (2)	N2—C21—C22—C23	174.5 (2)
C2—C3—C4—C5	−1.1 (3)	C21—C22—C23—C24	0.4 (4)
N3—C3—C4—C5	178.66 (19)	C22—C23—C24—C25	0.1 (4)
C3—C4—C5—C6	1.8 (3)	C23—C24—C25—C26	−0.3 (4)
C3—C4—C5—N5	−179.08 (19)	C24—C25—C26—C21	0.0 (3)
C4—C5—N5—O51	−13.6 (3)	C22—C21—C26—C25	0.5 (3)
C6—C5—N5—O51	165.6 (2)	N2—C21—C26—C25	−174.7 (2)
C4—C5—N5—O52	166.47 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O7ⁱ	0.88	1.97	2.806 (2)	157
N2—H2A···O31ⁱⁱ	0.88	2.16	3.020 (3)	165
C2—H2···O7ⁱ	0.95	2.47	3.355 (3)	155

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x, y, z+1.

Acknowledgements

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

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