N-Cyclo-heptyl-idene-N'-(2,4-dinitro-phenyl)hydrazine.

The title compound, C(13)H(16)N(4)O(4), is a new hydrazone. An intra-molecular N-H⋯O hydrogen bond generates a six-membered ring, producing an S(6) ring motif. The nitro groups in the ortho and para positions are almost coplanar with the benzene ring to which they are bound, making dihedral angles of 0.60 (11) and 3.18 (11)°, respectively. Pairs of inter-molecular C-H⋯O hydrogen bonds link neighbouring mol-ecules into inversion dimers with R(2) (2)(10) motifs. The crystal structure is further stabilized by inter-molecular π-π inter-actions, with a benzene centroid-to-centroid distance of 3.6601 (4) Å.

Related literature

For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related literature on the applications of hydrazone, see, for example: Niknam et al., (2005 ▶); Guillaumont & Nakamura (2000 ▶); Raj & Kurup (2006 ▶); Okabe et al. (1993 ▶).

Experimental

Crystal data

C13H16N4O4

M = 292.30

Monoclinic,

a = 6.9721 (1) Å

b = 23.7359 (5) Å

c = 8.2274 (2) Å

β = 102.351 (1)°

V = 1330.03 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100.0 (1) K

0.51 × 0.45 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.946, T max = 0.991

26146 measured reflections

5824 independent reflections

4916 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.113

S = 1.04

5824 reflections

194 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809002657/kj2114sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809002657/kj2114Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H16N4O4	F(000) = 616
Mr = 292.30	Dx = 1.460 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9967 reflections
a = 6.9721 (1) Å	θ = 2.7–40.2°
b = 23.7359 (5) Å	µ = 0.11 mm−1
c = 8.2274 (2) Å	T = 100 K
β = 102.351 (1)°	Plate, yellow
V = 1330.03 (5) Å3	0.51 × 0.45 × 0.08 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	5824 independent reflections
Radiation source: fine-focus sealed tube	4916 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 35.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→11
Tmin = 0.946, Tmax = 0.991	k = −38→38
26146 measured reflections	l = −12→13

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0637P)2 + 0.2167P] where P = (Fo2 + 2Fc2)/3
5824 reflections	(Δ/σ)max < 0.001
194 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Experimental. The low-temperature data was collected with the Oxford Cryosystem Cobra low-temperature attachment.

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.

	x	y	z	Uiso*/Ueq
O1	0.71910 (9)	−0.13041 (2)	0.17783 (8)	0.02285 (12)
O2	0.81378 (8)	−0.04726 (2)	0.11828 (8)	0.02030 (12)
O3	0.01157 (8)	−0.08982 (3)	0.49098 (7)	0.02059 (12)
O4	0.17434 (9)	−0.16037 (2)	0.41905 (8)	0.02340 (13)
N1	0.62623 (9)	0.04321 (3)	0.18111 (8)	0.01434 (11)
N2	0.58494 (9)	0.10007 (2)	0.19219 (8)	0.01495 (11)
N3	0.70085 (9)	−0.07900 (3)	0.17430 (8)	0.01533 (11)
N4	0.14350 (9)	−0.10960 (3)	0.42854 (8)	0.01614 (12)
C1	0.34898 (10)	0.02454 (3)	0.30373 (9)	0.01400 (12)
H1A	0.3228	0.0638	0.3054	0.017*
C2	0.23044 (10)	−0.01240 (3)	0.36477 (9)	0.01428 (12)
H2A	0.1231	0.0012	0.4077	0.017*
C3	0.26847 (10)	−0.07040 (3)	0.36355 (8)	0.01365 (12)
C4	0.42249 (10)	−0.09135 (3)	0.30138 (8)	0.01385 (12)
H4A	0.4470	−0.1307	0.3017	0.017*
C5	0.54189 (9)	−0.05386 (3)	0.23798 (8)	0.01284 (11)
C6	0.51047 (9)	0.00541 (3)	0.23793 (8)	0.01249 (11)
C7	0.71332 (10)	0.13537 (3)	0.16026 (9)	0.01369 (12)
C8	0.90306 (10)	0.11873 (3)	0.11327 (9)	0.01459 (12)
H8A	0.8734	0.1078	−0.0056	0.018*
H8B	0.9549	0.0849	0.1784	0.018*
C9	1.06529 (10)	0.16349 (3)	0.13962 (9)	0.01612 (13)
H9A	1.0778	0.1796	0.2524	0.019*
H9B	1.1911	0.1447	0.1362	0.019*
C10	1.03488 (12)	0.21200 (3)	0.01374 (11)	0.02085 (15)
H10A	1.1629	0.2307	0.0187	0.025*
H10B	0.9920	0.1959	−0.0993	0.025*
C11	0.88606 (11)	0.25661 (3)	0.03869 (10)	0.01808 (13)
H11A	0.9336	0.2747	0.1483	0.022*
H11B	0.8801	0.2860	−0.0475	0.022*
C12	0.67896 (11)	0.23445 (3)	0.03073 (10)	0.01820 (14)
H12A	0.6359	0.2131	−0.0741	0.022*
H12B	0.5890	0.2669	0.0276	0.022*
C13	0.66109 (11)	0.19625 (3)	0.17764 (10)	0.01816 (13)
H13A	0.7471	0.2115	0.2797	0.022*
H13B	0.5242	0.1982	0.1930	0.022*
H1N1	0.727 (2)	0.0296 (6)	0.1432 (17)	0.036 (3)*

	U11	U22	U33	U12	U13	U23
O1	0.0256 (3)	0.0139 (2)	0.0313 (3)	0.0047 (2)	0.0112 (2)	−0.0015 (2)
O2	0.0173 (2)	0.0201 (2)	0.0264 (3)	−0.00068 (19)	0.0112 (2)	−0.0007 (2)
O3	0.0189 (2)	0.0239 (3)	0.0216 (3)	−0.0013 (2)	0.0100 (2)	0.0012 (2)
O4	0.0262 (3)	0.0139 (2)	0.0317 (3)	−0.0030 (2)	0.0096 (2)	0.0025 (2)
N1	0.0135 (2)	0.0119 (2)	0.0186 (3)	−0.00005 (18)	0.00577 (19)	0.00008 (19)
N2	0.0142 (2)	0.0117 (2)	0.0198 (3)	0.00064 (18)	0.0055 (2)	0.0012 (2)
N3	0.0145 (2)	0.0153 (3)	0.0166 (3)	0.00157 (19)	0.00412 (19)	−0.0017 (2)
N4	0.0161 (3)	0.0163 (3)	0.0162 (3)	−0.0022 (2)	0.0037 (2)	0.0015 (2)
C1	0.0132 (3)	0.0127 (3)	0.0166 (3)	0.0010 (2)	0.0045 (2)	0.0005 (2)
C2	0.0133 (3)	0.0144 (3)	0.0158 (3)	0.0007 (2)	0.0045 (2)	0.0008 (2)
C3	0.0139 (3)	0.0132 (3)	0.0141 (3)	−0.0011 (2)	0.0036 (2)	0.0009 (2)
C4	0.0145 (3)	0.0128 (3)	0.0140 (3)	−0.0004 (2)	0.0025 (2)	−0.0003 (2)
C5	0.0122 (3)	0.0128 (3)	0.0138 (3)	0.0008 (2)	0.0036 (2)	−0.0014 (2)
C6	0.0119 (3)	0.0127 (3)	0.0127 (3)	−0.00011 (19)	0.00235 (19)	0.0000 (2)
C7	0.0131 (3)	0.0125 (3)	0.0160 (3)	0.0006 (2)	0.0043 (2)	0.0009 (2)
C8	0.0133 (3)	0.0130 (3)	0.0184 (3)	0.0002 (2)	0.0054 (2)	−0.0004 (2)
C9	0.0125 (3)	0.0149 (3)	0.0210 (3)	−0.0004 (2)	0.0037 (2)	0.0026 (2)
C10	0.0200 (3)	0.0173 (3)	0.0284 (4)	0.0029 (2)	0.0121 (3)	0.0069 (3)
C11	0.0199 (3)	0.0137 (3)	0.0218 (3)	0.0009 (2)	0.0071 (2)	0.0032 (2)
C12	0.0170 (3)	0.0142 (3)	0.0233 (3)	0.0029 (2)	0.0040 (2)	0.0029 (2)
C13	0.0191 (3)	0.0128 (3)	0.0256 (3)	0.0016 (2)	0.0115 (3)	0.0003 (2)

O1—N3	1.2265 (8)	C7—C13	1.5044 (10)
O2—N3	1.2471 (8)	C7—C8	1.5080 (10)
O3—N4	1.2380 (9)	C8—C9	1.5330 (10)
O4—N4	1.2296 (8)	C8—H8A	0.9900
N1—C6	1.3551 (9)	C8—H8B	0.9900
N1—N2	1.3871 (8)	C9—C10	1.5328 (10)
N1—H1N1	0.887 (14)	C9—H9A	0.9900
N2—C7	1.2934 (9)	C9—H9B	0.9900
N3—C5	1.4517 (9)	C10—C11	1.5269 (11)
N4—C3	1.4525 (9)	C10—H10A	0.9900
C1—C2	1.3717 (10)	C10—H10B	0.9900
C1—C6	1.4241 (10)	C11—C12	1.5249 (11)
C1—H1A	0.9500	C11—H11A	0.9900
C2—C3	1.4026 (10)	C11—H11B	0.9900
C2—H2A	0.9500	C12—C13	1.5373 (11)
C3—C4	1.3772 (10)	C12—H12A	0.9900
C4—C5	1.3938 (10)	C12—H12B	0.9900
C4—H4A	0.9500	C13—H13A	0.9900
C5—C6	1.4237 (9)	C13—H13B	0.9900
C6—N1—N2	118.31 (6)	C7—C8—H8B	108.2
C6—N1—H1N1	117.1 (9)	C9—C8—H8B	108.2
N2—N1—H1N1	124.6 (9)	H8A—C8—H8B	107.4
C7—N2—N1	117.04 (6)	C10—C9—C8	115.71 (6)
O1—N3—O2	122.64 (6)	C10—C9—H9A	108.4
O1—N3—C5	118.93 (6)	C8—C9—H9A	108.4
O2—N3—C5	118.43 (6)	C10—C9—H9B	108.4
O4—N4—O3	123.61 (7)	C8—C9—H9B	108.4
O4—N4—C3	118.53 (6)	H9A—C9—H9B	107.4
O3—N4—C3	117.86 (6)	C11—C10—C9	115.46 (6)
C2—C1—C6	121.51 (6)	C11—C10—H10A	108.4
C2—C1—H1A	119.2	C9—C10—H10A	108.4
C6—C1—H1A	119.2	C11—C10—H10B	108.4
C1—C2—C3	119.69 (6)	C9—C10—H10B	108.4
C1—C2—H2A	120.2	H10A—C10—H10B	107.5
C3—C2—H2A	120.2	C12—C11—C10	114.80 (6)
C4—C3—C2	121.37 (6)	C12—C11—H11A	108.6
C4—C3—N4	118.83 (6)	C10—C11—H11A	108.6
C2—C3—N4	119.79 (6)	C12—C11—H11B	108.6
C3—C4—C5	118.95 (6)	C10—C11—H11B	108.6
C3—C4—H4A	120.5	H11A—C11—H11B	107.5
C5—C4—H4A	120.5	C11—C12—C13	113.89 (6)
C4—C5—C6	121.79 (6)	C11—C12—H12A	108.8
C4—C5—N3	115.84 (6)	C13—C12—H12A	108.8
C6—C5—N3	122.37 (6)	C11—C12—H12B	108.8
N1—C6—C5	123.46 (6)	C13—C12—H12B	108.8
N1—C6—C1	119.84 (6)	H12A—C12—H12B	107.7
C5—C6—C1	116.69 (6)	C7—C13—C12	115.46 (6)
N2—C7—C13	114.26 (6)	C7—C13—H13A	108.4
N2—C7—C8	124.44 (6)	C12—C13—H13A	108.4
C13—C7—C8	121.29 (6)	C7—C13—H13B	108.4
C7—C8—C9	116.32 (6)	C12—C13—H13B	108.4
C7—C8—H8A	108.2	H13A—C13—H13B	107.5
C9—C8—H8A	108.2
C6—N1—N2—C7	170.12 (6)	C4—C5—C6—N1	178.35 (6)
C6—C1—C2—C3	0.28 (10)	N3—C5—C6—N1	−0.87 (10)
C1—C2—C3—C4	−0.32 (10)	C4—C5—C6—C1	−0.89 (9)
C1—C2—C3—N4	179.83 (6)	N3—C5—C6—C1	179.89 (6)
O4—N4—C3—C4	−3.17 (10)	C2—C1—C6—N1	−178.97 (6)
O3—N4—C3—C4	176.68 (6)	C2—C1—C6—C5	0.30 (10)
O4—N4—C3—C2	176.69 (7)	N1—N2—C7—C13	−178.94 (6)
O3—N4—C3—C2	−3.46 (10)	N1—N2—C7—C8	−0.34 (10)
C2—C3—C4—C5	−0.26 (10)	N2—C7—C8—C9	−159.23 (7)
N4—C3—C4—C5	179.60 (6)	C13—C7—C8—C9	19.27 (10)
C3—C4—C5—C6	0.88 (10)	C7—C8—C9—C10	−74.34 (8)
C3—C4—C5—N3	−179.85 (6)	C8—C9—C10—C11	76.57 (9)
O1—N3—C5—C4	0.89 (9)	C9—C10—C11—C12	−59.37 (9)
O2—N3—C5—C4	−179.00 (6)	C10—C11—C12—C13	68.70 (9)
O1—N3—C5—C6	−179.84 (6)	N2—C7—C13—C12	−131.11 (7)
O2—N3—C5—C6	0.26 (10)	C8—C7—C13—C12	50.25 (9)
N2—N1—C6—C5	−177.98 (6)	C11—C12—C13—C7	−84.10 (8)
N2—N1—C6—C1	1.24 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2	0.888 (14)	1.947 (14)	2.6225 (9)	131.7 (12)
C2—H2A···O3i	0.95	2.52	3.3165 (10)	142

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2	0.888 (14)	1.947 (14)	2.6225 (9)	131.7 (12)
C2—H2A⋯O3i	0.95	2.52	3.3165 (10)	142

Symmetry code: (i) .