4-[2-(2,2-Dimethyl-4,6-dioxo-1,3-dioxan-5-yl-idene)hydrazin-1-yl]benzo-nitrile.

In the title compound, C(13)H(11)N(3)O(4), the dioxane ring adopts an envelope conformation with the C atom bonded to the dimethyl group in the flap position [deviation = 0.613 (1) Å]. The nitrile group and the attached benzene ring are roughly coplanar [maximum deviation = 0.087 (1) Å]. An intra-molecular N-H⋯O hydrogen bond involving the hydrazinyl group generates an S(6) ring. The N-N and C-N bond lengths indicate that the compound may be a mixture of the azo and hydrazone tautomeric forms but the presence of the N-bound H atom supports the hydrazone form. The crystal structure is stabilized by weak inter-molecular C-H⋯O, C-H⋯N and C-H⋯π inter-actions.

Related literature

For the applications of related azo compounds, see: Branger et al. (1997 ▶); Buchel et al. (1995 ▶); Gale et al. (1998 ▶); Ikeda & Tsutsumi (1995 ▶); Kang et al. (2000 ▶); Karcı et al. (2004 ▶); Kim et al. (1995 ▶); Kobrakov et al. (2004 ▶); Natansohn et al. (1992 ▶); Rochon et al. (1995 ▶). For related hydrazone structures, see: Çolak et al. (2010 ▶); Pavlovic et al. (2009 ▶); Seferoğlu et al. (2008 ▶); Seferoğlu et al. (2009 ▶); Wojciechowski & Szymezak (2007 ▶).

Experimental

Crystal data

C13H11N3O4

M = 273.25

Monoclinic,

a = 9.7617 (2) Å

b = 11.0023 (2) Å

c = 11.4753 (3) Å

β = 93.796 (1)°

V = 1229.76 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.46 × 0.43 × 0.29 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.950, T max = 0.968

11746 measured reflections

3098 independent reflections

2591 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.108

S = 1.04

3098 reflections

225 parameters

All H-atom parameters refined

Δρmax = 0.38 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAIn class="Chemical">NT program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810024025/ci5104sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024025/ci5104Isup2.hkl

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

C13H11N3O4	F(000) = 568
Mr = 273.25	Dx = 1.476 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4103 reflections
a = 9.7617 (2) Å	θ = 2.6–28.4°
b = 11.0023 (2) Å	µ = 0.11 mm−1
c = 11.4753 (3) Å	T = 100 K
β = 93.796 (1)°	Block, yellow
V = 1229.76 (5) Å3	0.46 × 0.43 × 0.29 mm
Z = 4

Bruker Kappa APEXII CCD area-detector diffractometer	3098 independent reflections
Radiation source: fine-focus sealed tube	2591 reflections with I > 2σ(I)
graphite	Rint = 0.029
φ and ω scans	θmax = 28.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→13
Tmin = 0.950, Tmax = 0.968	k = −14→14
11746 measured reflections	l = −15→8

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	All H-atom parameters refined
S = 1.04	w = 1/[σ2(Fo2) + (0.0626P)2 + 0.2729P] where P = (Fo2 + 2Fc2)/3
3098 reflections	(Δ/σ)max = 0.001
225 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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	0.16363 (8)	0.74524 (7)	0.85585 (7)	0.0172 (2)
O2	0.17892 (8)	0.56739 (7)	0.97179 (7)	0.01470 (19)
O3	0.35656 (9)	0.44276 (8)	0.96914 (7)	0.0187 (2)
O4	0.32521 (9)	0.79574 (8)	0.73794 (8)	0.0249 (2)
N1	0.44403 (10)	0.56888 (9)	0.76510 (9)	0.0165 (2)
N2	0.51381 (10)	0.46953 (9)	0.78943 (9)	0.0159 (2)
H2	0.4942 (16)	0.4243 (15)	0.8538 (15)	0.028 (4)*
N3	1.03756 (11)	0.29578 (10)	0.47015 (10)	0.0232 (2)
C1	0.08704 (11)	0.64589 (10)	0.90176 (10)	0.0143 (2)
C2	0.27845 (12)	0.71950 (11)	0.79881 (10)	0.0172 (2)
C3	0.34022 (12)	0.59901 (10)	0.82608 (10)	0.0155 (2)
C4	0.29477 (11)	0.52812 (10)	0.92521 (10)	0.0144 (2)
C5	0.62374 (11)	0.43844 (10)	0.72180 (10)	0.0148 (2)
C6	0.64458 (13)	0.49922 (11)	0.61746 (10)	0.0173 (2)
H6	0.5852 (15)	0.5636 (14)	0.5904 (13)	0.020 (4)*
C7	0.75216 (13)	0.46401 (11)	0.55177 (10)	0.0175 (2)
H7	0.7668 (15)	0.5059 (14)	0.4788 (13)	0.024 (4)*
C8	0.83788 (12)	0.36875 (11)	0.59035 (10)	0.0155 (2)
C9	0.81720 (12)	0.30898 (11)	0.69557 (10)	0.0161 (2)
H9	0.8752 (14)	0.2457 (14)	0.7224 (12)	0.020 (4)*
C10	0.70992 (12)	0.34407 (11)	0.76131 (10)	0.0159 (2)
H10	0.6926 (14)	0.3023 (14)	0.8350 (13)	0.021 (4)*
C11	0.01442 (13)	0.57371 (11)	0.80405 (10)	0.0178 (2)
H111	0.0795 (15)	0.5338 (14)	0.7556 (13)	0.022 (4)*
H112	−0.0444 (15)	0.5101 (14)	0.8393 (13)	0.023 (4)*
H113	−0.0456 (15)	0.6270 (15)	0.7544 (14)	0.026 (4)*
C12	−0.00717 (13)	0.70098 (11)	0.98606 (10)	0.0169 (2)
H121	0.0494 (16)	0.7364 (15)	1.0534 (13)	0.026 (4)*
H122	−0.0616 (15)	0.7636 (14)	0.9446 (13)	0.021 (4)*
H123	−0.0673 (16)	0.6388 (16)	1.0133 (15)	0.035 (4)*
C13	0.94875 (12)	0.32918 (11)	0.52248 (10)	0.0177 (2)

	U11	U22	U33	U12	U13	U23
O1	0.0168 (4)	0.0111 (4)	0.0244 (4)	0.0003 (3)	0.0057 (3)	0.0024 (3)
O2	0.0132 (4)	0.0139 (4)	0.0169 (4)	0.0027 (3)	0.0012 (3)	0.0015 (3)
O3	0.0164 (4)	0.0178 (4)	0.0220 (4)	0.0033 (3)	0.0011 (3)	0.0027 (3)
O4	0.0244 (5)	0.0191 (5)	0.0321 (5)	0.0004 (4)	0.0096 (4)	0.0083 (4)
N1	0.0144 (5)	0.0146 (5)	0.0204 (5)	−0.0002 (4)	0.0009 (4)	−0.0023 (4)
N2	0.0151 (5)	0.0149 (5)	0.0179 (5)	0.0004 (4)	0.0031 (4)	−0.0005 (4)
N3	0.0227 (6)	0.0233 (6)	0.0244 (5)	0.0003 (4)	0.0076 (4)	0.0001 (4)
C1	0.0135 (5)	0.0111 (5)	0.0182 (5)	0.0005 (4)	0.0010 (4)	0.0024 (4)
C2	0.0152 (6)	0.0159 (6)	0.0208 (5)	−0.0001 (4)	0.0025 (4)	−0.0003 (4)
C3	0.0143 (5)	0.0140 (5)	0.0184 (5)	−0.0005 (4)	0.0017 (4)	−0.0006 (4)
C4	0.0127 (5)	0.0135 (5)	0.0170 (5)	−0.0010 (4)	0.0008 (4)	−0.0027 (4)
C5	0.0119 (5)	0.0143 (5)	0.0182 (5)	−0.0024 (4)	0.0014 (4)	−0.0037 (4)
C6	0.0178 (6)	0.0137 (5)	0.0205 (5)	−0.0001 (4)	0.0014 (4)	0.0001 (4)
C7	0.0196 (6)	0.0155 (5)	0.0178 (5)	−0.0026 (4)	0.0039 (4)	0.0004 (4)
C8	0.0134 (5)	0.0155 (5)	0.0179 (5)	−0.0031 (4)	0.0028 (4)	−0.0022 (4)
C9	0.0137 (5)	0.0160 (5)	0.0185 (5)	0.0003 (4)	0.0001 (4)	−0.0002 (4)
C10	0.0144 (5)	0.0177 (5)	0.0155 (5)	−0.0026 (4)	0.0010 (4)	−0.0004 (4)
C11	0.0174 (6)	0.0170 (6)	0.0188 (5)	0.0019 (5)	−0.0009 (4)	−0.0015 (4)
C12	0.0162 (6)	0.0141 (5)	0.0207 (5)	0.0032 (4)	0.0037 (4)	0.0007 (4)
C13	0.0178 (6)	0.0167 (6)	0.0188 (5)	−0.0029 (4)	0.0024 (4)	0.0006 (4)

O1—C1	1.4435 (13)	C6—C7	1.3878 (16)
O1—C2	1.3645 (13)	C6—H6	0.954 (15)
O2—C1	1.4493 (13)	C7—C8	1.3949 (17)
O2—C4	1.3533 (13)	C7—H7	0.974 (15)
O3—C4	1.2081 (14)	C8—C9	1.4012 (16)
O4—C2	1.2009 (14)	C8—C13	1.4418 (15)
N1—N2	1.3082 (14)	C9—C10	1.3854 (15)
N1—C3	1.3116 (14)	C9—H9	0.936 (15)
N2—C5	1.4075 (14)	C10—H10	0.986 (15)
N2—H2	0.922 (17)	C11—C1	1.5117 (16)
N3—C13	1.1473 (15)	C11—H111	0.976 (15)
C1—C12	1.5055 (15)	C11—H113	0.984 (16)
C2—C3	1.4812 (16)	C11—H112	1.007 (16)
C3—C4	1.4718 (15)	C12—H122	0.975 (15)
C5—C6	1.3981 (16)	C12—H121	0.999 (16)
C5—C10	1.3932 (17)	C12—H123	0.967 (17)
C2—O1—C1	118.66 (9)	C7—C6—H6	119.7 (9)
C4—O2—C1	118.29 (8)	C6—C7—C8	119.80 (11)
N2—N1—C3	120.47 (10)	C6—C7—H7	119.6 (9)
N1—N2—C5	119.38 (10)	C8—C7—H7	120.6 (9)
N1—N2—H2	119.3 (10)	C7—C8—C9	120.56 (10)
C5—N2—H2	121.1 (10)	C7—C8—C13	120.76 (10)
O1—C1—O2	109.71 (9)	C9—C8—C13	118.68 (11)
O1—C1—C11	110.85 (9)	C8—C9—H9	120.9 (9)
O1—C1—C12	106.43 (9)	C10—C9—C8	119.72 (11)
O2—C1—C11	109.92 (9)	C10—C9—H9	119.4 (9)
O2—C1—C12	105.40 (9)	C5—C10—H10	119.5 (9)
C12—C1—C11	114.31 (10)	C9—C10—C5	119.50 (10)
O1—C2—C3	114.85 (10)	C9—C10—H10	121.0 (9)
O4—C2—O1	119.33 (11)	C1—C11—H111	111.6 (9)
O4—C2—C3	125.66 (11)	C1—C11—H113	110.4 (9)
N1—C3—C2	115.57 (10)	C1—C11—H112	108.6 (9)
N1—C3—C4	124.16 (11)	H111—C11—H112	109.0 (12)
C4—C3—C2	119.88 (10)	H111—C11—H113	108.9 (13)
O2—C4—C3	116.02 (10)	H113—C11—H112	108.3 (12)
O3—C4—O2	119.38 (10)	C1—C12—H121	108.9 (9)
O3—C4—C3	124.52 (10)	C1—C12—H122	107.9 (8)
C6—C5—N2	121.03 (11)	C1—C12—H123	109.4 (10)
C10—C5—N2	117.89 (10)	H121—C12—H123	110.0 (13)
C10—C5—C6	121.08 (10)	H122—C12—H121	110.9 (13)
C5—C6—H6	120.9 (9)	H122—C12—H123	109.6 (13)
C7—C6—C5	119.34 (11)	N3—C13—C8	178.56 (13)
C2—O1—C1—O2	51.23 (12)	O4—C2—C3—N1	−9.81 (19)
C2—O1—C1—C11	−70.35 (13)	O4—C2—C3—C4	163.35 (12)
C2—O1—C1—C12	164.79 (10)	N1—C3—C4—O2	−174.73 (10)
C1—O1—C2—O4	163.20 (11)	N1—C3—C4—O3	8.59 (19)
C1—O1—C2—C3	−21.07 (14)	C2—C3—C4—O2	12.73 (16)
C4—O2—C1—O1	−50.36 (12)	C2—C3—C4—O3	−163.95 (11)
C4—O2—C1—C12	−164.59 (9)	N2—C5—C6—C7	−178.47 (10)
C4—O2—C1—C11	71.77 (12)	C10—C5—C6—C7	0.62 (18)
C1—O2—C4—O3	−163.46 (10)	N2—C5—C10—C9	178.44 (10)
C1—O2—C4—C3	19.68 (14)	C6—C5—C10—C9	−0.67 (18)
C3—N1—N2—C5	179.24 (10)	C5—C6—C7—C8	0.05 (18)
N2—N1—C3—C2	173.80 (10)	C6—C7—C8—C9	−0.65 (18)
N2—N1—C3—C4	0.97 (18)	C6—C7—C8—C13	178.87 (11)
N1—N2—C5—C6	−11.37 (17)	C7—C8—C9—C10	0.60 (18)
N1—N2—C5—C10	169.52 (10)	C13—C8—C9—C10	−178.93 (11)
O1—C2—C3—N1	174.77 (10)	C8—C9—C10—C5	0.06 (17)
O1—C2—C3—C4	−12.07 (16)

Cg1 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3	0.92 (2)	1.958 (16)	2.6674 (13)	132 (1)
C9—H9···N1i	0.94 (2)	2.624 (15)	3.5320 (16)	164 (1)
C10—H10···N3ii	0.99 (2)	2.485 (15)	3.3876 (16)	152 (1)
C12—H123···O2iii	0.97 (2)	2.527 (17)	3.4454 (15)	159 (1)
C12—H122···Cg1iv	0.98 (2)	2.491 (15)	3.4575 (13)	171 (1)

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3	0.92 (2)	1.958 (16)	2.6674 (13)	132 (1)
C9—H9⋯N1i	0.94 (2)	2.624 (15)	3.5320 (16)	164 (1)
C10—H10⋯N3ii	0.99 (2)	2.485 (15)	3.3876 (16)	152 (1)
C12—H123⋯O2iii	0.97 (2)	2.527 (17)	3.4454 (15)	159 (1)
C12—H122⋯Cg1iv	0.98 (2)	2.491 (15)	3.4575 (13)	171 (1)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .