2-Methoxy-benzaldehyde 2,4-dinitro-phenyl-hydrazone.

In the title compound, C(14)H(12)N(4)O(5), an intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. The dihedral angle between the two benzene rings is 3.91 (3)°, which shows the mol-ecule is almost planar. The para-nitro group is twisted from the benzene ring to which it is attached, making a dihedral angle of 8.50 (9)°. In the crystal structure, mol-ecules are linked together by inter-molecular C-H⋯O and inter-molecular three-centred O⋯O [2.8646 (12)-2.9213 (11) Å] and O⋯N [3.0518 (11) Å] inter-actions. The crystal structure is further stabilized by inter-molecular π-π inter-actions [centroid-to-centroid distances 3.5708 (6)-3.9728 (12) Å].

Related literature

For general background, see: Lamberton et al. (1974 ▶); Zegota (1999 ▶); Cordis et al. (1998 ▶); Zlotorzynska & Lai (1999 ▶); Niknam et al. (2005 ▶); Guillaumont & Nakamura (2000 ▶); Raj & Kurup (2006 ▶). For biological applications, see: Okabe et al. (1993 ▶). Standard bond-length data are given in: Allen et al. (1987 ▶). For details of the classification of ring motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C14H12N4O5

M = 316.28

Triclinic,

a = 7.0315 (1) Å

b = 7.6205 (2) Å

c = 14.1896 (4) Å

α = 98.048 (1)°

β = 97.064 (1)°

γ = 109.467 (1)°

V = 697.99 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 100.0 (1) K

0.57 × 0.23 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.936, T max = 0.988

14423 measured reflections

5023 independent reflections

4442 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.126

S = 1.06

5023 reflections

213 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.52 e Å−3

Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); 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/S1600536809000038/pk2139sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000038/pk2139Isup2.hkl

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

C14H12N4O5	Z = 2
Mr = 316.28	F(000) = 328
Triclinic, P1	Dx = 1.505 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0315 (1) Å	Cell parameters from 6651 reflections
b = 7.6205 (2) Å	θ = 2.9–40.3°
c = 14.1896 (4) Å	µ = 0.12 mm−1
α = 98.048 (1)°	T = 100 K
β = 97.064 (1)°	Block, orange
γ = 109.467 (1)°	0.57 × 0.23 × 0.10 mm
V = 697.99 (3) Å3

Bruker SMART APEXII CCD area-detector diffractometer	5023 independent reflections
Radiation source: fine-focus sealed tube	4442 reflections with I > 2σ(I)
graphite	Rint = 0.021
φ and ω scans	θmax = 32.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.936, Tmax = 0.988	k = −11→11
14423 measured reflections	l = −21→21

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0683P)2 + 0.1626P] where P = (Fo2 + 2Fc2)/3
5023 reflections	(Δ/σ)max < 0.001
213 parameters	Δρmax = 0.52 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.52355 (11)	0.19077 (9)	0.30740 (5)	0.01789 (14)
O2	0.31793 (12)	0.47602 (10)	−0.06604 (5)	0.02132 (15)
O3	0.20422 (12)	0.51054 (10)	−0.20851 (5)	0.02350 (16)
O4	−0.18137 (11)	−0.00408 (11)	−0.45869 (5)	0.02104 (15)
O5	−0.19171 (12)	−0.28928 (10)	−0.44929 (5)	0.02410 (16)
N1	0.27092 (11)	0.00256 (11)	0.02604 (5)	0.01410 (14)
N2	0.26656 (12)	0.13732 (11)	−0.02830 (5)	0.01416 (14)
N3	0.22761 (12)	0.40930 (10)	−0.15138 (6)	0.01487 (15)
N4	−0.14093 (12)	−0.11921 (11)	−0.41450 (5)	0.01611 (15)
C1	0.46732 (13)	0.00043 (12)	0.27560 (6)	0.01377 (15)
C2	0.48758 (14)	−0.12628 (13)	0.33510 (6)	0.01710 (17)
H2A	0.5476	−0.0815	0.4001	0.021*
C3	0.41767 (15)	−0.31935 (14)	0.29676 (7)	0.01947 (18)
H3A	0.4306	−0.4035	0.3365	0.023*
C4	0.32856 (14)	−0.38821 (13)	0.19954 (7)	0.01804 (17)
H4A	0.2814	−0.5177	0.1745	0.022*
C5	0.31052 (13)	−0.26234 (12)	0.14015 (6)	0.01530 (16)
H5A	0.2514	−0.3085	0.0751	0.018*
C6	0.38009 (12)	−0.06701 (12)	0.17671 (6)	0.01284 (15)
C7	0.36703 (13)	0.06671 (12)	0.11394 (6)	0.01371 (15)
H7A	0.4276	0.1967	0.1373	0.016*
C8	0.17242 (12)	0.07996 (12)	−0.12228 (6)	0.01178 (15)
C9	0.09189 (13)	−0.11672 (12)	−0.16426 (6)	0.01378 (15)
H9A	0.1056	−0.2038	−0.1266	0.017*
C10	−0.00529 (13)	−0.18102 (12)	−0.25882 (6)	0.01405 (15)
H10A	−0.0547	−0.3101	−0.2852	0.017*
C11	−0.02975 (12)	−0.05112 (12)	−0.31553 (6)	0.01291 (15)
C12	0.04681 (12)	0.14065 (12)	−0.27956 (6)	0.01311 (15)
H12A	0.0307	0.2253	−0.3184	0.016*
C13	0.14893 (12)	0.20609 (11)	−0.18400 (6)	0.01222 (15)
C14	0.64623 (15)	0.27271 (14)	0.40200 (7)	0.01993 (18)
H14A	0.6876	0.4084	0.4120	0.030*
H14B	0.7657	0.2377	0.4074	0.030*
H14C	0.5675	0.2269	0.4500	0.030*
H1N2	0.329 (2)	0.256 (2)	−0.0027 (11)	0.035 (4)*

	U11	U22	U33	U12	U13	U23
O1	0.0227 (3)	0.0151 (3)	0.0117 (3)	0.0049 (2)	−0.0022 (2)	−0.0014 (2)
O2	0.0294 (4)	0.0137 (3)	0.0151 (3)	0.0053 (3)	−0.0036 (3)	−0.0028 (2)
O3	0.0317 (4)	0.0130 (3)	0.0239 (4)	0.0077 (3)	−0.0032 (3)	0.0055 (3)
O4	0.0218 (3)	0.0268 (4)	0.0147 (3)	0.0103 (3)	−0.0016 (2)	0.0048 (3)
O5	0.0274 (4)	0.0189 (3)	0.0185 (3)	0.0055 (3)	−0.0040 (3)	−0.0063 (3)
N1	0.0153 (3)	0.0149 (3)	0.0115 (3)	0.0049 (2)	0.0015 (2)	0.0030 (2)
N2	0.0173 (3)	0.0123 (3)	0.0109 (3)	0.0042 (3)	−0.0004 (2)	0.0014 (2)
N3	0.0162 (3)	0.0115 (3)	0.0158 (3)	0.0051 (2)	0.0007 (3)	0.0007 (2)
N4	0.0144 (3)	0.0190 (3)	0.0126 (3)	0.0052 (3)	−0.0001 (2)	−0.0002 (3)
C1	0.0130 (3)	0.0156 (4)	0.0116 (3)	0.0044 (3)	0.0017 (3)	0.0018 (3)
C2	0.0164 (4)	0.0212 (4)	0.0130 (4)	0.0057 (3)	0.0011 (3)	0.0049 (3)
C3	0.0199 (4)	0.0207 (4)	0.0195 (4)	0.0072 (3)	0.0041 (3)	0.0091 (3)
C4	0.0191 (4)	0.0142 (4)	0.0199 (4)	0.0042 (3)	0.0047 (3)	0.0040 (3)
C5	0.0151 (3)	0.0150 (4)	0.0136 (4)	0.0032 (3)	0.0024 (3)	0.0014 (3)
C6	0.0123 (3)	0.0145 (3)	0.0108 (3)	0.0040 (3)	0.0017 (3)	0.0018 (3)
C7	0.0145 (3)	0.0138 (3)	0.0118 (3)	0.0042 (3)	0.0019 (3)	0.0016 (3)
C8	0.0120 (3)	0.0124 (3)	0.0103 (3)	0.0042 (3)	0.0013 (3)	0.0010 (3)
C9	0.0160 (3)	0.0113 (3)	0.0128 (4)	0.0039 (3)	0.0015 (3)	0.0020 (3)
C10	0.0151 (3)	0.0111 (3)	0.0136 (4)	0.0030 (3)	0.0014 (3)	0.0001 (3)
C11	0.0119 (3)	0.0144 (3)	0.0103 (3)	0.0034 (3)	0.0000 (3)	0.0007 (3)
C12	0.0128 (3)	0.0139 (3)	0.0124 (3)	0.0051 (3)	0.0008 (3)	0.0022 (3)
C13	0.0128 (3)	0.0100 (3)	0.0129 (3)	0.0039 (3)	0.0007 (3)	0.0007 (3)
C14	0.0188 (4)	0.0225 (4)	0.0131 (4)	0.0048 (3)	−0.0019 (3)	−0.0032 (3)

O1—C1	1.3618 (11)	C4—C5	1.3883 (13)
O1—C14	1.4344 (11)	C4—H4A	0.9300
O2—N3	1.2456 (10)	C5—C6	1.4001 (12)
O3—N3	1.2274 (10)	C5—H5A	0.9300
O4—N4	1.2329 (10)	C6—C7	1.4617 (12)
O5—N4	1.2328 (10)	C7—H7A	0.9300
N1—C7	1.2858 (11)	C8—C9	1.4224 (11)
N1—N2	1.3736 (10)	C8—C13	1.4227 (11)
N2—C8	1.3545 (10)	C9—C10	1.3692 (11)
N2—H1N2	0.864 (16)	C9—H9A	0.9300
N3—C13	1.4435 (11)	C10—C11	1.3998 (12)
N4—C11	1.4520 (11)	C10—H10A	0.9300
C1—C2	1.3985 (12)	C11—C12	1.3730 (12)
C1—C6	1.4092 (11)	C12—C13	1.3912 (11)
C2—C3	1.3894 (14)	C12—H12A	0.9300
C2—H2A	0.9300	C14—H14A	0.9600
C3—C4	1.3916 (13)	C14—H14B	0.9600
C3—H3A	0.9300	C14—H14C	0.9600
C1—O1—C14	118.36 (7)	C1—C6—C7	119.95 (7)
C7—N1—N2	115.65 (7)	N1—C7—C6	119.25 (8)
C8—N2—N1	118.87 (7)	N1—C7—H7A	120.4
C8—N2—H1N2	121.6 (10)	C6—C7—H7A	120.4
N1—N2—H1N2	119.4 (10)	N2—C8—C9	119.67 (7)
O3—N3—O2	122.20 (7)	N2—C8—C13	123.82 (7)
O3—N3—C13	119.09 (7)	C9—C8—C13	116.51 (7)
O2—N3—C13	118.71 (7)	C10—C9—C8	121.61 (8)
O5—N4—O4	123.66 (8)	C10—C9—H9A	119.2
O5—N4—C11	118.19 (7)	C8—C9—H9A	119.2
O4—N4—C11	118.15 (7)	C9—C10—C11	119.52 (8)
O1—C1—C2	123.98 (8)	C9—C10—H10A	120.2
O1—C1—C6	115.86 (7)	C11—C10—H10A	120.2
C2—C1—C6	120.14 (8)	C12—C11—C10	121.62 (8)
C3—C2—C1	119.74 (8)	C12—C11—N4	118.64 (7)
C3—C2—H2A	120.1	C10—C11—N4	119.74 (7)
C1—C2—H2A	120.1	C11—C12—C13	118.80 (8)
C2—C3—C4	120.73 (8)	C11—C12—H12A	120.6
C2—C3—H3A	119.6	C13—C12—H12A	120.6
C4—C3—H3A	119.6	C12—C13—C8	121.90 (7)
C5—C4—C3	119.58 (8)	C12—C13—N3	115.84 (7)
C5—C4—H4A	120.2	C8—C13—N3	122.26 (7)
C3—C4—H4A	120.2	O1—C14—H14A	109.5
C4—C5—C6	120.96 (8)	O1—C14—H14B	109.5
C4—C5—H5A	119.5	H14A—C14—H14B	109.5
C6—C5—H5A	119.5	O1—C14—H14C	109.5
C5—C6—C1	118.84 (8)	H14A—C14—H14C	109.5
C5—C6—C7	121.21 (7)	H14B—C14—H14C	109.5
C7—N1—N2—C8	178.35 (7)	C13—C8—C9—C10	−0.77 (12)
C14—O1—C1—C2	12.61 (13)	C8—C9—C10—C11	−1.15 (13)
C14—O1—C1—C6	−168.81 (8)	C9—C10—C11—C12	1.96 (13)
O1—C1—C2—C3	177.25 (8)	C9—C10—C11—N4	−177.18 (8)
C6—C1—C2—C3	−1.27 (13)	O5—N4—C11—C12	173.05 (8)
C1—C2—C3—C4	0.36 (14)	O4—N4—C11—C12	−7.77 (12)
C2—C3—C4—C5	0.38 (14)	O5—N4—C11—C10	−7.78 (12)
C3—C4—C5—C6	−0.21 (14)	O4—N4—C11—C10	171.39 (8)
C4—C5—C6—C1	−0.69 (13)	C10—C11—C12—C13	−0.75 (13)
C4—C5—C6—C7	178.17 (8)	N4—C11—C12—C13	178.40 (7)
O1—C1—C6—C5	−177.21 (7)	C11—C12—C13—C8	−1.28 (13)
C2—C1—C6—C5	1.43 (13)	C11—C12—C13—N3	179.24 (7)
O1—C1—C6—C7	3.91 (12)	N2—C8—C13—C12	−178.46 (8)
C2—C1—C6—C7	−177.45 (8)	C9—C8—C13—C12	2.01 (12)
N2—N1—C7—C6	−179.67 (7)	N2—C8—C13—N3	0.98 (13)
C5—C6—C7—N1	7.29 (13)	C9—C8—C13—N3	−178.55 (7)
C1—C6—C7—N1	−173.86 (8)	O3—N3—C13—C12	−1.30 (12)
N1—N2—C8—C9	−3.93 (12)	O2—N3—C13—C12	178.99 (8)
N1—N2—C8—C13	176.55 (8)	O3—N3—C13—C8	179.23 (8)
N2—C8—C9—C10	179.68 (8)	O2—N3—C13—C8	−0.48 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O2	0.864 (15)	2.029 (15)	2.6253 (11)	125.4 (13)
N2—H1N2···O2i	0.864 (15)	2.599 (15)	3.3475 (11)	145.6 (13)
C2—H2A···O4ii	0.93	2.44	3.3113 (12)	155
C5—H5A···O2iii	0.93	2.60	3.3184 (11)	135

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O2	0.864 (15)	2.029 (15)	2.6253 (11)	125.4 (13)
N2—H1N2⋯O2i	0.864 (15)	2.599 (15)	3.3475 (11)	145.6 (13)
C2—H2A⋯O4ii	0.93	2.44	3.3113 (12)	155
C5—H5A⋯O2iii	0.93	2.60	3.3184 (11)	135

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