2,4,6-Trinitro-phenyl 3-methyl-benzoate.

In the title benzoate derivative, C(14)H(9)N(3)O(8), the benzene rings form a dihedral angle of 87.48 (5)°. The central ester unit forms an angle of 19.42 (7)° with the methyl-benzene ring, indicating a significant twist. In the crystal, the mol-ecules are linked by weak C-H⋯O inter-actions forming a helical chain along [010].

Related literature

For synthesis of picric acid with charge-transfer complexes, see: Siddaraju et al. (2012 ▶); Refat et al. (2010 ▶); El-Medania et al. (2003 ▶). For the pharmacological and biochemical activity of picric acid, see: Khan & Ovesb (2010 ▶); Khan et al. (2011 ▶). For the non-linear optical properties of picric acid, see: Zaderenko et al. (1997 ▶). For the synthesis of nitro­aromatic compounds with industrial use, see: Ju & Parales (2010 ▶). For similar structures, see: Adams & Morsi (1976 ▶); Gowda et al. (2007 ▶, 2008 ▶, 2009 ▶). For hydrogen bonding, see: Nardelli (1995 ▶). For hydrogen-bond graph-set motifs, see: Etter (1990 ▶).

Experimental

Crystal data

C14H9N3O8

M = 347.24

Monoclinic,

a = 7.4947 (1) Å

b = 8.4366 (2) Å

c = 23.8574 (6) Å

β = 99.365 (1)°

V = 1488.39 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 295 K

0.38 × 0.34 × 0.28 mm

Data collection

Nonius KappaCCD diffractometer

5874 measured reflections

3043 independent reflections

2373 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.126

S = 1.04

3043 reflections

226 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.22 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; 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 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812027407/tk5112sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027407/tk5112Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812027407/tk5112Isup3.cml

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

C14H9N3O8	F(000) = 712
Mr = 347.24	Dx = 1.550 Mg m−3
Monoclinic, P21/c	Melting point: 425(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.4947 (1) Å	Cell parameters from 5756 reflections
b = 8.4366 (2) Å	θ = 3.0–26.4°
c = 23.8574 (6) Å	µ = 0.13 mm−1
β = 99.365 (1)°	T = 295 K
V = 1488.39 (6) Å3	Block, pale-yellow
Z = 4	0.38 × 0.34 × 0.28 mm

Nonius KappaCCD diffractometer	2373 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.016
Graphite monochromator	θmax = 26.4°, θmin = 3.0°
CCD rotation images, thick slices scans	h = −9→9
5874 measured reflections	k = −10→10
3043 independent reflections	l = −29→29

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0676P)2 + 0.2831P] where P = (Fo2 + 2Fc2)/3
3043 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.19 e Å−3
1 restraint	Δρmin = −0.22 e Å−3

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 > 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
O7	0.90799 (14)	0.93604 (12)	0.81583 (5)	0.0483 (3)
O8	0.89917 (15)	1.20129 (13)	0.81861 (5)	0.0505 (3)
C1	0.80954 (19)	0.93669 (16)	0.76227 (6)	0.0391 (3)
C5	0.7782 (2)	0.95541 (18)	0.66027 (7)	0.0454 (4)
H5	0.8253	0.9833	0.6279	0.054*
C3	0.5283 (2)	0.85846 (18)	0.70267 (6)	0.0420 (4)
H3	0.4117	0.8176	0.6989	0.050*
C7	0.95268 (19)	1.08060 (17)	0.84158 (6)	0.0394 (3)
C2	0.63119 (19)	0.88363 (17)	0.75520 (6)	0.0392 (3)
O6	1.17307 (17)	1.0163 (2)	0.75989 (6)	0.0837 (5)
C4	0.6059 (2)	0.89658 (18)	0.65603 (6)	0.0440 (4)
N1	0.54579 (18)	0.85492 (17)	0.80541 (6)	0.0503 (4)
C8	1.0651 (2)	1.05927 (19)	0.89762 (6)	0.0440 (4)
C6	0.88038 (19)	0.97246 (17)	0.71349 (7)	0.0423 (4)
O2	0.45102 (19)	0.73845 (17)	0.80489 (6)	0.0738 (4)
N3	1.06867 (19)	1.02766 (17)	0.71553 (7)	0.0549 (4)
N2	0.4983 (2)	0.8763 (2)	0.59912 (6)	0.0605 (4)
O1	0.5703 (2)	0.95298 (19)	0.84340 (5)	0.0800 (5)
C13	1.0733 (2)	1.1822 (2)	0.93617 (7)	0.0534 (4)
H13	1.0100	1.2754	0.9260	0.064*
O4	0.5610 (2)	0.9263 (2)	0.55895 (6)	0.0926 (5)
C9	1.1597 (2)	0.9197 (2)	0.91180 (8)	0.0561 (4)
H9	1.1550	0.8373	0.8857	0.067*
O5	1.1103 (2)	1.07925 (18)	0.67223 (7)	0.0818 (5)
O3	0.3529 (2)	0.8124 (2)	0.59560 (6)	0.0989 (6)
C10	1.2612 (3)	0.9054 (3)	0.96550 (9)	0.0725 (6)
H10	1.3260	0.8129	0.9756	0.087*
C12	1.1757 (3)	1.1678 (3)	0.99043 (7)	0.0637 (5)
C11	1.2666 (3)	1.0267 (3)	1.00373 (8)	0.0739 (6)
H11	1.3335	1.0139	1.0398	0.089*
C14	1.1835 (4)	1.3021 (3)	1.03270 (9)	0.0947 (8)
H14A	1.1121	1.3893	1.0156	0.142*
H14B	1.3066	1.3358	1.0436	0.142*
H14C	1.1367	1.2667	1.0657	0.142*

	U11	U22	U33	U12	U13	U23
O7	0.0535 (6)	0.0349 (6)	0.0487 (6)	−0.0045 (4)	−0.0147 (5)	0.0028 (5)
O8	0.0610 (7)	0.0369 (6)	0.0502 (6)	−0.0019 (5)	−0.0013 (5)	0.0013 (5)
C1	0.0426 (8)	0.0275 (7)	0.0432 (8)	0.0017 (6)	−0.0056 (6)	−0.0010 (6)
C5	0.0509 (9)	0.0403 (8)	0.0461 (9)	0.0085 (7)	0.0115 (7)	−0.0015 (7)
C3	0.0398 (7)	0.0385 (8)	0.0444 (8)	−0.0002 (6)	−0.0028 (6)	−0.0039 (6)
C7	0.0369 (7)	0.0375 (8)	0.0425 (8)	−0.0071 (6)	0.0030 (6)	0.0001 (6)
C2	0.0439 (8)	0.0318 (7)	0.0397 (8)	−0.0014 (6)	0.0002 (6)	0.0002 (6)
O6	0.0411 (7)	0.1268 (14)	0.0802 (10)	−0.0085 (7)	0.0011 (7)	−0.0216 (9)
C4	0.0473 (8)	0.0421 (8)	0.0395 (8)	0.0081 (6)	−0.0020 (6)	−0.0064 (6)
N1	0.0515 (8)	0.0516 (8)	0.0451 (8)	−0.0095 (7)	−0.0002 (6)	0.0054 (6)
C8	0.0380 (7)	0.0521 (9)	0.0402 (8)	−0.0120 (7)	0.0011 (6)	0.0028 (7)
C6	0.0386 (7)	0.0328 (7)	0.0543 (9)	0.0026 (6)	0.0040 (7)	−0.0036 (6)
O2	0.0792 (9)	0.0595 (8)	0.0852 (10)	−0.0265 (7)	0.0204 (7)	0.0087 (7)
N3	0.0453 (8)	0.0413 (8)	0.0786 (11)	0.0013 (6)	0.0114 (8)	−0.0086 (7)
N2	0.0637 (10)	0.0724 (10)	0.0417 (8)	0.0131 (8)	−0.0023 (7)	−0.0065 (7)
O1	0.0935 (10)	0.1009 (12)	0.0478 (7)	−0.0366 (9)	0.0178 (7)	−0.0204 (8)
C13	0.0520 (9)	0.0604 (10)	0.0471 (9)	−0.0178 (8)	0.0060 (7)	−0.0026 (8)
O4	0.0837 (10)	0.1518 (16)	0.0412 (7)	0.0160 (10)	0.0066 (7)	0.0088 (9)
C9	0.0489 (9)	0.0654 (11)	0.0502 (9)	−0.0012 (8)	−0.0035 (7)	0.0051 (8)
O5	0.0700 (9)	0.0748 (10)	0.1047 (12)	−0.0148 (7)	0.0267 (8)	0.0253 (8)
O3	0.0843 (11)	0.1433 (16)	0.0592 (9)	−0.0384 (11)	−0.0183 (7)	−0.0077 (9)
C10	0.0568 (11)	0.0928 (16)	0.0612 (12)	0.0017 (10)	−0.0103 (9)	0.0176 (11)
C12	0.0622 (11)	0.0871 (14)	0.0417 (9)	−0.0342 (11)	0.0078 (8)	−0.0066 (9)
C11	0.0560 (11)	0.1151 (18)	0.0453 (10)	−0.0233 (12)	−0.0081 (8)	0.0099 (11)
C14	0.1136 (18)	0.118 (2)	0.0529 (12)	−0.0513 (16)	0.0130 (11)	−0.0233 (12)

O7—C1	1.3676 (17)	C8—C9	1.388 (2)
O7—C7	1.3820 (18)	C6—N3	1.479 (2)
O8—C7	1.1942 (18)	N3—O5	1.208 (2)
C1—C6	1.389 (2)	N2—O3	1.207 (2)
C1—C2	1.394 (2)	N2—O4	1.210 (2)
C5—C4	1.372 (2)	C13—C12	1.399 (2)
C5—C6	1.379 (2)	C13—H13	0.9300
C5—H5	0.9300	C9—C10	1.385 (2)
C3—C4	1.375 (2)	C9—H9	0.9300
C3—C2	1.377 (2)	C10—C11	1.367 (3)
C3—H3	0.9300	C10—H10	0.9300
C7—C8	1.471 (2)	C12—C11	1.382 (3)
C2—N1	1.467 (2)	C12—C14	1.512 (3)
O6—N3	1.2132 (19)	C11—H11	0.9300
C4—N2	1.472 (2)	C14—H14A	0.9600
N1—O2	1.2113 (18)	C14—H14B	0.9600
N1—O1	1.2188 (19)	C14—H14C	0.9600
C8—C13	1.381 (2)
C1—O7—C7	117.82 (11)	O5—N3—O6	123.69 (16)
O7—C1—C6	124.20 (13)	O5—N3—C6	117.60 (15)
O7—C1—C2	118.21 (14)	O6—N3—C6	118.70 (15)
C6—C1—C2	117.29 (13)	O3—N2—O4	124.29 (16)
C4—C5—C6	118.72 (15)	O3—N2—C4	117.98 (16)
C4—C5—H5	120.6	O4—N2—C4	117.73 (16)
C6—C5—H5	120.6	C8—C13—C12	120.63 (18)
C4—C3—C2	116.89 (14)	C8—C13—H13	119.7
C4—C3—H3	121.6	C12—C13—H13	119.7
C2—C3—H3	121.6	C10—C9—C8	118.80 (18)
O8—C7—O7	120.62 (13)	C10—C9—H9	120.6
O8—C7—C8	128.42 (14)	C8—C9—H9	120.6
O7—C7—C8	110.95 (12)	C11—C10—C9	120.3 (2)
C3—C2—C1	122.95 (14)	C11—C10—H10	119.9
C3—C2—N1	117.60 (13)	C9—C10—H10	119.9
C1—C2—N1	119.44 (13)	C11—C12—C13	117.58 (18)
C5—C4—C3	122.82 (14)	C11—C12—C14	121.89 (19)
C5—C4—N2	118.55 (15)	C13—C12—C14	120.5 (2)
C3—C4—N2	118.61 (14)	C10—C11—C12	122.12 (17)
O2—N1—O1	125.12 (15)	C10—C11—H11	118.9
O2—N1—C2	117.30 (14)	C12—C11—H11	118.9
O1—N1—C2	117.52 (13)	C12—C14—H14A	109.5
C13—C8—C9	120.61 (15)	C12—C14—H14B	109.5
C13—C8—C7	118.07 (15)	H14A—C14—H14B	109.5
C9—C8—C7	121.32 (15)	C12—C14—H14C	109.5
C5—C6—C1	121.20 (14)	H14A—C14—H14C	109.5
C5—C6—N3	116.54 (15)	H14B—C14—H14C	109.5
C1—C6—N3	122.25 (14)
C7—O7—C1—C6	75.78 (19)	C4—C5—C6—N3	176.60 (13)
C7—O7—C1—C2	−110.65 (15)	O7—C1—C6—C5	173.36 (13)
C1—O7—C7—O8	3.5 (2)	C2—C1—C6—C5	−0.3 (2)
C1—O7—C7—C8	−177.40 (13)	O7—C1—C6—N3	−5.5 (2)
C4—C3—C2—C1	−3.5 (2)	C2—C1—C6—N3	−179.14 (13)
C4—C3—C2—N1	175.52 (13)	C5—C6—N3—O5	12.3 (2)
O7—C1—C2—C3	−170.71 (13)	C1—C6—N3—O5	−168.75 (15)
C6—C1—C2—C3	3.3 (2)	C5—C6—N3—O6	−166.39 (15)
O7—C1—C2—N1	10.3 (2)	C1—C6—N3—O6	12.5 (2)
C6—C1—C2—N1	−175.72 (13)	C5—C4—N2—O3	173.96 (18)
C6—C5—C4—C3	2.1 (2)	C3—C4—N2—O3	−7.2 (2)
C6—C5—C4—N2	−179.10 (13)	C5—C4—N2—O4	−6.7 (2)
C2—C3—C4—C5	0.7 (2)	C3—C4—N2—O4	172.15 (16)
C2—C3—C4—N2	−178.05 (13)	C9—C8—C13—C12	−0.6 (2)
C3—C2—N1—O2	41.7 (2)	C7—C8—C13—C12	179.01 (15)
C1—C2—N1—O2	−139.18 (15)	C13—C8—C9—C10	0.5 (3)
C3—C2—N1—O1	−135.63 (16)	C7—C8—C9—C10	−179.05 (16)
C1—C2—N1—O1	43.4 (2)	C8—C9—C10—C11	0.4 (3)
O8—C7—C8—C13	19.5 (2)	C8—C13—C12—C11	−0.3 (3)
O7—C7—C8—C13	−159.49 (14)	C8—C13—C12—C14	−179.62 (17)
O8—C7—C8—C9	−160.88 (17)	C9—C10—C11—C12	−1.3 (3)
O7—C7—C8—C9	20.1 (2)	C13—C12—C11—C10	1.3 (3)
C4—C5—C6—C1	−2.3 (2)	C14—C12—C11—C10	−179.43 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O8i	0.93	2.50	3.4276 (19)	176
C13—H13···O3ii	0.93	2.70	3.346 (2)	127

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O8i	0.93	2.50	3.4276 (19)	176
C13—H13⋯O3ii	0.93	2.70	3.346 (2)	127

Symmetry codes: (i) ; (ii) .