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

In the title compound, C(14)H(9)N(3)O(8), the benzene rings form a dihedral angle of 69.02 (5)°. The central ester group is rotated by 25.86 (9)° relative to the p-tolyl group. In the crystal, the mol-ecules are linked by C-H⋯O inter-actions into helical chains along [010].

Related literature

For optical, pharmacological and crystalline properties of picric acid, see: Khan et al. (2010 ▶); Zaderenko et al. (1997 ▶). For picric acid derivatives, see: Bertolasi et al. (2011 ▶). For bond-length data, see: Allen et al. (1987 ▶). For similar structures, see: Moreno-Fuquen et al. (2012 ▶); Bibi et al. (2009 ▶); Shibakami et al. (1994 ▶); Shibakami & Sekiya (1995 ▶); For hydrogen bonding, see: Nardelli (1995 ▶) and for supra­molecular aggregation behaviour of isomers, see: Glidewell et al. (2005 ▶).

Experimental

Crystal data

C14H9N3O8

M = 347.24

Monoclinic,

a = 7.6126 (2) Å

b = 8.2124 (2) Å

c = 23.9893 (7) Å

β = 94.448 (1)°

V = 1495.24 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 295 K

0.27 × 0.22 × 0.18 mm

Data collection

Nonius KappaCCD diffractometer

5494 measured reflections

3044 independent reflections

2296 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.123

S = 1.02

3044 reflections

227 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.24 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: HKL 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812041773/ld2074sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812041773/ld2074Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812041773/ld2074Isup3.cml

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

C14H9N3O8	F(000) = 712
Mr = 347.24	Dx = 1.543 Mg m−3
Monoclinic, P21/c	Melting point: 417(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.6126 (2) Å	Cell parameters from 3076 reflections
b = 8.2124 (2) Å	θ = 3.0–26.4°
c = 23.9893 (7) Å	µ = 0.13 mm−1
β = 94.448 (1)°	T = 295 K
V = 1495.24 (7) Å3	Block, pale-yellow
Z = 4	0.27 × 0.22 × 0.18 mm

Nonius KappaCCD diffractometer	2296 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 26.4°, θmin = 3.0°
CCD rotation images, thick slices scans	h = −9→9
5494 measured reflections	k = −9→10
3044 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0698P)2 + 0.224P] where P = (Fo2 + 2Fc2)/3
3044 reflections	(Δ/σ)max < 0.001
227 parameters	Δρmax = 0.18 e Å−3
1 restraint	Δρmin = −0.24 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
O1	0.4307 (2)	0.4914 (2)	0.33344 (6)	0.0840 (5)
O2	0.56533 (16)	0.66653 (15)	0.28637 (6)	0.0633 (4)
O3	0.5292 (2)	0.5772 (3)	0.08518 (7)	0.1011 (6)
O4	0.3254 (2)	0.4222 (3)	0.04835 (7)	0.1007 (6)
O5	−0.18224 (17)	0.33867 (18)	0.14637 (6)	0.0732 (4)
O6	−0.17197 (15)	0.33696 (15)	0.23563 (5)	0.0595 (3)
O7	0.09683 (13)	0.46979 (12)	0.29293 (4)	0.0407 (3)
O8	0.16920 (15)	0.20662 (13)	0.30759 (5)	0.0525 (3)
N1	0.45379 (16)	0.56271 (17)	0.29052 (6)	0.0469 (3)
N2	0.3987 (2)	0.4953 (2)	0.08753 (7)	0.0664 (4)
N3	−0.10536 (17)	0.35918 (15)	0.19191 (6)	0.0460 (3)
C1	0.17239 (18)	0.46265 (16)	0.24291 (6)	0.0362 (3)
C2	0.34413 (18)	0.51938 (17)	0.23953 (6)	0.0386 (3)
C3	0.41940 (19)	0.53543 (18)	0.18945 (7)	0.0433 (4)
H3	0.5318	0.5787	0.1878	0.052*
C4	0.3213 (2)	0.48477 (19)	0.14189 (7)	0.0462 (4)
C5	0.1537 (2)	0.42336 (19)	0.14288 (7)	0.0457 (4)
H5	0.0918	0.3878	0.1102	0.055*
C6	0.07943 (18)	0.41560 (17)	0.19332 (6)	0.0393 (3)
C7	0.09911 (18)	0.32603 (18)	0.32354 (7)	0.0396 (4)
C8	0.00660 (19)	0.34449 (18)	0.37471 (7)	0.0420 (4)
C9	−0.1286 (2)	0.4560 (2)	0.37848 (7)	0.0516 (4)
H9	−0.1580	0.5273	0.3491	0.062*
C10	−0.2198 (2)	0.4607 (2)	0.42623 (8)	0.0618 (5)
H10	−0.3118	0.5344	0.4283	0.074*
C11	−0.1768 (2)	0.3578 (3)	0.47078 (7)	0.0595 (5)
C12	−0.0394 (2)	0.2490 (2)	0.46659 (7)	0.0617 (5)
H12	−0.0074	0.1803	0.4965	0.074*
C13	0.0511 (2)	0.2402 (2)	0.41905 (7)	0.0537 (4)
H13	0.1414	0.1648	0.4167	0.064*
C14	−0.2789 (3)	0.3625 (4)	0.52240 (9)	0.0880 (7)
H14A	−0.2015	0.3370	0.5547	0.132*
H14B	−0.3727	0.2841	0.5187	0.132*
H14C	−0.3274	0.4693	0.5265	0.132*

	U11	U22	U33	U12	U13	U23
O1	0.0738 (9)	0.1154 (12)	0.0599 (8)	−0.0385 (9)	−0.0135 (7)	0.0239 (8)
O2	0.0497 (7)	0.0579 (8)	0.0813 (9)	−0.0212 (6)	−0.0008 (6)	−0.0053 (6)
O3	0.0687 (10)	0.1650 (17)	0.0728 (10)	−0.0334 (11)	0.0253 (8)	0.0139 (11)
O4	0.0954 (12)	0.1528 (17)	0.0567 (9)	−0.0247 (12)	0.0243 (8)	−0.0252 (10)
O5	0.0516 (7)	0.0986 (11)	0.0677 (9)	−0.0220 (7)	−0.0064 (6)	−0.0147 (7)
O6	0.0435 (6)	0.0694 (8)	0.0667 (8)	−0.0163 (6)	0.0113 (6)	0.0084 (6)
O7	0.0426 (6)	0.0342 (5)	0.0468 (6)	−0.0005 (4)	0.0123 (5)	0.0012 (4)
O8	0.0546 (7)	0.0402 (6)	0.0648 (8)	0.0080 (5)	0.0179 (6)	0.0051 (5)
N1	0.0364 (7)	0.0469 (8)	0.0571 (8)	−0.0044 (6)	0.0021 (5)	−0.0011 (6)
N2	0.0529 (9)	0.0924 (12)	0.0560 (10)	−0.0001 (9)	0.0169 (8)	0.0064 (9)
N3	0.0384 (7)	0.0389 (7)	0.0608 (9)	−0.0058 (5)	0.0028 (7)	−0.0017 (6)
C1	0.0359 (7)	0.0275 (7)	0.0461 (8)	0.0019 (5)	0.0083 (6)	0.0008 (6)
C2	0.0350 (7)	0.0306 (7)	0.0504 (8)	0.0001 (6)	0.0036 (6)	0.0003 (6)
C3	0.0338 (7)	0.0396 (8)	0.0576 (10)	−0.0003 (6)	0.0103 (7)	0.0051 (7)
C4	0.0440 (8)	0.0482 (9)	0.0478 (9)	0.0046 (7)	0.0117 (7)	0.0044 (7)
C5	0.0443 (8)	0.0447 (8)	0.0481 (9)	0.0007 (7)	0.0036 (7)	−0.0014 (7)
C6	0.0334 (7)	0.0331 (7)	0.0515 (9)	−0.0006 (6)	0.0038 (6)	0.0007 (6)
C7	0.0318 (7)	0.0368 (8)	0.0503 (9)	−0.0017 (6)	0.0035 (6)	0.0033 (7)
C8	0.0362 (7)	0.0431 (8)	0.0469 (9)	−0.0026 (6)	0.0037 (6)	0.0027 (7)
C9	0.0464 (9)	0.0600 (10)	0.0492 (10)	0.0113 (8)	0.0083 (7)	0.0104 (8)
C10	0.0504 (10)	0.0798 (13)	0.0566 (11)	0.0186 (9)	0.0125 (8)	0.0066 (9)
C11	0.0529 (10)	0.0821 (13)	0.0440 (10)	−0.0031 (9)	0.0074 (8)	0.0034 (9)
C12	0.0652 (11)	0.0722 (12)	0.0472 (10)	0.0042 (10)	0.0009 (8)	0.0161 (9)
C13	0.0493 (9)	0.0575 (10)	0.0542 (10)	0.0091 (8)	0.0031 (8)	0.0082 (8)
C14	0.0818 (15)	0.130 (2)	0.0552 (13)	0.0046 (14)	0.0247 (11)	0.0093 (13)

O1—N1	1.2089 (18)	C5—C6	1.376 (2)
O2—N1	1.2128 (17)	C5—H5	0.9300
O3—N2	1.204 (2)	C7—C8	1.470 (2)
O4—N2	1.214 (2)	C8—C9	1.386 (2)
O5—N3	1.2106 (18)	C8—C13	1.387 (2)
O6—N3	1.2135 (17)	C9—C10	1.385 (2)
O7—C1	1.3715 (17)	C9—H9	0.9300
O7—C7	1.3898 (17)	C10—C11	1.382 (3)
O8—C7	1.1936 (18)	C10—H10	0.9300
N1—C2	1.470 (2)	C11—C12	1.385 (3)
N2—C4	1.474 (2)	C11—C14	1.513 (2)
N3—C6	1.4790 (19)	C12—C13	1.379 (2)
C1—C6	1.391 (2)	C12—H12	0.9300
C1—C2	1.396 (2)	C13—H13	0.9300
C2—C3	1.377 (2)	C14—H14A	0.9600
C3—C4	1.378 (2)	C14—H14B	0.9600
C3—H3	0.9300	C14—H14C	0.9600
C4—C5	1.374 (2)
C1—O7—C7	115.91 (11)	O8—C7—O7	121.07 (13)
O1—N1—O2	124.00 (14)	O8—C7—C8	127.42 (14)
O1—N1—C2	118.73 (13)	O7—C7—C8	111.50 (12)
O2—N1—C2	117.24 (13)	C9—C8—C13	119.77 (15)
O3—N2—O4	124.83 (17)	C9—C8—C7	121.94 (14)
O3—N2—C4	117.50 (17)	C13—C8—C7	118.19 (14)
O4—N2—C4	117.66 (16)	C10—C9—C8	119.65 (15)
O5—N3—O6	123.63 (13)	C10—C9—H9	120.2
O5—N3—C6	117.16 (13)	C8—C9—H9	120.2
O6—N3—C6	119.20 (13)	C11—C10—C9	121.23 (16)
O7—C1—C6	122.69 (12)	C11—C10—H10	119.4
O7—C1—C2	119.66 (13)	C9—C10—H10	119.4
C6—C1—C2	117.35 (13)	C10—C11—C12	118.26 (16)
C3—C2—C1	122.52 (14)	C10—C11—C14	120.74 (18)
C3—C2—N1	117.06 (13)	C12—C11—C14	120.99 (18)
C1—C2—N1	120.41 (13)	C13—C12—C11	121.48 (16)
C2—C3—C4	117.26 (14)	C13—C12—H12	119.3
C2—C3—H3	121.4	C11—C12—H12	119.3
C4—C3—H3	121.4	C12—C13—C8	119.59 (16)
C5—C4—C3	122.72 (15)	C12—C13—H13	120.2
C5—C4—N2	118.18 (15)	C8—C13—H13	120.2
C3—C4—N2	119.10 (15)	C11—C14—H14A	109.5
C4—C5—C6	118.54 (15)	C11—C14—H14B	109.5
C4—C5—H5	120.7	H14A—C14—H14B	109.5
C6—C5—H5	120.7	C11—C14—H14C	109.5
C5—C6—C1	121.51 (13)	H14A—C14—H14C	109.5
C5—C6—N3	116.71 (13)	H14B—C14—H14C	109.5
C1—C6—N3	121.76 (13)
C7—O7—C1—C6	87.32 (16)	C2—C1—C6—C5	0.5 (2)
C7—O7—C1—C2	−99.17 (15)	O7—C1—C6—N3	−4.2 (2)
O7—C1—C2—C3	−171.34 (12)	C2—C1—C6—N3	−177.83 (12)
C6—C1—C2—C3	2.5 (2)	O5—N3—C6—C5	−6.7 (2)
O7—C1—C2—N1	9.53 (19)	O6—N3—C6—C5	173.77 (13)
C6—C1—C2—N1	−176.61 (12)	O5—N3—C6—C1	171.70 (14)
O1—N1—C2—C3	−148.89 (16)	O6—N3—C6—C1	−7.9 (2)
O2—N1—C2—C3	29.57 (19)	C1—O7—C7—O8	2.8 (2)
O1—N1—C2—C1	30.3 (2)	C1—O7—C7—C8	−176.87 (12)
O2—N1—C2—C1	−151.26 (14)	O8—C7—C8—C9	−151.99 (17)
C1—C2—C3—C4	−3.3 (2)	O7—C7—C8—C9	27.6 (2)
N1—C2—C3—C4	175.80 (13)	O8—C7—C8—C13	24.5 (2)
C2—C3—C4—C5	1.3 (2)	O7—C7—C8—C13	−155.96 (14)
C2—C3—C4—N2	−178.25 (13)	C13—C8—C9—C10	−0.9 (3)
O3—N2—C4—C5	165.82 (18)	C7—C8—C9—C10	175.47 (16)
O4—N2—C4—C5	−13.5 (3)	C8—C9—C10—C11	1.1 (3)
O3—N2—C4—C3	−14.6 (3)	C9—C10—C11—C12	0.0 (3)
O4—N2—C4—C3	166.10 (18)	C9—C10—C11—C14	−179.2 (2)
C3—C4—C5—C6	1.5 (2)	C10—C11—C12—C13	−1.2 (3)
N2—C4—C5—C6	−178.95 (14)	C14—C11—C12—C13	178.0 (2)
C4—C5—C6—C1	−2.4 (2)	C11—C12—C13—C8	1.3 (3)
C4—C5—C6—N3	175.99 (13)	C9—C8—C13—C12	−0.2 (3)
O7—C1—C6—C5	174.10 (13)	C7—C8—C13—C12	−176.76 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O8i	0.93	2.50	3.4286 (19)	175

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	3.4286 (19)	175

Symmetry code: (i) .