Triethyl-ammonium 1,3-dimethyl-5-(2,4,6-trinitro-phenyl)barbiturate.

In the title mol-ecular salt [systematic name: triethyl-ammonium 1,3-dimethyl-2,6-dioxo-5-(2,4,6-trinitro-phen-yl)-1,2,3,6-tetra-hydro-pyrimidin-4-olate], C(6)H(16)N(+)·C(12)H(8)N(5)O(9) (-), the dihedral angle between the aromatic rings in the anion is 46.88 (8)°. The nitro group para to the ring junction is almost coplanar with its attached ring [dihedral angle = 0.76 (3)°], but the two ortho-nitro groups are substanti-ally twisted from the ring plane, by 47.91 (2) and 42.90 (1)°. In the crystal, the cation and anion are linked by an N-H⋯O=C hydrogen bond; these dimeric associations are further connected by weak C-H⋯O bonds to form linear supra-molecular chains extending in the [001] direction.

Related literature

For background to barbiturates, see: Tripathi (2009 ▶). For our recent work in this area, see: Kalaivani & Buvaneswari, 2010 ▶); Kalaivani & Malarvizhi (2009 ▶); Buvaneswari & Kalaivani (2011 ▶); Babykala & Kalaivani (2012 ▶).

Experimental

Crystal data

C6H16N+·C12H8N5O9 −

M = 468.43

Monoclinic,

a = 10.967 (5) Å

b = 20.301 (5) Å

c = 11.072 (5) Å

β = 119.268 (5)°

V = 2150.4 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.941, T max = 0.988

18535 measured reflections

3785 independent reflections

2955 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.108

S = 1.01

3785 reflections

304 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812030450/hb6883sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812030450/hb6883Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812030450/hb6883Isup3.cml

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

C6H16N+·C12H8N5O9−	F(000) = 984
Mr = 468.43	Dx = 1.447 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.967 (5) Å	Cell parameters from 6627 reflections
b = 20.301 (5) Å	θ = 2.9–26.1°
c = 11.072 (5) Å	µ = 0.12 mm−1
β = 119.268 (5)°	T = 293 K
V = 2150.4 (15) Å3	Block, red
Z = 4	0.30 × 0.20 × 0.20 mm

Bruker Kappa APEXII CCD diffractometer	3785 independent reflections
Radiation source: fine-focus sealed tube	2955 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω and φ scan	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −13→12
Tmin = 0.941, Tmax = 0.988	k = −24→24
18535 measured reflections	l = −13→13

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036	H-atom parameters constrained
wR(F2) = 0.108	w = 1/[σ2(Fo2) + (0.0548P)2 + 0.6716P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.001
3785 reflections	Δρmax = 0.28 e Å−3
304 parameters	Δρmin = −0.17 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0019 (6)

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
C1	0.88311 (17)	0.10654 (8)	0.91121 (17)	0.0341 (4)
C2	1.02255 (18)	0.12113 (9)	0.98506 (17)	0.0362 (4)
H2	1.0876	0.0978	0.9710	0.043*
C3	1.06380 (16)	0.17129 (9)	1.08071 (16)	0.0335 (4)
C4	0.96883 (17)	0.20600 (9)	1.10282 (17)	0.0354 (4)
H4	0.9979	0.2388	1.1700	0.042*
C5	0.82951 (17)	0.19082 (8)	1.02269 (16)	0.0330 (4)
C6	0.77688 (17)	0.14087 (8)	0.92164 (16)	0.0318 (4)
C7	0.62923 (17)	0.12556 (9)	0.83656 (16)	0.0345 (4)
C8	0.54703 (18)	0.11973 (9)	0.90224 (17)	0.0378 (4)
C9	0.34306 (18)	0.09753 (9)	0.67628 (17)	0.0369 (4)
C10	0.57272 (17)	0.11594 (8)	0.69361 (17)	0.0344 (4)
C11	0.3184 (2)	0.09483 (14)	0.8813 (2)	0.0681 (7)
H11A	0.2885	0.1368	0.8971	0.102*
H11B	0.3712	0.0723	0.9679	0.102*
H11C	0.2381	0.0689	0.8211	0.102*
C12	0.3617 (2)	0.09733 (12)	0.46746 (19)	0.0578 (6)
H12A	0.3738	0.0528	0.4458	0.087*
H12B	0.4041	0.1271	0.4313	0.087*
H12C	0.2638	0.1070	0.4266	0.087*
C13	0.63642 (18)	0.12726 (9)	0.33536 (18)	0.0409 (4)
H13A	0.5743	0.1558	0.3506	0.049*
H13B	0.6456	0.1453	0.2591	0.049*
C14	0.5725 (2)	0.06017 (10)	0.2963 (2)	0.0527 (5)
H14A	0.6219	0.0345	0.2612	0.079*
H14B	0.4762	0.0641	0.2263	0.079*
H14C	0.5783	0.0388	0.3763	0.079*
C15	0.87815 (18)	0.07822 (9)	0.45773 (18)	0.0420 (4)
H15A	0.9655	0.0800	0.5444	0.050*
H15B	0.8402	0.0342	0.4487	0.050*
C16	0.9074 (2)	0.09033 (12)	0.3404 (2)	0.0554 (5)
H16A	0.8216	0.0880	0.2541	0.083*
H16B	0.9710	0.0575	0.3418	0.083*
H16C	0.9481	0.1332	0.3504	0.083*
C17	0.8343 (2)	0.19556 (10)	0.4964 (2)	0.0514 (5)
H17A	0.8565	0.2100	0.4259	0.062*
H17B	0.7625	0.2246	0.4930	0.062*
C18	0.9621 (2)	0.20199 (12)	0.6351 (2)	0.0648 (6)
H18A	0.9427	0.1854	0.7052	0.097*
H18B	0.9885	0.2475	0.6530	0.097*
H18C	1.0371	0.1772	0.6360	0.097*
N1	0.85117 (16)	0.04632 (8)	0.82617 (16)	0.0453 (4)
N2	1.21193 (15)	0.18730 (8)	1.16185 (15)	0.0395 (4)
N3	0.73551 (15)	0.23498 (7)	1.04510 (15)	0.0397 (4)
N4	0.40581 (14)	0.10460 (8)	0.81685 (14)	0.0403 (4)
N5	0.42801 (14)	0.10512 (7)	0.61771 (14)	0.0373 (4)
N6	0.77754 (14)	0.12699 (7)	0.46335 (14)	0.0370 (3)
H6	0.7634	0.1141	0.5343	0.044*
O1	0.77641 (16)	0.00505 (7)	0.83646 (16)	0.0609 (4)
O2	0.90781 (17)	0.03998 (8)	0.75520 (16)	0.0690 (5)
O3	1.29408 (13)	0.15560 (8)	1.14104 (15)	0.0588 (4)
O4	1.24725 (14)	0.23153 (8)	1.24621 (15)	0.0605 (4)
O5	0.77284 (14)	0.25027 (7)	1.16504 (13)	0.0534 (4)
O6	0.63133 (14)	0.25617 (7)	0.94531 (14)	0.0532 (4)
O7	0.59132 (14)	0.12529 (8)	1.02758 (13)	0.0545 (4)
O8	0.21962 (12)	0.08442 (7)	0.60642 (13)	0.0507 (4)
O9	0.63886 (13)	0.11793 (7)	0.62877 (12)	0.0470 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0351 (9)	0.0377 (9)	0.0296 (9)	−0.0007 (7)	0.0159 (7)	−0.0015 (7)
C2	0.0339 (9)	0.0426 (10)	0.0369 (9)	0.0050 (7)	0.0209 (8)	0.0019 (8)
C3	0.0277 (8)	0.0425 (10)	0.0299 (8)	0.0000 (7)	0.0137 (7)	0.0021 (7)
C4	0.0359 (9)	0.0407 (10)	0.0294 (9)	−0.0018 (7)	0.0160 (7)	−0.0026 (7)
C5	0.0326 (9)	0.0397 (10)	0.0303 (9)	0.0024 (7)	0.0183 (7)	0.0007 (7)
C6	0.0331 (9)	0.0404 (9)	0.0245 (8)	−0.0003 (7)	0.0160 (7)	0.0039 (7)
C7	0.0305 (9)	0.0446 (10)	0.0288 (9)	−0.0012 (7)	0.0147 (7)	0.0001 (7)
C8	0.0336 (9)	0.0498 (11)	0.0305 (9)	−0.0024 (8)	0.0161 (8)	−0.0021 (7)
C9	0.0310 (10)	0.0413 (10)	0.0356 (9)	0.0009 (7)	0.0143 (8)	−0.0021 (7)
C10	0.0328 (9)	0.0406 (10)	0.0301 (9)	−0.0002 (7)	0.0157 (8)	0.0008 (7)
C11	0.0449 (12)	0.119 (2)	0.0525 (13)	−0.0154 (12)	0.0337 (11)	−0.0137 (12)
C12	0.0460 (12)	0.0905 (17)	0.0299 (10)	−0.0027 (11)	0.0132 (9)	−0.0005 (10)
C13	0.0357 (10)	0.0494 (11)	0.0360 (10)	0.0086 (8)	0.0162 (8)	0.0042 (8)
C14	0.0371 (10)	0.0581 (13)	0.0529 (12)	0.0011 (9)	0.0142 (9)	−0.0018 (10)
C15	0.0344 (10)	0.0454 (11)	0.0410 (10)	0.0055 (8)	0.0145 (8)	0.0017 (8)
C16	0.0458 (12)	0.0736 (15)	0.0521 (12)	0.0104 (10)	0.0281 (10)	−0.0039 (10)
C17	0.0601 (13)	0.0454 (11)	0.0546 (12)	−0.0036 (9)	0.0327 (11)	−0.0063 (9)
C18	0.0546 (13)	0.0687 (15)	0.0713 (15)	−0.0167 (11)	0.0310 (12)	−0.0205 (12)
N1	0.0412 (9)	0.0464 (10)	0.0439 (9)	0.0012 (7)	0.0173 (8)	−0.0074 (7)
N2	0.0323 (8)	0.0496 (9)	0.0372 (8)	−0.0013 (7)	0.0176 (7)	0.0010 (7)
N3	0.0360 (8)	0.0470 (9)	0.0385 (9)	0.0034 (7)	0.0202 (7)	−0.0026 (7)
N4	0.0307 (8)	0.0596 (10)	0.0345 (8)	−0.0039 (7)	0.0190 (7)	−0.0033 (7)
N5	0.0305 (8)	0.0527 (9)	0.0261 (7)	−0.0019 (6)	0.0118 (6)	−0.0007 (6)
N6	0.0377 (8)	0.0433 (8)	0.0336 (8)	0.0024 (6)	0.0203 (7)	0.0031 (6)
O1	0.0591 (9)	0.0453 (8)	0.0744 (10)	−0.0100 (7)	0.0295 (8)	−0.0083 (7)
O2	0.0717 (10)	0.0792 (11)	0.0714 (10)	−0.0022 (8)	0.0470 (9)	−0.0295 (8)
O3	0.0326 (7)	0.0740 (10)	0.0692 (10)	0.0027 (7)	0.0244 (7)	−0.0134 (8)
O4	0.0431 (8)	0.0759 (10)	0.0599 (9)	−0.0148 (7)	0.0232 (7)	−0.0280 (8)
O5	0.0512 (8)	0.0702 (10)	0.0411 (8)	0.0074 (7)	0.0244 (6)	−0.0139 (7)
O6	0.0412 (8)	0.0656 (9)	0.0472 (8)	0.0187 (6)	0.0172 (7)	0.0046 (7)
O7	0.0452 (8)	0.0924 (11)	0.0289 (7)	−0.0134 (7)	0.0205 (6)	−0.0051 (6)
O8	0.0282 (7)	0.0692 (9)	0.0474 (8)	−0.0049 (6)	0.0127 (6)	−0.0074 (6)
O9	0.0398 (7)	0.0745 (9)	0.0324 (7)	−0.0049 (6)	0.0220 (6)	−0.0027 (6)

C1—C2	1.368 (2)	C13—C14	1.496 (3)
C1—C6	1.410 (2)	C13—N6	1.503 (2)
C1—N1	1.477 (2)	C13—H13A	0.9700
C2—C3	1.376 (2)	C13—H13B	0.9700
C2—H2	0.9300	C14—H14A	0.9600
C3—C4	1.375 (2)	C14—H14B	0.9600
C3—N2	1.458 (2)	C14—H14C	0.9600
C4—C5	1.375 (2)	C15—C16	1.502 (3)
C4—H4	0.9300	C15—N6	1.506 (2)
C5—C6	1.408 (2)	C15—H15A	0.9700
C5—N3	1.476 (2)	C15—H15B	0.9700
C6—C7	1.454 (2)	C16—H16A	0.9600
C7—C10	1.403 (2)	C16—H16B	0.9600
C7—C8	1.413 (2)	C16—H16C	0.9600
C8—O7	1.231 (2)	C17—C18	1.494 (3)
C8—N4	1.398 (2)	C17—N6	1.496 (2)
C9—O8	1.216 (2)	C17—H17A	0.9700
C9—N4	1.367 (2)	C17—H17B	0.9700
C9—N5	1.379 (2)	C18—H18A	0.9600
C10—O9	1.246 (2)	C18—H18B	0.9600
C10—N5	1.403 (2)	C18—H18C	0.9600
C11—N4	1.461 (2)	N1—O1	1.216 (2)
C11—H11A	0.9600	N1—O2	1.224 (2)
C11—H11B	0.9600	N2—O4	1.214 (2)
C11—H11C	0.9600	N2—O3	1.2174 (19)
C12—N5	1.462 (2)	N3—O6	1.2153 (19)
C12—H12A	0.9600	N3—O5	1.2231 (19)
C12—H12B	0.9600	N6—H6	0.9100
C12—H12C	0.9600
C2—C1—C6	124.81 (16)	H14A—C14—H14B	109.5
C2—C1—N1	114.05 (15)	C13—C14—H14C	109.5
C6—C1—N1	120.89 (15)	H14A—C14—H14C	109.5
C1—C2—C3	118.09 (15)	H14B—C14—H14C	109.5
C1—C2—H2	121.0	C16—C15—N6	113.47 (15)
C3—C2—H2	121.0	C16—C15—H15A	108.9
C4—C3—C2	121.56 (15)	N6—C15—H15A	108.9
C4—C3—N2	119.27 (15)	C16—C15—H15B	108.9
C2—C3—N2	119.16 (15)	N6—C15—H15B	108.9
C3—C4—C5	118.02 (16)	H15A—C15—H15B	107.7
C3—C4—H4	121.0	C15—C16—H16A	109.5
C5—C4—H4	121.0	C15—C16—H16B	109.5
C4—C5—C6	124.66 (15)	H16A—C16—H16B	109.5
C4—C5—N3	113.74 (15)	C15—C16—H16C	109.5
C6—C5—N3	121.49 (14)	H16A—C16—H16C	109.5
C5—C6—C1	112.77 (15)	H16B—C16—H16C	109.5
C5—C6—C7	124.26 (15)	C18—C17—N6	113.69 (18)
C1—C6—C7	122.98 (15)	C18—C17—H17A	108.8
C10—C7—C8	121.86 (15)	N6—C17—H17A	108.8
C10—C7—C6	119.90 (15)	C18—C17—H17B	108.8
C8—C7—C6	118.23 (15)	N6—C17—H17B	108.8
O7—C8—N4	118.59 (15)	H17A—C17—H17B	107.7
O7—C8—C7	124.97 (16)	C17—C18—H18A	109.5
N4—C8—C7	116.41 (15)	C17—C18—H18B	109.5
O8—C9—N4	122.11 (16)	H18A—C18—H18B	109.5
O8—C9—N5	121.55 (16)	C17—C18—H18C	109.5
N4—C9—N5	116.33 (15)	H18A—C18—H18C	109.5
O9—C10—C7	125.81 (16)	H18B—C18—H18C	109.5
O9—C10—N5	117.82 (15)	O1—N1—O2	124.41 (17)
C7—C10—N5	116.35 (15)	O1—N1—C1	118.11 (16)
N4—C11—H11A	109.5	O2—N1—C1	117.37 (16)
N4—C11—H11B	109.5	O4—N2—O3	123.31 (15)
H11A—C11—H11B	109.5	O4—N2—C3	118.63 (15)
N4—C11—H11C	109.5	O3—N2—C3	118.05 (15)
H11A—C11—H11C	109.5	O6—N3—O5	124.33 (15)
H11B—C11—H11C	109.5	O6—N3—C5	119.06 (14)
N5—C12—H12A	109.5	O5—N3—C5	116.51 (14)
N5—C12—H12B	109.5	C9—N4—C8	124.58 (14)
H12A—C12—H12B	109.5	C9—N4—C11	117.14 (15)
N5—C12—H12C	109.5	C8—N4—C11	118.28 (15)
H12A—C12—H12C	109.5	C9—N5—C10	124.20 (14)
H12B—C12—H12C	109.5	C9—N5—C12	116.65 (15)
C14—C13—N6	112.98 (15)	C10—N5—C12	119.06 (15)
C14—C13—H13A	109.0	C17—N6—C13	109.94 (14)
N6—C13—H13A	109.0	C17—N6—C15	113.33 (14)
C14—C13—H13B	109.0	C13—N6—C15	113.64 (14)
N6—C13—H13B	109.0	C17—N6—H6	106.5
H13A—C13—H13B	107.8	C13—N6—H6	106.5
C13—C14—H14A	109.5	C15—N6—H6	106.5
C13—C14—H14B	109.5
C6—C1—C2—C3	2.7 (3)	C6—C1—N1—O2	138.16 (18)
N1—C1—C2—C3	−171.73 (15)	C4—C3—N2—O4	−0.7 (2)
C1—C2—C3—C4	0.2 (3)	C2—C3—N2—O4	−179.81 (16)
C1—C2—C3—N2	179.31 (15)	C4—C3—N2—O3	179.52 (16)
C2—C3—C4—C5	−2.3 (3)	C2—C3—N2—O3	0.4 (2)
N2—C3—C4—C5	178.59 (15)	C4—C5—N3—O6	135.01 (17)
C3—C4—C5—C6	1.8 (3)	C6—C5—N3—O6	−41.4 (2)
C3—C4—C5—N3	−174.45 (15)	C4—C5—N3—O5	−41.5 (2)
C4—C5—C6—C1	0.7 (2)	C6—C5—N3—O5	142.10 (16)
N3—C5—C6—C1	176.70 (14)	O8—C9—N4—C8	−179.90 (17)
C4—C5—C6—C7	−179.45 (16)	N5—C9—N4—C8	1.0 (3)
N3—C5—C6—C7	−3.4 (2)	O8—C9—N4—C11	0.8 (3)
C2—C1—C6—C5	−3.0 (2)	N5—C9—N4—C11	−178.25 (18)
N1—C1—C6—C5	171.01 (15)	O7—C8—N4—C9	179.50 (17)
C2—C1—C6—C7	177.13 (16)	C7—C8—N4—C9	−2.3 (3)
N1—C1—C6—C7	−8.8 (2)	O7—C8—N4—C11	−1.2 (3)
C5—C6—C7—C10	134.21 (17)	C7—C8—N4—C11	176.98 (18)
C1—C6—C7—C10	−46.0 (2)	O8—C9—N5—C10	−175.62 (17)
C5—C6—C7—C8	−46.9 (2)	N4—C9—N5—C10	3.4 (2)
C1—C6—C7—C8	132.98 (18)	O8—C9—N5—C12	0.7 (3)
C10—C7—C8—O7	177.32 (18)	N4—C9—N5—C12	179.73 (17)
C6—C7—C8—O7	−1.6 (3)	O9—C10—N5—C9	175.68 (16)
C10—C7—C8—N4	−0.7 (3)	C7—C10—N5—C9	−6.2 (2)
C6—C7—C8—N4	−179.65 (16)	O9—C10—N5—C12	−0.5 (2)
C8—C7—C10—O9	−177.38 (17)	C7—C10—N5—C12	177.61 (17)
C6—C7—C10—O9	1.5 (3)	C18—C17—N6—C13	169.79 (16)
C8—C7—C10—N5	4.7 (2)	C18—C17—N6—C15	−61.8 (2)
C6—C7—C10—N5	−176.45 (15)	C14—C13—N6—C17	−179.66 (16)
C2—C1—N1—O1	129.19 (17)	C14—C13—N6—C15	52.1 (2)
C6—C1—N1—O1	−45.4 (2)	C16—C15—N6—C17	−66.4 (2)
C2—C1—N1—O2	−47.2 (2)	C16—C15—N6—C13	60.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6···O9	0.91	2.09	2.903 (2)	148
C13—H13B···O7i	0.97	2.37	3.195 (3)	143
C14—H14B···O3ii	0.96	2.55	3.301 (3)	136
C15—H15A···O8iii	0.97	2.52	3.275 (3)	134
C15—H15B···O8iv	0.97	2.49	3.437 (3)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6⋯O9	0.91	2.09	2.903 (2)	148
C13—H13B⋯O7i	0.97	2.37	3.195 (3)	143
C14—H14B⋯O3ii	0.96	2.55	3.301 (3)	136
C15—H15A⋯O8iii	0.97	2.52	3.275 (3)	134
C15—H15B⋯O8iv	0.97	2.49	3.437 (3)	165

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