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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2548.
Published online 2009 September 26. doi:  10.1107/S1600536809036976
PMCID: PMC2970263

Triethyl­ammonium 2,4-dinitro­phenyl­barbiturate

Abstract

In the title mol­ecular salt [systematic name: triethylammonium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropyrim­idin-4-olate], C6H16N+·C10H5N4O7 , the cation and anion are linked by an N—H(...)O hydrogen bond. In the crystal, inversion-related barbiturate rings are centrosymmetrically connected through pairs of N—H(...)O hydrogen bonds, forming R 2 2(8)R 2 2(8) ring motifs.

Related literature

For further information on the anti­convulsant properties of the title compound and general background, see: Kalaivani et al. (2008 [triangle]). For a related structure, see: Craven (1964 [triangle]). For data on hydrogen-bond motifs in organic crystals, see: Allen et al. (1998 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2548-scheme1.jpg

Experimental

Crystal data

  • C6H16N+·C10H5N4O7
  • M r = 395.38
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2548-efi1.jpg
  • a = 29.7900 (8) Å
  • b = 10.4533 (3) Å
  • c = 11.9606 (3) Å
  • β = 97.903 (1)°
  • V = 3689.20 (17) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.11 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 [triangle]) T min = 0.942, T max = 0.971
  • 32882 measured reflections
  • 3217 independent reflections
  • 2493 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.109
  • S = 1.04
  • 3217 reflections
  • 268 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT-Plus (Bruker, 2004 [triangle]); data reduction: SAINT-Plus and XPREP (Bruker, 2004 [triangle]); program(s) used to solve structure: SIR92 (Altornare et al., 1993 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809036976/hb5061sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036976/hb5061Isup2.hkl

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

Acknowledgments

The authors are thankful to SAIF, IIT Madras, for the crystal data.

supplementary crystallographic information

Comment

We have recently prepared the title compound, (I), which has anticonvulsant activity (Kalaivani et al., 2008). We now report its crystal structure.

ORTEP view of the title compound is shown in Fig. 1. The presence of the leaving group (chlorine atom) para with respect to the nitrogroup of the starting molecule (1 – chloro – 2,4 – dinitrobenzene) facilitates the formation of the title compound in the presence of barbituric acid and triethylamine. Absence of chlorine atom, as indicated by the qualitative test on the synthesized barbirutrate has been supported by the crystallographic data. The title molecule is coloured red and it has been attributed to the delocalization of negative charge (Kalaivani et al., 2008) which has also been substantiated by the bond angles and bond lengths of single-crystal X-ray data of 2,4-dinitrophenyl and barbiturate rings. The bond angles and bond lengths of barbiturate residue of the title molecule are compatible with that of barbiturate ion (Craven, 1964), evidencing the delocalization of negative charge in the barbiturate ring.

Presence of double bond (delocalized) between C3 and C5 atoms fixes the configuration of the molecule as depicted in Fig. 1. The N5—H5···O2 hydrogen bond between the asymmetric units is the main driving force for the orientation of the triethylammonium cation (Fig. 2). Two inversion related barbiturate anions interact through a pair of N—H···O=C hydrogen bonds involving N1—H1 atoms and the carbonyl oxygen atom (O1) forming a R22(8) ring motif. The same ring motif is also due to a pair of N—H···O hydrogen bonds involving N2—H2 atoms and the carbonyl oxygen atom (O3). This motif is one of the 24 most frequently observed bimolecular cyclic hydrogen-bonded motifs in organic crystal structures (Allen et al., 1998). The hydrogen bonds observed in the title molecule are mainly responsible for its stability. The high solubility of the title drug molecule in water (4 g cc-1 at 298 K) is due to the positively charged triethylammonium cation and negatively charged 2,4-dinitrophenylbarbiturate anion of the asymmetric unit.

Experimental

The title compound was prepared as described previously (Kalaivani et al., 2008) and recrystallized from absolute ethanol to yield maroon blocks of (I).

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.

Figures

Fig. 1.
The molecular structure of (I) showing 50% displacement ellipsoids.
Fig. 2.
Packing view of (I).

Crystal data

C6H16N+·C10H5N4O7F(000) = 1664
Mr = 395.38Dx = 1.424 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8875 reflections
a = 29.7900 (8) Åθ = 2.5–24.5°
b = 10.4533 (3) ŵ = 0.11 mm1
c = 11.9606 (3) ÅT = 293 K
β = 97.903 (1)°Block, maroon
V = 3689.20 (17) Å30.30 × 0.20 × 0.20 mm
Z = 8

Data collection

Bruker Kappa APEXII CCD diffractometer3217 independent reflections
Radiation source: fine-focus sealed tube2493 reflections with I > 2σ(I)
graphiteRint = 0.036
ω and [var phi] scanθmax = 24.9°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 1999)h = −35→35
Tmin = 0.942, Tmax = 0.971k = −12→12
32882 measured reflectionsl = −13→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.04w = 1/[σ2(Fo2) + (0.0467P)2 + 3.5895P] where P = (Fo2 + 2Fc2)/3
3217 reflections(Δ/σ)max < 0.001
268 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = −0.19 e Å3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C10.49607 (6)0.30537 (17)0.47768 (17)0.0402 (5)
C20.43235 (6)0.33505 (16)0.32947 (15)0.0336 (4)
C30.42904 (6)0.20117 (16)0.31524 (15)0.0339 (4)
C40.45876 (6)0.11860 (16)0.38266 (15)0.0348 (4)
C50.39223 (6)0.15178 (15)0.23248 (14)0.0321 (4)
C60.34717 (6)0.18925 (16)0.22995 (14)0.0317 (4)
C70.31314 (6)0.15443 (17)0.14568 (15)0.0372 (4)
H70.28350.18200.14630.045*
C80.32439 (6)0.07760 (17)0.06070 (15)0.0371 (4)
C90.36810 (7)0.03485 (18)0.05876 (16)0.0408 (5)
H90.3751−0.01730.00060.049*
C100.40118 (7)0.07127 (17)0.14501 (16)0.0387 (5)
H100.43050.04110.14490.046*
C110.39539 (7)0.7557 (2)0.27509 (19)0.0498 (5)
H11A0.41260.76590.34950.060*
H11B0.37790.83310.25770.060*
C120.42740 (9)0.7390 (3)0.1905 (2)0.0700 (7)
H12A0.44250.65800.20220.105*
H12B0.44950.80650.19910.105*
H12C0.41090.74190.11580.105*
C130.33902 (8)0.6466 (2)0.37901 (18)0.0570 (6)
H13A0.32680.73160.38770.068*
H13B0.31370.58770.36590.068*
C140.36764 (10)0.6107 (2)0.48412 (19)0.0702 (7)
H14A0.38030.52740.47570.105*
H14B0.34970.60920.54480.105*
H14C0.39160.67200.50060.105*
C150.33107 (7)0.6313 (2)0.17207 (18)0.0494 (5)
H15A0.31450.55210.17680.059*
H15B0.34780.62430.10830.059*
C160.29765 (8)0.7386 (3)0.1498 (2)0.0690 (7)
H16A0.27920.74240.20960.104*
H16B0.27870.72400.07930.104*
H16C0.31360.81790.14640.104*
N10.46707 (5)0.37959 (15)0.40826 (14)0.0416 (4)
N20.49133 (5)0.17742 (14)0.46111 (14)0.0387 (4)
N30.33250 (6)0.26868 (15)0.31972 (14)0.0414 (4)
N40.28841 (7)0.04383 (17)−0.03058 (15)0.0515 (5)
N50.36397 (6)0.64590 (15)0.27695 (13)0.0387 (4)
O10.52439 (5)0.35119 (13)0.55104 (13)0.0575 (4)
O20.40649 (4)0.41466 (11)0.27608 (11)0.0425 (4)
O30.45764 (5)−0.00016 (12)0.38115 (12)0.0496 (4)
O40.35005 (6)0.25162 (15)0.41664 (12)0.0582 (4)
O50.30234 (5)0.34649 (15)0.29215 (14)0.0582 (4)
O60.24947 (6)0.0672 (2)−0.01885 (17)0.0964 (7)
O70.29920 (6)−0.00325 (19)−0.11540 (15)0.0808 (6)
H10.4688 (7)0.459 (2)0.4188 (17)0.046 (6)*
H20.5078 (7)0.133 (2)0.5064 (19)0.050 (6)*
H50.3796 (7)0.577 (2)0.2791 (17)0.044 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0371 (10)0.0255 (9)0.0527 (12)−0.0008 (8)−0.0122 (9)−0.0017 (8)
C20.0337 (10)0.0252 (9)0.0386 (10)0.0012 (7)−0.0070 (8)0.0001 (7)
C30.0353 (10)0.0231 (9)0.0395 (10)0.0002 (7)−0.0087 (8)−0.0012 (7)
C40.0373 (10)0.0231 (9)0.0408 (10)0.0002 (7)−0.0061 (8)−0.0025 (7)
C50.0393 (10)0.0194 (8)0.0344 (10)−0.0015 (7)−0.0058 (8)0.0035 (7)
C60.0388 (10)0.0247 (9)0.0300 (9)−0.0034 (7)−0.0005 (8)0.0003 (7)
C70.0349 (10)0.0353 (10)0.0394 (11)−0.0039 (8)−0.0016 (8)0.0028 (8)
C80.0443 (11)0.0295 (9)0.0335 (10)−0.0057 (8)−0.0092 (8)−0.0003 (8)
C90.0537 (12)0.0284 (9)0.0382 (10)0.0004 (9)−0.0019 (9)−0.0062 (8)
C100.0410 (11)0.0283 (9)0.0441 (11)0.0031 (8)−0.0044 (9)−0.0032 (8)
C110.0497 (13)0.0374 (11)0.0579 (13)−0.0010 (9)−0.0077 (10)0.0042 (10)
C120.0664 (16)0.0652 (16)0.0797 (18)−0.0033 (13)0.0145 (14)0.0200 (14)
C130.0710 (15)0.0484 (13)0.0549 (14)0.0046 (11)0.0203 (12)−0.0038 (11)
C140.107 (2)0.0575 (15)0.0484 (14)0.0062 (14)0.0207 (14)0.0066 (11)
C150.0528 (13)0.0432 (12)0.0495 (12)−0.0039 (10)−0.0029 (10)−0.0025 (10)
C160.0522 (14)0.0725 (17)0.0766 (17)0.0098 (12)−0.0119 (12)0.0106 (14)
N10.0444 (10)0.0180 (8)0.0554 (10)−0.0014 (7)−0.0185 (8)−0.0011 (7)
N20.0391 (9)0.0227 (8)0.0480 (10)0.0024 (7)−0.0161 (8)0.0015 (7)
N30.0436 (10)0.0370 (9)0.0435 (10)−0.0082 (8)0.0053 (8)−0.0049 (7)
N40.0576 (12)0.0441 (10)0.0466 (11)−0.0041 (9)−0.0151 (9)−0.0070 (8)
N50.0508 (10)0.0255 (8)0.0392 (9)0.0094 (8)0.0041 (7)0.0014 (7)
O10.0558 (9)0.0284 (7)0.0756 (10)−0.0022 (6)−0.0366 (8)−0.0024 (7)
O20.0464 (8)0.0225 (6)0.0522 (8)0.0041 (6)−0.0162 (6)0.0014 (6)
O30.0594 (9)0.0205 (7)0.0600 (9)0.0023 (6)−0.0234 (7)−0.0011 (6)
O40.0764 (11)0.0639 (10)0.0330 (8)−0.0074 (8)0.0031 (7)−0.0084 (7)
O50.0499 (9)0.0512 (9)0.0730 (11)0.0085 (8)0.0067 (8)−0.0125 (8)
O60.0495 (11)0.150 (2)0.0822 (14)−0.0072 (12)−0.0177 (10)−0.0414 (13)
O70.0883 (13)0.0883 (14)0.0564 (11)0.0148 (11)−0.0234 (9)−0.0350 (10)

Geometric parameters (Å, °)

C1—O11.228 (2)C12—H12A0.9600
C1—N21.357 (2)C12—H12B0.9600
C1—N11.357 (2)C12—H12C0.9600
C2—O21.248 (2)C13—C141.467 (3)
C2—N11.381 (2)C13—N51.514 (3)
C2—C31.412 (2)C13—H13A0.9700
C3—C41.408 (2)C13—H13B0.9700
C3—C51.466 (2)C14—H14A0.9600
C4—O31.242 (2)C14—H14B0.9600
C4—N21.396 (2)C14—H14C0.9600
C5—C61.395 (2)C15—N51.490 (2)
C5—C101.397 (3)C15—C161.498 (3)
C6—C71.377 (2)C15—H15A0.9700
C6—N31.471 (2)C15—H15B0.9700
C7—C81.373 (3)C16—H16A0.9600
C7—H70.9300C16—H16B0.9600
C8—C91.380 (3)C16—H16C0.9600
C8—N41.464 (2)N1—H10.84 (2)
C9—C101.379 (3)N2—H20.82 (2)
C9—H90.9300N3—O41.217 (2)
C10—H100.9300N3—O51.223 (2)
C11—N51.483 (3)N4—O71.210 (2)
C11—C121.492 (3)N4—O61.212 (2)
C11—H11A0.9700N5—H50.85 (2)
C11—H11B0.9700
O1—C1—N2122.44 (17)C14—C13—N5113.4 (2)
O1—C1—N1122.11 (17)C14—C13—H13A108.9
N2—C1—N1115.45 (16)N5—C13—H13A108.9
O2—C2—N1118.42 (15)C14—C13—H13B108.9
O2—C2—C3124.84 (16)N5—C13—H13B108.9
N1—C2—C3116.74 (15)H13A—C13—H13B107.7
C4—C3—C2120.71 (16)C13—C14—H14A109.5
C4—C3—C5121.58 (15)C13—C14—H14B109.5
C2—C3—C5117.63 (15)H14A—C14—H14B109.5
O3—C4—N2117.69 (16)C13—C14—H14C109.5
O3—C4—C3126.22 (16)H14A—C14—H14C109.5
N2—C4—C3116.04 (15)H14B—C14—H14C109.5
C6—C5—C10115.80 (16)N5—C15—C16114.65 (18)
C6—C5—C3122.95 (16)N5—C15—H15A108.6
C10—C5—C3121.05 (17)C16—C15—H15A108.6
C7—C6—C5123.46 (16)N5—C15—H15B108.6
C7—C6—N3114.89 (16)C16—C15—H15B108.6
C5—C6—N3121.64 (15)H15A—C15—H15B107.6
C8—C7—C6117.81 (17)C15—C16—H16A109.5
C8—C7—H7121.1C15—C16—H16B109.5
C6—C7—H7121.1H16A—C16—H16B109.5
C7—C8—C9121.94 (16)C15—C16—H16C109.5
C7—C8—N4117.70 (18)H16A—C16—H16C109.5
C9—C8—N4120.34 (17)H16B—C16—H16C109.5
C10—C9—C8118.50 (17)C1—N1—C2125.39 (16)
C10—C9—H9120.8C1—N1—H1116.9 (14)
C8—C9—H9120.8C2—N1—H1117.4 (14)
C9—C10—C5122.44 (18)C1—N2—C4125.53 (16)
C9—C10—H10118.8C1—N2—H2114.8 (16)
C5—C10—H10118.8C4—N2—H2119.4 (16)
N5—C11—C12112.55 (18)O4—N3—O5123.88 (17)
N5—C11—H11A109.1O4—N3—C6118.73 (16)
C12—C11—H11A109.1O5—N3—C6117.36 (16)
N5—C11—H11B109.1O7—N4—O6123.20 (18)
C12—C11—H11B109.1O7—N4—C8118.14 (19)
H11A—C11—H11B107.8O6—N4—C8118.64 (19)
C11—C12—H12A109.5C11—N5—C15114.20 (16)
C11—C12—H12B109.5C11—N5—C13112.90 (17)
H12A—C12—H12B109.5C15—N5—C13109.90 (17)
C11—C12—H12C109.5C11—N5—H5107.9 (14)
H12A—C12—H12C109.5C15—N5—H5103.4 (14)
H12B—C12—H12C109.5C13—N5—H5107.9 (14)
O2—C2—C3—C4−177.48 (19)C3—C5—C10—C9−172.52 (17)
N1—C2—C3—C42.8 (3)O1—C1—N1—C2−175.1 (2)
O2—C2—C3—C5−0.7 (3)N2—C1—N1—C24.3 (3)
N1—C2—C3—C5179.64 (17)O2—C2—N1—C1175.63 (19)
C2—C3—C4—O3176.4 (2)C3—C2—N1—C1−4.7 (3)
C5—C3—C4—O3−0.2 (3)O1—C1—N2—C4177.2 (2)
C2—C3—C4—N2−1.0 (3)N1—C1—N2—C4−2.2 (3)
C5—C3—C4—N2−177.72 (17)O3—C4—N2—C1−177.0 (2)
C4—C3—C5—C6126.7 (2)C3—C4—N2—C10.7 (3)
C2—C3—C5—C6−50.1 (3)C7—C6—N3—O4142.69 (17)
C4—C3—C5—C10−58.6 (3)C5—C6—N3—O4−36.5 (2)
C2—C3—C5—C10124.63 (19)C7—C6—N3—O5−35.6 (2)
C10—C5—C6—C7−2.2 (3)C5—C6—N3—O5145.17 (17)
C3—C5—C6—C7172.76 (17)C7—C8—N4—O7166.62 (19)
C10—C5—C6—N3176.93 (15)C9—C8—N4—O7−12.1 (3)
C3—C5—C6—N3−8.1 (3)C7—C8—N4—O6−11.6 (3)
C5—C6—C7—C80.7 (3)C9—C8—N4—O6169.7 (2)
N3—C6—C7—C8−178.44 (16)C12—C11—N5—C15−66.8 (2)
C6—C7—C8—C90.5 (3)C12—C11—N5—C13166.72 (18)
C6—C7—C8—N4−178.22 (16)C16—C15—N5—C11−65.2 (3)
C7—C8—C9—C10−0.2 (3)C16—C15—N5—C1362.8 (2)
N4—C8—C9—C10178.53 (17)C14—C13—N5—C11−73.7 (2)
C8—C9—C10—C5−1.4 (3)C14—C13—N5—C15157.55 (19)
C6—C5—C10—C92.5 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.84 (2)2.02 (2)2.861 (2)177 (2)
N2—H2···O3ii0.82 (2)2.10 (2)2.918 (2)172 (2)
N5—H5···O20.85 (2)1.88 (2)2.730 (2)172 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5061).

References

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