Z =4 Mo K radiation = 0.10 mm 1. Data collection. Refinement. R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections

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1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN N,N 0,N 00 -Triphenylguanidinium 5-nitro- 2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1- ide P. S. Pereira Silva, S. R. Domingos, M. Ramos Silva, J. A. Paixão and A. Matos Beja* CEMDRX, Physics Department, University of Coimbra, P Coimbra, Portugal Correspondence psidonio@pollux.fis.uc.pt Received 30 April 2008; accepted 12 May 2008 Key indicators: single-crystal X-ray study; T = 293 K; mean (C C) = Å; R factor = 0.051; wr factor = 0.154; data-to-parameter ratio = In the title compound, C 19 H 18 N 3 +. C 4 H 2 N 3 O 4, the dihedral angles between the phenyl rings and the plane defined by the central guanidinium fragment are in the range 41.3 (1) 66.6 (1). The pyrimidine ring of the anion is distorted towards a boat conformation and the nitro group is rotated 11.4 (2) out of the uracil plane. Hydrogen bonds assemble the ions in infinite helical chains along the b axis. Related literature For the non-linear optical properties of 5-nitrouracil, see: Puccetti et al. (1993), Youping et al. (1992). For reports of other triphenylguanidine salts, see: Pereira Silva et al. (2006, 2007a,b), Pereira Silva, Cardoso et al. (2007). For related literature, see: Allen et al. (1987); Kemme et al. (1988); Klement et al. (1995); Largent et al. (1987); Pettier & Byrn (1982); Rao et al. (1995); Weber et al. (1986); Zyss et al. (1993). Experimental Crystal data C 19 H 18 N 3 + C 4 H 2 N 3 O 4 M r = Monoclinic, P2 1 =c a = (4) Å b = (7) Å c = (7) Å = (3) V = (18) Å 3 Z =4 Mo K radiation = 0.10 mm 1 Data collection Bruker APEX2 CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 2003) T min = 0.822, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections Table 1 Hydrogen-bond geometry (Å, ). T = 293 (2) K mm measured reflections 5534 independent reflections 2650 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.22 e Å 3 min = 0.17 e Å 3 D HA D H HA DA D HA N6 H6AO2 i (2) 174 N7 H7N1 i (2) 142 N8 H8O4 ii (2) 163 Symmetry codes: (i) x þ 2; y; z þ 1; (ii) x; y þ 1 2 ; z 1 2. Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97. This work was supported by FundaçãoparaaCiência e a Tecnologia (FCT) under project POCI/FIS/58309/2004 Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2707). References Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1 19. Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Kemme, A., Rutkis, M. & Eiduss, J. (1988). Latv. PSR Zinat. Akad. Vestis Kim. Ser. 5, Klement, U., Range, K.-J., Hayessen, R. & Heckmann, K.-D. (1995). Z. Kristallogr. 220, 611. Largent, B. L., Wikström, H., Gundlach, A. L. & Snyder, S. H. (1987). Mol. Pharmacol. 32, Pereira Silva, P. S., Cardoso, C., Ramos Silva, M. & Paixão, J. A. (2007). Acta Cryst. E63, o501 o503. Pereira Silva, P. S., Paixão, J. A., Ramos Silva, M. & Matos Beja, A. (2006). Acta Cryst. E62, o3073 o3075. Pereira Silva, P. S., Ramos Silva, M., Paixão, J. A. & Matos Beja, A. (2007a). Acta Cryst. E63, o2243 o2245. Pereira Silva, P. S., Ramos Silva, M., Paixão, J. A. & Matos Beja, A. (2007b). Acta Cryst. E63, o2524 o2526. Pettier, P. R. & Byrn, S. R. (1982). J. Org. Chem. 47, Puccetti, G., Perigaud, A., Badan, J., Ledoux, I. & Zyss, J. (1993). J. Opt. Soc. Am. B, 10, Rao, T. S., Rando, R. F., Huffman, J. H. & Revankar, G. R. (1995). Nucleosides Nucleotides, 14, o1082 Pereira Silva et al. doi: /s

2 organic compounds Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, Spek, A. L. (2003). J. Appl. Cryst. 36, Weber, E., Sonders, M., Quarum, M., McLean, S., Pou, S. & Keana, J. F. W. (1986). Proc. Natl Acad. Sci. USA, 83, Youping, H., Genbo, S., Bochang, W. & Rihong, J. (1992). J. Cryst. Growth, 119, Zyss, J., Pecaut, J., Levy, J. P. & Masse, R. (1993). Acta Cryst. B49, Pereira Silva et al. C 19 H 18 N 3 + C 4 H 2 N 3 O 4 o1083

3 supporting information [doi: /s ] N,N,N -Triphenylguanidinium 5-nitro-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ide P. S. Pereira Silva, S. R. Domingos, M. Ramos Silva, J. A. Paixão and A. Matos Beja S1. Comment 5-Nitrouracil is currently of prime interest to the non-linear optical community (Puccetti et al., 1993; Youping et al., 1992) and is also of relevance to the biological and pharmaceutical sciences (Rao et al., 1995; Pettier & Byrn, 1982). Much of the interest in guanidine compounds and its derivatives is due to their biological activity, in particular their neuroleptic and antipsychotic properties (Weber et al., 1986; Largent et al., 1987). Our interest is focused on the physical properties of guanidine compounds, which are regarded as potentially interesting for non-linear optics applications (Zyss et al., 1993). We are currently engaged in a research project aimed at investigating the structural, dielectric and optical properties of triphenylguanidine compounds. Compound (I) (Fig.1) is built up from triphenylguanidinium cations and 5-nitrouracilate anions. The pyrimidine ring is almost planar with a slight distortion towards a boat configuration. The nitro group is rotated 11.4 (2) out of the plane of the uracil fragment. The central guanidine fragment of the cation of the title salt is planar with bond lengths and angles close to those expected for a central Csp 2 atom, accounting for some charge delocalization between the three C N bonds. The bond lengths C7 N6 [1.333 (2) Å], C7 N7 [1.330 (2) Å] and C7 N8 [1.337 (2) Å] are comparable with literature averages for substituted and unsubstituted guanidinium cations (1.321 and Å, respectively; Allen et al., 1987) The dihedral angles between the ring planes and the plane defined by the central guanidinium fragment are 41.3 (1)(C8 C13), 57.5 (1)(C14 C19) and 66.6 (1) (C20 C25). The corresponding angles for other triphenylguanidinium salts reported in the literature are within the range 32.6 (3) 70.2 (3) (Kemme et al., 1988; Klement et al., 1995; Pereira Silva et al., 2006, 2007a, 2007b, Pereira Silva, Cardoso et al.,(2007). The anions and cations are linked into infinite helical chains running parallel to the b axis, via hydrogen bonds involving all the NH groups of the guanidinium fragment, the carbonyl O atoms and the deprotonated N atom of the anion (Fig. 2, Table 2). Atoms O2 and N1 accept each one H atom across a crystallographic centre of symmetry, while the O4 atom accept one hydrogen from the N8 atom related by a twofold screw axis. S2. Experimental The title compound was prepared by adding 5-nitrouracil (Aldrich, 98%, 1 mmol) to triphenylguanidine (TCI 97%, 1 mmol) in a ethanol solution (80 ml). The solution was slowly warmed and then left to evaporate under ambient conditions. After a few days, small yellow transparent single crystals were deposited. S3. Refinement All H atoms were located in a difference Fourier synthesis, placed at calculated positions and refined as riding on their parent atoms, using SHELXL97 (Sheldrick, 2008) defaults [C H = 0.93 Å, N H = 0.86 Å and U iso (H) = 1.2U eq (C,N)]. sup-1

4 Figure 1 ORTEPII (Spek,2003) plot of the title compound. Displacement ellipsoids are drawn at the 50% probability level. sup-2

5 Figure 2 Packing diagram, viewed down the c axis, with the hydrogen bonds depicted as dashed lines. The phenyl rings have been omitted for clarity. N,N,N -Triphenylguanidinium 5-nitro-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ide Crystal data C 19 H 18 N 3+ C 4 H 2 N 3 O 4 M r = Monoclinic, P2 1 /c Hall symbol: -P 2ybc a = (4) Å b = (7) Å c = (7) Å β = (3) V = (18) Å 3 Z = 4 F(000) = 928 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 5110 reflections θ = µ = 0.10 mm 1 T = 293 K Block, yellow mm sup-3

6 Data collection Bruker APEX2 CCD area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 2003) T min = 0.822, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 299 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map measured reflections 5534 independent reflections 2650 reflections with I > 2σ(I) R int = θ max = 28.6, θ min = 2.0 h = k = l = Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0713P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.22 e Å 3 Δρ min = 0.17 e Å 3 Extinction correction: SHELXL97 (Sheldrick, 2008), Fc * =kfc[ xfc 2 λ 3 /sin(2θ)] -1/4 Extinction coefficient: (11) 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 F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq O (16) (11) (13) (5) O (16) (11) (15) (6) O (2) (11) (15) (6) O (2) (12) (16) (6) N (17) (12) (13) (5) N (18) (13) (16) (6) H * N (2) (13) (13) (5) C (2) (17) (16) (6) C (2) (16) (17) (6) C (2) (14) (14) (5) C (2) (15) (15) (6) H * N (16) (10) (12) (4) H6A * sup-4

7 N (16) (10) (12) (4) H * N (16) (10) (12) (4) H * C (19) (12) (14) (5) C (2) (13) (14) (5) C (3) (15) (2) (7) H * C (4) (18) (2) (10) H * C (4) (2) (2) (12) H * C (3) (2) (2) (10) H * C (2) (17) (16) (7) H * C (19) (11) (15) (5) C (3) (14) (19) (7) H * C (4) (18) (2) (11) H * C (3) (17) (2) (8) H * C (2) (15) (18) (6) H * C (2) (13) (15) (5) H * C (19) (11) (14) (5) C (2) (14) (16) (5) H * C (3) (15) (2) (6) H * C (3) (17) (2) (7) H * C (2) (17) (2) (7) H * C (2) (14) (16) (6) H * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 O (9) (11) (12) (8) (8) (9) O (9) (13) (16) (8) (10) (12) O (16) (12) (14) (11) (13) (10) O (12) (14) (15) (10) (12) (11) N (9) (13) (10) (8) (8) (9) N (9) (14) (16) (9) (10) (11) sup-5

8 N (11) (14) (11) (10) (9) (9) C (10) (16) (13) (10) (9) (12) C (10) (17) (14) (10) (10) (12) C (10) (15) (11) (10) (9) (10) C (11) (16) (12) (10) (9) (11) N (8) (10) (10) (7) (8) (8) N (8) (9) (10) (7) (7) (7) N (8) (9) (10) (7) (7) (8) C (10) (12) (11) (8) (8) (9) C (10) (13) (11) (9) (9) (9) C (15) (16) (18) (12) (14) (13) C (2) (17) (2) (16) (18) (15) C (2) (2) (19) (18) (17) (15) C (19) (2) (18) (18) (15) (16) C (12) (18) (13) (12) (10) (12) C (9) (11) (12) (8) (9) (9) C (18) (14) (15) (13) (13) (11) C (3) (2) (2) (19) (2) (16) C (18) (18) (2) (14) (16) (14) C (13) (15) (14) (11) (11) (11) C (11) (12) (13) (9) (10) (10) C (10) (11) (12) (8) (9) (9) C (12) (13) (13) (10) (11) (10) C (16) (16) (17) (13) (15) (13) C (14) (18) (2) (12) (16) (15) C (11) (19) (17) (11) (11) (14) C (11) (15) (13) (10) (10) (11) Geometric parameters (Å, º) O2 C (3) C11 C (4) O4 C (2) C11 H O7 N (2) C12 C (4) O8 N (2) C12 H N1 C (3) C13 H N1 C (3) C14 C (3) N3 C (3) C14 C (3) N3 C (3) C15 C (3) N3 H C15 H N5 C (3) C16 C (4) C4 C (3) C16 H C5 C (3) C17 C (3) C6 H C17 H N6 C (2) C18 C (3) N6 C (2) C18 H N6 H6A C19 H N7 C (2) C20 C (3) N7 C (2) C20 C (3) sup-6

9 N7 H C21 C (3) N8 C (2) C21 H N8 C (2) C22 C (3) N8 H C22 H C8 C (3) C23 C (3) C8 C (3) C23 H C9 C (4) C24 C (3) C9 H C24 H C10 C (5) C25 H C10 H C6 N1 C (18) C11 C12 C (3) C4 N3 C (2) C11 C12 H C4 N3 H C13 C12 H C2 N3 H C12 C13 C (3) O7 N5 O (2) C12 C13 H O7 N5 C (2) C8 C13 H O8 N5 C (18) C15 C14 C (18) O2 C2 N (19) C15 C14 N (18) O2 C2 N (2) C19 C14 N (17) N1 C2 N (2) C14 C15 C (2) O4 C4 N (2) C14 C15 H O4 C4 C (2) C16 C15 H N3 C4 C (18) C17 C16 C (2) C6 C5 N (2) C17 C16 H C6 C5 C (2) C15 C16 H N5 C5 C (18) C18 C17 C (2) N1 C6 C (2) C18 C17 H N1 C6 H C16 C17 H C5 C6 H C17 C18 C (2) C7 N6 C (17) C17 C18 H C7 N6 H6A C19 C18 H C8 N6 H6A C18 C19 C (2) C7 N7 C (15) C18 C19 H C7 N7 H C14 C19 H C14 N7 H C25 C20 C (18) C7 N8 C (15) C25 C20 N (18) C7 N8 H C21 C20 N (17) C20 N8 H C20 C21 C (2) N7 C7 N (16) C20 C21 H N7 C7 N (16) C22 C21 H N6 C7 N (17) C23 C22 C (2) C9 C8 C (2) C23 C22 H C9 C8 N (19) C21 C22 H C13 C8 N (2) C24 C23 C (2) C8 C9 C (3) C24 C23 H C8 C9 H C22 C23 H C10 C9 H C23 C24 C (2) sup-7

10 C11 C10 C (3) C23 C24 H C11 C10 H C25 C24 H C9 C10 H C20 C25 C (2) C12 C11 C (3) C20 C25 H C12 C11 H C24 C25 H C10 C11 H C6 N1 C2 O (19) C8 C9 C10 C (4) C6 N1 C2 N3 2.8 (3) C9 C10 C11 C (4) C4 N3 C2 O (2) C10 C11 C12 C (4) C4 N3 C2 N1 6.2 (3) C11 C12 C13 C8 0.2 (4) C2 N3 C4 O (2) C9 C8 C13 C (3) C2 N3 C4 C5 5.8 (3) N6 C8 C13 C (19) O7 N5 C5 C (19) C7 N7 C14 C (2) O8 N5 C5 C (3) C7 N7 C14 C (3) O7 N5 C5 C4 9.4 (3) C19 C14 C15 C (4) O8 N5 C5 C (2) N7 C14 C15 C (2) O4 C4 C5 C (2) C14 C15 C16 C (5) N3 C4 C5 C6 2.4 (3) C15 C16 C17 C (5) O4 C4 C5 N5 0.4 (3) C16 C17 C18 C (4) N3 C4 C5 N (18) C17 C18 C19 C (3) C2 N1 C6 C5 0.1 (3) C15 C14 C19 C (3) N5 C5 C6 N (18) N7 C14 C19 C (18) C4 C5 C6 N1 0.2 (3) C7 N8 C20 C (19) C14 N7 C7 N (18) C7 N8 C20 C (3) C14 N7 C7 N (3) C25 C20 C21 C (3) C8 N6 C7 N (18) N8 C20 C21 C (19) C8 N6 C7 N (3) C20 C21 C22 C (4) C20 N8 C7 N (3) C21 C22 C23 C (4) C20 N8 C7 N (18) C22 C23 C24 C (4) C7 N6 C8 C (3) C21 C20 C25 C (3) C7 N6 C8 C (2) N8 C20 C25 C (2) C13 C8 C9 C (3) C23 C24 C25 C (4) N6 C8 C9 C (2) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A N6 H6A O2 i (2) 174 N7 H7 N1 i (2) 142 N8 H8 O4 ii (2) 163 Symmetry codes: (i) x+2, y, z+1; (ii) x, y+1/2, z 1/2. sup-8