Experimental. Crystal data

Transcription

1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN N-(Diphenylcarbamoyl)-N,N 0,N 0,N 00,N 00 - pentamethylguanidinium tetraphenylborate Ioannis Tiritiris Fakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D Aalen, Germany Correspondence Ioannis.Tiritiris@htw-aalen.de Received 11 December 2012; accepted 11 December 2012 Key indicators: single-crystal X-ray study; T = 100 K; mean (C C) = Å; R factor = 0.043; wr factor = 0.121; data-to-parameter ratio = In the title salt, C 19 H 25 N 4 O + C 24 H 20 B, the C NandC N bond lengths in the CN 3 unit are (8)/ (9) and (9) Å, indicating double- and single-bond character, respectively. The N C N angles are (6), (6) and (6), showing only a small deviation of the CN 3 plane from an ideal trigonal-planar geometry. The bonds between the N atoms and the terminal methyl C atoms all have values close to a typical single bond [ (9) (9) Å]. The crystal packing is caused by electrostatic interactions between cations and anions. Related literature For the synthesis and crystal structure of 3-[bis(dimethylamino)methylene]-1,1-diphenylurea, see: Tiritiris (2012). For the crystal structures of alkali metal tetraphenylborates, see: Behrens et al. (2012). Experimental Crystal data C 19 H 25 N 4 O + C 24 H 20 B M r = Monoclinic, P2 1 =n a = (4) Å b = (3) Å c = (12) Å = (2) Data collection Bruker Kappa APEXII DUO diffractometer measured reflections Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections V = (2) Å 3 Z =4 Mo K radiation = 0.07 mm 1 T = 100 K mm independent reflections reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.51 e Å 3 min = 0.22 e Å 3 Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97. The author thanks Dr W. Frey (Institut für Organische Chemie, Universität Stuttgart) for the data collection. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FK2067). References Behrens, U., Hoffmann, F. & Olbrich, F. (2012). Organometallics, 31, Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Sheldrick, G. M. (2008). Acta Cryst. A64, Tiritiris, I. (2012). Acta Cryst. E68, o3085. o98 Ioannis Tiritiris doi: /s

2 supplementary materials [doi: /s ] N-(Diphenylcarbamoyl)-N,N,N,N,N -pentamethylguanidinium tetraphenylborate Ioannis Tiritiris Comment 3-[bis(dimethylamino)methylene]-1,1-diphenylurea - also known as N-diphenylcarbamoyl-N,N,N,N - tetramethylguanidine (Tiritiris, 2012) - is a guanidine derivative bearing additionally an urea moiety. By alkylation of the nitrogen atom, many structurally different guanidinium salts can be obtained. One of them is the here presented title compound. In the crystal structure of the salt, isolated cations and anions are present. One C N bond of the CN 3 unit in the cationic part is elongated (C1 N3 = (9) Å), indicating single bond character. The two remaining C N bonds (C1 N2 = (8) Å and C1 N1 = (9) Å) are shorter and they show double bond character. As a consequence, the positive charge is not delocalized over the entire CN 3 unit, but only between the two dimethylamino groups. The N C1 N angles are: (6) (N1 C1 N2), (6) (N2 C1 N3) and (6) (N1 C1 N3), which indicate only a slight deviation of the CN 3 plane from an ideal trigonal-planar geometry. The bonds between the N atoms and the terminal C-methyl groups, all have values close to a typical single bond ( (9) (9) Å). The C O bond length in the diphenylcarbamoyl group is C7 O1 = (8) Å, and shows the expected double-bond character. The N C bond lengths are: N3 C7 = (9) Å, N4 C7 = (8) Å, N4 C8 = (9) Å and N4 C14 = (9) Å. They are comparable with the data from the crystal structure analysis of 3-[bis(dimethylamino)methylene]- 1,1-diphenylurea (Tiritiris, 2012). The dihedral angle C1 N3 C7 N4 is 35.9 (1) and the angle between the planes N1/C1/N2 and O1/C7/N4 is 61.5 (1), which show a significant twisting of the diphenylcarbamoyl group relative to the CN 3 plane (Fig. 1). The bond lengths and angles in the tetraphenylborate ion are in good agreement with the data from the crystal structure analysis of the alkali metal tetraphenylborates (Behrens et al., 2012). No specific interactions between the guanidinium ions and tetraphenylborate ions have been observed. Crystal packing is caused by electrostatic interactions between cations and anions. Experimental The title compound was obtained by reacting one equivalent of 3-[bis(dimethylamino)methylene]-1,1-diphenylurea (Tiritiris, 2012) with one equivalent of dimethyl sulfate in acetonitrile for two hours at room temperature. After evaporation of the solvent, the remaining viscous mass is washed with diethyl ether and dried, giving N-diphenylcarbamoyl- N,N,N,N,N -pentamethylguanidinium methyl sulfate (I). To 1.0 g (2.29 mmol) of (I) in 20 ml acetonitrile, 0.78 g (2.29 mmol) of sodium tetraphenylborate in 20 ml acetonitrile was added. After fifteen minutes of stirring at room temperature, the precipitated sodium methyl sulfate was filtered off. The title compound crystallized from a saturated acetonitrile solution during storage for several days at 273 K, forming colorless single crystals. Yield: 1.3 g (88%). 1 H NMR (500 MHz, CD 3 CN): δ = 2.83 [s, 12 H, N(CH 3 ) 2 ], 2.95 [s, 3 H, NCH 3 ], [t, J = 7 Hz, 4 H, C 6 H 5 ], [t, J = 6 Hz, 8 H, C 6 H 5 ], [m, 8 H, C 6 H 5 ], [m, 10 H, C 6 H 5 ]. 13 C NMR (125 MHz, CD 3 CN): δ = 38.0 (NCH 3 ), 40.9 [N(CH 3 ) 2 ], (C 6 H 5 ), (C 6 H 5 ), (C 6 H 5 ), (C 6 H 5 ), (C 6 H 5 ), (N 3 C + ), sup-1

3 161.6 (C O). Refinement The hydrogen atoms of the methyl groups were derived from difference Fourier maps and allowed to rotate with a fixed angle around the C N bond to best fit the experimental electron density, with U(H) set to 1.5 U eq (C) and d(c H) = 0.98 Å. The H atoms in the aromatic rings were placed at calculated positions with (C H) = 0.95 Å. They were included in the refinement in the riding model approximation, with U(H) set to 1.2 U eq (C). Computing details Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008). Figure 1 The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H-atoms are omitted for the sake of clarity. N-(Diphenylcarbamoyl)- N,N,N,N,N -pentamethylguanidinium tetraphenylborate Crystal data C 19 H 25 N 4 O + C 24 H 20 B M r = Monoclinic, P2 1 /n Hall symbol: -P 2yn a = (4) Å b = (3) Å c = (12) Å β = (2) V = (2) Å 3 Z = 4 F(000) = 1376 D x = Mg m 3 Melting point: 499 K Mo Kα radiation, λ = Å Cell parameters from reflections θ = µ = 0.07 mm 1 T = 100 K Block, colourless mm sup-2

4 Data collection Bruker Kappa APEXII DUO diffractometer Radiation source: sealed tube Graphite monochromator φ scans, and ω scans measured reflections independent reflections Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 447 parameters 0 restraints Primary atom site location: structure-invariant direct methods reflections with I > 2σ(I) R int = θ max = 36.3, θ min = 1.9 h = k = l = Secondary atom site location: difference Fourier map Hydrogen site location: difference Fourier map H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.058P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.51 e Å 3 Δρ min = 0.22 e Å 3 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 C (5) (7) (19) (10) N (5) (7) (18) (10) N (5) (6) (17) (9) N (5) (7) (17) (10) C (7) (11) (3) (17) H2A * H2B * H2C * C (7) (8) (2) (13) H3A * H3B * H3C * C (6) (8) (2) (12) H4A * H4B * H4C * C (7) (8) (3) (13) H5A * sup-3

5 H5B * H5C * C (7) (10) (2) (16) H6A * H6B * H6C * C (6) (7) (19) (10) O (5) (6) (17) (10) N (5) (6) (17) (9) C (6) (7) (19) (10) C (7) (8) (2) (12) H9A * C (8) (9) (3) (15) H10A * C (8) (8) (3) (14) H11A * C (7) (8) (2) (13) H12A * C (6) (7) (2) (11) H13A * C (6) (7) (19) (10) C (7) (8) (2) (12) H15A * C (8) (9) (2) (15) H16A * C (8) (9) (3) (15) H17A * C (8) (9) (2) (14) H18A * C (7) (8) (2) (12) H19A * B (6) (8) (2) (11) C (6) (7) (19) (10) C (6) (7) (2) (11) H21A * C (7) (8) (2) (12) H22A * C (6) (8) (2) (11) H23A * C (6) (8) (2) (11) H24A * C (6) (7) (2) (10) H25A * C (5) (7) (19) (10) C (6) (8) (2) (12) H27A * C (7) (8) (2) (14) H28A * C (7) (8) (2) (13) sup-4

6 H29A * C (7) (8) (2) (12) H30A * C (6) (7) (2) (10) H31A * C (6) (7) (19) (10) C (7) (10) (2) (14) H33A * C (7) (10) (3) (16) H34A * C (7) (8) (3) (14) H35A * C (6) (7) (2) (12) H36A * C (6) (7) (2) (10) H37A * C (5) (7) (18) (10) C (6) (7) (2) (11) H39A * C (6) (8) (2) (12) H40A * C (6) (8) (2) (12) H41A * C (7) (8) (2) (12) H42A * C (6) (7) (2) (11) H43A * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 C (2) (2) (2) (18) (17) (19) N (2) (3) (2) (19) (17) (19) N (2) (2) (2) (16) (16) (17) N (2) (2) (2) (18) (16) (18) C (3) (5) (4) (3) (3) (3) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (4) (3) (3) (2) (3) C (2) (3) (2) (2) (18) (19) O (2) (2) (2) (18) (18) (18) N (2) (2) (2) (18) (17) (17) C (2) (2) (2) (19) (18) (19) C (3) (3) (3) (2) (2) (2) C (3) (3) (4) (3) (3) (3) C (4) (3) (3) (3) (3) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (3) (2) (2) (19) (19) sup-5

7 C (3) (3) (3) (2) (2) (2) C (4) (4) (3) (3) (3) (2) C (4) (4) (3) (3) (3) (3) C (3) (3) (3) (3) (3) (3) C (3) (3) (3) (2) (2) (2) B (2) (3) (3) (2) (19) (2) C (2) (2) (2) (18) (18) (18) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (19) (2) C (2) (3) (3) (19) (18) (2) C (2) (2) (2) (18) (17) (19) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (3) (2) C (3) (3) (3) (3) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (2) (3) (19) (19) (19) C (2) (3) (2) (19) (18) (19) C (3) (4) (3) (3) (2) (3) C (3) (5) (3) (3) (2) (3) C (3) (3) (4) (2) (2) (3) C (2) (3) (3) (2) (2) (2) C (2) (2) (3) (18) (19) (19) C (2) (2) (2) (18) (17) (19) C (2) (3) (2) (2) (19) (2) C (3) (3) (3) (2) (2) (2) C (2) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) Geometric parameters (Å, º) C1 N (8) C19 H19A C1 N (9) B1 C (9) C1 N (9) B1 C (9) N1 C (10) B1 C (9) N1 C (10) B1 C (10) N2 C (9) C20 C (9) N2 C (9) C20 C (9) N3 C (9) C21 C (10) N3 C (9) C21 H21A C2 H2A C22 C (11) C2 H2B C22 H22A C2 H2C C23 C (10) C3 H3A C23 H23A C3 H3B C24 C (9) C3 H3C C24 H24A C4 H4A C25 H25A C4 H4B C26 C (9) sup-6

8 C4 H4C C26 C (9) C5 H5A C27 C (10) C5 H5B C27 H27A C5 H5C C28 C (11) C6 H6A C28 H28A C6 H6B C29 C (11) C6 H6C C29 H29A C7 O (8) C30 C (10) C7 N (8) C30 H30A N4 C (9) C31 H31A N4 C (9) C32 C (9) C8 C (10) C32 C (10) C8 C (9) C33 C (11) C9 C (11) C33 H33A C9 H9A C34 C (13) C10 C (13) C34 H34A C10 H10A C35 C (11) C11 C (12) C35 H35A C11 H11A C36 C (9) C12 C (10) C36 H36A C12 H12A C37 H37A C13 H13A C38 C (9) C14 C (10) C38 C (9) C14 C (10) C39 C (10) C15 C (11) C39 H39A C15 H15A C40 C (11) C16 C (13) C40 H40A C16 H16A C41 C (11) C17 C (12) C41 H41A C17 H17A C42 C (10) C18 C (10) C42 H42A C18 H18A C43 H43A N2 C1 N (6) C18 C19 C (7) N2 C1 N (6) C18 C19 H19A N1 C1 N (6) C14 C19 H19A C1 N1 C (6) C20 B1 C (5) C1 N1 C (6) C20 B1 C (5) C2 N1 C (6) C26 B1 C (5) C1 N2 C (6) C20 B1 C (5) C1 N2 C (6) C26 B1 C (5) C5 N2 C (6) C32 B1 C (5) C1 N3 C (5) C21 C20 C (6) C1 N3 C (6) C21 C20 B (6) C7 N3 C (6) C25 C20 B (5) N1 C2 H2A C22 C21 C (6) N1 C2 H2B C22 C21 H21A H2A C2 H2B C20 C21 H21A N1 C2 H2C C23 C22 C (6) sup-7

9 H2A C2 H2C C23 C22 H22A H2B C2 H2C C21 C22 H22A N1 C3 H3A C22 C23 C (6) N1 C3 H3B C22 C23 H23A H3A C3 H3B C24 C23 H23A N1 C3 H3C C23 C24 C (6) H3A C3 H3C C23 C24 H24A H3B C3 H3C C25 C24 H24A N2 C4 H4A C24 C25 C (6) N2 C4 H4B C24 C25 H25A H4A C4 H4B C20 C25 H25A N2 C4 H4C C31 C26 C (6) H4A C4 H4C C31 C26 B (5) H4B C4 H4C C27 C26 B (6) N2 C5 H5A C28 C27 C (7) N2 C5 H5B C28 C27 H27A H5A C5 H5B C26 C27 H27A N2 C5 H5C C29 C28 C (7) H5A C5 H5C C29 C28 H28A H5B C5 H5C C27 C28 H28A N3 C6 H6A C28 C29 C (7) N3 C6 H6B C28 C29 H29A H6A C6 H6B C30 C29 H29A N3 C6 H6C C29 C30 C (7) H6A C6 H6C C29 C30 H30A H6B C6 H6C C31 C30 H30A O1 C7 N (6) C30 C31 C (6) O1 C7 N (6) C30 C31 H31A N4 C7 N (6) C26 C31 H31A C7 N4 C (6) C37 C32 C (6) C7 N4 C (6) C37 C32 B (6) C8 N4 C (5) C33 C32 B (6) C9 C8 C (6) C34 C33 C (7) C9 C8 N (6) C34 C33 H33A C13 C8 N (6) C32 C33 H33A C8 C9 C (7) C33 C34 C (7) C8 C9 H9A C33 C34 H34A C10 C9 H9A C35 C34 H34A C11 C10 C (8) C36 C35 C (7) C11 C10 H10A C36 C35 H35A C9 C10 H10A C34 C35 H35A C10 C11 C (7) C35 C36 C (7) C10 C11 H11A C35 C36 H36A C12 C11 H11A C37 C36 H36A C11 C12 C (7) C36 C37 C (6) C11 C12 H12A C36 C37 H37A C13 C12 H12A C32 C37 H37A C12 C13 C (7) C43 C38 C (6) C12 C13 H13A C43 C38 B (6) sup-8

10 C8 C13 H13A C39 C38 B (6) C15 C14 C (6) C40 C39 C (6) C15 C14 N (6) C40 C39 H39A C19 C14 N (6) C38 C39 H39A C14 C15 C (7) C41 C40 C (7) C14 C15 H15A C41 C40 H40A C16 C15 H15A C39 C40 H40A C17 C16 C (7) C40 C41 C (7) C17 C16 H16A C40 C41 H41A C15 C16 H16A C42 C41 H41A C16 C17 C (7) C41 C42 C (7) C16 C17 H17A C41 C42 H42A C18 C17 H17A C43 C42 H42A C19 C18 C (8) C42 C43 C (6) C19 C18 H18A C42 C43 H43A C17 C18 H18A C38 C43 H43A N2 C1 N1 C (7) C25 C20 C21 C (10) N3 C1 N1 C (10) B1 C20 C21 C (7) N2 C1 N1 C (10) C20 C21 C22 C (12) N3 C1 N1 C (7) C21 C22 C23 C (11) N1 C1 N2 C (7) C22 C23 C24 C (11) N3 C1 N2 C (10) C23 C24 C25 C (11) N1 C1 N2 C (9) C21 C20 C25 C (10) N3 C1 N2 C (6) B1 C20 C25 C (6) N2 C1 N3 C (10) C20 B1 C26 C (7) N1 C1 N3 C (7) C32 B1 C26 C (9) N2 C1 N3 C (7) C38 B1 C26 C (6) N1 C1 N3 C (9) C20 B1 C26 C (7) C1 N3 C7 O (7) C32 B1 C26 C (6) C6 N3 C7 O (10) C38 B1 C26 C (8) C1 N3 C7 N (10) C31 C26 C27 C (11) C6 N3 C7 N (7) B1 C26 C27 C (7) O1 C7 N4 C (7) C26 C27 C28 C (13) N3 C7 N4 C (9) C27 C28 C29 C (13) O1 C7 N4 C (10) C28 C29 C30 C (12) N3 C7 N4 C (6) C29 C30 C31 C (11) C7 N4 C8 C (10) C27 C26 C31 C (10) C14 N4 C8 C (7) B1 C26 C31 C (6) C7 N4 C8 C (7) C20 B1 C32 C (6) C14 N4 C8 C (8) C26 B1 C32 C (9) C13 C8 C9 C (11) C38 B1 C32 C (7) N4 C8 C9 C (7) C20 B1 C32 C (9) C8 C9 C10 C (13) C26 B1 C32 C (7) C9 C10 C11 C (13) C38 B1 C32 C (8) C10 C11 C12 C (12) C37 C32 C33 C (12) C11 C12 C13 C (11) B1 C32 C33 C (8) C9 C8 C13 C (10) C32 C33 C34 C (14) N4 C8 C13 C (6) C33 C34 C35 C (13) sup-9

11 C7 N4 C14 C (7) C34 C35 C36 C (12) C8 N4 C14 C (9) C35 C36 C37 C (11) C7 N4 C14 C (9) C33 C32 C37 C (10) C8 N4 C14 C (7) B1 C32 C37 C (6) C19 C14 C15 C (11) C20 B1 C38 C (8) N4 C14 C15 C (7) C26 B1 C38 C (6) C14 C15 C16 C (12) C32 B1 C38 C (7) C15 C16 C17 C (13) C20 B1 C38 C (6) C16 C17 C18 C (13) C26 B1 C38 C (8) C17 C18 C19 C (13) C32 B1 C38 C (7) C15 C14 C19 C (12) C43 C38 C39 C (9) N4 C14 C19 C (7) B1 C38 C39 C (6) C26 B1 C20 C (7) C38 C39 C40 C (10) C32 B1 C20 C (9) C39 C40 C41 C (10) C38 B1 C20 C (6) C40 C41 C42 C (10) C26 B1 C20 C (7) C41 C42 C43 C (11) C32 B1 C20 C (6) C39 C38 C43 C (10) C38 B1 C20 C (8) B1 C38 C43 C (6) sup-10