organic compounds
N-(Diphenylcarbamoyl)-N,N′,N′,N′′,N′′-pentamethylguanidinium tetraphenylborate
aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
*Correspondence e-mail: Ioannis.Tiritiris@htw-aalen.de
In the title salt, C19H25N4O+·C24H20B−, the C=N and C—N bond lengths in the CN3 unit are 1.3327 (8)/1.3364 (9) and 1.3802 (9) Å, indicating double- and single-bond character, respectively. The N—C—N angles are 118.77 (6), 120.29 (6) and 120.81 (6)°, showing only a small deviation of the CN3 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 [1.4636 (9)–1.4772 (9) Å]. The crystal packing is caused by electrostatic interactions between cations and anions.
Related literature
For the synthesis and ). For the crystal structures of alkali metal tetraphenylborates, see: Behrens et al. (2012).
of 3-[bis(dimethylamino)methylene]-1,1-diphenylurea, see: Tiritiris (2012Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2008); cell 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.
Supporting information
https://doi.org/10.1107/S1600536812050507/fk2067sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812050507/fk2067Isup2.hkl
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%). 1H NMR (500 MHz, CD3CN): δ = 2.83 [s, 12 H, N(CH3)2], 2.95 [s, 3 H, NCH3], 6.85–6.88 [t, J = 7 Hz, 4 H, C6H5], 7.06–7.09 [t, J = 6 Hz, 8 H, C6H5], 7.25–7.29 [m, 8 H, C6H5], 7.30–7.48 [m, 10 H, C6H5]. 13C NMR (125 MHz, CD3CN): δ = 38.0 (NCH3), 40.9 [N(CH3)2], 122.6 (C6H5), 125.4 (C6H5), 126.5–130.9 (C6H5), 136.5 (C6H5), 143.3 (C6H5), 156.8 (N3C+), 161.6 (C═O).
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 Ueq(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
in the riding model approximation, with U(H) set to 1.2 Ueq(C).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
of the salt, isolated cations and anions are present. One C–N bond of the CN3 unit in the cationic part is elongated (C1–N3 = 1.3802 (9) Å), indicating single bond character. The two remaining C–N bonds (C1–N2 = 1.3327 (8) Å and C1–N1 = 1.3364 (9) Å) are shorter and they show double bond character. As a consequence, the positive charge is not delocalized over the entire CN3 unit, but only between the two dimethylamino groups. The N–C1–N angles are: 120.29 (6)° (N1–C1–N2), 120.81 (6)° (N2–C1–N3) and 118.77 (6)° (N1–C1–N3), which indicate only a slight deviation of the CN3 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 (1.4636 (9)–1.4772 (9) Å). The C–O bond length in the diphenylcarbamoyl group is C7–O1 = 1.2148 (8) Å, and shows the expected double-bond character. The N–C bond lengths are: N3–C7 = 1.4267 (9) Å, N4–C7 = 1.3771 (8) Å, N4–C8 = 1.4348 (9) Å and N4–C14 = 1.4395 (9) Å. They are comparable with the data from the 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 CN3 plane (Fig. 1). The bond lengths and angles in the tetraphenylborate ion are in good agreement with the data from the 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.For the synthesis and
of 3-[bis(dimethylamino)methylene]-1,1-diphenylurea, see: Tiritiris (2012). For the crystal structures of alkali metal tetraphenylborates, see: Behrens et al. (2012).Data collection: APEX2 (Bruker, 2008); cell
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).Fig. 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. |
C19H25N4O+·C24H20B− | F(000) = 1376 |
Mr = 644.64 | Dx = 1.208 Mg m−3 |
Monoclinic, P21/n | Melting point: 499 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 11.0564 (4) Å | Cell parameters from 119072 reflections |
b = 9.5942 (3) Å | θ = 1.9–36.3° |
c = 33.4312 (12) Å | µ = 0.07 mm−1 |
β = 91.684 (2)° | T = 100 K |
V = 3544.8 (2) Å3 | Block, colourless |
Z = 4 | 0.24 × 0.17 × 0.15 mm |
Bruker Kappa APEXII DUO diffractometer | 14383 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 36.3°, θmin = 1.9° |
φ scans, and ω scans | h = −18→18 |
119072 measured reflections | k = −15→15 |
17178 independent reflections | l = −49→55 |
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: difference Fourier map |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.058P)2 + 0.8563P] where P = (Fo2 + 2Fc2)/3 |
17178 reflections | (Δ/σ)max < 0.001 |
447 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C19H25N4O+·C24H20B− | V = 3544.8 (2) Å3 |
Mr = 644.64 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.0564 (4) Å | µ = 0.07 mm−1 |
b = 9.5942 (3) Å | T = 100 K |
c = 33.4312 (12) Å | 0.24 × 0.17 × 0.15 mm |
β = 91.684 (2)° |
Bruker Kappa APEXII DUO diffractometer | 14383 reflections with I > 2σ(I) |
119072 measured reflections | Rint = 0.026 |
17178 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.51 e Å−3 |
17178 reflections | Δρmin = −0.22 e Å−3 |
447 parameters |
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 | 1.00096 (5) | 0.67518 (7) | 0.146331 (19) | 0.01387 (10) | |
N1 | 1.07031 (5) | 0.77454 (7) | 0.163107 (18) | 0.01749 (10) | |
N2 | 0.88355 (5) | 0.66826 (6) | 0.154064 (17) | 0.01423 (9) | |
N3 | 1.05465 (5) | 0.57515 (7) | 0.123078 (17) | 0.01599 (10) | |
C2 | 1.18186 (7) | 0.82630 (11) | 0.14580 (3) | 0.02881 (17) | |
H2A | 1.1908 | 0.7857 | 0.1192 | 0.043* | |
H2B | 1.2513 | 0.7998 | 0.1631 | 0.043* | |
H2C | 1.1781 | 0.9281 | 0.1436 | 0.043* | |
C3 | 1.04672 (7) | 0.82704 (8) | 0.20332 (2) | 0.02133 (13) | |
H3A | 1.0080 | 0.9187 | 0.2013 | 0.032* | |
H3B | 1.1233 | 0.8353 | 0.2187 | 0.032* | |
H3C | 0.9931 | 0.7622 | 0.2169 | 0.032* | |
C4 | 0.81203 (6) | 0.79278 (8) | 0.16271 (2) | 0.01889 (12) | |
H4A | 0.7991 | 0.7984 | 0.1915 | 0.028* | |
H4B | 0.7337 | 0.7872 | 0.1483 | 0.028* | |
H4C | 0.8555 | 0.8760 | 0.1540 | 0.028* | |
C5 | 0.81622 (7) | 0.53704 (8) | 0.15524 (3) | 0.02161 (13) | |
H5A | 0.8727 | 0.4586 | 0.1536 | 0.032* | |
H5B | 0.7580 | 0.5334 | 0.1326 | 0.032* | |
H5C | 0.7729 | 0.5313 | 0.1803 | 0.032* | |
C6 | 1.16588 (7) | 0.50748 (10) | 0.13910 (2) | 0.02623 (16) | |
H6A | 1.1864 | 0.5455 | 0.1657 | 0.039* | |
H6B | 1.2325 | 0.5253 | 0.1211 | 0.039* | |
H6C | 1.1525 | 0.4068 | 0.1412 | 0.039* | |
C7 | 0.99758 (6) | 0.50474 (7) | 0.090013 (19) | 0.01514 (10) | |
O1 | 1.02242 (5) | 0.38358 (6) | 0.083615 (17) | 0.02006 (10) | |
N4 | 0.91755 (5) | 0.58089 (6) | 0.066452 (17) | 0.01539 (9) | |
C8 | 0.92431 (6) | 0.72938 (7) | 0.061944 (19) | 0.01458 (10) | |
C9 | 1.03421 (7) | 0.79385 (8) | 0.05482 (2) | 0.02053 (12) | |
H9A | 1.1060 | 0.7400 | 0.0533 | 0.025* | |
C10 | 1.03832 (8) | 0.93813 (9) | 0.04998 (3) | 0.02628 (15) | |
H10A | 1.1138 | 0.9831 | 0.0464 | 0.032* | |
C11 | 0.93289 (8) | 1.01653 (8) | 0.05035 (3) | 0.02490 (14) | |
H11A | 0.9360 | 1.1148 | 0.0469 | 0.030* | |
C12 | 0.82267 (7) | 0.95055 (8) | 0.05573 (2) | 0.02075 (13) | |
H12A | 0.7500 | 1.0035 | 0.0550 | 0.025* | |
C13 | 0.81810 (6) | 0.80749 (7) | 0.06212 (2) | 0.01723 (11) | |
H13A | 0.7429 | 0.7632 | 0.0666 | 0.021* | |
C14 | 0.83769 (6) | 0.50707 (7) | 0.039062 (19) | 0.01551 (10) | |
C15 | 0.82544 (7) | 0.55132 (8) | −0.00044 (2) | 0.01974 (12) | |
H15A | 0.8745 | 0.6247 | −0.0100 | 0.024* | |
C16 | 0.74043 (8) | 0.48695 (9) | −0.02581 (2) | 0.02552 (15) | |
H16A | 0.7303 | 0.5182 | −0.0527 | 0.031* | |
C17 | 0.67023 (8) | 0.37747 (9) | −0.01230 (3) | 0.02613 (15) | |
H17A | 0.6124 | 0.3343 | −0.0298 | 0.031* | |
C18 | 0.68496 (8) | 0.33128 (9) | 0.02700 (2) | 0.02390 (14) | |
H18A | 0.6383 | 0.2552 | 0.0362 | 0.029* | |
C19 | 0.76810 (7) | 0.39665 (8) | 0.05277 (2) | 0.02067 (12) | |
H19A | 0.7775 | 0.3661 | 0.0797 | 0.025* | |
B1 | 0.52389 (6) | 0.21514 (8) | 0.15651 (2) | 0.01335 (11) | |
C20 | 0.44464 (6) | 0.14317 (7) | 0.191805 (19) | 0.01352 (10) | |
C21 | 0.48685 (6) | 0.03020 (7) | 0.21503 (2) | 0.01834 (11) | |
H21A | 0.5659 | −0.0046 | 0.2108 | 0.022* | |
C22 | 0.41710 (7) | −0.03286 (8) | 0.24409 (2) | 0.02053 (12) | |
H22A | 0.4494 | −0.1085 | 0.2593 | 0.025* | |
C23 | 0.30066 (6) | 0.01450 (8) | 0.25084 (2) | 0.01820 (11) | |
H23A | 0.2530 | −0.0278 | 0.2707 | 0.022* | |
C24 | 0.25530 (6) | 0.12485 (8) | 0.22803 (2) | 0.01747 (11) | |
H24A | 0.1758 | 0.1583 | 0.2322 | 0.021* | |
C25 | 0.32589 (6) | 0.18668 (7) | 0.19911 (2) | 0.01539 (10) | |
H25A | 0.2925 | 0.2612 | 0.1837 | 0.018* | |
C26 | 0.47738 (5) | 0.13982 (7) | 0.114657 (19) | 0.01352 (10) | |
C27 | 0.37644 (6) | 0.19096 (8) | 0.09256 (2) | 0.01912 (12) | |
H27A | 0.3359 | 0.2710 | 0.1022 | 0.023* | |
C28 | 0.33342 (7) | 0.12931 (8) | 0.05717 (2) | 0.02290 (14) | |
H28A | 0.2657 | 0.1684 | 0.0431 | 0.027* | |
C29 | 0.38922 (7) | 0.01102 (8) | 0.04241 (2) | 0.02233 (13) | |
H29A | 0.3613 | −0.0305 | 0.0181 | 0.027* | |
C30 | 0.48676 (7) | −0.04526 (8) | 0.06403 (2) | 0.01926 (12) | |
H30A | 0.5251 | −0.1271 | 0.0547 | 0.023* | |
C31 | 0.52867 (6) | 0.01772 (7) | 0.09943 (2) | 0.01514 (10) | |
H31A | 0.5947 | −0.0238 | 0.1138 | 0.018* | |
C32 | 0.66957 (6) | 0.19811 (7) | 0.166723 (19) | 0.01444 (10) | |
C33 | 0.71593 (7) | 0.22033 (10) | 0.20592 (2) | 0.02351 (14) | |
H33A | 0.6606 | 0.2388 | 0.2265 | 0.028* | |
C34 | 0.83882 (7) | 0.21646 (10) | 0.21588 (3) | 0.02745 (16) | |
H34A | 0.8658 | 0.2312 | 0.2428 | 0.033* | |
C35 | 0.92237 (7) | 0.19095 (8) | 0.18636 (3) | 0.02348 (14) | |
H35A | 1.0065 | 0.1879 | 0.1929 | 0.028* | |
C36 | 0.88095 (6) | 0.17006 (7) | 0.14723 (2) | 0.01941 (12) | |
H36A | 0.9369 | 0.1533 | 0.1267 | 0.023* | |
C37 | 0.75681 (6) | 0.17376 (7) | 0.13797 (2) | 0.01473 (10) | |
H37A | 0.7305 | 0.1591 | 0.1110 | 0.018* | |
C38 | 0.50307 (5) | 0.38509 (7) | 0.154358 (18) | 0.01357 (10) | |
C39 | 0.51311 (6) | 0.46073 (7) | 0.11854 (2) | 0.01621 (11) | |
H39A | 0.5259 | 0.4110 | 0.0945 | 0.019* | |
C40 | 0.50512 (6) | 0.60585 (8) | 0.11693 (2) | 0.01927 (12) | |
H40A | 0.5124 | 0.6525 | 0.0920 | 0.023* | |
C41 | 0.48660 (6) | 0.68271 (8) | 0.15148 (2) | 0.01973 (12) | |
H41A | 0.4806 | 0.7814 | 0.1505 | 0.024* | |
C42 | 0.47705 (7) | 0.61176 (8) | 0.18754 (2) | 0.01958 (12) | |
H42A | 0.4648 | 0.6624 | 0.2115 | 0.023* | |
C43 | 0.48534 (6) | 0.46658 (7) | 0.18870 (2) | 0.01693 (11) | |
H43A | 0.4787 | 0.4208 | 0.2137 | 0.020* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0132 (2) | 0.0150 (2) | 0.0133 (2) | 0.00064 (18) | −0.00187 (17) | 0.00090 (19) |
N1 | 0.0149 (2) | 0.0200 (3) | 0.0174 (2) | −0.00287 (19) | −0.00295 (17) | −0.00106 (19) |
N2 | 0.0131 (2) | 0.0132 (2) | 0.0164 (2) | −0.00042 (16) | 0.00001 (16) | −0.00077 (17) |
N3 | 0.0144 (2) | 0.0196 (2) | 0.0138 (2) | 0.00508 (18) | −0.00286 (16) | −0.00122 (18) |
C2 | 0.0179 (3) | 0.0382 (5) | 0.0302 (4) | −0.0107 (3) | −0.0011 (3) | −0.0005 (3) |
C3 | 0.0237 (3) | 0.0208 (3) | 0.0191 (3) | −0.0004 (2) | −0.0063 (2) | −0.0046 (2) |
C4 | 0.0165 (3) | 0.0171 (3) | 0.0230 (3) | 0.0031 (2) | −0.0004 (2) | −0.0032 (2) |
C5 | 0.0209 (3) | 0.0161 (3) | 0.0281 (3) | −0.0051 (2) | 0.0047 (2) | −0.0016 (2) |
C6 | 0.0216 (3) | 0.0357 (4) | 0.0209 (3) | 0.0142 (3) | −0.0074 (2) | −0.0037 (3) |
C7 | 0.0158 (2) | 0.0164 (3) | 0.0132 (2) | 0.0025 (2) | −0.00034 (18) | 0.00101 (19) |
O1 | 0.0235 (2) | 0.0166 (2) | 0.0200 (2) | 0.00525 (18) | −0.00059 (18) | −0.00018 (18) |
N4 | 0.0178 (2) | 0.0140 (2) | 0.0140 (2) | 0.00098 (18) | −0.00418 (17) | 0.00090 (17) |
C8 | 0.0161 (2) | 0.0145 (2) | 0.0130 (2) | 0.00119 (19) | −0.00102 (18) | 0.00093 (19) |
C9 | 0.0174 (3) | 0.0209 (3) | 0.0233 (3) | −0.0002 (2) | 0.0016 (2) | 0.0040 (2) |
C10 | 0.0266 (3) | 0.0217 (3) | 0.0307 (4) | −0.0053 (3) | 0.0023 (3) | 0.0055 (3) |
C11 | 0.0355 (4) | 0.0162 (3) | 0.0231 (3) | −0.0004 (3) | 0.0013 (3) | 0.0021 (2) |
C12 | 0.0274 (3) | 0.0176 (3) | 0.0173 (3) | 0.0063 (2) | 0.0005 (2) | −0.0003 (2) |
C13 | 0.0177 (3) | 0.0178 (3) | 0.0161 (3) | 0.0030 (2) | −0.0002 (2) | 0.0002 (2) |
C14 | 0.0182 (2) | 0.0153 (3) | 0.0129 (2) | 0.0014 (2) | −0.00250 (19) | −0.00088 (19) |
C15 | 0.0261 (3) | 0.0198 (3) | 0.0132 (3) | 0.0008 (2) | −0.0019 (2) | 0.0000 (2) |
C16 | 0.0359 (4) | 0.0254 (4) | 0.0147 (3) | 0.0010 (3) | −0.0078 (3) | −0.0018 (2) |
C17 | 0.0305 (4) | 0.0251 (4) | 0.0222 (3) | −0.0008 (3) | −0.0096 (3) | −0.0062 (3) |
C18 | 0.0278 (3) | 0.0214 (3) | 0.0222 (3) | −0.0051 (3) | −0.0043 (3) | −0.0036 (3) |
C19 | 0.0268 (3) | 0.0192 (3) | 0.0158 (3) | −0.0040 (2) | −0.0033 (2) | 0.0003 (2) |
B1 | 0.0125 (2) | 0.0153 (3) | 0.0122 (3) | −0.0002 (2) | −0.00062 (19) | 0.0003 (2) |
C20 | 0.0141 (2) | 0.0132 (2) | 0.0132 (2) | −0.00016 (18) | −0.00034 (18) | 0.00006 (18) |
C21 | 0.0193 (3) | 0.0166 (3) | 0.0192 (3) | 0.0037 (2) | 0.0019 (2) | 0.0039 (2) |
C22 | 0.0242 (3) | 0.0171 (3) | 0.0203 (3) | 0.0006 (2) | 0.0009 (2) | 0.0062 (2) |
C23 | 0.0198 (3) | 0.0191 (3) | 0.0158 (3) | −0.0053 (2) | 0.0003 (2) | 0.0020 (2) |
C24 | 0.0138 (2) | 0.0214 (3) | 0.0172 (3) | −0.0023 (2) | 0.00034 (19) | 0.0014 (2) |
C25 | 0.0135 (2) | 0.0167 (3) | 0.0159 (3) | −0.00022 (19) | −0.00057 (18) | 0.0022 (2) |
C26 | 0.0129 (2) | 0.0144 (2) | 0.0132 (2) | −0.00080 (18) | −0.00111 (17) | 0.00018 (19) |
C27 | 0.0169 (3) | 0.0185 (3) | 0.0216 (3) | 0.0026 (2) | −0.0068 (2) | −0.0036 (2) |
C28 | 0.0241 (3) | 0.0199 (3) | 0.0239 (3) | 0.0008 (2) | −0.0123 (3) | −0.0019 (2) |
C29 | 0.0278 (3) | 0.0194 (3) | 0.0192 (3) | −0.0027 (3) | −0.0079 (2) | −0.0030 (2) |
C30 | 0.0222 (3) | 0.0150 (3) | 0.0204 (3) | −0.0011 (2) | −0.0025 (2) | −0.0035 (2) |
C31 | 0.0157 (2) | 0.0131 (2) | 0.0165 (3) | −0.00082 (19) | −0.00221 (19) | 0.00027 (19) |
C32 | 0.0132 (2) | 0.0163 (3) | 0.0137 (2) | −0.00047 (19) | −0.00181 (18) | 0.00037 (19) |
C33 | 0.0175 (3) | 0.0376 (4) | 0.0152 (3) | −0.0030 (3) | −0.0035 (2) | −0.0015 (3) |
C34 | 0.0204 (3) | 0.0393 (5) | 0.0221 (3) | −0.0035 (3) | −0.0093 (2) | 0.0016 (3) |
C35 | 0.0147 (3) | 0.0220 (3) | 0.0333 (4) | 0.0002 (2) | −0.0074 (2) | 0.0004 (3) |
C36 | 0.0132 (2) | 0.0156 (3) | 0.0293 (3) | 0.0000 (2) | 0.0001 (2) | −0.0025 (2) |
C37 | 0.0134 (2) | 0.0132 (2) | 0.0176 (3) | −0.00071 (18) | −0.00013 (19) | −0.00067 (19) |
C38 | 0.0125 (2) | 0.0154 (2) | 0.0127 (2) | −0.00173 (18) | −0.00025 (17) | 0.00052 (19) |
C39 | 0.0160 (2) | 0.0181 (3) | 0.0145 (2) | −0.0014 (2) | −0.00031 (19) | 0.0023 (2) |
C40 | 0.0174 (3) | 0.0193 (3) | 0.0210 (3) | −0.0024 (2) | −0.0019 (2) | 0.0060 (2) |
C41 | 0.0151 (2) | 0.0153 (3) | 0.0287 (3) | −0.0023 (2) | −0.0009 (2) | 0.0019 (2) |
C42 | 0.0198 (3) | 0.0169 (3) | 0.0222 (3) | −0.0034 (2) | 0.0021 (2) | −0.0036 (2) |
C43 | 0.0195 (3) | 0.0161 (3) | 0.0152 (3) | −0.0030 (2) | 0.0013 (2) | −0.0007 (2) |
C1—N2 | 1.3327 (8) | C19—H19A | 0.9500 |
C1—N1 | 1.3364 (9) | B1—C20 | 1.6424 (9) |
C1—N3 | 1.3802 (9) | B1—C26 | 1.6437 (9) |
N1—C2 | 1.4643 (10) | B1—C32 | 1.6447 (9) |
N1—C3 | 1.4662 (10) | B1—C38 | 1.6480 (10) |
N2—C5 | 1.4636 (9) | C20—C21 | 1.4050 (9) |
N2—C4 | 1.4662 (9) | C20—C25 | 1.4059 (9) |
N3—C7 | 1.4267 (9) | C21—C22 | 1.3960 (10) |
N3—C6 | 1.4772 (9) | C21—H21A | 0.9500 |
C2—H2A | 0.9800 | C22—C23 | 1.3898 (11) |
C2—H2B | 0.9800 | C22—H22A | 0.9500 |
C2—H2C | 0.9800 | C23—C24 | 1.3899 (10) |
C3—H3A | 0.9800 | C23—H23A | 0.9500 |
C3—H3B | 0.9800 | C24—C25 | 1.3929 (9) |
C3—H3C | 0.9800 | C24—H24A | 0.9500 |
C4—H4A | 0.9800 | C25—H25A | 0.9500 |
C4—H4B | 0.9800 | C26—C31 | 1.4036 (9) |
C4—H4C | 0.9800 | C26—C27 | 1.4083 (9) |
C5—H5A | 0.9800 | C27—C28 | 1.3939 (10) |
C5—H5B | 0.9800 | C27—H27A | 0.9500 |
C5—H5C | 0.9800 | C28—C29 | 1.3893 (11) |
C6—H6A | 0.9800 | C28—H28A | 0.9500 |
C6—H6B | 0.9800 | C29—C30 | 1.3895 (11) |
C6—H6C | 0.9800 | C29—H29A | 0.9500 |
C7—O1 | 1.2148 (8) | C30—C31 | 1.3960 (10) |
C7—N4 | 1.3771 (8) | C30—H30A | 0.9500 |
N4—C8 | 1.4348 (9) | C31—H31A | 0.9500 |
N4—C14 | 1.4395 (9) | C32—C37 | 1.4012 (9) |
C8—C9 | 1.3903 (10) | C32—C33 | 1.4092 (10) |
C8—C13 | 1.3932 (9) | C33—C34 | 1.3899 (11) |
C9—C10 | 1.3945 (11) | C33—H33A | 0.9500 |
C9—H9A | 0.9500 | C34—C35 | 1.3930 (13) |
C10—C11 | 1.3877 (13) | C34—H34A | 0.9500 |
C10—H10A | 0.9500 | C35—C36 | 1.3879 (11) |
C11—C12 | 1.3896 (12) | C35—H35A | 0.9500 |
C11—H11A | 0.9500 | C36—C37 | 1.3985 (9) |
C12—C13 | 1.3903 (10) | C36—H36A | 0.9500 |
C12—H12A | 0.9500 | C37—H37A | 0.9500 |
C13—H13A | 0.9500 | C38—C43 | 1.4074 (9) |
C14—C15 | 1.3902 (10) | C38—C39 | 1.4075 (9) |
C14—C19 | 1.3947 (10) | C39—C40 | 1.3960 (10) |
C15—C16 | 1.3918 (11) | C39—H39A | 0.9500 |
C15—H15A | 0.9500 | C40—C41 | 1.3906 (11) |
C16—C17 | 1.3894 (13) | C40—H40A | 0.9500 |
C16—H16A | 0.9500 | C41—C42 | 1.3911 (11) |
C17—C18 | 1.3915 (12) | C41—H41A | 0.9500 |
C17—H17A | 0.9500 | C42—C43 | 1.3964 (10) |
C18—C19 | 1.3906 (10) | C42—H42A | 0.9500 |
C18—H18A | 0.9500 | C43—H43A | 0.9500 |
N2—C1—N1 | 120.29 (6) | C18—C19—C14 | 120.00 (7) |
N2—C1—N3 | 120.81 (6) | C18—C19—H19A | 120.0 |
N1—C1—N3 | 118.77 (6) | C14—C19—H19A | 120.0 |
C1—N1—C2 | 123.76 (6) | C20—B1—C26 | 105.46 (5) |
C1—N1—C3 | 120.96 (6) | C20—B1—C32 | 110.42 (5) |
C2—N1—C3 | 114.86 (6) | C26—B1—C32 | 114.39 (5) |
C1—N2—C5 | 123.17 (6) | C20—B1—C38 | 111.75 (5) |
C1—N2—C4 | 122.12 (6) | C26—B1—C38 | 110.98 (5) |
C5—N2—C4 | 114.70 (6) | C32—B1—C38 | 104.01 (5) |
C1—N3—C7 | 125.30 (5) | C21—C20—C25 | 115.45 (6) |
C1—N3—C6 | 117.95 (6) | C21—C20—B1 | 123.08 (6) |
C7—N3—C6 | 114.67 (6) | C25—C20—B1 | 121.37 (5) |
N1—C2—H2A | 109.5 | C22—C21—C20 | 122.52 (6) |
N1—C2—H2B | 109.5 | C22—C21—H21A | 118.7 |
H2A—C2—H2B | 109.5 | C20—C21—H21A | 118.7 |
N1—C2—H2C | 109.5 | C23—C22—C21 | 120.31 (6) |
H2A—C2—H2C | 109.5 | C23—C22—H22A | 119.8 |
H2B—C2—H2C | 109.5 | C21—C22—H22A | 119.8 |
N1—C3—H3A | 109.5 | C22—C23—C24 | 118.75 (6) |
N1—C3—H3B | 109.5 | C22—C23—H23A | 120.6 |
H3A—C3—H3B | 109.5 | C24—C23—H23A | 120.6 |
N1—C3—H3C | 109.5 | C23—C24—C25 | 120.32 (6) |
H3A—C3—H3C | 109.5 | C23—C24—H24A | 119.8 |
H3B—C3—H3C | 109.5 | C25—C24—H24A | 119.8 |
N2—C4—H4A | 109.5 | C24—C25—C20 | 122.64 (6) |
N2—C4—H4B | 109.5 | C24—C25—H25A | 118.7 |
H4A—C4—H4B | 109.5 | C20—C25—H25A | 118.7 |
N2—C4—H4C | 109.5 | C31—C26—C27 | 115.02 (6) |
H4A—C4—H4C | 109.5 | C31—C26—B1 | 123.77 (5) |
H4B—C4—H4C | 109.5 | C27—C26—B1 | 121.10 (6) |
N2—C5—H5A | 109.5 | C28—C27—C26 | 122.88 (7) |
N2—C5—H5B | 109.5 | C28—C27—H27A | 118.6 |
H5A—C5—H5B | 109.5 | C26—C27—H27A | 118.6 |
N2—C5—H5C | 109.5 | C29—C28—C27 | 120.27 (7) |
H5A—C5—H5C | 109.5 | C29—C28—H28A | 119.9 |
H5B—C5—H5C | 109.5 | C27—C28—H28A | 119.9 |
N3—C6—H6A | 109.5 | C28—C29—C30 | 118.60 (7) |
N3—C6—H6B | 109.5 | C28—C29—H29A | 120.7 |
H6A—C6—H6B | 109.5 | C30—C29—H29A | 120.7 |
N3—C6—H6C | 109.5 | C29—C30—C31 | 120.40 (7) |
H6A—C6—H6C | 109.5 | C29—C30—H30A | 119.8 |
H6B—C6—H6C | 109.5 | C31—C30—H30A | 119.8 |
O1—C7—N4 | 123.49 (6) | C30—C31—C26 | 122.76 (6) |
O1—C7—N3 | 119.50 (6) | C30—C31—H31A | 118.6 |
N4—C7—N3 | 117.00 (6) | C26—C31—H31A | 118.6 |
C7—N4—C8 | 123.53 (6) | C37—C32—C33 | 115.09 (6) |
C7—N4—C14 | 118.33 (6) | C37—C32—B1 | 124.32 (6) |
C8—N4—C14 | 117.04 (5) | C33—C32—B1 | 120.35 (6) |
C9—C8—C13 | 120.16 (6) | C34—C33—C32 | 123.03 (7) |
C9—C8—N4 | 120.55 (6) | C34—C33—H33A | 118.5 |
C13—C8—N4 | 119.15 (6) | C32—C33—H33A | 118.5 |
C8—C9—C10 | 119.55 (7) | C33—C34—C35 | 119.93 (7) |
C8—C9—H9A | 120.2 | C33—C34—H34A | 120.0 |
C10—C9—H9A | 120.2 | C35—C34—H34A | 120.0 |
C11—C10—C9 | 120.44 (8) | C36—C35—C34 | 119.07 (7) |
C11—C10—H10A | 119.8 | C36—C35—H35A | 120.5 |
C9—C10—H10A | 119.8 | C34—C35—H35A | 120.5 |
C10—C11—C12 | 119.63 (7) | C35—C36—C37 | 119.96 (7) |
C10—C11—H11A | 120.2 | C35—C36—H36A | 120.0 |
C12—C11—H11A | 120.2 | C37—C36—H36A | 120.0 |
C11—C12—C13 | 120.37 (7) | C36—C37—C32 | 122.92 (6) |
C11—C12—H12A | 119.8 | C36—C37—H37A | 118.5 |
C13—C12—H12A | 119.8 | C32—C37—H37A | 118.5 |
C12—C13—C8 | 119.73 (7) | C43—C38—C39 | 115.08 (6) |
C12—C13—H13A | 120.1 | C43—C38—B1 | 122.46 (6) |
C8—C13—H13A | 120.1 | C39—C38—B1 | 122.20 (6) |
C15—C14—C19 | 120.32 (6) | C40—C39—C38 | 122.71 (6) |
C15—C14—N4 | 119.66 (6) | C40—C39—H39A | 118.6 |
C19—C14—N4 | 119.92 (6) | C38—C39—H39A | 118.6 |
C14—C15—C16 | 119.24 (7) | C41—C40—C39 | 120.51 (7) |
C14—C15—H15A | 120.4 | C41—C40—H40A | 119.7 |
C16—C15—H15A | 120.4 | C39—C40—H40A | 119.7 |
C17—C16—C15 | 120.75 (7) | C40—C41—C42 | 118.50 (7) |
C17—C16—H16A | 119.6 | C40—C41—H41A | 120.8 |
C15—C16—H16A | 119.6 | C42—C41—H41A | 120.8 |
C16—C17—C18 | 119.77 (7) | C41—C42—C43 | 120.36 (7) |
C16—C17—H17A | 120.1 | C41—C42—H42A | 119.8 |
C18—C17—H17A | 120.1 | C43—C42—H42A | 119.8 |
C19—C18—C17 | 119.89 (8) | C42—C43—C38 | 122.83 (6) |
C19—C18—H18A | 120.1 | C42—C43—H43A | 118.6 |
C17—C18—H18A | 120.1 | C38—C43—H43A | 118.6 |
N2—C1—N1—C2 | −154.84 (7) | C25—C20—C21—C22 | −1.46 (10) |
N3—C1—N1—C2 | 29.32 (10) | B1—C20—C21—C22 | −177.94 (7) |
N2—C1—N1—C3 | 33.03 (10) | C20—C21—C22—C23 | 0.59 (12) |
N3—C1—N1—C3 | −142.81 (7) | C21—C22—C23—C24 | 0.32 (11) |
N1—C1—N2—C5 | −147.91 (7) | C22—C23—C24—C25 | −0.27 (11) |
N3—C1—N2—C5 | 27.85 (10) | C23—C24—C25—C20 | −0.70 (11) |
N1—C1—N2—C4 | 31.14 (9) | C21—C20—C25—C24 | 1.52 (10) |
N3—C1—N2—C4 | −153.11 (6) | B1—C20—C25—C24 | 178.06 (6) |
N2—C1—N3—C7 | 34.10 (10) | C20—B1—C26—C31 | −89.37 (7) |
N1—C1—N3—C7 | −150.08 (7) | C32—B1—C26—C31 | 32.16 (9) |
N2—C1—N3—C6 | −128.56 (7) | C38—B1—C26—C31 | 149.45 (6) |
N1—C1—N3—C6 | 47.25 (9) | C20—B1—C26—C27 | 86.83 (7) |
C1—N3—C7—O1 | −145.19 (7) | C32—B1—C26—C27 | −151.64 (6) |
C6—N3—C7—O1 | 17.98 (10) | C38—B1—C26—C27 | −34.35 (8) |
C1—N3—C7—N4 | 35.91 (10) | C31—C26—C27—C28 | −2.83 (11) |
C6—N3—C7—N4 | −160.93 (7) | B1—C26—C27—C28 | −179.34 (7) |
O1—C7—N4—C8 | −152.04 (7) | C26—C27—C28—C29 | 0.91 (13) |
N3—C7—N4—C8 | 26.82 (9) | C27—C28—C29—C30 | 1.16 (13) |
O1—C7—N4—C14 | 15.60 (10) | C28—C29—C30—C31 | −1.13 (12) |
N3—C7—N4—C14 | −165.54 (6) | C29—C30—C31—C26 | −0.98 (11) |
C7—N4—C8—C9 | 46.21 (10) | C27—C26—C31—C30 | 2.86 (10) |
C14—N4—C8—C9 | −121.57 (7) | B1—C26—C31—C30 | 179.27 (6) |
C7—N4—C8—C13 | −138.05 (7) | C20—B1—C32—C37 | 143.05 (6) |
C14—N4—C8—C13 | 54.16 (8) | C26—B1—C32—C37 | 24.28 (9) |
C13—C8—C9—C10 | 3.42 (11) | C38—B1—C32—C37 | −96.93 (7) |
N4—C8—C9—C10 | 179.11 (7) | C20—B1—C32—C33 | −42.78 (9) |
C8—C9—C10—C11 | −3.07 (13) | C26—B1—C32—C33 | −161.54 (7) |
C9—C10—C11—C12 | 0.25 (13) | C38—B1—C32—C33 | 77.25 (8) |
C10—C11—C12—C13 | 2.24 (12) | C37—C32—C33—C34 | −0.99 (12) |
C11—C12—C13—C8 | −1.89 (11) | B1—C32—C33—C34 | −175.68 (8) |
C9—C8—C13—C12 | −0.96 (10) | C32—C33—C34—C35 | 0.61 (14) |
N4—C8—C13—C12 | −176.71 (6) | C33—C34—C35—C36 | 0.16 (13) |
C7—N4—C14—C15 | −132.19 (7) | C34—C35—C36—C37 | −0.47 (12) |
C8—N4—C14—C15 | 36.25 (9) | C35—C36—C37—C32 | 0.05 (11) |
C7—N4—C14—C19 | 51.37 (9) | C33—C32—C37—C36 | 0.66 (10) |
C8—N4—C14—C19 | −140.18 (7) | B1—C32—C37—C36 | 175.11 (6) |
C19—C14—C15—C16 | 1.91 (11) | C20—B1—C38—C43 | 35.08 (8) |
N4—C14—C15—C16 | −174.52 (7) | C26—B1—C38—C43 | 152.49 (6) |
C14—C15—C16—C17 | −1.50 (12) | C32—B1—C38—C43 | −84.04 (7) |
C15—C16—C17—C18 | −0.08 (13) | C20—B1—C38—C39 | −151.05 (6) |
C16—C17—C18—C19 | 1.27 (13) | C26—B1—C38—C39 | −33.64 (8) |
C17—C18—C19—C14 | −0.86 (13) | C32—B1—C38—C39 | 89.83 (7) |
C15—C14—C19—C18 | −0.74 (12) | C43—C38—C39—C40 | −0.53 (9) |
N4—C14—C19—C18 | 175.67 (7) | B1—C38—C39—C40 | −174.82 (6) |
C26—B1—C20—C21 | 95.42 (7) | C38—C39—C40—C41 | 0.05 (10) |
C32—B1—C20—C21 | −28.65 (9) | C39—C40—C41—C42 | 0.39 (10) |
C38—B1—C20—C21 | −143.90 (6) | C40—C41—C42—C43 | −0.33 (10) |
C26—B1—C20—C25 | −80.85 (7) | C41—C42—C43—C38 | −0.18 (11) |
C32—B1—C20—C25 | 155.07 (6) | C39—C38—C43—C42 | 0.59 (10) |
C38—B1—C20—C25 | 39.83 (8) | B1—C38—C43—C42 | 174.87 (6) |
Experimental details
Crystal data | |
Chemical formula | C19H25N4O+·C24H20B− |
Mr | 644.64 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 11.0564 (4), 9.5942 (3), 33.4312 (12) |
β (°) | 91.684 (2) |
V (Å3) | 3544.8 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.24 × 0.17 × 0.15 |
Data collection | |
Diffractometer | Bruker Kappa APEXII DUO |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 119072, 17178, 14383 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.834 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.121, 1.06 |
No. of reflections | 17178 |
No. of parameters | 447 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.22 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).
Acknowledgements
The author thanks Dr W. Frey (Institut für Organische Chemie, Universität Stuttgart) for the data collection.
References
Behrens, U., Hoffmann, F. & Olbrich, F. (2012). Organometallics, 31, 905–913. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tiritiris, I. (2012). Acta Cryst. E68, o3085. CSD CrossRef IUCr Journals Google Scholar
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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 CN3 unit in the cationic part is elongated (C1–N3 = 1.3802 (9) Å), indicating single bond character. The two remaining C–N bonds (C1–N2 = 1.3327 (8) Å and C1–N1 = 1.3364 (9) Å) are shorter and they show double bond character. As a consequence, the positive charge is not delocalized over the entire CN3 unit, but only between the two dimethylamino groups. The N–C1–N angles are: 120.29 (6)° (N1–C1–N2), 120.81 (6)° (N2–C1–N3) and 118.77 (6)° (N1–C1–N3), which indicate only a slight deviation of the CN3 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 (1.4636 (9)–1.4772 (9) Å). The C–O bond length in the diphenylcarbamoyl group is C7–O1 = 1.2148 (8) Å, and shows the expected double-bond character. The N–C bond lengths are: N3–C7 = 1.4267 (9) Å, N4–C7 = 1.3771 (8) Å, N4–C8 = 1.4348 (9) Å and N4–C14 = 1.4395 (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 CN3 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.