organic compounds
(Butoxymethylidene)dimethylazanium tetraphenylborate acetonitrile monosolvate
aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
*Correspondence e-mail: willi.kantlehner@htw-aalen.de
In the title solvated salt, C7H16NO+·C24H20B−·C2H3N, the C—N bond lengths in the cation are 1.2831 (19), 1.467 (2) and 1.465 (2) Å, indicating double- and single-bond character, respectively. The C—O bond length of 1.2950 (18) Å shows a double-bond character, pointing towards charge delocalization within the NCO plane of the iminium ion. The two C atoms of the n-butyl group are disordered over the two sites, with refined occupancy ratios of 0.890 (5):0.110 (5) and 0.888 (4):0.112 (4). In the crystal, C—H⋯π interactions occur between the methine H atom, H atoms of the –N(CH3)2 and –CH2 groups of the cation, and two of the phenyl rings of the tetraphenylborate anion. The latter interaction forms an aromatic pocket in which the cation is embedded. Thus, a two-dimensional pattern is created in the ac plane.
CCDC reference: 991457
Related literature
For the crystal structures of alkali metal tetraphenylborates, see: Behrens et al. (2012). For the of (methoxymethylidene)dimethylazanium tetraphenylborate acetonitrile monosolvate, see: Tiritiris et al. (2014).
Experimental
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
CCDC reference: 991457
10.1107/S1600536814005674/kp2466sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814005674/kp2466Isup2.hkl
The title compound was obtained by reacting of equimolar amounts of N,N-dimethylformamide with dimethyl sulfate at room temperature forming (methoxymethylidene)dimethylazanium methyl sulfate (I). One mol of (I) was heated with 2.2 mol n-butanol for eight hours at 313 K. The methanol formed was distilled off and (butoxymethylidene)dimethylazanium butyl sulfate (II) was obtained in nearly quantitative yield. 1.00 g (3.66 mmol) of crude (II) was dissolved in 20 ml acetonitrile and 1.25 g (3.66 mmol) of sodium tetraphenylborate in 20 ml acetonitrile was added. After stirring for one hour at room temperature, the precipitated sodium butyl sulfate was filtered off. The title compound crystallized from a saturated acetonitrile solution after several days at 273 K, forming colourless single crystals suitable for X-ray analysis.
Dimethyl sulfate is carcinogenic, mutagenic and highly poisonous. During the use appropriate precautions must be taken.
The H atom bound to C3 was located in a difference Fourier map and was refined freely [C—H = 0.95 (2) Å]. The hydrogen atoms of the methyl groups were allowed to rotate with a fixed angle around the C–N, C–O and C–C bonds to best fit the experimental electron density, with Uiso(H) set to 1.5Ueq(C) and d(C—H) = 0.98 Å. The remaining H atoms were placed in calculated positions with d(C—H) = 0.99 Å (H atoms in CH2 groups) and (C—H) = 0.95 Å (H atoms in aromatic rings). They were included in the
in the riding model approximation, with U(H) set to 1.2 Ueq(C).Atoms C5 and C6 of the n-butyl group are disordered over two sites (C5A, C6A and C5B,C6B) with refined occupancies of 0.888 (5) and 0.112 (5). A free
of the anisotropic displacement parameters of the atoms C5B and C6B (minor moiety) was not possible, so an ISOR = 0.001 instruction for C6B was established, which solves this problem. Finally, the atoms C5B and C6B were restrained to have similar anisotropic displacement parameters. Nevertheless, it was not possible to prevent the detection of an A-alert in the checkcif utility. There is a large Ueq(max)/Ueq(min) ratio of the hydrogen atoms, caused by the large Ueq of the terminal methyl group hydrogen atoms and the small Ueq of the hydrogen atoms attached to the atoms C5B and C6B in the disordered n-butyl moiety.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 structure of the title compound with displacement ellipsoids at the 50% probability level. All carbon bonded hydrogen atoms (except of H3) were omitted for the sake of clarity. Only the major orientation [pp = 0.888 (5)] of the n-butyl group is shown. | |
Fig. 2. C—H···π interactions (red dashed lines) between the hydrogen atoms of the cation and the phenyl carbon atoms (centroids) of the tetraphenylborate ion. Both orientations of the n-butyl group are shown. |
C7H16NO+·C24H20B−·C2H3N | F(000) = 1056 |
Mr = 490.47 | Dx = 1.130 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 27626 reflections |
a = 11.2463 (4) Å | θ = 1.8–28.3° |
b = 17.7975 (9) Å | µ = 0.07 mm−1 |
c = 14.6666 (7) Å | T = 100 K |
β = 100.821 (3)° | Block, colourless |
V = 2883.4 (2) Å3 | 0.23 × 0.17 × 0.13 mm |
Z = 4 |
Bruker Kappa APEXII DUO diffractometer | 4718 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.054 |
Graphite monochromator | θmax = 28.3°, θmin = 1.8° |
ϕ scans, and ω scans | h = −14→14 |
27626 measured reflections | k = −23→23 |
7019 independent reflections | l = −18→19 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0513P)2 + 0.6909P] where P = (Fo2 + 2Fc2)/3 |
7019 reflections | (Δ/σ)max < 0.001 |
352 parameters | Δρmax = 0.28 e Å−3 |
6 restraints | Δρmin = −0.31 e Å−3 |
C7H16NO+·C24H20B−·C2H3N | V = 2883.4 (2) Å3 |
Mr = 490.47 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.2463 (4) Å | µ = 0.07 mm−1 |
b = 17.7975 (9) Å | T = 100 K |
c = 14.6666 (7) Å | 0.23 × 0.17 × 0.13 mm |
β = 100.821 (3)° |
Bruker Kappa APEXII DUO diffractometer | 4718 reflections with I > 2σ(I) |
27626 measured reflections | Rint = 0.054 |
7019 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 6 restraints |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.28 e Å−3 |
7019 reflections | Δρmin = −0.31 e Å−3 |
352 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 | Occ. (<1) | |
N1 | 1.05819 (11) | 0.19695 (7) | 1.00987 (8) | 0.0190 (3) | |
C1 | 1.14020 (14) | 0.25442 (10) | 1.05776 (12) | 0.0283 (4) | |
H1A | 1.0929 | 0.2939 | 1.0810 | 0.042* | |
H1B | 1.1870 | 0.2763 | 1.0144 | 0.042* | |
H1C | 1.1955 | 0.2315 | 1.1099 | 0.042* | |
C2 | 1.11443 (15) | 0.13197 (10) | 0.97325 (12) | 0.0275 (4) | |
H2A | 1.0513 | 0.0972 | 0.9437 | 0.041* | |
H2B | 1.1680 | 0.1063 | 1.0242 | 0.041* | |
H2C | 1.1616 | 0.1490 | 0.9274 | 0.041* | |
C3 | 0.94283 (13) | 0.20482 (9) | 0.99683 (10) | 0.0189 (3) | |
H3 | 0.9082 (15) | 0.2476 (10) | 1.0209 (11) | 0.025 (4)* | |
O1 | 0.87394 (9) | 0.15411 (6) | 0.95062 (7) | 0.0196 (2) | |
C4 | 0.74205 (13) | 0.16696 (9) | 0.93430 (11) | 0.0218 (3) | |
H4A | 0.7242 | 0.2209 | 0.9218 | 0.026* | |
H4B | 0.7093 | 0.1521 | 0.9898 | 0.026* | |
C5A | 0.68533 (15) | 0.12077 (10) | 0.85260 (13) | 0.0197 (5) | 0.890 (5) |
H5A | 0.7175 | 0.1374 | 0.7976 | 0.024* | 0.890 (5) |
H5B | 0.5969 | 0.1300 | 0.8398 | 0.024* | 0.890 (5) |
C6A | 0.70789 (17) | 0.03642 (10) | 0.86623 (14) | 0.0277 (5) | 0.888 (4) |
H6A | 0.7962 | 0.0271 | 0.8814 | 0.033* | 0.888 (4) |
H6B | 0.6722 | 0.0190 | 0.9193 | 0.033* | 0.888 (4) |
C5B | 0.6903 (11) | 0.0909 (7) | 0.8972 (10) | 0.009 (3) | 0.110 (5) |
H5C | 0.7235 | 0.0513 | 0.9422 | 0.011* | 0.110 (5) |
H5D | 0.6014 | 0.0917 | 0.8928 | 0.011* | 0.110 (5) |
C6B | 0.7178 (10) | 0.0710 (6) | 0.8041 (8) | 0.009 (3) | 0.112 (4) |
H6C | 0.8062 | 0.0669 | 0.8069 | 0.011* | 0.112 (4) |
H6D | 0.6845 | 0.1091 | 0.7570 | 0.011* | 0.112 (4) |
C7 | 0.65349 (17) | −0.00822 (11) | 0.78020 (14) | 0.0410 (5) | |
H7A | 0.6697 | −0.0618 | 0.7917 | 0.062* | |
H7B | 0.6898 | 0.0082 | 0.7278 | 0.062* | |
H7C | 0.5659 | 0.0002 | 0.7656 | 0.062* | |
B1 | 0.29162 (15) | 0.22427 (9) | 0.73749 (11) | 0.0157 (3) | |
C8 | 0.35342 (12) | 0.18276 (8) | 0.83517 (10) | 0.0145 (3) | |
C9 | 0.35346 (13) | 0.10426 (8) | 0.84668 (10) | 0.0173 (3) | |
H9A | 0.3228 | 0.0737 | 0.7945 | 0.021* | |
C10 | 0.39659 (13) | 0.06971 (9) | 0.93151 (11) | 0.0208 (3) | |
H10A | 0.3966 | 0.0165 | 0.9361 | 0.025* | |
C11 | 0.43964 (13) | 0.11303 (9) | 1.00947 (11) | 0.0223 (3) | |
H11A | 0.4693 | 0.0897 | 1.0675 | 0.027* | |
C12 | 0.43886 (13) | 0.19056 (9) | 1.00171 (10) | 0.0202 (3) | |
H12A | 0.4663 | 0.2207 | 1.0549 | 0.024* | |
C13 | 0.39780 (13) | 0.22429 (8) | 0.91588 (10) | 0.0179 (3) | |
H13A | 0.3999 | 0.2775 | 0.9117 | 0.022* | |
C14 | 0.29953 (13) | 0.17201 (8) | 0.64632 (10) | 0.0162 (3) | |
C15 | 0.40218 (14) | 0.12851 (8) | 0.64120 (11) | 0.0209 (3) | |
H15A | 0.4655 | 0.1264 | 0.6941 | 0.025* | |
C16 | 0.41546 (15) | 0.08837 (9) | 0.56222 (11) | 0.0259 (4) | |
H16A | 0.4866 | 0.0596 | 0.5622 | 0.031* | |
C17 | 0.32541 (15) | 0.09030 (9) | 0.48393 (11) | 0.0269 (4) | |
H17A | 0.3336 | 0.0627 | 0.4300 | 0.032* | |
C18 | 0.22291 (15) | 0.13319 (9) | 0.48557 (10) | 0.0242 (3) | |
H18A | 0.1604 | 0.1354 | 0.4322 | 0.029* | |
C19 | 0.21100 (14) | 0.17302 (8) | 0.56495 (10) | 0.0188 (3) | |
H19A | 0.1400 | 0.2021 | 0.5641 | 0.023* | |
C20 | 0.15186 (13) | 0.24097 (8) | 0.75026 (9) | 0.0168 (3) | |
C21 | 0.05601 (13) | 0.19093 (9) | 0.72214 (10) | 0.0207 (3) | |
H21A | 0.0714 | 0.1458 | 0.6919 | 0.025* | |
C22 | −0.06111 (14) | 0.20452 (10) | 0.73668 (11) | 0.0263 (4) | |
H22A | −0.1240 | 0.1695 | 0.7153 | 0.032* | |
C23 | −0.08547 (14) | 0.26923 (10) | 0.78234 (11) | 0.0289 (4) | |
H23A | −0.1653 | 0.2793 | 0.7916 | 0.035* | |
C24 | 0.00722 (15) | 0.31904 (10) | 0.81425 (11) | 0.0281 (4) | |
H24A | −0.0082 | 0.3629 | 0.8470 | 0.034* | |
C25 | 0.12320 (14) | 0.30481 (9) | 0.79832 (11) | 0.0222 (3) | |
H25A | 0.1857 | 0.3397 | 0.8209 | 0.027* | |
C26 | 0.36367 (13) | 0.30231 (8) | 0.72107 (10) | 0.0160 (3) | |
C27 | 0.30508 (14) | 0.36477 (8) | 0.67425 (10) | 0.0194 (3) | |
H27A | 0.2197 | 0.3630 | 0.6544 | 0.023* | |
C28 | 0.36669 (15) | 0.42920 (9) | 0.65570 (11) | 0.0247 (4) | |
H28A | 0.3233 | 0.4700 | 0.6235 | 0.030* | |
C29 | 0.49117 (15) | 0.43391 (9) | 0.68403 (11) | 0.0260 (4) | |
H29A | 0.5335 | 0.4780 | 0.6723 | 0.031* | |
C30 | 0.55292 (14) | 0.37329 (9) | 0.72968 (11) | 0.0235 (3) | |
H30A | 0.6383 | 0.3756 | 0.7492 | 0.028* | |
C31 | 0.49002 (14) | 0.30897 (8) | 0.74708 (10) | 0.0192 (3) | |
H31A | 0.5345 | 0.2679 | 0.7778 | 0.023* | |
N2 | 0.8185 (2) | 0.08990 (10) | 0.54785 (13) | 0.0595 (5) | |
C32 | 0.83893 (19) | 0.06303 (10) | 0.48185 (14) | 0.0384 (5) | |
C33 | 0.86399 (19) | 0.02888 (10) | 0.39784 (13) | 0.0388 (5) | |
H33A | 0.7999 | −0.0072 | 0.3738 | 0.058* | |
H33B | 0.9420 | 0.0028 | 0.4116 | 0.058* | |
H33C | 0.8670 | 0.0680 | 0.3512 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0166 (6) | 0.0248 (7) | 0.0156 (6) | −0.0002 (5) | 0.0029 (5) | 0.0000 (5) |
C1 | 0.0179 (8) | 0.0332 (9) | 0.0324 (9) | −0.0040 (7) | 0.0015 (7) | −0.0103 (7) |
C2 | 0.0190 (8) | 0.0326 (9) | 0.0315 (9) | 0.0040 (7) | 0.0065 (7) | −0.0064 (7) |
C3 | 0.0166 (7) | 0.0227 (8) | 0.0172 (7) | 0.0002 (6) | 0.0026 (6) | −0.0008 (6) |
O1 | 0.0124 (5) | 0.0246 (6) | 0.0212 (6) | 0.0001 (4) | 0.0018 (4) | −0.0037 (4) |
C4 | 0.0116 (7) | 0.0268 (8) | 0.0270 (8) | 0.0014 (6) | 0.0037 (6) | −0.0049 (6) |
C5A | 0.0159 (8) | 0.0226 (10) | 0.0202 (10) | 0.0005 (7) | 0.0025 (7) | −0.0003 (8) |
C6A | 0.0216 (10) | 0.0234 (10) | 0.0371 (12) | 0.0006 (7) | 0.0030 (8) | −0.0020 (8) |
C5B | 0.009 (3) | 0.009 (3) | 0.009 (3) | 0.0001 (10) | 0.0018 (11) | 0.0003 (10) |
C6B | 0.009 (3) | 0.009 (3) | 0.009 (3) | 0.0001 (10) | 0.0018 (11) | 0.0003 (10) |
C7 | 0.0358 (11) | 0.0293 (10) | 0.0552 (13) | 0.0015 (8) | 0.0014 (9) | −0.0192 (9) |
B1 | 0.0142 (8) | 0.0163 (8) | 0.0163 (8) | 0.0005 (6) | 0.0019 (6) | −0.0007 (6) |
C8 | 0.0095 (6) | 0.0175 (7) | 0.0168 (7) | 0.0009 (5) | 0.0032 (5) | −0.0007 (5) |
C9 | 0.0142 (7) | 0.0185 (7) | 0.0188 (7) | 0.0006 (6) | 0.0022 (6) | −0.0023 (6) |
C10 | 0.0179 (7) | 0.0181 (7) | 0.0262 (8) | 0.0036 (6) | 0.0032 (6) | 0.0020 (6) |
C11 | 0.0154 (7) | 0.0313 (9) | 0.0190 (8) | 0.0024 (6) | −0.0004 (6) | 0.0061 (6) |
C12 | 0.0148 (7) | 0.0292 (8) | 0.0162 (7) | −0.0036 (6) | 0.0015 (6) | −0.0043 (6) |
C13 | 0.0152 (7) | 0.0180 (7) | 0.0210 (8) | −0.0003 (6) | 0.0045 (6) | −0.0015 (6) |
C14 | 0.0167 (7) | 0.0151 (7) | 0.0172 (7) | −0.0030 (6) | 0.0043 (6) | 0.0016 (6) |
C15 | 0.0202 (8) | 0.0230 (8) | 0.0196 (8) | −0.0002 (6) | 0.0041 (6) | −0.0015 (6) |
C16 | 0.0294 (9) | 0.0238 (8) | 0.0274 (9) | 0.0022 (7) | 0.0131 (7) | −0.0040 (7) |
C17 | 0.0390 (10) | 0.0238 (8) | 0.0206 (8) | −0.0076 (7) | 0.0130 (7) | −0.0066 (7) |
C18 | 0.0294 (9) | 0.0273 (8) | 0.0149 (8) | −0.0091 (7) | 0.0015 (6) | −0.0003 (6) |
C19 | 0.0192 (7) | 0.0189 (7) | 0.0181 (7) | −0.0029 (6) | 0.0031 (6) | 0.0023 (6) |
C20 | 0.0168 (7) | 0.0203 (7) | 0.0132 (7) | 0.0030 (6) | 0.0028 (6) | 0.0041 (6) |
C21 | 0.0181 (8) | 0.0252 (8) | 0.0191 (8) | −0.0006 (6) | 0.0042 (6) | 0.0040 (6) |
C22 | 0.0163 (8) | 0.0407 (10) | 0.0214 (8) | −0.0030 (7) | 0.0024 (6) | 0.0082 (7) |
C23 | 0.0167 (8) | 0.0460 (11) | 0.0259 (9) | 0.0091 (7) | 0.0090 (7) | 0.0134 (8) |
C24 | 0.0295 (9) | 0.0312 (9) | 0.0265 (9) | 0.0127 (7) | 0.0127 (7) | 0.0056 (7) |
C25 | 0.0209 (8) | 0.0237 (8) | 0.0230 (8) | 0.0015 (6) | 0.0066 (6) | 0.0020 (6) |
C26 | 0.0178 (7) | 0.0171 (7) | 0.0137 (7) | −0.0005 (6) | 0.0041 (6) | −0.0026 (5) |
C27 | 0.0184 (7) | 0.0211 (8) | 0.0187 (8) | 0.0016 (6) | 0.0035 (6) | −0.0006 (6) |
C28 | 0.0296 (9) | 0.0200 (8) | 0.0255 (9) | 0.0026 (7) | 0.0074 (7) | 0.0039 (6) |
C29 | 0.0314 (9) | 0.0212 (8) | 0.0269 (9) | −0.0086 (7) | 0.0095 (7) | 0.0007 (7) |
C30 | 0.0196 (8) | 0.0285 (9) | 0.0227 (8) | −0.0052 (7) | 0.0045 (6) | −0.0007 (7) |
C31 | 0.0187 (7) | 0.0212 (8) | 0.0179 (7) | 0.0011 (6) | 0.0037 (6) | 0.0008 (6) |
N2 | 0.0909 (16) | 0.0368 (10) | 0.0494 (11) | −0.0001 (10) | 0.0097 (11) | −0.0072 (9) |
C32 | 0.0497 (12) | 0.0227 (9) | 0.0394 (11) | −0.0011 (8) | −0.0005 (9) | 0.0051 (8) |
C33 | 0.0516 (12) | 0.0290 (10) | 0.0366 (11) | 0.0036 (9) | 0.0107 (9) | 0.0084 (8) |
N1—C3 | 1.2831 (19) | C11—H11A | 0.9500 |
N1—C1 | 1.465 (2) | C12—C13 | 1.393 (2) |
N1—C2 | 1.467 (2) | C12—H12A | 0.9500 |
C1—H1A | 0.9800 | C13—H13A | 0.9500 |
C1—H1B | 0.9800 | C14—C19 | 1.403 (2) |
C1—H1C | 0.9800 | C14—C15 | 1.404 (2) |
C2—H2A | 0.9800 | C15—C16 | 1.393 (2) |
C2—H2B | 0.9800 | C15—H15A | 0.9500 |
C2—H2C | 0.9800 | C16—C17 | 1.382 (2) |
C3—O1 | 1.2950 (18) | C16—H16A | 0.9500 |
C3—H3 | 0.954 (18) | C17—C18 | 1.387 (2) |
O1—C4 | 1.4752 (17) | C17—H17A | 0.9500 |
C4—C5A | 1.494 (2) | C18—C19 | 1.391 (2) |
C4—C5B | 1.531 (12) | C18—H18A | 0.9500 |
C4—H4A | 0.9900 | C19—H19A | 0.9500 |
C4—H4B | 0.9900 | C20—C21 | 1.399 (2) |
C5A—C6A | 1.530 (3) | C20—C25 | 1.406 (2) |
C5A—H5A | 0.9900 | C21—C22 | 1.394 (2) |
C5A—H5B | 0.9900 | C21—H21A | 0.9500 |
C6A—C7 | 1.520 (3) | C22—C23 | 1.385 (2) |
C6A—H6A | 0.9900 | C22—H22A | 0.9500 |
C6A—H6B | 0.9900 | C23—C24 | 1.381 (2) |
C5B—C6B | 1.486 (13) | C23—H23A | 0.9500 |
C5B—H5C | 0.9900 | C24—C25 | 1.391 (2) |
C5B—H5D | 0.9900 | C24—H24A | 0.9500 |
C6B—C7 | 1.5972 | C25—H25A | 0.9500 |
C6B—H6C | 0.9900 | C26—C27 | 1.404 (2) |
C6B—H6D | 0.9900 | C26—C31 | 1.406 (2) |
C7—H7A | 0.9800 | C27—C28 | 1.393 (2) |
C7—H7B | 0.9800 | C27—H27A | 0.9500 |
C7—H7C | 0.9800 | C28—C29 | 1.386 (2) |
B1—C20 | 1.645 (2) | C28—H28A | 0.9500 |
B1—C14 | 1.645 (2) | C29—C30 | 1.386 (2) |
B1—C8 | 1.645 (2) | C29—H29A | 0.9500 |
B1—C26 | 1.648 (2) | C30—C31 | 1.394 (2) |
C8—C13 | 1.405 (2) | C30—H30A | 0.9500 |
C8—C9 | 1.407 (2) | C31—H31A | 0.9500 |
C9—C10 | 1.391 (2) | N2—C32 | 1.141 (3) |
C9—H9A | 0.9500 | C32—C33 | 1.448 (3) |
C10—C11 | 1.389 (2) | C33—H33A | 0.9800 |
C10—H10A | 0.9500 | C33—H33B | 0.9800 |
C11—C12 | 1.384 (2) | C33—H33C | 0.9800 |
C3—N1—C1 | 121.54 (14) | C11—C10—C9 | 120.02 (14) |
C3—N1—C2 | 121.65 (13) | C11—C10—H10A | 120.0 |
C1—N1—C2 | 116.73 (12) | C9—C10—H10A | 120.0 |
N1—C1—H1A | 109.5 | C12—C11—C10 | 119.33 (14) |
N1—C1—H1B | 109.5 | C12—C11—H11A | 120.3 |
H1A—C1—H1B | 109.5 | C10—C11—H11A | 120.3 |
N1—C1—H1C | 109.5 | C11—C12—C13 | 119.99 (14) |
H1A—C1—H1C | 109.5 | C11—C12—H12A | 120.0 |
H1B—C1—H1C | 109.5 | C13—C12—H12A | 120.0 |
N1—C2—H2A | 109.5 | C12—C13—C8 | 122.66 (14) |
N1—C2—H2B | 109.5 | C12—C13—H13A | 118.7 |
H2A—C2—H2B | 109.5 | C8—C13—H13A | 118.7 |
N1—C2—H2C | 109.5 | C19—C14—C15 | 114.89 (14) |
H2A—C2—H2C | 109.5 | C19—C14—B1 | 123.09 (13) |
H2B—C2—H2C | 109.5 | C15—C14—B1 | 121.73 (13) |
N1—C3—O1 | 119.39 (14) | C16—C15—C14 | 123.03 (14) |
N1—C3—H3 | 120.3 (10) | C16—C15—H15A | 118.5 |
O1—C3—H3 | 120.3 (10) | C14—C15—H15A | 118.5 |
C3—O1—C4 | 117.47 (12) | C17—C16—C15 | 120.15 (15) |
O1—C4—C5A | 108.05 (12) | C17—C16—H16A | 119.9 |
O1—C4—C5B | 102.9 (5) | C15—C16—H16A | 119.9 |
O1—C4—H4A | 110.1 | C16—C17—C18 | 118.77 (15) |
C5A—C4—H4A | 110.1 | C16—C17—H17A | 120.6 |
C5B—C4—H4A | 137.7 | C18—C17—H17A | 120.6 |
O1—C4—H4B | 110.1 | C17—C18—C19 | 120.41 (14) |
C5A—C4—H4B | 110.1 | C17—C18—H18A | 119.8 |
C5B—C4—H4B | 83.2 | C19—C18—H18A | 119.8 |
H4A—C4—H4B | 108.4 | C18—C19—C14 | 122.74 (15) |
C4—C5A—C6A | 113.56 (16) | C18—C19—H19A | 118.6 |
C4—C5A—H5A | 108.9 | C14—C19—H19A | 118.6 |
C6A—C5A—H5A | 108.9 | C21—C20—C25 | 115.19 (14) |
C4—C5A—H5B | 108.9 | C21—C20—B1 | 123.45 (13) |
C6A—C5A—H5B | 108.9 | C25—C20—B1 | 121.14 (13) |
H5A—C5A—H5B | 107.7 | C22—C21—C20 | 122.83 (15) |
C7—C6A—C5A | 111.92 (16) | C22—C21—H21A | 118.6 |
C7—C6A—H6A | 109.2 | C20—C21—H21A | 118.6 |
C5A—C6A—H6A | 109.2 | C23—C22—C21 | 119.75 (16) |
C7—C6A—H6B | 109.2 | C23—C22—H22A | 120.1 |
C5A—C6A—H6B | 109.2 | C21—C22—H22A | 120.1 |
H6A—C6A—H6B | 107.9 | C24—C23—C22 | 119.48 (15) |
C6B—C5B—C4 | 113.8 (9) | C24—C23—H23A | 120.3 |
C6B—C5B—H5C | 108.8 | C22—C23—H23A | 120.3 |
C4—C5B—H5C | 108.8 | C23—C24—C25 | 119.87 (16) |
C6B—C5B—H5D | 108.8 | C23—C24—H24A | 120.1 |
C4—C5B—H5D | 108.8 | C25—C24—H24A | 120.1 |
H5C—C5B—H5D | 107.7 | C24—C25—C20 | 122.81 (15) |
C5B—C6B—C7 | 104.7 (5) | C24—C25—H25A | 118.6 |
C5B—C6B—H6C | 110.8 | C20—C25—H25A | 118.6 |
C7—C6B—H6C | 110.8 | C27—C26—C31 | 115.07 (13) |
C5B—C6B—H6D | 110.8 | C27—C26—B1 | 122.69 (13) |
C7—C6B—H6D | 110.8 | C31—C26—B1 | 122.08 (13) |
H6C—C6B—H6D | 108.9 | C28—C27—C26 | 122.85 (14) |
C6A—C7—H7A | 109.5 | C28—C27—H27A | 118.6 |
C6B—C7—H7A | 139.2 | C26—C27—H27A | 118.6 |
C6A—C7—H7B | 109.5 | C29—C28—C27 | 120.17 (15) |
C6B—C7—H7B | 71.2 | C29—C28—H28A | 119.9 |
H7A—C7—H7B | 109.5 | C27—C28—H28A | 119.9 |
C6A—C7—H7C | 109.5 | C30—C29—C28 | 118.96 (15) |
C6B—C7—H7C | 108.2 | C30—C29—H29A | 120.5 |
H7A—C7—H7C | 109.5 | C28—C29—H29A | 120.5 |
H7B—C7—H7C | 109.5 | C29—C30—C31 | 120.15 (15) |
C20—B1—C14 | 113.17 (12) | C29—C30—H30A | 119.9 |
C20—B1—C8 | 103.80 (11) | C31—C30—H30A | 119.9 |
C14—B1—C8 | 112.05 (12) | C30—C31—C26 | 122.78 (14) |
C20—B1—C26 | 111.78 (12) | C30—C31—H31A | 118.6 |
C14—B1—C26 | 104.75 (11) | C26—C31—H31A | 118.6 |
C8—B1—C26 | 111.51 (11) | N2—C32—C33 | 179.6 (2) |
C13—C8—C9 | 115.41 (13) | C32—C33—H33A | 109.5 |
C13—C8—B1 | 121.50 (12) | C32—C33—H33B | 109.5 |
C9—C8—B1 | 122.73 (12) | H33A—C33—H33B | 109.5 |
C10—C9—C8 | 122.57 (13) | C32—C33—H33C | 109.5 |
C10—C9—H9A | 118.7 | H33A—C33—H33C | 109.5 |
C8—C9—H9A | 118.7 | H33B—C33—H33C | 109.5 |
C1—N1—C3—O1 | 177.02 (13) | C14—C15—C16—C17 | 0.2 (2) |
C2—N1—C3—O1 | 0.4 (2) | C15—C16—C17—C18 | 0.5 (2) |
N1—C3—O1—C4 | −177.73 (13) | C16—C17—C18—C19 | −0.4 (2) |
C3—O1—C4—C5A | 158.30 (14) | C17—C18—C19—C14 | −0.3 (2) |
C3—O1—C4—C5B | −168.8 (6) | C15—C14—C19—C18 | 0.9 (2) |
O1—C4—C5A—C6A | 60.11 (19) | B1—C14—C19—C18 | 174.79 (13) |
C5B—C4—C5A—C6A | −25.5 (8) | C14—B1—C20—C21 | 30.61 (19) |
C4—C5A—C6A—C7 | −177.50 (15) | C8—B1—C20—C21 | −91.10 (16) |
O1—C4—C5B—C6B | −66.3 (9) | C26—B1—C20—C21 | 148.59 (13) |
C5A—C4—C5B—C6B | 37.1 (6) | C14—B1—C20—C25 | −155.05 (13) |
C4—C5B—C6B—C7 | −178.7 (6) | C8—B1—C20—C25 | 83.24 (16) |
C5A—C6A—C7—C6B | 35.93 (11) | C26—B1—C20—C25 | −37.07 (18) |
C5B—C6B—C7—C6A | −27.7 (5) | C25—C20—C21—C22 | 2.8 (2) |
C20—B1—C8—C13 | −81.68 (15) | B1—C20—C21—C22 | 177.43 (14) |
C14—B1—C8—C13 | 155.86 (13) | C20—C21—C22—C23 | −1.3 (2) |
C26—B1—C8—C13 | 38.81 (18) | C21—C22—C23—C24 | −1.0 (2) |
C20—B1—C8—C9 | 91.09 (15) | C22—C23—C24—C25 | 1.6 (2) |
C14—B1—C8—C9 | −31.36 (18) | C23—C24—C25—C20 | 0.1 (2) |
C26—B1—C8—C9 | −148.42 (13) | C21—C20—C25—C24 | −2.2 (2) |
C13—C8—C9—C10 | −1.2 (2) | B1—C20—C25—C24 | −176.95 (14) |
B1—C8—C9—C10 | −174.43 (13) | C20—B1—C26—C27 | −32.58 (18) |
C8—C9—C10—C11 | 1.3 (2) | C14—B1—C26—C27 | 90.33 (15) |
C9—C10—C11—C12 | 0.1 (2) | C8—B1—C26—C27 | −148.27 (13) |
C10—C11—C12—C13 | −1.5 (2) | C20—B1—C26—C31 | 152.20 (13) |
C11—C12—C13—C8 | 1.5 (2) | C14—B1—C26—C31 | −84.89 (15) |
C9—C8—C13—C12 | −0.2 (2) | C8—B1—C26—C31 | 36.51 (18) |
B1—C8—C13—C12 | 173.10 (13) | C31—C26—C27—C28 | −0.8 (2) |
C20—B1—C14—C19 | 30.90 (19) | B1—C26—C27—C28 | −176.32 (14) |
C8—B1—C14—C19 | 147.85 (13) | C26—C27—C28—C29 | −0.3 (2) |
C26—B1—C14—C19 | −91.11 (16) | C27—C28—C29—C30 | 0.9 (2) |
C20—B1—C14—C15 | −155.60 (13) | C28—C29—C30—C31 | −0.4 (2) |
C8—B1—C14—C15 | −38.64 (18) | C29—C30—C31—C26 | −0.7 (2) |
C26—B1—C14—C15 | 82.40 (16) | C27—C26—C31—C30 | 1.3 (2) |
C19—C14—C15—C16 | −0.8 (2) | B1—C26—C31—C30 | 176.85 (14) |
B1—C14—C15—C16 | −174.84 (14) |
Cg1 and Cg2 are the centroids of the C14–C19 and C8–C13 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cg1i | 0.95 (2) | 2.55 (2) | 3.493 (2) | 172 (2) |
C2—H2C···Cg2ii | 0.98 | 2.65 | 3.399 (2) | 133 |
C5A—H5B···Cg2 | 0.99 | 2.78 | 3.621 (2) | 144 |
C5B—H5D···Cg2 | 0.99 | 2.62 | 3.542 (2) | 154 |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x+1, y, z. |
Cg1 and Cg2 are the centroids of the C14–C19 and C8–C13 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cg1i | 0.95 (2) | 2.55 (2) | 3.493 (2) | 172 (2) |
C2—H2C···Cg2ii | 0.98 | 2.65 | 3.399 (2) | 133 |
C5A—H5B···Cg2 | 0.99 | 2.78 | 3.621 (2) | 144 |
C5B—H5D···Cg2 | 0.99 | 2.62 | 3.542 (2) | 154 |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x+1, y, z. |
Acknowledgements
The authors thank Dr W. Frey (Institut für Organische Chemie, Universität Stuttgart) for measuring the crystal data.
References
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(Butoxymethylidene)dimethylazanium tetraphenylborate acetonitrile monosolvate is similar to the structurally known compound (methoxymethylidene)dimethylazanium tetraphenylborate acetonitrile monosolvate (Tiritiris et al., 2014). According to the structure analysis, the C1–N1 bond length is 1.465 (2) Å, C2–N1 = 1.467 (2) Å and C3–N1 = 1.2831 (19) Å, showing single and double bond character, respectively. The C–N1–C angles are: 116.73 (12)° (C1–N1–C2), 121.54 (14)° (C1–N1–C3) and 121.65 (13)° (C3–N1–C2) indicating a nearly trigonal-planar surrounding of the nitrogen centre by the carbon atoms (Fig. 1). The C–O bond length of 1.2950 (18) Å reveals a double bond character. The positive charge is completely delocalized in the plane of the atoms N1, C3 and O1. The n-butyl group is disordered over the two sites with refined occupancies of 0.888 (5) and 0.112 (5). The bond lengths and angles in the tetraphenylborate anion are in good agreement with the data from the crystal structure analysis of the alkali metal tetraphenylborates (Behrens et al., 2012). A strong C–H···π interaction between the hydrogen atom H3 of the cation and one phenyl ring (Cg1) of the tetraphenylborate anion is observed (Fig. 2). Slightly weaker C–H···π interactions between the hydrogen atoms of –N(CH3)2 and –CH2 groups and a second phenyl ring (Cg2) are also present (Fig. 2, Table 1). The hydrogen centroid distances are 2.55, 2.62, 2.65 and 2.78 Å (Tab. 1), respectively. The phenyl rings form aromatic pockets, in which the iminium ion is embedded. This leads to the formation of a two-dimensional supramolecular pattern in the ac plane. In contrast to the crystal structure of (methoxymethylidene)dimethylazanium tetraphenylborate acetonitrile monosolvate (Tiritiris et al., 2014), the acetonitrile molecule is hardly involved in a C–H···N hydrogen bond system.