organic compounds
3-Methyl-4,5-dihydrooxazolium tetraphenylborate
aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
*Correspondence e-mail: willi.kantlehner@htw-aalen.de
In the cation of the title salt, C4H8NO+·C24H20B−, the C—N bond lengths are 1.272 (2), 1.4557 (19) and 1.4638 (19) Å, indicating double- and single-bond character, respectively. The C—O bond length of 1.3098 (19) Å shows that double-bond character and charge delocalization occurs within the NCO plane of the cation. In the crystal, a C—H⋯π interaction is present between the methylene H atom of the cation and one phenyl ring of the tetraphenylborate ion. The latter forms an aromatic pocket in which the cation is embedded.
CCDC reference: 987236
Related literature
For the crystal structures of alkali metal tetraphenylborates, see: Behrens et al. (2012). For the synthesis of 1,3-dioxolanes and 1,3-dioxanes from methoxymethylene-N,N-dimethyliminium methyl sulfate, diols and see: Kantlehner & Gutbrod (1979).
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: 987236
10.1107/S1600536814003456/kp2465sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814003456/kp2465Isup2.hkl
The title compound was obtained by reacting of equimolar amounts of N,N-dimethylformamide with dimethyl sulfate at room temperature giving methoxymethylene-N,N-dimethyliminium methyl sulfate (I). 3-methyl-4,5-dihydro-oxazolium methyl sulfate (II) was obtained by reacting equimolar amounts of (I) with ethane-1,2-diol under reflux (Kantlehner et al., 1979). The methanol formed was distilled off and (II) was obtained in nearly quantitative yield. In an alternative synthesis, an equimolar mixture of formic acid methyl ester and 2-methylaminoethanol was heated to reflux for four hours, giving 4,5-dihydrooxazole as product. Reaction of 4,5-dihydro-oxazole with dimethyl sulfate for eight hours at 313 K, leads to (II). 1.00 g (5.0 mmol) of crude (II) was dissolved in 20 mL acetonitrile and 1.74 g (5.0 mmol) of sodium tetraphenylborate in 20 mL acetonitrile was added. After stirring for one hour at room temperature, the precipitated sodium methyl 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 C2 was located in a difference Fourier map and was refined freely [C—H = 0.97 (2) Å]. The hydrogen atoms of the methyl group were allowed to rotate with a fixed angle around the C–N 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).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).C4H8NO+·C24H20B− | F(000) = 864 |
Mr = 405.32 | Dx = 1.195 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 38200 reflections |
a = 11.5335 (5) Å | θ = 2.1–28.3° |
b = 12.7336 (5) Å | µ = 0.07 mm−1 |
c = 15.4615 (6) Å | T = 100 K |
β = 97.209 (2)° | Block, colourless |
V = 2252.77 (16) Å3 | 0.18 × 0.14 × 0.10 mm |
Z = 4 |
Bruker Kappa APEXII DUO diffractometer | 4094 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.045 |
Graphite monochromator | θmax = 28.3°, θmin = 2.1° |
φ scans, and ω scans | h = −15→15 |
38200 measured reflections | k = −16→16 |
5603 independent reflections | l = −20→20 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0454P)2 + 1.1695P] where P = (Fo2 + 2Fc2)/3 |
5603 reflections | (Δ/σ)max < 0.001 |
285 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C4H8NO+·C24H20B− | V = 2252.77 (16) Å3 |
Mr = 405.32 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.5335 (5) Å | µ = 0.07 mm−1 |
b = 12.7336 (5) Å | T = 100 K |
c = 15.4615 (6) Å | 0.18 × 0.14 × 0.10 mm |
β = 97.209 (2)° |
Bruker Kappa APEXII DUO diffractometer | 4094 reflections with I > 2σ(I) |
38200 measured reflections | Rint = 0.045 |
5603 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.48 e Å−3 |
5603 reflections | Δρmin = −0.29 e Å−3 |
285 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 | ||
O1 | 0.29582 (10) | 0.82850 (9) | 0.05090 (7) | 0.0279 (3) | |
N1 | 0.19131 (11) | 0.72170 (10) | −0.03783 (8) | 0.0213 (3) | |
C1 | 0.12968 (15) | 0.62651 (13) | −0.06886 (12) | 0.0315 (4) | |
H1A | 0.1308 | 0.5763 | −0.0207 | 0.047* | |
H1B | 0.1682 | 0.5953 | −0.1157 | 0.047* | |
H1C | 0.0486 | 0.6438 | −0.0910 | 0.047* | |
C2 | 0.24007 (14) | 0.73900 (13) | 0.03931 (10) | 0.0235 (3) | |
H2 | 0.2373 (14) | 0.6909 (14) | 0.0874 (11) | 0.025 (4)* | |
C3 | 0.20739 (15) | 0.81045 (13) | −0.09530 (10) | 0.0259 (3) | |
H3A | 0.1326 | 0.8469 | −0.1140 | 0.031* | |
H3B | 0.2430 | 0.7881 | −0.1473 | 0.031* | |
C4 | 0.29105 (16) | 0.87944 (13) | −0.03477 (11) | 0.0321 (4) | |
H4A | 0.3695 | 0.8815 | −0.0545 | 0.039* | |
H4B | 0.2608 | 0.9520 | −0.0327 | 0.039* | |
B1 | 0.03919 (13) | 0.66080 (11) | 0.24639 (10) | 0.0128 (3) | |
C5 | 0.17365 (12) | 0.62690 (10) | 0.23467 (8) | 0.0138 (3) | |
C6 | 0.19991 (13) | 0.53557 (11) | 0.18986 (9) | 0.0176 (3) | |
H6A | 0.1382 | 0.4886 | 0.1702 | 0.021* | |
C7 | 0.31271 (13) | 0.51105 (12) | 0.17311 (10) | 0.0218 (3) | |
H7A | 0.3268 | 0.4483 | 0.1429 | 0.026* | |
C8 | 0.40428 (13) | 0.57852 (13) | 0.20057 (10) | 0.0222 (3) | |
H8A | 0.4816 | 0.5619 | 0.1900 | 0.027* | |
C9 | 0.38210 (13) | 0.67054 (12) | 0.24360 (9) | 0.0209 (3) | |
H9A | 0.4441 | 0.7178 | 0.2619 | 0.025* | |
C10 | 0.26874 (12) | 0.69362 (11) | 0.26002 (9) | 0.0170 (3) | |
H10A | 0.2553 | 0.7570 | 0.2895 | 0.020* | |
C11 | −0.00704 (12) | 0.72451 (10) | 0.15633 (9) | 0.0137 (3) | |
C12 | −0.07167 (12) | 0.67791 (11) | 0.08382 (9) | 0.0163 (3) | |
H12A | −0.0935 | 0.6063 | 0.0874 | 0.020* | |
C13 | −0.10532 (13) | 0.73228 (12) | 0.00652 (9) | 0.0190 (3) | |
H13A | −0.1496 | 0.6976 | −0.0411 | 0.023* | |
C14 | −0.07460 (13) | 0.83657 (12) | −0.00123 (10) | 0.0218 (3) | |
H14A | −0.0981 | 0.8742 | −0.0535 | 0.026* | |
C15 | −0.00877 (14) | 0.88524 (12) | 0.06884 (10) | 0.0223 (3) | |
H15A | 0.0136 | 0.9567 | 0.0644 | 0.027* | |
C16 | 0.02451 (13) | 0.83001 (11) | 0.14535 (9) | 0.0177 (3) | |
H16A | 0.0704 | 0.8648 | 0.1921 | 0.021* | |
C17 | 0.03362 (12) | 0.73485 (10) | 0.33271 (9) | 0.0133 (3) | |
C18 | −0.04958 (12) | 0.81456 (11) | 0.33464 (9) | 0.0158 (3) | |
H18A | −0.1012 | 0.8287 | 0.2831 | 0.019* | |
C19 | −0.05996 (13) | 0.87411 (11) | 0.40894 (10) | 0.0191 (3) | |
H19A | −0.1178 | 0.9274 | 0.4074 | 0.023* | |
C20 | 0.01404 (13) | 0.85559 (12) | 0.48497 (10) | 0.0215 (3) | |
H20A | 0.0082 | 0.8964 | 0.5357 | 0.026* | |
C21 | 0.09683 (13) | 0.77662 (12) | 0.48592 (9) | 0.0210 (3) | |
H21A | 0.1481 | 0.7629 | 0.5377 | 0.025* | |
C22 | 0.10522 (12) | 0.71728 (11) | 0.41142 (9) | 0.0173 (3) | |
H22A | 0.1617 | 0.6627 | 0.4140 | 0.021* | |
C23 | −0.04396 (12) | 0.56074 (10) | 0.26411 (9) | 0.0140 (3) | |
C24 | 0.00033 (13) | 0.46996 (11) | 0.30783 (9) | 0.0184 (3) | |
H24A | 0.0827 | 0.4615 | 0.3195 | 0.022* | |
C25 | −0.07142 (13) | 0.39159 (11) | 0.33491 (10) | 0.0215 (3) | |
H25A | −0.0376 | 0.3313 | 0.3643 | 0.026* | |
C26 | −0.19191 (13) | 0.40137 (11) | 0.31916 (10) | 0.0202 (3) | |
H26A | −0.2412 | 0.3486 | 0.3380 | 0.024* | |
C27 | −0.23932 (12) | 0.48955 (11) | 0.27534 (9) | 0.0170 (3) | |
H27A | −0.3217 | 0.4972 | 0.2637 | 0.020* | |
C28 | −0.16617 (12) | 0.56695 (10) | 0.24834 (9) | 0.0148 (3) | |
H28A | −0.2006 | 0.6263 | 0.2180 | 0.018* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0312 (6) | 0.0292 (6) | 0.0229 (6) | −0.0069 (5) | 0.0025 (5) | −0.0015 (5) |
N1 | 0.0218 (7) | 0.0247 (6) | 0.0185 (6) | 0.0002 (5) | 0.0074 (5) | 0.0002 (5) |
C1 | 0.0275 (9) | 0.0262 (8) | 0.0434 (10) | −0.0083 (7) | 0.0149 (8) | −0.0153 (7) |
C2 | 0.0244 (8) | 0.0260 (8) | 0.0212 (8) | 0.0006 (6) | 0.0066 (6) | 0.0026 (6) |
C3 | 0.0290 (9) | 0.0289 (8) | 0.0207 (8) | 0.0034 (7) | 0.0067 (7) | 0.0064 (6) |
C4 | 0.0373 (10) | 0.0284 (8) | 0.0311 (9) | −0.0078 (7) | 0.0059 (8) | 0.0040 (7) |
B1 | 0.0125 (7) | 0.0122 (6) | 0.0135 (7) | −0.0008 (5) | 0.0010 (6) | 0.0005 (6) |
C5 | 0.0154 (7) | 0.0155 (6) | 0.0103 (6) | 0.0013 (5) | 0.0013 (5) | 0.0044 (5) |
C6 | 0.0193 (7) | 0.0156 (6) | 0.0186 (7) | 0.0010 (5) | 0.0050 (6) | 0.0036 (5) |
C7 | 0.0256 (8) | 0.0207 (7) | 0.0208 (8) | 0.0073 (6) | 0.0097 (6) | 0.0050 (6) |
C8 | 0.0159 (7) | 0.0335 (8) | 0.0183 (7) | 0.0081 (6) | 0.0059 (6) | 0.0078 (6) |
C9 | 0.0143 (7) | 0.0324 (8) | 0.0159 (7) | −0.0026 (6) | 0.0010 (6) | 0.0032 (6) |
C10 | 0.0175 (7) | 0.0207 (7) | 0.0131 (7) | −0.0004 (5) | 0.0029 (5) | 0.0006 (5) |
C11 | 0.0116 (6) | 0.0159 (6) | 0.0137 (6) | 0.0023 (5) | 0.0023 (5) | 0.0008 (5) |
C12 | 0.0162 (7) | 0.0169 (6) | 0.0161 (7) | −0.0001 (5) | 0.0033 (5) | −0.0005 (5) |
C13 | 0.0164 (7) | 0.0268 (7) | 0.0133 (7) | 0.0001 (6) | −0.0002 (5) | −0.0014 (6) |
C14 | 0.0230 (8) | 0.0267 (8) | 0.0153 (7) | 0.0030 (6) | 0.0002 (6) | 0.0075 (6) |
C15 | 0.0286 (8) | 0.0187 (7) | 0.0194 (7) | −0.0024 (6) | 0.0018 (6) | 0.0057 (6) |
C16 | 0.0197 (7) | 0.0181 (7) | 0.0148 (7) | −0.0034 (5) | 0.0003 (6) | 0.0016 (5) |
C17 | 0.0121 (6) | 0.0141 (6) | 0.0142 (7) | −0.0029 (5) | 0.0035 (5) | 0.0021 (5) |
C18 | 0.0138 (7) | 0.0164 (6) | 0.0172 (7) | −0.0018 (5) | 0.0016 (5) | 0.0008 (5) |
C19 | 0.0181 (7) | 0.0170 (6) | 0.0236 (8) | −0.0011 (5) | 0.0077 (6) | −0.0020 (6) |
C20 | 0.0244 (8) | 0.0252 (7) | 0.0168 (7) | −0.0074 (6) | 0.0096 (6) | −0.0053 (6) |
C21 | 0.0205 (8) | 0.0306 (8) | 0.0120 (7) | −0.0060 (6) | 0.0023 (6) | 0.0024 (6) |
C22 | 0.0160 (7) | 0.0207 (7) | 0.0159 (7) | 0.0003 (5) | 0.0041 (6) | 0.0037 (6) |
C23 | 0.0163 (7) | 0.0137 (6) | 0.0121 (6) | −0.0006 (5) | 0.0027 (5) | −0.0011 (5) |
C24 | 0.0143 (7) | 0.0204 (7) | 0.0208 (7) | 0.0011 (5) | 0.0032 (6) | 0.0057 (6) |
C25 | 0.0213 (8) | 0.0174 (7) | 0.0258 (8) | 0.0017 (6) | 0.0031 (6) | 0.0080 (6) |
C26 | 0.0209 (8) | 0.0179 (7) | 0.0224 (8) | −0.0056 (6) | 0.0055 (6) | 0.0011 (6) |
C27 | 0.0136 (7) | 0.0188 (7) | 0.0186 (7) | −0.0019 (5) | 0.0018 (6) | −0.0026 (5) |
C28 | 0.0171 (7) | 0.0132 (6) | 0.0138 (6) | 0.0015 (5) | 0.0013 (5) | 0.0000 (5) |
O1—C2 | 1.3098 (19) | C12—C13 | 1.3936 (19) |
O1—C4 | 1.470 (2) | C12—H12A | 0.9500 |
N1—C2 | 1.272 (2) | C13—C14 | 1.383 (2) |
N1—C1 | 1.4557 (19) | C13—H13A | 0.9500 |
N1—C3 | 1.4638 (19) | C14—C15 | 1.388 (2) |
C1—H1A | 0.9800 | C14—H14A | 0.9500 |
C1—H1B | 0.9800 | C15—C16 | 1.388 (2) |
C1—H1C | 0.9800 | C15—H15A | 0.9500 |
C2—H2 | 0.968 (18) | C16—H16A | 0.9500 |
C3—C4 | 1.534 (2) | C17—C18 | 1.3998 (19) |
C3—H3A | 0.9900 | C17—C22 | 1.4002 (19) |
C3—H3B | 0.9900 | C18—C19 | 1.394 (2) |
C4—H4A | 0.9900 | C18—H18A | 0.9500 |
C4—H4B | 0.9900 | C19—C20 | 1.383 (2) |
B1—C23 | 1.638 (2) | C19—H19A | 0.9500 |
B1—C5 | 1.642 (2) | C20—C21 | 1.386 (2) |
B1—C11 | 1.642 (2) | C20—H20A | 0.9500 |
B1—C17 | 1.642 (2) | C21—C22 | 1.391 (2) |
C5—C10 | 1.4036 (19) | C21—H21A | 0.9500 |
C5—C6 | 1.4060 (19) | C22—H22A | 0.9500 |
C6—C7 | 1.394 (2) | C23—C28 | 1.4022 (19) |
C6—H6A | 0.9500 | C23—C24 | 1.4027 (19) |
C7—C8 | 1.386 (2) | C24—C25 | 1.394 (2) |
C7—H7A | 0.9500 | C24—H24A | 0.9500 |
C8—C9 | 1.387 (2) | C25—C26 | 1.386 (2) |
C8—H8A | 0.9500 | C25—H25A | 0.9500 |
C9—C10 | 1.394 (2) | C26—C27 | 1.388 (2) |
C9—H9A | 0.9500 | C26—H26A | 0.9500 |
C10—H10A | 0.9500 | C27—C28 | 1.3949 (19) |
C11—C12 | 1.3982 (19) | C27—H27A | 0.9500 |
C11—C16 | 1.4076 (19) | C28—H28A | 0.9500 |
C2—O1—C4 | 107.37 (12) | C13—C12—C11 | 122.67 (13) |
C2—N1—C1 | 126.38 (14) | C13—C12—H12A | 118.7 |
C2—N1—C3 | 111.14 (13) | C11—C12—H12A | 118.7 |
C1—N1—C3 | 122.46 (13) | C14—C13—C12 | 120.29 (14) |
N1—C1—H1A | 109.5 | C14—C13—H13A | 119.9 |
N1—C1—H1B | 109.5 | C12—C13—H13A | 119.9 |
H1A—C1—H1B | 109.5 | C13—C14—C15 | 118.81 (13) |
N1—C1—H1C | 109.5 | C13—C14—H14A | 120.6 |
H1A—C1—H1C | 109.5 | C15—C14—H14A | 120.6 |
H1B—C1—H1C | 109.5 | C16—C15—C14 | 120.29 (14) |
N1—C2—O1 | 115.50 (14) | C16—C15—H15A | 119.9 |
N1—C2—H2 | 123.9 (10) | C14—C15—H15A | 119.9 |
O1—C2—H2 | 120.6 (10) | C15—C16—C11 | 122.56 (13) |
N1—C3—C4 | 100.93 (12) | C15—C16—H16A | 118.7 |
N1—C3—H3A | 111.6 | C11—C16—H16A | 118.7 |
C4—C3—H3A | 111.6 | C18—C17—C22 | 115.37 (12) |
N1—C3—H3B | 111.6 | C18—C17—B1 | 122.04 (12) |
C4—C3—H3B | 111.6 | C22—C17—B1 | 122.40 (12) |
H3A—C3—H3B | 109.4 | C19—C18—C17 | 122.81 (13) |
O1—C4—C3 | 104.28 (12) | C19—C18—H18A | 118.6 |
O1—C4—H4A | 110.9 | C17—C18—H18A | 118.6 |
C3—C4—H4A | 110.9 | C20—C19—C18 | 119.99 (14) |
O1—C4—H4B | 110.9 | C20—C19—H19A | 120.0 |
C3—C4—H4B | 110.9 | C18—C19—H19A | 120.0 |
H4A—C4—H4B | 108.9 | C19—C20—C21 | 118.92 (13) |
C23—B1—C5 | 113.26 (11) | C19—C20—H20A | 120.5 |
C23—B1—C11 | 113.04 (11) | C21—C20—H20A | 120.5 |
C5—B1—C11 | 104.30 (10) | C20—C21—C22 | 120.33 (14) |
C23—B1—C17 | 103.14 (10) | C20—C21—H21A | 119.8 |
C5—B1—C17 | 112.00 (11) | C22—C21—H21A | 119.8 |
C11—B1—C17 | 111.35 (11) | C21—C22—C17 | 122.56 (14) |
C10—C5—C6 | 115.41 (13) | C21—C22—H22A | 118.7 |
C10—C5—B1 | 121.73 (12) | C17—C22—H22A | 118.7 |
C6—C5—B1 | 122.46 (12) | C28—C23—C24 | 115.32 (12) |
C7—C6—C5 | 122.73 (14) | C28—C23—B1 | 121.59 (12) |
C7—C6—H6A | 118.6 | C24—C23—B1 | 122.41 (12) |
C5—C6—H6A | 118.6 | C25—C24—C23 | 122.73 (13) |
C8—C7—C6 | 119.83 (14) | C25—C24—H24A | 118.6 |
C8—C7—H7A | 120.1 | C23—C24—H24A | 118.6 |
C6—C7—H7A | 120.1 | C26—C25—C24 | 120.19 (13) |
C7—C8—C9 | 119.42 (14) | C26—C25—H25A | 119.9 |
C7—C8—H8A | 120.3 | C24—C25—H25A | 119.9 |
C9—C8—H8A | 120.3 | C25—C26—C27 | 118.91 (13) |
C8—C9—C10 | 119.94 (14) | C25—C26—H26A | 120.5 |
C8—C9—H9A | 120.0 | C27—C26—H26A | 120.5 |
C10—C9—H9A | 120.0 | C26—C27—C28 | 120.12 (13) |
C9—C10—C5 | 122.64 (14) | C26—C27—H27A | 119.9 |
C9—C10—H10A | 118.7 | C28—C27—H27A | 119.9 |
C5—C10—H10A | 118.7 | C27—C28—C23 | 122.72 (13) |
C12—C11—C16 | 115.36 (12) | C27—C28—H28A | 118.6 |
C12—C11—B1 | 123.65 (12) | C23—C28—H28A | 118.6 |
C16—C11—B1 | 120.83 (12) | ||
C1—N1—C2—O1 | 176.49 (14) | C14—C15—C16—C11 | −0.8 (2) |
C3—N1—C2—O1 | −1.79 (19) | C12—C11—C16—C15 | 1.7 (2) |
C4—O1—C2—N1 | −4.22 (19) | B1—C11—C16—C15 | 177.28 (13) |
C2—N1—C3—C4 | 6.54 (17) | C23—B1—C17—C18 | −91.56 (14) |
C1—N1—C3—C4 | −171.83 (14) | C5—B1—C17—C18 | 146.32 (12) |
C2—O1—C4—C3 | 7.95 (17) | C11—B1—C17—C18 | 29.96 (17) |
N1—C3—C4—O1 | −8.35 (16) | C23—B1—C17—C22 | 83.19 (15) |
C23—B1—C5—C10 | −148.97 (12) | C5—B1—C17—C22 | −38.93 (17) |
C11—B1—C5—C10 | 87.71 (14) | C11—B1—C17—C22 | −155.29 (12) |
C17—B1—C5—C10 | −32.83 (17) | C22—C17—C18—C19 | 1.08 (19) |
C23—B1—C5—C6 | 38.57 (17) | B1—C17—C18—C19 | 176.17 (12) |
C11—B1—C5—C6 | −84.75 (14) | C17—C18—C19—C20 | 0.1 (2) |
C17—B1—C5—C6 | 154.70 (12) | C18—C19—C20—C21 | −0.7 (2) |
C10—C5—C6—C7 | 1.4 (2) | C19—C20—C21—C22 | 0.1 (2) |
B1—C5—C6—C7 | 174.27 (13) | C20—C21—C22—C17 | 1.2 (2) |
C5—C6—C7—C8 | −0.4 (2) | C18—C17—C22—C21 | −1.7 (2) |
C6—C7—C8—C9 | −0.8 (2) | B1—C17—C22—C21 | −176.79 (13) |
C7—C8—C9—C10 | 1.0 (2) | C5—B1—C23—C28 | −159.23 (12) |
C8—C9—C10—C5 | 0.0 (2) | C11—B1—C23—C28 | −40.87 (17) |
C6—C5—C10—C9 | −1.2 (2) | C17—B1—C23—C28 | 79.50 (15) |
B1—C5—C10—C9 | −174.13 (13) | C5—B1—C23—C24 | 30.67 (18) |
C23—B1—C11—C12 | −27.84 (18) | C11—B1—C23—C24 | 149.03 (13) |
C5—B1—C11—C12 | 95.62 (14) | C17—B1—C23—C24 | −90.60 (15) |
C17—B1—C11—C12 | −143.40 (13) | C28—C23—C24—C25 | −0.7 (2) |
C23—B1—C11—C16 | 157.00 (12) | B1—C23—C24—C25 | 169.93 (13) |
C5—B1—C11—C16 | −79.54 (15) | C23—C24—C25—C26 | −0.1 (2) |
C17—B1—C11—C16 | 41.44 (17) | C24—C25—C26—C27 | 0.7 (2) |
C16—C11—C12—C13 | −1.5 (2) | C25—C26—C27—C28 | −0.4 (2) |
B1—C11—C12—C13 | −176.90 (13) | C26—C27—C28—C23 | −0.5 (2) |
C11—C12—C13—C14 | 0.3 (2) | C24—C23—C28—C27 | 1.1 (2) |
C12—C13—C14—C15 | 0.7 (2) | B1—C23—C28—C27 | −169.69 (13) |
C13—C14—C15—C16 | −0.5 (2) |
Cg1 is the centroid of the C5–C10 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cg1 | 0.97 (2) | 2.31 (2) | 3.239 (2) | 161 (2) |
Cg1 is the centroid of the C5–C10 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cg1 | 0.97 (2) | 2.31 (2) | 3.239 (2) | 161 (2) |
Acknowledgements
The authors thank Dr W. Frey (Institut für Organische Chemie, Universität Stuttgart) for measuring the crystal data.
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
Kantlehner, W. & Gutbrod, H.-D. (1979). Liebigs Ann. Chem. pp. 1362–1369. CrossRef Google Scholar
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According to the solved molecular structure of the title salt (Fig. 1) the C1–N1 bond is 1.4557 (19) Å, C3–N1 = 1.4638 (19) Å and C2–N1 = 1.272 (2) Å show single and double bond character, respectively. The C–N1–C angles are: 126.38 (14)° (C1–N1–C2), 122.46 (13)° (C1–N1–C3) and 111.14 (13)° (C3–N1–C2), which indicates a deviation from an ideal trigonal-planar surrounding of the nitrogen centre by the carbon atoms. The C–O length shows with 1.3098 (19) Å double bond character (Fig. 1). The positive charge is delocalized on the plane formed by the atoms N1, C2 and O1. 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). A C–H···π interaction between the hydrogen atom H2 of the cation and one phenyl ring (centroid) of the tetraphenylborate ion is present (Fig. 2). Here, a short aromatic hydrogen bond (H2···Cg1 = 2.31 Å) have been determined (Tab. 1). The phenyl rings are forming aromatic pockets, in which the cation is embedded.