Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104000356/sq1147sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104000356/sq1147Isup2.hkl |
CCDC reference: 235344
The title compound was isolated from a reaction mixture containing NEt3, Na[BPh4], [Ru(p-cymene)Cl2]2 (p-cymene is 4–i–CH(CH3)2-1– CH3–C6H6) and 2-phenylpyridine in CH2Cl2. Crystals were grown by slow diffusion of hexane into a CH2Cl2 solution of the crude reaction mixture.
The coordinates of atom H1A were refined, but the displacement parameters were constrained [Uiso(H1A) = 1.2Ueq(N1)]. All other H atoms were placed in ideal positions and constrained to ride on their parent atoms, with C—H distances in the range 0.95–0.99 Å and Uiso(H) values of 1.2Ueq(C). Attempts to refine the coordinates of the H atoms on the disordered CH2Cl2 molecule were unsuccessful.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
C6H16N+·C24H20B−·CH2Cl2 | F(000) = 1080 |
Mr = 506.33 | Dx = 1.199 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2yn | Cell parameters from 998 reflections |
a = 9.9331 (17) Å | θ = 2.6–25.0° |
b = 18.258 (3) Å | µ = 0.25 mm−1 |
c = 15.958 (3) Å | T = 173 K |
β = 104.168 (3)° | Block, light yellow |
V = 2806.1 (9) Å3 | 0.21 × 0.08 × 0.05 mm |
Z = 4 |
Siemens SMART platfrom CCD diffractometer | 4946 independent reflections |
Radiation source: normal-focus sealed tube | 3943 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
area detector, ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | h = −11→11 |
Tmin = 0.936, Tmax = 0.99 | k = −15→21 |
13804 measured reflections | l = −11→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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0387P)2 + 4P] where P = (Fo2 + 2Fc2)/3 |
4946 reflections | (Δ/σ)max = 0.001 |
335 parameters | Δρmax = 0.47 e Å−3 |
9 restraints | Δρmin = −0.23 e Å−3 |
C6H16N+·C24H20B−·CH2Cl2 | V = 2806.1 (9) Å3 |
Mr = 506.33 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.9331 (17) Å | µ = 0.25 mm−1 |
b = 18.258 (3) Å | T = 173 K |
c = 15.958 (3) Å | 0.21 × 0.08 × 0.05 mm |
β = 104.168 (3)° |
Siemens SMART platfrom CCD diffractometer | 4946 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | 3943 reflections with I > 2σ(I) |
Tmin = 0.936, Tmax = 0.99 | Rint = 0.032 |
13804 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 9 restraints |
wR(F2) = 0.140 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.47 e Å−3 |
4946 reflections | Δρmin = −0.23 e Å−3 |
335 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) | |
B1 | 0.6549 (3) | 0.21465 (17) | 0.43490 (19) | 0.0239 (7) | |
N1 | 0.3190 (3) | 0.14622 (14) | 0.64405 (16) | 0.0352 (6) | |
H1A | 0.312 (3) | 0.1762 (17) | 0.595 (2) | 0.042* | |
C1 | 0.7232 (3) | 0.16764 (15) | 0.52360 (17) | 0.0249 (6) | |
C2 | 0.7086 (3) | 0.09146 (16) | 0.52384 (19) | 0.0335 (7) | |
H2A | 0.6672 | 0.0675 | 0.4710 | 0.040* | |
C3 | 0.7520 (3) | 0.04940 (18) | 0.5980 (2) | 0.0400 (8) | |
H3A | 0.7400 | −0.0022 | 0.5952 | 0.048* | |
C4 | 0.8123 (3) | 0.0825 (2) | 0.6756 (2) | 0.0442 (9) | |
H4A | 0.8436 | 0.0539 | 0.7264 | 0.053* | |
C5 | 0.8265 (3) | 0.1576 (2) | 0.67857 (19) | 0.0423 (8) | |
H5A | 0.8662 | 0.1811 | 0.7320 | 0.051* | |
C6 | 0.7830 (3) | 0.19924 (17) | 0.60343 (18) | 0.0327 (7) | |
H6A | 0.7945 | 0.2509 | 0.6069 | 0.039* | |
C7 | 0.4898 (3) | 0.21982 (15) | 0.43521 (16) | 0.0248 (6) | |
C8 | 0.3910 (3) | 0.16846 (15) | 0.39498 (18) | 0.0294 (6) | |
H8A | 0.4190 | 0.1301 | 0.3628 | 0.035* | |
C9 | 0.2526 (3) | 0.17095 (17) | 0.39998 (19) | 0.0350 (7) | |
H9A | 0.1887 | 0.1349 | 0.3715 | 0.042* | |
C10 | 0.2091 (3) | 0.22611 (17) | 0.44648 (19) | 0.0358 (7) | |
H10A | 0.1148 | 0.2289 | 0.4491 | 0.043* | |
C11 | 0.3040 (3) | 0.27712 (17) | 0.48908 (19) | 0.0361 (7) | |
H11A | 0.2755 | 0.3148 | 0.5221 | 0.043* | |
C12 | 0.4416 (3) | 0.27332 (16) | 0.48360 (18) | 0.0301 (6) | |
H12A | 0.5056 | 0.3086 | 0.5140 | 0.036* | |
C13 | 0.7238 (3) | 0.29619 (15) | 0.43230 (16) | 0.0238 (6) | |
C14 | 0.6482 (3) | 0.35597 (15) | 0.38951 (17) | 0.0285 (6) | |
H14A | 0.5513 | 0.3501 | 0.3659 | 0.034* | |
C15 | 0.7080 (3) | 0.42311 (16) | 0.37996 (18) | 0.0322 (7) | |
H15A | 0.6519 | 0.4620 | 0.3509 | 0.039* | |
C16 | 0.8491 (3) | 0.43361 (16) | 0.41265 (18) | 0.0339 (7) | |
H16A | 0.8909 | 0.4794 | 0.4061 | 0.041* | |
C17 | 0.9281 (3) | 0.37620 (16) | 0.45503 (17) | 0.0319 (7) | |
H17A | 1.0251 | 0.3824 | 0.4778 | 0.038* | |
C18 | 0.8660 (3) | 0.30952 (15) | 0.46438 (17) | 0.0276 (6) | |
H18A | 0.9228 | 0.2711 | 0.4940 | 0.033* | |
C19 | 0.6822 (3) | 0.17348 (14) | 0.34858 (17) | 0.0246 (6) | |
C20 | 0.5921 (3) | 0.18034 (15) | 0.26664 (18) | 0.0309 (7) | |
H20A | 0.5074 | 0.2061 | 0.2612 | 0.037* | |
C21 | 0.6215 (3) | 0.15102 (17) | 0.19274 (19) | 0.0378 (7) | |
H21A | 0.5569 | 0.1567 | 0.1384 | 0.045* | |
C23 | 0.8361 (3) | 0.10581 (16) | 0.27720 (19) | 0.0349 (7) | |
H23A | 0.9208 | 0.0802 | 0.2818 | 0.042* | |
C24 | 0.8053 (3) | 0.13538 (15) | 0.35100 (18) | 0.0295 (6) | |
H24A | 0.8706 | 0.1294 | 0.4051 | 0.035* | |
C22 | 0.7443 (3) | 0.11366 (16) | 0.19789 (19) | 0.0369 (7) | |
H22A | 0.7649 | 0.0937 | 0.1475 | 0.044* | |
C25 | 0.4204 (3) | 0.08928 (17) | 0.63049 (19) | 0.0369 (7) | |
H25A | 0.5071 | 0.1138 | 0.6257 | 0.044* | |
H25B | 0.3812 | 0.0635 | 0.5753 | 0.044* | |
C26 | 0.4549 (4) | 0.03314 (18) | 0.7035 (2) | 0.0481 (9) | |
H26A | 0.5214 | −0.0025 | 0.6915 | 0.072* | |
H26B | 0.3698 | 0.0078 | 0.7076 | 0.072* | |
H26C | 0.4954 | 0.0581 | 0.7582 | 0.072* | |
C27 | 0.3708 (3) | 0.19340 (17) | 0.7229 (2) | 0.0405 (8) | |
H27A | 0.3024 | 0.2328 | 0.7231 | 0.049* | |
H27B | 0.3771 | 0.1632 | 0.7752 | 0.049* | |
C28 | 0.5097 (4) | 0.2274 (2) | 0.7274 (2) | 0.0513 (9) | |
H28A | 0.5373 | 0.2573 | 0.7798 | 0.077* | |
H28B | 0.5040 | 0.2584 | 0.6765 | 0.077* | |
H28C | 0.5788 | 0.1888 | 0.7289 | 0.077* | |
C29 | 0.1767 (3) | 0.11822 (19) | 0.6440 (2) | 0.0436 (8) | |
H29A | 0.1826 | 0.0904 | 0.6980 | 0.052* | |
H29B | 0.1148 | 0.1607 | 0.6443 | 0.052* | |
C30 | 0.1122 (3) | 0.0701 (2) | 0.5686 (2) | 0.0469 (9) | |
H30A | 0.0199 | 0.0545 | 0.5732 | 0.070* | |
H30B | 0.1708 | 0.0268 | 0.5688 | 0.070* | |
H30C | 0.1039 | 0.0973 | 0.5147 | 0.070* | |
Cl1 | 0.2843 (4) | 0.45763 (13) | 0.41332 (17) | 0.0627 (7) | 0.799 (10) |
C31 | 0.2569 (7) | 0.5516 (2) | 0.3951 (4) | 0.0527 (15) | 0.799 (10) |
H31A | 0.2798 | 0.5775 | 0.4514 | 0.063* | 0.799 (10) |
H31B | 0.1574 | 0.5602 | 0.3679 | 0.063* | 0.799 (10) |
Cl2 | 0.3574 (6) | 0.58884 (19) | 0.3283 (3) | 0.0834 (12) | 0.799 (10) |
Cl1' | 0.3336 (13) | 0.4666 (6) | 0.4225 (8) | 0.0627 (7) | 0.201 (10) |
C31' | 0.338 (3) | 0.5572 (8) | 0.4220 (11) | 0.0527 (15) | 0.201 (10) |
H31C | 0.4319 | 0.5741 | 0.4523 | 0.063* | 0.201 (10) |
H31D | 0.2714 | 0.5764 | 0.4538 | 0.063* | 0.201 (10) |
Cl2' | 0.2954 (11) | 0.5929 (7) | 0.3158 (7) | 0.055 (2) | 0.201 (10) |
π2 | 0.7872 | 0.3658 | 0.4223 | 0.040* | 0.00 |
π1 | 0.2566 | 0.2516 | 0.4678 | 0.040* | 0.00 |
U11 | U22 | U33 | U12 | U13 | U23 | |
B1 | 0.0250 (16) | 0.0244 (17) | 0.0212 (16) | 0.0025 (13) | 0.0033 (12) | −0.0001 (13) |
N1 | 0.0384 (14) | 0.0381 (15) | 0.0313 (14) | −0.0006 (12) | 0.0127 (12) | −0.0019 (12) |
C1 | 0.0201 (13) | 0.0290 (16) | 0.0279 (15) | 0.0038 (12) | 0.0104 (11) | 0.0029 (12) |
C2 | 0.0367 (16) | 0.0343 (18) | 0.0324 (16) | 0.0069 (14) | 0.0138 (13) | 0.0038 (14) |
C3 | 0.0428 (18) | 0.0335 (18) | 0.049 (2) | 0.0103 (15) | 0.0225 (16) | 0.0136 (16) |
C4 | 0.0366 (17) | 0.057 (2) | 0.041 (2) | 0.0122 (16) | 0.0146 (15) | 0.0269 (17) |
C5 | 0.0353 (17) | 0.063 (2) | 0.0263 (16) | −0.0040 (16) | 0.0040 (13) | 0.0066 (16) |
C6 | 0.0309 (15) | 0.0372 (17) | 0.0303 (16) | −0.0034 (13) | 0.0078 (13) | 0.0052 (13) |
C7 | 0.0288 (14) | 0.0255 (15) | 0.0191 (13) | 0.0035 (12) | 0.0043 (11) | 0.0049 (12) |
C8 | 0.0329 (15) | 0.0254 (16) | 0.0311 (16) | 0.0035 (12) | 0.0099 (12) | −0.0010 (13) |
C9 | 0.0279 (15) | 0.0366 (18) | 0.0379 (17) | 0.0015 (13) | 0.0030 (13) | 0.0045 (14) |
C10 | 0.0248 (15) | 0.0429 (19) | 0.0419 (18) | 0.0078 (14) | 0.0124 (13) | 0.0086 (15) |
C11 | 0.0398 (17) | 0.0381 (18) | 0.0334 (17) | 0.0104 (15) | 0.0148 (14) | 0.0017 (14) |
C12 | 0.0329 (15) | 0.0292 (16) | 0.0279 (15) | 0.0032 (13) | 0.0069 (12) | −0.0019 (13) |
C13 | 0.0282 (14) | 0.0280 (15) | 0.0172 (13) | 0.0029 (12) | 0.0098 (11) | −0.0026 (11) |
C14 | 0.0302 (15) | 0.0312 (16) | 0.0234 (14) | 0.0015 (13) | 0.0053 (12) | 0.0014 (12) |
C15 | 0.0390 (17) | 0.0294 (17) | 0.0287 (15) | 0.0060 (13) | 0.0089 (13) | 0.0043 (13) |
C16 | 0.0462 (18) | 0.0295 (16) | 0.0303 (16) | −0.0063 (14) | 0.0176 (14) | 0.0005 (13) |
C17 | 0.0297 (15) | 0.0400 (18) | 0.0266 (15) | −0.0034 (13) | 0.0080 (12) | −0.0003 (13) |
C18 | 0.0296 (15) | 0.0309 (16) | 0.0232 (14) | 0.0046 (12) | 0.0082 (12) | 0.0035 (12) |
C19 | 0.0311 (14) | 0.0186 (14) | 0.0245 (14) | 0.0012 (12) | 0.0075 (11) | 0.0019 (11) |
C20 | 0.0347 (16) | 0.0295 (16) | 0.0294 (16) | 0.0027 (13) | 0.0097 (12) | 0.0006 (13) |
C21 | 0.0524 (19) | 0.0361 (18) | 0.0236 (15) | −0.0024 (15) | 0.0067 (14) | 0.0015 (13) |
C23 | 0.0400 (17) | 0.0304 (17) | 0.0413 (18) | 0.0046 (14) | 0.0235 (14) | −0.0013 (14) |
C24 | 0.0333 (15) | 0.0289 (16) | 0.0274 (15) | 0.0002 (13) | 0.0093 (12) | 0.0010 (13) |
C22 | 0.058 (2) | 0.0275 (17) | 0.0325 (17) | −0.0058 (15) | 0.0244 (15) | −0.0060 (13) |
C25 | 0.0345 (16) | 0.0384 (18) | 0.0400 (18) | −0.0002 (14) | 0.0134 (14) | −0.0093 (15) |
C26 | 0.052 (2) | 0.040 (2) | 0.054 (2) | 0.0051 (16) | 0.0152 (17) | 0.0035 (17) |
C27 | 0.051 (2) | 0.0341 (18) | 0.0375 (18) | 0.0031 (15) | 0.0140 (15) | −0.0061 (14) |
C28 | 0.056 (2) | 0.054 (2) | 0.044 (2) | −0.0154 (18) | 0.0120 (17) | −0.0139 (17) |
C29 | 0.0326 (17) | 0.056 (2) | 0.0461 (19) | −0.0011 (15) | 0.0167 (15) | 0.0001 (17) |
C30 | 0.0371 (18) | 0.057 (2) | 0.046 (2) | −0.0101 (16) | 0.0089 (15) | 0.0020 (17) |
Cl1 | 0.090 (2) | 0.0404 (8) | 0.0649 (9) | −0.0110 (10) | 0.0323 (12) | 0.0002 (6) |
C31 | 0.069 (4) | 0.043 (2) | 0.056 (3) | −0.009 (3) | 0.033 (3) | −0.006 (2) |
Cl2 | 0.145 (3) | 0.0566 (14) | 0.0719 (18) | −0.0354 (18) | 0.072 (2) | −0.0162 (12) |
Cl1' | 0.090 (2) | 0.0404 (8) | 0.0649 (9) | −0.0110 (10) | 0.0323 (12) | 0.0002 (6) |
C31' | 0.069 (4) | 0.043 (2) | 0.056 (3) | −0.009 (3) | 0.033 (3) | −0.006 (2) |
Cl2' | 0.066 (5) | 0.058 (4) | 0.042 (3) | 0.009 (4) | 0.015 (4) | 0.015 (3) |
B1—C13 | 1.643 (4) | C17—H17A | 0.9500 |
B1—C7 | 1.644 (4) | C18—H18A | 0.9500 |
B1—C19 | 1.649 (4) | C19—C20 | 1.398 (4) |
B1—C1 | 1.652 (4) | C19—C24 | 1.399 (4) |
N1—C25 | 1.500 (4) | C20—C21 | 1.389 (4) |
N1—C29 | 1.503 (4) | C20—H20A | 0.9500 |
N1—C27 | 1.508 (4) | C21—C22 | 1.382 (4) |
N1—H1A | 0.94 (3) | C21—H21A | 0.9500 |
C1—C6 | 1.392 (4) | C23—C22 | 1.374 (4) |
C1—C2 | 1.399 (4) | C23—C24 | 1.396 (4) |
C2—C3 | 1.388 (4) | C23—H23A | 0.9500 |
C2—H2A | 0.9500 | C24—H24A | 0.9500 |
C3—C4 | 1.376 (5) | C22—H22A | 0.9500 |
C3—H3A | 0.9500 | C25—C26 | 1.526 (4) |
C4—C5 | 1.378 (5) | C25—H25A | 0.9900 |
C4—H4A | 0.9500 | C25—H25B | 0.9900 |
C5—C6 | 1.396 (4) | C26—H26A | 0.9800 |
C5—H5A | 0.9500 | C26—H26B | 0.9800 |
C6—H6A | 0.9500 | C26—H26C | 0.9800 |
C7—C8 | 1.395 (4) | C27—C28 | 1.499 (4) |
C7—C12 | 1.400 (4) | C27—H27A | 0.9900 |
C8—C9 | 1.396 (4) | C27—H27B | 0.9900 |
C8—H8A | 0.9500 | C28—H28A | 0.9800 |
C9—C10 | 1.382 (4) | C28—H28B | 0.9800 |
C9—H9A | 0.9500 | C28—H28C | 0.9800 |
C10—C11 | 1.380 (4) | C29—C30 | 1.500 (4) |
C10—H10A | 0.9500 | C29—H29A | 0.9900 |
C11—C12 | 1.392 (4) | C29—H29B | 0.9900 |
C11—H11A | 0.9500 | C30—H30A | 0.9800 |
C12—H12A | 0.9500 | C30—H30B | 0.9800 |
C13—C18 | 1.401 (4) | C30—H30C | 0.9800 |
C13—C14 | 1.403 (4) | Cl1—C31 | 1.750 (5) |
C14—C15 | 1.387 (4) | C31—Cl2 | 1.766 (5) |
C14—H14A | 0.9500 | C31—H31A | 0.9900 |
C15—C16 | 1.384 (4) | C31—H31B | 0.9900 |
C15—H15A | 0.9500 | Cl1'—C31' | 1.656 (15) |
C16—C17 | 1.383 (4) | C31'—Cl2' | 1.767 (15) |
C16—H16A | 0.9500 | C31'—H31C | 0.9900 |
C17—C18 | 1.389 (4) | C31'—H31D | 0.9900 |
C13—B1—C7 | 111.7 (2) | C20—C19—C24 | 115.2 (2) |
C13—B1—C19 | 103.7 (2) | C20—C19—B1 | 122.8 (2) |
C7—B1—C19 | 113.4 (2) | C24—C19—B1 | 121.7 (2) |
C13—B1—C1 | 113.9 (2) | C21—C20—C19 | 122.7 (3) |
C7—B1—C1 | 103.2 (2) | C21—C20—H20A | 118.6 |
C19—B1—C1 | 111.2 (2) | C19—C20—H20A | 118.6 |
C25—N1—C29 | 115.4 (2) | C22—C21—C20 | 120.3 (3) |
C25—N1—C27 | 114.4 (2) | C22—C21—H21A | 119.8 |
C29—N1—C27 | 108.9 (2) | C20—C21—H21A | 119.8 |
C25—N1—H1A | 101.5 (19) | C22—C23—C24 | 120.2 (3) |
C29—N1—H1A | 108.4 (19) | C22—C23—H23A | 119.9 |
C27—N1—H1A | 107.7 (19) | C24—C23—H23A | 119.9 |
C6—C1—C2 | 115.5 (3) | C23—C24—C19 | 122.7 (3) |
C6—C1—B1 | 124.2 (2) | C23—C24—H24A | 118.7 |
C2—C1—B1 | 119.9 (2) | C19—C24—H24A | 118.7 |
C3—C2—C1 | 122.8 (3) | C23—C22—C21 | 118.9 (3) |
C3—C2—H2A | 118.6 | C23—C22—H22A | 120.6 |
C1—C2—H2A | 118.6 | C21—C22—H22A | 120.6 |
C4—C3—C2 | 120.0 (3) | N1—C25—C26 | 112.9 (2) |
C4—C3—H3A | 120.0 | N1—C25—H25A | 109.0 |
C2—C3—H3A | 120.0 | C26—C25—H25A | 109.0 |
C3—C4—C5 | 119.1 (3) | N1—C25—H25B | 109.0 |
C3—C4—H4A | 120.5 | C26—C25—H25B | 109.0 |
C5—C4—H4A | 120.5 | H25A—C25—H25B | 107.8 |
C4—C5—C6 | 120.3 (3) | C25—C26—H26A | 109.5 |
C4—C5—H5A | 119.8 | C25—C26—H26B | 109.5 |
C6—C5—H5A | 119.8 | H26A—C26—H26B | 109.5 |
C1—C6—C5 | 122.2 (3) | C25—C26—H26C | 109.5 |
C1—C6—H6A | 118.9 | H26A—C26—H26C | 109.5 |
C5—C6—H6A | 118.9 | H26B—C26—H26C | 109.5 |
C8—C7—C12 | 115.2 (2) | C28—C27—N1 | 113.5 (3) |
C8—C7—B1 | 123.4 (2) | C28—C27—H27A | 108.9 |
C12—C7—B1 | 121.2 (2) | N1—C27—H27A | 108.9 |
C7—C8—C9 | 122.9 (3) | C28—C27—H27B | 108.9 |
C7—C8—H8A | 118.6 | N1—C27—H27B | 108.9 |
C9—C8—H8A | 118.6 | H27A—C27—H27B | 107.7 |
C10—C9—C8 | 119.7 (3) | C27—C28—H28A | 109.5 |
C10—C9—H9A | 120.1 | C27—C28—H28B | 109.5 |
C8—C9—H9A | 120.1 | H28A—C28—H28B | 109.5 |
C11—C10—C9 | 119.4 (3) | C27—C28—H28C | 109.5 |
C11—C10—H10A | 120.3 | H28A—C28—H28C | 109.5 |
C9—C10—H10A | 120.3 | H28B—C28—H28C | 109.5 |
C10—C11—C12 | 119.9 (3) | C30—C29—N1 | 114.6 (3) |
C10—C11—H11A | 120.1 | C30—C29—H29A | 108.6 |
C12—C11—H11A | 120.1 | N1—C29—H29A | 108.6 |
C11—C12—C7 | 122.9 (3) | C30—C29—H29B | 108.6 |
C11—C12—H12A | 118.6 | N1—C29—H29B | 108.6 |
C7—C12—H12A | 118.6 | H29A—C29—H29B | 107.6 |
C18—C13—C14 | 114.4 (2) | C29—C30—H30A | 109.5 |
C18—C13—B1 | 122.5 (2) | C29—C30—H30B | 109.5 |
C14—C13—B1 | 122.7 (2) | H30A—C30—H30B | 109.5 |
C15—C14—C13 | 123.3 (3) | C29—C30—H30C | 109.5 |
C15—C14—H14A | 118.4 | H30A—C30—H30C | 109.5 |
C13—C14—H14A | 118.4 | H30B—C30—H30C | 109.5 |
C16—C15—C14 | 120.1 (3) | Cl1—C31—Cl2 | 112.9 (3) |
C16—C15—H15A | 119.9 | Cl1—C31—H31A | 109.0 |
C14—C15—H15A | 119.9 | Cl2—C31—H31A | 109.0 |
C17—C16—C15 | 118.7 (3) | Cl1—C31—H31B | 109.0 |
C17—C16—H16A | 120.6 | Cl2—C31—H31B | 109.0 |
C15—C16—H16A | 120.6 | H31A—C31—H31B | 107.8 |
C16—C17—C18 | 120.2 (3) | Cl1'—C31'—Cl2' | 111.9 (11) |
C16—C17—H17A | 119.9 | Cl1'—C31'—H31C | 109.2 |
C18—C17—H17A | 119.9 | Cl2'—C31'—H31C | 109.2 |
C17—C18—C13 | 123.2 (3) | Cl1'—C31'—H31D | 109.2 |
C17—C18—H18A | 118.4 | Cl2'—C31'—H31D | 109.2 |
C13—C18—H18A | 118.4 | H31C—C31'—H31D | 107.9 |
C13—B1—C1—C6 | 27.9 (4) | C7—B1—C13—C14 | −32.7 (3) |
C7—B1—C1—C6 | −93.4 (3) | C19—B1—C13—C14 | 89.8 (3) |
C19—B1—C1—C6 | 144.7 (3) | C1—B1—C13—C14 | −149.1 (2) |
C13—B1—C1—C2 | −159.7 (2) | C18—C13—C14—C15 | −0.5 (4) |
C7—B1—C1—C2 | 79.0 (3) | B1—C13—C14—C15 | −173.8 (2) |
C19—B1—C1—C2 | −42.9 (3) | C13—C14—C15—C16 | 0.7 (4) |
C6—C1—C2—C3 | −0.8 (4) | C14—C15—C16—C17 | −0.3 (4) |
B1—C1—C2—C3 | −173.9 (3) | C15—C16—C17—C18 | −0.1 (4) |
C1—C2—C3—C4 | 0.0 (4) | C16—C17—C18—C13 | 0.2 (4) |
C2—C3—C4—C5 | 1.1 (4) | C14—C13—C18—C17 | 0.1 (4) |
C3—C4—C5—C6 | −1.3 (5) | B1—C13—C18—C17 | 173.4 (2) |
C2—C1—C6—C5 | 0.5 (4) | C13—B1—C19—C20 | −85.9 (3) |
B1—C1—C6—C5 | 173.2 (3) | C7—B1—C19—C20 | 35.5 (4) |
C4—C5—C6—C1 | 0.5 (4) | C1—B1—C19—C20 | 151.2 (2) |
C13—B1—C7—C8 | 146.1 (2) | C13—B1—C19—C24 | 87.2 (3) |
C19—B1—C7—C8 | 29.4 (4) | C7—B1—C19—C24 | −151.4 (2) |
C1—B1—C7—C8 | −91.0 (3) | C1—B1—C19—C24 | −35.6 (3) |
C13—B1—C7—C12 | −40.0 (3) | C24—C19—C20—C21 | 0.5 (4) |
C19—B1—C7—C12 | −156.8 (2) | B1—C19—C20—C21 | 174.1 (3) |
C1—B1—C7—C12 | 82.8 (3) | C19—C20—C21—C22 | −0.5 (5) |
C12—C7—C8—C9 | 1.9 (4) | C22—C23—C24—C19 | 0.2 (4) |
B1—C7—C8—C9 | 176.1 (3) | C20—C19—C24—C23 | −0.4 (4) |
C7—C8—C9—C10 | −0.1 (4) | B1—C19—C24—C23 | −174.0 (3) |
C8—C9—C10—C11 | −1.5 (4) | C24—C23—C22—C21 | −0.1 (4) |
C9—C10—C11—C12 | 1.1 (4) | C20—C21—C22—C23 | 0.3 (4) |
C10—C11—C12—C7 | 0.8 (4) | C29—N1—C25—C26 | −64.4 (3) |
C8—C7—C12—C11 | −2.2 (4) | C27—N1—C25—C26 | 63.0 (3) |
B1—C7—C12—C11 | −176.6 (3) | C25—N1—C27—C28 | 52.1 (4) |
C7—B1—C13—C18 | 154.6 (2) | C29—N1—C27—C28 | −177.2 (3) |
C19—B1—C13—C18 | −83.0 (3) | C25—N1—C29—C30 | −49.7 (4) |
C1—B1—C13—C18 | 38.1 (3) | C27—N1—C29—C30 | −179.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···π1 | 0.94 (3) | 2.40 (3) | 3.338 (3) | 172 (3) |
C31—H31A···π2i | 0.99 | 2.50 | 3.403 (5) | 152 |
C31′—H31D···π2i | 0.99 | 2.43 | 3.347 (19) | 153 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C6H16N+·C24H20B−·CH2Cl2 |
Mr | 506.33 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 9.9331 (17), 18.258 (3), 15.958 (3) |
β (°) | 104.168 (3) |
V (Å3) | 2806.1 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.21 × 0.08 × 0.05 |
Data collection | |
Diffractometer | Siemens SMART platfrom CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.936, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13804, 4946, 3943 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.140, 1.03 |
No. of reflections | 4946 |
No. of parameters | 335 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.23 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···π1 | 0.94 (3) | 2.40 (3) | 3.338 (3) | 172 (3) |
C31—H31A···π2i | 0.99 | 2.50 | 3.403 (5) | 152 |
C31'—H31D···π2i | 0.99 | 2.43 | 3.347 (19) | 153 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Structures with strong hydrogen-bonding donors lacking traditional acceptor groups can exhibit intermolecular interactions with π systems of aromatic rings as hydrogen-bond acceptors (Hanton et al., 1992). Two unsolvated structures of the salt triethylammonium tetraphenylborate have been determined previously (King & Bryant, 1991; Bakshi et al., 1994). Both of these structures reveal N—H···π interactions with phenyl rings. In each case the closest N—H···π system contact is not with the center of the aromatic ring, but rather a clear interaction with one C atom of a phenyl ring. Malone et al.(1997) have investigated X—H···π interactions with phenyl rings in a variety of structures and established six possible categories of these interactions on the basis of geometry and distance considerations. We report here the structure of the title compound, (I), a dichloromethane solvate of triethylammonium tetraphenylborate (Fig. 1).
Molecules of (I) show intermolecular N—H···π interactions between ammonium atom H1A and the edge of one phenyl ring of the tetraphenylborate anion (Table 1). Fig. 2 shows a view of this interaction. Atom H1A is directed at the center of the bond between atoms C10 and C11. The distance between atom H1A and the centroid (π1) calculated from the atomic positions of atoms C10 and C11 is 2.40 Å. The angle formed by atom N1, atom H1A, and π1 is 172°, and the angle formed by atom H1A, π1 and the centroid of the entire phenyl ring (calculated from the positions of atoms C7–C12) is 90.4°. The approach geometry of the N/H group to the π system of the phenyl ring is characterized as a type II interaction in the scheme of Malone et al. (1997).
The dichloromethane molecule is disordered, and this molecule was refined anisotropically over two similar positions. The site occupancy of atoms C31, Cl1 and Cl2 is 0.80, with sites C31', Cl1' and Cl2' being occupied for the remainder. Atoms H31A and H31D of the dichloromethane molecule also show intermolecular C—H···π interactions with the center of a phenyl ring of the tetraphenylborate anion. Atoms H31A and H31D are directed at the centroid (π2) of the C13–C18 phenyl ring. The angles of the dichloromethane C—H···π interactions deviate significantly from 180° (Table 1). The angles formed by atoms H31A and H31D with π2 and the phenyl ring plane are both 90°.