Acta Cryst.(2001). E57, o1141±o1142 DOI: 10.1107/S1600536801018396 Bond and Davies C8H11N
o1141
organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
2,4,6-Collidine
Andrew D. Bond* and John E. Davies
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK
Correspondence e-mail: [email protected]
Key indicators Single-crystal X-ray study T= 180 K
Mean(C±C) = 0.004 AÊ Rfactor = 0.071 wRfactor = 0.193
Data-to-parameter ratio = 15.8
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2001 International Union of Crystallography Printed in Great Britain ± all rights reserved
The crystal structure of 2,4,6-collidine (2,4,6-trimethyl-pyridine, C8H11N) has been determined at 180 (2) K following
in situ crystal growth from the liquid. In space groupP21/c,
there are two molecules in the asymmetric unit. Molecules are linked into one-dimensional chainsviaCÐH N interactions.
Comment
This work forms part of a study devoted to improving the techniques for determining the crystal structures of substances that are liquids at room temperature. We have reported recently the crystal structures of 3-methylpyridine (3-picoline) and 2-methylpyridine (2-picoline) (Bond & Davies, 2001a,b), and report here the structure of the trisubstituted molecule 2,4,6-trimethylpyridine (2,4,6-collidine), (I).
In space group P21/c, there are two molecules in the
asymmetric unit (Fig. 1). The two independent molecules form an interplanar angle of ca 68 and the C3AÐH3A N1B angle of 154 is indicative of a directional hydrogen-bond interaction (H3A N1B = 2.75 AÊ). These interactions, toge-ther with a second CÐH N contact [H5B N1Ai= 2.56 AÊ,
C5BÐH5B N1Ai = 171; symmetry code (i): ÿ1 +x, y,
ÿ1 +z] link the molecules into one-dimensional chains running along the vector [101] (Fig. 2). Between adjacent chains, pyridyl rings adopt both face-to-face offset (with interplanar separation ca 3.6 AÊ), and edge-to-face arrange-ments (Fig. 3).
Experimental
The sample (99%) was obtained from the Aldrich Company and was used without further puri®cation. The crystal was grown in a 0.3 mm glass capillary tube using a technique described previously (Davies & Bond, 2001). In this case, however, the sample remained liquid at the low-temperature limit of the cooling device (ca110 K), and the initial solid material could only be obtained by immersing the sealed capillary tube directly in liquid nitrogen. The capillary was then transferred to the diffractometer and warmed, and the crystal was grown atca212 K (a temperature only slightly less than the melting point of the solid in the capillary tube). Once formed, the crystal was
cooled to 180 (2) K for data collection. Although the diffraction pattern contained contributions from more than one crystal, the pattern associated with the major crystal component was indexed successfully, and only re¯ections associated with this component were included in the integration. The length of the cylindrical crystal could not be estimated accurately, but it exceeded the diameter of the collimator (0.35 mm).
Crystal data
C8H11N
Mr= 121.18
Monoclinic, P21=c
a= 8.7773 (5) AÊ
b= 20.3849 (11) AÊ
c= 8.9935 (4) AÊ
= 107.427 (3)
V= 1535.29 (14) AÊ3
Z= 8
Dx= 1.049 Mg mÿ3
MoKradiation
Cell parameters from 16 950 re¯ections
= 1.0±25.0
= 0.06 mmÿ1
T= 180 (2) K Cylinder, colourless 0.15 mm (radius)
Data collection
Nonius KappaCCD diffractometer Thin-slice!and'scans Absorption correction: multi-scan
(SORTAV; Blessing, 1997)
Tmin= 0.796,Tmax= 0.955
11 768 measured re¯ections 2701 independent re¯ections
2056 re¯ections withI> 2(I)
Rint= 0.069
max= 25.1
h=ÿ10!10
k=ÿ24!24
l=ÿ10!10
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.071
wR(F2) = 0.193
S= 1.13 2701 re¯ections 171 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0746P)2
+ 0.8878P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.024 max= 0.21 e AÊÿ3 min=ÿ0.19 e AÊÿ3
The methyl-H atoms associated with atom C8Bare disordered and were modelled as two sets of idealized positions. All H atoms were placed geometrically and allowed to re®ne with isotropic displace-ment parameters (one common parameter for all methyl-H atoms and one common displacement parameter for the other H atoms). Each methyl group was allowed to rotate about its local threefold axis.
Data collection:COLLECT(Nonius, 1998); cell re®nement:HKL SCALEPACK(Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:XP(Sheldrick, 1993) andCAMERON(Watkinet al., 1996); software used to prepare material for publication:
SHELXL97.
We thank the EPSRC for ®nancial assistance towards the purchase of the Nonius CCD diffractometer.
References
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994).J. Appl. Cryst.27, 435±436.
Blessing, R. H. (1997).J. Appl. Cryst.30, 421±429.
Bond, A. D. & Davies, J. E. (2001a).Acta Cryst.E57, o1087±o1088. Bond, A. D. & Davies, J. E. (2001b).Acta Cryst.E57, o1089±o1090. Davies, J. E. & Bond, A. D. (2001).Acta Cryst.E57, o947±o949. Nonius (1998).COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
Macromolecular Crystallography, Part A, edited by C. W. Carter & R. M. Sweet, pp. 307±326. London: Academic Press.
Sheldrick, G. M. (1993).XP. University of GoÈttingen, Germany. Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996).CAMERON. Chemical
Crystallography Laboratory, University of Oxford, UK.
Figure 1
Molecular structure and atom-labelling scheme for (I) showing displace-ment ellipsoids at the 50% probability level for non-H atoms. The two molecules in the asymmetric unit are denoted by the suf®xesAandB, and disorder of the H atoms in the methyl group C8Bhas been omitted for clarity.
Figure 2
Molecules of (I) linked into one-dimensional chains via CÐH N interactions.
Figure 3
supporting information
sup-1 Acta Cryst. (2001). E57, o1141–o1142
supporting information
Acta Cryst. (2001). E57, o1141–o1142 [https://doi.org/10.1107/S1600536801018396]
2,4,6-Collidine
Andrew D. Bond and John E. Davies
2,4,6-Trimethylpyridine
Crystal data C8H11N Mr = 121.18 Monoclinic, P21/c a = 8.7773 (5) Å b = 20.3849 (11) Å c = 8.9935 (4) Å β = 107.427 (3)° V = 1535.29 (14) Å3 Z = 8
F(000) = 528
Dx = 1.049 Mg m−3 Melting point: 230 K
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 16950 reflections θ = 1.0–25.0°
µ = 0.06 mm−1 T = 180 K
Cylinder, colourless 0.15 mm (radius)
Data collection Nonius KappaCCD
diffractometer
Radiation source: fine-focus sealed tube Thin slice ω and φ scans
Absorption correction: multi-scan (SORTAV; Blessing, 1995) Tmin = 0.796, Tmax = 0.955 11768 measured reflections
2701 independent reflections 2056 reflections with I > 2σ(I) Rint = 0.069
θmax = 25.1°, θmin = 3.8° h = −10→10
k = −24→24 l = −10→10
Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.071 wR(F2) = 0.193 S = 1.13 2701 reflections 171 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.0746P)2 + 0.8878P] where P = (Fo2 + 2Fc2)/3
Special details
Experimental. Grown in situ in a 0.3 mm Lindemann capillary at 212 K
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.
Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) Pyridine ring 1
-0.1873 (0.0074)x + 20.3784 (0.0013)y + 0.1741 (0.0082)z = 18.5838 (0.0098)
* 0.0012 (0.0014) N1A * 0.0024 (0.0015) C2A * -0.0049 (0.0015) C3A * 0.0040 (0.0015) C4A * -0.0006 (0.0016) C5A * -0.0021 (0.0015) C6A
Rms deviation of fitted atoms = 0.0030 Pyridine ring 2
5.8307 (0.0061)x + 8.1727 (0.0178)y - 7.2024 (0.0048)z = 9.1850 (0.0147)
* -0.0034 (0.0015) N1B * -0.0059 (0.0016) C2B * 0.0102 (0.0017) C3B * -0.0056 (0.0016) C4B * -0.0033 (0.0015) C5B * 0.0079 (0.0015) C6B
Rms deviation of fitted atoms = 0.0065
Angle to previous plane (with approximate e.s.d.) = 67.79 (0.07)
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq Occ. (<1)
N1A 1.3594 (2) 0.91500 (9) 1.1117 (2) 0.0369 (5) C2A 1.2878 (3) 0.91572 (11) 0.9567 (3) 0.0372 (6) C3A 1.1226 (3) 0.91440 (11) 0.8918 (3) 0.0386 (6)
H3A 1.0765 0.9144 0.7818 0.051 (4)*
C4A 1.0248 (3) 0.91311 (10) 0.9885 (3) 0.0392 (6) C5A 1.1001 (3) 0.91222 (11) 1.1481 (3) 0.0397 (6)
H5A 1.0381 0.9109 1.2184 0.051 (4)*
C6A 1.2649 (3) 0.91317 (11) 1.2051 (3) 0.0375 (6) C7A 1.3977 (3) 0.91774 (14) 0.8560 (3) 0.0517 (7)
H7AA 1.4762 0.8823 0.8866 0.098 (3)*
H7BA 1.4531 0.9601 0.8694 0.098 (3)*
H7CA 1.3350 0.9122 0.7465 0.098 (3)*
C8A 0.8456 (3) 0.91212 (13) 0.9243 (3) 0.0510 (7)
H8AA 0.8013 0.9501 0.9639 0.098 (3)*
H8BA 0.8044 0.8717 0.9570 0.098 (3)*
H8CA 0.8144 0.9140 0.8103 0.098 (3)*
C9A 1.3493 (3) 0.91192 (14) 1.3778 (3) 0.0519 (7)
H9AA 1.4208 0.8739 1.4029 0.098 (3)*
H9BA 1.2702 0.9088 1.4347 0.098 (3)*
H9CA 1.4117 0.9522 1.4081 0.098 (3)*
N1B 0.9841 (2) 0.85586 (9) 0.4930 (2) 0.0411 (5) C2B 1.0232 (3) 0.79541 (11) 0.4565 (3) 0.0416 (6) C3B 0.9255 (3) 0.75946 (12) 0.3343 (3) 0.0445 (6)
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sup-3 Acta Cryst. (2001). E57, o1141–o1142
C4B 0.7790 (3) 0.78423 (12) 0.2460 (3) 0.0419 (6) C5B 0.7392 (3) 0.84653 (12) 0.2841 (3) 0.0399 (6)
H5B 0.6404 0.8657 0.2268 0.051 (4)*
C6B 0.8433 (3) 0.88085 (12) 0.4059 (3) 0.0392 (6) C7B 1.1806 (3) 0.76838 (14) 0.5575 (4) 0.0578 (8)
H7AB 1.2513 0.8047 0.6055 0.098 (3)*
H7BB 1.2306 0.7423 0.4932 0.098 (3)*
H7CB 1.1619 0.7405 0.6391 0.098 (3)*
C8B 0.6669 (4) 0.74532 (16) 0.1172 (3) 0.0609 (8)
H8AB 0.5869 0.7747 0.0504 0.098 (3)* 0.49 (4)
H8BB 0.6133 0.7120 0.1621 0.098 (3)* 0.49 (4)
H8CB 0.7273 0.7239 0.0552 0.098 (3)* 0.49 (4)
H8DB 0.6980 0.6990 0.1281 0.098 (3)* 0.51 (4)
H8EB 0.6717 0.7618 0.0164 0.098 (3)* 0.51 (4)
H8FB 0.5577 0.7498 0.1233 0.098 (3)* 0.51 (4)
C9B 0.8038 (3) 0.94906 (13) 0.4465 (4) 0.0578 (8)
H9AB 0.8214 0.9521 0.5592 0.098 (3)*
H9BB 0.6917 0.9588 0.3914 0.098 (3)*
H9CB 0.8726 0.9807 0.4155 0.098 (3)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23 N1A 0.0324 (11) 0.0377 (11) 0.0391 (11) 0.0020 (8) 0.0084 (8) 0.0019 (8) C2A 0.0332 (12) 0.0376 (13) 0.0395 (13) 0.0005 (10) 0.0088 (10) 0.0040 (9) C3A 0.0349 (13) 0.0386 (13) 0.0389 (13) 0.0009 (10) 0.0059 (10) 0.0048 (10) C4A 0.0325 (13) 0.0306 (12) 0.0522 (14) −0.0004 (9) 0.0091 (11) 0.0029 (10) C5A 0.0372 (13) 0.0376 (13) 0.0470 (14) 0.0013 (10) 0.0165 (11) 0.0010 (10) C6A 0.0373 (13) 0.0340 (12) 0.0411 (13) 0.0010 (9) 0.0116 (10) 0.0011 (9) C7A 0.0413 (15) 0.0690 (18) 0.0474 (15) 0.0037 (13) 0.0174 (12) 0.0062 (13) C8A 0.0293 (13) 0.0515 (16) 0.0681 (18) −0.0022 (11) 0.0084 (12) 0.0052 (12) C9A 0.0490 (16) 0.0683 (18) 0.0378 (14) 0.0018 (13) 0.0123 (12) −0.0027 (12) N1B 0.0346 (11) 0.0420 (11) 0.0449 (11) 0.0024 (9) 0.0091 (9) 0.0061 (9) C2B 0.0324 (13) 0.0397 (13) 0.0512 (14) 0.0013 (10) 0.0103 (11) 0.0071 (11) C3B 0.0377 (14) 0.0423 (14) 0.0536 (15) 0.0012 (11) 0.0140 (12) −0.0014 (11) C4B 0.0354 (13) 0.0512 (15) 0.0403 (13) −0.0016 (11) 0.0133 (11) −0.0007 (10) C5B 0.0308 (12) 0.0525 (15) 0.0364 (12) 0.0050 (10) 0.0101 (10) 0.0082 (10) C6B 0.0332 (13) 0.0427 (13) 0.0428 (13) 0.0043 (10) 0.0131 (10) 0.0079 (10) C7B 0.0397 (16) 0.0497 (16) 0.0745 (19) 0.0076 (12) 0.0028 (14) 0.0085 (13) C8B 0.0492 (17) 0.074 (2) 0.0540 (16) −0.0015 (14) 0.0078 (13) −0.0152 (14) C9B 0.0476 (17) 0.0473 (16) 0.074 (2) 0.0065 (13) 0.0116 (14) −0.0012 (13)
Geometric parameters (Å, º)
N1A—C6A 1.345 (3) C2B—C3B 1.384 (3)
N1A—C2A 1.347 (3) C2B—C7B 1.512 (3)
C2A—C3A 1.392 (3) C3B—C4B 1.388 (3)
C3A—C4A 1.393 (3) C4B—C5B 1.387 (3)
C3A—H3A 0.950 C4B—C8B 1.502 (4)
C4A—C5A 1.389 (3) C5B—C6B 1.387 (3)
C4A—C8A 1.505 (3) C5B—H5B 0.950
C5A—C6A 1.383 (3) C6B—C9B 1.504 (4)
C5A—H5A 0.950 C7B—H7AB 0.980
C6A—C9A 1.508 (3) C7B—H7BB 0.980
C7A—H7AA 0.980 C7B—H7CB 0.980
C7A—H7BA 0.980 C8B—H8AB 0.980
C7A—H7CA 0.980 C8B—H8BB 0.980
C8A—H8AA 0.980 C8B—H8CB 0.980
C8A—H8BA 0.980 C8B—H8DB 0.980
C8A—H8CA 0.980 C8B—H8EB 0.980
C9A—H9AA 0.980 C8B—H8FB 0.980
C9A—H9BA 0.980 C9B—H9AB 0.980
C9A—H9CA 0.980 C9B—H9BB 0.980
N1B—C2B 1.346 (3) C9B—H9CB 0.980
N1B—C6B 1.349 (3)
C6A—N1A—C2A 117.6 (2) C5B—C4B—C8B 121.2 (2)
N1A—C2A—C3A 122.5 (2) C3B—C4B—C8B 122.0 (2)
N1A—C2A—C7A 116.0 (2) C4B—C5B—C6B 120.1 (2)
C3A—C2A—C7A 121.5 (2) C4B—C5B—H5B 120.0
C2A—C3A—C4A 119.9 (2) C6B—C5B—H5B 120.0
C2A—C3A—H3A 120.1 N1B—C6B—C5B 122.7 (2)
C4A—C3A—H3A 120.1 N1B—C6B—C9B 116.5 (2)
C5A—C4A—C3A 117.0 (2) C5B—C6B—C9B 120.8 (2)
C5A—C4A—C8A 121.0 (2) C2B—C7B—H7AB 109.5
C3A—C4A—C8A 121.9 (2) C2B—C7B—H7BB 109.5
C6A—C5A—C4A 120.2 (2) H7AB—C7B—H7BB 109.5
C6A—C5A—H5A 119.9 C2B—C7B—H7CB 109.5
C4A—C5A—H5A 119.9 H7AB—C7B—H7CB 109.5
N1A—C6A—C5A 122.8 (2) H7BB—C7B—H7CB 109.5
N1A—C6A—C9A 116.1 (2) C4B—C8B—H8AB 109.5
C5A—C6A—C9A 121.2 (2) C4B—C8B—H8BB 109.5
C2A—C7A—H7AA 109.5 H8AB—C8B—H8BB 109.5
C2A—C7A—H7BA 109.5 C4B—C8B—H8CB 109.5
H7AA—C7A—H7BA 109.5 H8AB—C8B—H8CB 109.5
C2A—C7A—H7CA 109.5 H8BB—C8B—H8CB 109.5
H7AA—C7A—H7CA 109.5 C4B—C8B—H8DB 109.5
H7BA—C7A—H7CA 109.5 H8AB—C8B—H8DB 141.1
C4A—C8A—H8AA 109.5 H8BB—C8B—H8DB 56.3
C4A—C8A—H8BA 109.5 H8CB—C8B—H8DB 56.3
H8AA—C8A—H8BA 109.5 C4B—C8B—H8EB 109.5
C4A—C8A—H8CA 109.5 H8AB—C8B—H8EB 56.3
H8AA—C8A—H8CA 109.5 H8BB—C8B—H8EB 141.1
H8BA—C8A—H8CA 109.5 H8CB—C8B—H8EB 56.3
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sup-5 Acta Cryst. (2001). E57, o1141–o1142
C6A—C9A—H9BA 109.5 C4B—C8B—H8FB 109.5
H9AA—C9A—H9BA 109.5 H8AB—C8B—H8FB 56.3
C6A—C9A—H9CA 109.5 H8BB—C8B—H8FB 56.3
H9AA—C9A—H9CA 109.5 H8CB—C8B—H8FB 141.1
H9BA—C9A—H9CA 109.5 H8DB—C8B—H8FB 109.5
C2B—N1B—C6B 117.4 (2) H8EB—C8B—H8FB 109.5
N1B—C2B—C3B 122.4 (2) C6B—C9B—H9AB 109.5
N1B—C2B—C7B 116.2 (2) C6B—C9B—H9BB 109.5
C3B—C2B—C7B 121.4 (2) H9AB—C9B—H9BB 109.5
C2B—C3B—C4B 120.6 (2) C6B—C9B—H9CB 109.5
C2B—C3B—H3B 119.7 H9AB—C9B—H9CB 109.5
C4B—C3B—H3B 119.7 H9BB—C9B—H9CB 109.5
C5B—C4B—C3B 116.8 (2)
C6A—N1A—C2A—C3A −0.3 (3) C6B—N1B—C2B—C3B 0.4 (3)
C6A—N1A—C2A—C7A −180.0 (2) C6B—N1B—C2B—C7B −179.2 (2)
N1A—C2A—C3A—C4A 0.8 (3) N1B—C2B—C3B—C4B −1.7 (4)
C7A—C2A—C3A—C4A −179.5 (2) C7B—C2B—C3B—C4B 177.9 (2)
C2A—C3A—C4A—C5A −1.0 (3) C2B—C3B—C4B—C5B 1.6 (4)
C2A—C3A—C4A—C8A 179.6 (2) C2B—C3B—C4B—C8B −177.3 (2)
C3A—C4A—C5A—C6A 0.5 (3) C3B—C4B—C5B—C6B −0.3 (3)
C8A—C4A—C5A—C6A −180.0 (2) C8B—C4B—C5B—C6B 178.6 (2)
C2A—N1A—C6A—C5A −0.2 (3) C2B—N1B—C6B—C5B 1.0 (3)
C2A—N1A—C6A—C9A 179.6 (2) C2B—N1B—C6B—C9B −178.7 (2)
C4A—C5A—C6A—N1A 0.0 (3) C4B—C5B—C6B—N1B −1.0 (3)