Styrene at 120 K

Acta Cryst.(2001). E57, o1191±o1193 DOI: 10.1107/S1600536801019195 Bond and Davies C₈H₈

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organic papers

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

Styrene at 120 K

Andrew D. Bond* and John E. Davies

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study

T= 120 K

Mean(C±C) = 0.002 AÊ

Rfactor = 0.038

wRfactor = 0.100

Data-to-parameter ratio = 13.4

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 styrene, C8H8, has been determined at

120 (2) K following in situ crystal growth from the liquid. Molecules crystallize in the orthorhombic space groupPbcn

and contains intermolecular CÐH interactions, with both the phenyl ring and the alkene unit acting as acceptors.

Comment

Styrene occurs in nature inLiquidambar orientalisand oil of

Xanthorrhoea hastilis. It is an important industrial chemical (ca 4.01 million tons per year produced in the USA), manu-factured mainly by the dehydrogenation of ethylbenzene. It is used to produce polystyrene and is a component of SBR synthetic rubber, ABS terpolymer and styrene/butadiene and styrene/acrylonitrile copolymers. From a study of Debye± Scherrer patterns recorded from frozen styrene at 93 K, Roy (1958) determined correctly that the crystal structure of styrene is orthorhombic and suggested a possible (although unfortunately incorrect) set of unit-cell parameters. We report here the results of a full determination of the crystal structure of styrene at 120 (2) K. This work forms part of a study devoted to improving techniques for determining the crystal structures of substances that are liquid at room temperature (see, for example, Bond & Davies, 2001a,b).

Styrene, (I), crystallizes in the orthorhombic space group

Pbcnwith one whole molecule in the asymmetric unit (Fig. 1). The terminal CH2group of the alkene unit is displaced slightly

from the plane of the phenyl ring, giving a C6ÐC1ÐC7ÐC8 torsion angle of 6.5 (2)_{. Between molecules, CÐH}

interactions exist in which the -CÐH group of the alkene unit acts as a hydrogen-bond donor and the phenyl ring of an adjacent molecule acts as an acceptor [H7 centroid(C1Ð C6)i _{= 2.76 AÊ, C7ÐH7 centroid(C1ÐC6) = 161.7;}

sym-metry code: (i) 3/2ÿx, 1/2ÿy, 1/2+z]. In addition, edge-to-face arrangements between adjacent molecules give rise to further CÐH interactions in which the double bond of the alkene unit acts as an acceptor [H8A centroid(C7ÐC8)ii_{= 3.26 AÊ,}

organic papers

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C8ÐH8A centroid(C7ÐC8)ii_{= 160.6; symmetry code: (ii)}

x,ÿy, 1/2+z]. The directional nature of CÐH interactions in organic crystals has been established previously (Umezawa

et al., 1998). The two sets of interactions may be considered to link the molecules into layers parallel to the (100) plane (Fig. 2). Adjacent layers are stacked along theadirection (Fig. 3).

Note added to proof: this work and the preceding study of Yasudaet al. (2001) were carried out independently.

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 atca220 K (a temperature only slightly less than the melting point of the solid in the capillary tube) using a technique described previously (Davies & Bond, 2001). Once grown, the crystal was cooled to 120 (2) K for data collection. The length of the cyl-indrical crystal could not be measured accurately but it exceeded the diameter of the collimator (0.35 mm).

Crystal data C8H8

Mr= 104.14

Orthorhombic,Pbcn a= 15.6898 (6) AÊ b= 10.5854 (4) AÊ c= 7.5745 (2) AÊ V= 1257.99 (8) AÊ3

Z= 8

Dx= 1.100 Mg mÿ3

MoKradiation Cell parameters from 4669

re¯ections = 1.0±27.5

= 0.06 mmÿ1

T= 120 (2) K Cylinder, colourless 0.15 mm (radius)

Data collection

Nonius KappaCCD diffractometer Thin-slice!and'scans Absorption correction: none 2559 measured re¯ections 1411 independent re¯ections 1111 re¯ections withI> 2(I)

Rint= 0.020

max= 27.4

h=ÿ20!20 k=ÿ13!13 l=ÿ9!9

Re®nement Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.038}

wR(F2_{) = 0.100}

S= 1.06 1411 re¯ections 105 parameters

All H-atom parameters re®ned

w= 1/[2_(F

o2) + (0.0488P)2

+ 0.1803P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.14 e AÊÿ3

min=ÿ0.14 e AÊÿ3

Figure 1

The molecular structure and atom-labelling scheme showing displace-ment ellipsoids for non-H atoms at the 50% probability level (XP; Sheldrick, 1993).

Figure 2

Projection on to (100) of a single layer of (I), showing CÐH

interactions as dotted lines (CAMERON; Watkinet al., 1996).

Figure 3

All H atoms were located in difference Fourier maps and allowed to re®ne freely with independent isotropic displacement parameters. 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 (Altomareet 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 Professor R. M. Lambert (University of Cambridge) for suggesting this study and the EPSRC for ®nancial assistance towards the purchase of the Nonius KappaCCD diffractometer.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994).J. Appl. Cryst.27, 435±436.

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.

Roy, N. K. (1958).Indian J. Phys.32, 137±140.

Sheldrick, G. M. (1993).XP. University of GoÈttingen, Germany. Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Umezawa, Y., Tsuboyama, S., Honda, K., Uzawa, J. & Nishio, M. (1998).Bull.

Chem. Soc. Jpn,71, 1207±1231.

Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996).CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.

Yasuda, N., Uekusa, H. & Ohashi, Y. (2001).Acta Cryst.E57, o1189±o1190.

Acta Cryst.(2001). E57, o1191±o1193 Bond and Davies C₈H₈

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Acta Cryst. (2001). E57, o1191–o1193

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Acta Cryst. (2001). E57, o1191–o1193 [https://doi.org/10.1107/S1600536801019195]

Styrene at 120

K

Andrew D. Bond and John E. Davies

Styrene

Crystal data

C8H8 Mr = 104.14

Orthorhombic, Pbcn a = 15.6898 (6) Å

b = 10.5854 (4) Å

c = 7.5745 (2) Å

V = 1257.99 (8) Å3 Z = 8

F(000) = 448

Dx = 1.100 Mg m−3

Melting point: 242 K

Mo Kα radiation, λ = 0.7107 Å Cell parameters from 4669 reflections

θ = 1.0–27.5°

µ = 0.06 mm−1 T = 120 K

Cylinder, colourless 0.15 mm (radius)

Data collection

Nonius KappaCCD diffractometer

Radiation source: fine-focus sealed tube Thin–slice ω and φ scans

2559 measured reflections 1411 independent reflections

1111 reflections with I > 2σ(I)

Rint = 0.020

θmax = 27.4°, θmin = 3.6° h = −20→20

k = −13→13

l = −9→9

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.038} wR(F2_{) = 0.100} S = 1.06 1411 reflections 105 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: difference Fourier map All H-atom parameters refined

w = 1/[σ2_(F

o2) + (0.0488P)2 + 0.1803P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.14 e Å−3

Δρmin = −0.14 e Å−3

Special details

Experimental. Crystal grown in situ in a 0.3 mm Lindemann tube at ca 220 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.

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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

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Acta Cryst. (2001). E57, o1191–o1193

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

C1 0.73539 (6) 0.14843 (9) −0.06363 (12) 0.0279 (2)

C2 0.67816 (7) 0.24001 (10) −0.12281 (13) 0.0319 (3)

H2 0.6993 (7) 0.3088 (10) −0.1979 (15) 0.040 (3)*

C3 0.59281 (7) 0.23632 (10) −0.07546 (14) 0.0342 (3)

H3 0.5524 (8) 0.3035 (11) −0.1194 (15) 0.043 (3)*

C4 0.56301 (7) 0.14089 (10) 0.03352 (13) 0.0349 (3)

H4 0.5009 (9) 0.1370 (10) 0.0649 (15) 0.045 (3)*

C5 0.61904 (7) 0.04872 (10) 0.09343 (13) 0.0339 (3)

H5 0.5988 (7) −0.0204 (11) 0.1713 (17) 0.044 (3)*

C6 0.70412 (7) 0.05179 (9) 0.04508 (13) 0.0306 (3)

H6 0.7441 (7) −0.0152 (12) 0.0879 (14) 0.038 (3)*

C7 0.82548 (7) 0.15667 (10) −0.11697 (14) 0.0356 (3)

H7 0.8381 (7) 0.2230 (12) −0.2019 (18) 0.052 (3)*

C8 0.88888 (8) 0.08554 (12) −0.06109 (17) 0.0443 (3)

H8A 0.8807 (9) 0.0176 (15) 0.0296 (19) 0.058 (4)*

H8B 0.9479 (9) 0.0991 (12) −0.1040 (17) 0.054 (4)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C1 0.0310 (5) 0.0302 (5) 0.0226 (4) −0.0044 (4) −0.0010 (3) −0.0032 (4)

C2 0.0374 (6) 0.0312 (5) 0.0271 (5) −0.0048 (4) −0.0003 (4) 0.0028 (4)

C3 0.0345 (6) 0.0355 (6) 0.0325 (5) 0.0015 (4) −0.0047 (4) −0.0037 (4)

C4 0.0292 (6) 0.0425 (6) 0.0330 (5) −0.0078 (4) 0.0005 (4) −0.0070 (4)

C5 0.0383 (6) 0.0345 (6) 0.0289 (5) −0.0120 (4) 0.0005 (4) 0.0008 (4)

C6 0.0351 (6) 0.0297 (5) 0.0270 (5) −0.0030 (4) −0.0029 (4) 0.0007 (4)

C7 0.0345 (6) 0.0394 (6) 0.0329 (5) −0.0065 (5) 0.0036 (4) 0.0005 (4)

C8 0.0327 (6) 0.0471 (7) 0.0532 (7) −0.0019 (5) 0.0029 (5) −0.0059 (6)

Geometric parameters (Å, º)

C1—C2 1.3954 (14) C4—H4 1.004 (14)

C1—C6 1.4018 (14) C5—C6 1.3845 (15)

C1—C7 1.4727 (14) C5—H5 0.992 (13)

C2—C3 1.3868 (15) C6—H6 1.000 (12)

C2—H2 0.982 (12) C7—C8 1.3175 (16)

C3—C4 1.3858 (15) C7—H7 0.973 (14)

C3—H3 1.009 (12) C8—H8A 1.003 (16)

C4—C5 1.3895 (16) C8—H8B 0.992 (14)

C2—C1—C6 118.06 (9) C6—C5—C4 120.47 (10)

C2—C1—C7 119.23 (9) C6—C5—H5 118.9 (7)

C6—C1—C7 122.71 (9) C4—C5—H5 120.6 (7)

C3—C2—C1 121.24 (10) C5—C6—C1 120.66 (10)

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Acta Cryst. (2001). E57, o1191–o1193

C1—C2—H2 119.0 (6) C1—C6—H6 119.2 (7)

C4—C3—C2 120.02 (10) C8—C7—C1 127.06 (11)

C4—C3—H3 119.9 (7) C8—C7—H7 118.1 (7)

C2—C3—H3 120.1 (7) C1—C7—H7 114.8 (7)

C3—C4—C5 119.54 (10) C7—C8—H8A 122.2 (8)

C3—C4—H4 119.9 (7) C7—C8—H8B 121.2 (7)

C5—C4—H4 120.5 (7) H8A—C8—H8B 116.6 (11)

C6—C1—C2—C3 0.21 (14) C4—C5—C6—C1 0.61 (15)

C7—C1—C2—C3 −179.77 (9) C2—C1—C6—C5 −0.72 (14)

C1—C2—C3—C4 0.42 (15) C7—C1—C6—C5 179.26 (9)

C2—C3—C4—C5 −0.54 (15) C2—C1—C7—C8 173.49 (11)