(E) 5 Methyl 2 (2 methyl­styryl)­pyrrole

Acta Cryst.(2002). E58, o909±o910 DOI: 10.1107/S1600536802012886 Aleksandar VisÏnjevacet al. C₁₄H₁₅N

o909

organic papers

Acta Crystallographica Section E Structure Reports

Online ISSN 1600-5368

(E)-5-Methyl-2-(2-methylstyryl)pyrrole

Aleksandar VisÏnjevac,a_{* Nikola} BasaricÂ,b_{Biserka KojicÂ-ProdicÂ}a and Marija SÆindler-Kulykb

a_{Rudjer BosÏkovic Institute, PO Box 180,}

HR-10002 Zagreb, Croatia, andb_Department

of Organic Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb, MarulicÂev trg 19, HR-10000 Zagreb, Croatia

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.006 AÊ

Rfactor = 0.054

wRfactor = 0.186

Data-to-parameter ratio = 16.7

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

Evaporation of a dichloromethane solution of the title compound, C14H15N, yielded a tar from which single crystals

were obtained by sublimation. The title compound consists of two essentially planar moieties that are oriented in a synperiplanar fashion with respect to each other. The geometrical parameters are in accordance with literature values.

Comment

Stereochemical changes in 2-styrylpyrroles might affect the electronic structure and in¯uence their photophysical and photochemical properties (SÆindler-Kulyket al., 1995; BasaricÂ

et al., 2000, 2001). The synthesis and conformational analysis, based on the UV photoelectron spectra, of the title compound, (I), have been reported previously (Rademacheret al., 2002). This paper deals with the structure of (I) in the solid state, and is to be regarded as a contribution to the overall under-standing of the conformational behaviour of the title compound.

Evaporation of a dichloromethane solution of (I) resulted in the formation of a tarry material, which was recrystallized by sublimation at 277 K. Yellow plates were obtained. The bond lengths and angles are in accordance with the literature values for related compounds (Allen & Kennard, 1993). The average bond distance in a toluene ring is 1.377 (6) AÊ. The molecule consists of two planar moieties: the toluene ring and the pyrrole group with the central double bond C7 C8 (Fig. 1). The N1ÐC2ÐC7ÐC8 torsion angle [' = 6.5 (6)_] (Rademacheret al., 2002) suggests an almost planar arrange-ment of the pyrrole group and the central double bond. The deviations from the least-squares plane drawn through atoms N1/C2ÐC8 range fromÿ0.001 (4) AÊ for C2 to 0.041 (4) AÊ for C7. The relevant torsion angle (') de®nes the synperiplanar orientation of the pyrrole ring with respect to the double bond C7 C8. The toluene ring is twisted with respect to the plane of the central double bond by 29.7 (5) _{(torsion angle C7Ð} C8ÐC9ÐC10,) (Rademacheret al., 2002). This value de®nes the synperiplanar orientation of the toluene ring with respect to the central double bond. The dihedral angle between the

plane of the toluene ring and the least-squares plane through atoms N1/C2±C8 is 36.90 (16)_{, and suggests the borderline} synperiplanar orientation of the toluene ring with respect to the remaining (essentially planar) part of the molecule, hence the overall synperiplanar conformation. The results are in accordance with ab initio calculations (Rademacher et al., 2002).

The crystal packing of (I) is governed only by weak van der Waals forces.

Experimental

Compound (I) was prepared according to the literature procedure of Rademacheret al.(2002).

Crystal data

C14H15N Mr= 197.27

Monoclinic, P21=n a= 12.056 (2) AÊ

b= 7.545 (1) AÊ

c= 12.62 (2) AÊ

= 99.04 (4)

V= 1133.7 (18) AÊ3 Z= 4

Dx= 1.156 Mg mÿ3

MoKradiation Cell parameters from 15

re¯ections

= 3.2±19.7

= 0.07 mmÿ1 T= 293 (2) K Plate, yellow

0.200.150.06 mm

Data collection

Enraf±Nonius CAD-4 diffractometer

!/2scans

Absorption correction: scan (Northet al., 1968)

Tmin= 0.893,Tmax= 0.935 2404 measured re¯ections 2299 independent re¯ections 774 re¯ections withI> 2(I)

Rint= 0.053 max= 26.3 h=ÿ15!14

k= 0!9

l= 0!15

3 standard re¯ections frequency: 120 min intensity decay: none

Re®nement

Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.054} wR(F2_{) = 0.186} S= 0.90 2299 re¯ections 138 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.08P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001 max= 0.20 e AÊÿ3 min=ÿ0.17 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

N1ÐC2 1.372 (5) N1ÐC5 1.368 (5)

C2ÐN1ÐC5 111.5 (3) N1ÐC2ÐC7 123.6 (3) N1ÐC2ÐC3 105.1 (3)

N1ÐC5ÐC6 121.9 (3) N1ÐC5ÐC4 105.9 (3)

H-atom coordinates were calculated geometrically and re®ned using theSHELXL97 riding model. The methyl groups were allowed to rotate, but not to tip.

Data collection: CAD-4 Software (Enraf±Nonius, 1989); cell re®nement:SET4 andCELDIMinCAD-4Software; data reduction:

HELENA(Spek, 1997); program(s) used to solve structure:SIR97 (Altomare et al., 1999); program(s) used to re®ne structure:

SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication:

PLATON(Spek, 1990).

The authors kindly acknowledge grants No. 00980608 and 125004 of the Croatian Ministry of Science and Technology.

References

Allen, F. H. & Kennard, O. (1993).Chem. Des. Autom. News,8, 1, 31±37. Altomare, A., Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C.,

Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999).J. Appl. Cryst.32, 115±119.

BasaricÂ, N., MarinicÂ, ZÏ. & SÆindler-Kulyk, M. (2001).Tetrahedron Lett.42, 3641±3643.

BasaricÂ, N., TomsÏicÂ, S., MarinicÂ, ZÏ. & SÆindler-Kulyk, M. (2000).Tetrahedron,

56, 1587±1593.

Enraf±Nonius (1989).CAD-4Software. Version 5.0. Enraf±Nonius, Delft, The Netherlands.

Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351± 359.

Rademacher, P., BasaricÂ, N., Kowski, K. & SÆindler-Kulyk, M. (2002).Eur. J. Org. Chem.pp. 551±556.

Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Spek, A. L. (1990).Acta Cryst.A46, C-34.

Spek, A. L. (1997).HELENA.Utrecht University, The Netherlands. SÆindler-Kulyk, M., TomsÏicÂ, S., MarinicÂ, ZÏ. & Metelko, B. (1995).Recl. Trav.

Chim. Pay-Bas,114, 476±479.

Figure 1

supporting information

sup-1 Acta Cryst. (2002). E58, o909–o910

supporting information

Acta Cryst. (2002). E58, o909–o910 [https://doi.org/10.1107/S1600536802012886]

(

E

)-5-Methyl-2-(2-methylstyryl)pyrrole

Aleksandar Vi

š

njevac, Nikola Basari

ć

, Biserka Koji

ć

-Prodi

ć

and Marija

Š

indler-Kulyk

(E)-5-Methyl-2-(2-methylstyryl)pyrrole

Crystal data

C14H15N

Mr = 197.27 Monoclinic, P21/n Hall symbol: -P 2yn

a = 12.056 (2) Å

b = 7.545 (1) Å

c = 12.62 (2) Å

β = 99.04 (4)°

V = 1133.7 (18) Å3

Z = 4

F(000) = 424

Dx = 1.156 Mg m−3

Mo Kα radiation, λ = 0.71069 Å Cell parameters from 15 reflections

θ = 3.2–19.7°

µ = 0.07 mm−1

T = 293 K Plate, yellow

0.20 × 0.15 × 0.06 mm

Data collection

Enraf-Nonius CAD-4 diffractometer

Radiation source: X-ray tube Graphite monochromator

θ/2θ scans

Absorption correction: ψ scan (North et al., 1968)

Tmin = 0.893, Tmax = 0.935 2404 measured reflections

2299 independent reflections 774 reflections with I > 2σ(I)

Rint = 0.053

θmax = 26.3°, θmin = 2.2°

h = −15→14

k = 0→9

l = 0→15

3 standard reflections every 120 min intensity decay: none

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.054}

wR(F2_{) = 0.186}

S = 0.90 2299 reflections 138 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) + (0.08P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001

Δρmax = 0.20 e Å−3 Δρmin = −0.17 e Å−3

Special details

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 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

N1 0.2419 (2) 0.5444 (4) −0.1835 (2) 0.0521 (11)

C2 0.3098 (3) 0.5709 (5) −0.0869 (3) 0.0477 (12)

C3 0.4101 (3) 0.6283 (5) −0.1127 (3) 0.0580 (16)

C4 0.4028 (3) 0.6355 (5) −0.2231 (3) 0.0568 (16)

C5 0.2969 (3) 0.5822 (5) −0.2678 (3) 0.0497 (12)

C6 0.2417 (3) 0.5665 (6) −0.3794 (3) 0.0708 (17)

C7 0.2739 (3) 0.5461 (5) 0.0137 (3) 0.0512 (14)

C8 0.1761 (3) 0.4801 (5) 0.0323 (3) 0.0524 (14)

C9 0.1405 (3) 0.4691 (5) 0.1386 (3) 0.0443 (12)

C10 0.1794 (3) 0.5916 (5) 0.2175 (3) 0.0553 (14)

C11 0.1493 (3) 0.5839 (6) 0.3177 (3) 0.0636 (17)

C12 0.0789 (3) 0.4530 (6) 0.3400 (3) 0.0622 (16)

C13 0.0372 (3) 0.3307 (5) 0.2624 (3) 0.0548 (16)

C14 0.0676 (3) 0.3364 (5) 0.1624 (3) 0.0489 (12)

C15 0.0255 (3) 0.1941 (5) 0.0833 (3) 0.0721 (17)

H1 0.17350 0.50848 −0.19026 0.0627*

H3 0.47321 0.65795 −0.06354 0.0695*

H4 0.45976 0.67025 −0.26047 0.0680*

H6A 0.18691 0.65900 −0.39510 0.1064*

H6B 0.29681 0.57703 −0.42634 0.1064*

H6C 0.20534 0.45331 −0.38993 0.1064*

H7 0.32437 0.57965 0.07377 0.0615*

H8 0.12662 0.43796 −0.02625 0.0625*

H10 0.22718 0.68140 0.20207 0.0665*

H11 0.17663 0.66698 0.36975 0.0765*

H12 0.05872 0.44581 0.40797 0.0747*

H13 −0.01206 0.24339 0.27836 0.0656*

H15A −0.02876 0.12253 0.11165 0.1079*

H15B −0.00893 0.24750 0.01716 0.1079*

H15C 0.08724 0.12120 0.07029 0.1079*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

N1 0.0464 (16) 0.055 (2) 0.054 (2) −0.0079 (16) 0.0053 (16) 0.0105 (17)

C2 0.043 (2) 0.044 (2) 0.055 (2) −0.0010 (18) 0.0041 (18) 0.0012 (19)

C3 0.045 (2) 0.057 (3) 0.071 (3) −0.001 (2) 0.0060 (19) −0.009 (2)

C4 0.052 (2) 0.059 (3) 0.062 (3) −0.004 (2) 0.0170 (19) 0.001 (2)

C5 0.054 (2) 0.041 (2) 0.055 (2) 0.0000 (19) 0.0112 (19) 0.0021 (19)

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sup-3 Acta Cryst. (2002). E58, o909–o910

C7 0.052 (2) 0.048 (3) 0.052 (2) 0.000 (2) 0.0030 (18) 0.0011 (19)

C8 0.050 (2) 0.054 (3) 0.051 (2) −0.0052 (19) 0.0008 (18) −0.0021 (19)

C9 0.042 (2) 0.044 (2) 0.045 (2) 0.0023 (19) 0.0012 (17) −0.0017 (18)

C10 0.050 (2) 0.053 (3) 0.062 (2) −0.007 (2) 0.0064 (19) −0.007 (2)

C11 0.060 (3) 0.072 (3) 0.058 (3) −0.004 (2) 0.007 (2) −0.011 (2)

C12 0.057 (2) 0.077 (3) 0.055 (3) 0.010 (2) 0.016 (2) 0.004 (2)

C13 0.046 (2) 0.058 (3) 0.060 (3) 0.002 (2) 0.0070 (19) 0.003 (2)

C14 0.045 (2) 0.044 (2) 0.057 (2) −0.0009 (18) 0.0061 (18) −0.0039 (19)

C15 0.070 (3) 0.064 (3) 0.084 (3) −0.014 (2) 0.017 (2) −0.009 (2)

Geometric parameters (Å, º)

N1—C2 1.372 (5) C14—C15 1.499 (6)

N1—C5 1.368 (5) C3—H3 0.9303

N1—H1 0.8606 C4—H4 0.9298

C2—C7 1.417 (6) C6—H6A 0.9600

C2—C3 1.371 (6) C6—H6B 0.9604

C3—C4 1.383 (6) C6—H6C 0.9596

C4—C5 1.372 (6) C7—H7 0.9295

C5—C6 1.465 (6) C8—H8 0.9297

C7—C8 1.334 (6) C10—H10 0.9295

C8—C9 1.474 (6) C11—H11 0.9300

C9—C14 1.396 (6) C12—H12 0.9292

C9—C10 1.385 (6) C13—H13 0.9299

C10—C11 1.371 (6) C15—H15A 0.9597

C11—C12 1.360 (6) C15—H15B 0.9604

C12—C13 1.382 (6) C15—H15C 0.9602

C13—C14 1.369 (6)

N1···H8 2.7176 H6C···C2vii _2.9029

C2···H6Ci _{2.9029 H6C···C3}vii _2.8224

C3···H6Ci _{2.8224 H7···C10 2.7109}

C4···H13ii _{3.0365 H7···H10 2.2760}

C4···H15Aii _{3.0595 H7···C13}viii _3.0925

C7···H10 2.7261 H8···N1 2.7176

C8···H1 2.8121 H8···C15 2.7042

C8···H15B 2.8211 H8···H1 2.2922

C8···H15C 2.9785 H8···H15B 2.3059

C8···H11iii _{3.0939 H10···C7 2.7261}

C8···H15Biv _{2.8775 H10···H7 2.2760}

C10···H7 2.7109 H10···C13viii _3.0231

C11···H4v _{2.9879 H10···C14}viii _3.0141

C13···H7iii _{3.0925 H11···C8}viii _3.0939

C13···H10iii _{3.0231 H13···H15A 2.2727}

C13···H1iv _{2.8332 H13···C4}ix _3.0365

C14···H10iii _{3.0141 H15A···H13 2.2727}

C15···H8 2.7042 H15A···C4ix _3.0595

H1···H8 2.2922 H15B···C8 2.8211

H1···C13iv _{2.8332 H15B···H8 2.3059}

H4···C11vi _{2.9879 H15B···C8}iv _2.8775

H6B···H15Ci _{2.4826 H15C···C8 2.9785}

H6B···H15Aii _{2.5695 H15C···H6B}vii _2.4826

C2—N1—C5 111.5 (3) C5—C4—H4 125.99

C5—N1—H1 124.22 C5—C6—H6A 109.49

C2—N1—H1 124.24 C5—C6—H6B 109.42

N1—C2—C7 123.6 (3) C5—C6—H6C 109.50

N1—C2—C3 105.1 (3) H6A—C6—H6B 109.44

C3—C2—C7 131.3 (4) H6A—C6—H6C 109.51

C2—C3—C4 109.4 (3) H6B—C6—H6C 109.48

C3—C4—C5 108.1 (3) C2—C7—H7 116.23

C4—C5—C6 132.2 (4) C8—C7—H7 116.20

N1—C5—C6 121.9 (3) C7—C8—H8 117.53

N1—C5—C4 105.9 (3) C9—C8—H8 117.51

C2—C7—C8 127.6 (4) C9—C10—H10 119.12

C7—C8—C9 125.0 (3) C11—C10—H10 119.13

C10—C9—C14 118.5 (3) C10—C11—H11 120.49

C8—C9—C10 120.2 (3) C12—C11—H11 120.44

C8—C9—C14 121.3 (3) C11—C12—H12 119.72

C9—C10—C11 121.7 (4) C13—C12—H12 119.77

C10—C11—C12 119.1 (4) C12—C13—H13 119.56

C11—C12—C13 120.5 (4) C14—C13—H13 119.64

C12—C13—C14 120.8 (4) C14—C15—H15A 109.51

C13—C14—C15 118.7 (3) C14—C15—H15B 109.46

C9—C14—C13 119.3 (3) C14—C15—H15C 109.49

C9—C14—C15 122.0 (3) H15A—C15—H15B 109.46

C2—C3—H3 125.24 H15A—C15—H15C 109.48

C4—C3—H3 125.32 H15B—C15—H15C 109.42

C3—C4—H4 125.93

C5—N1—C2—C3 0.4 (4) C7—C8—C9—C10 29.1 (6)

C5—N1—C2—C7 178.4 (4) C14—C9—C10—C11 0.9 (6)

C2—N1—C5—C4 −0.4 (4) C8—C9—C14—C13 179.7 (3)

C2—N1—C5—C6 −179.2 (4) C8—C9—C14—C15 2.6 (6)

N1—C2—C3—C4 −0.2 (4) C8—C9—C10—C11 −179.1 (4)

C7—C2—C3—C4 −178.1 (4) C10—C9—C14—C13 −0.3 (5)

C3—C2—C7—C8 −176.0 (4) C10—C9—C14—C15 −177.3 (3)

N1—C2—C7—C8 6.5 (6) C9—C10—C11—C12 −0.3 (6)

C2—C3—C4—C5 0.0 (5) C10—C11—C12—C13 −0.8 (6)

C3—C4—C5—N1 0.2 (4) C11—C12—C13—C14 1.4 (6)

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sup-5 Acta Cryst. (2002). E58, o909–o910

C2—C7—C8—C9 −175.5 (4) C12—C13—C14—C15 176.3 (4)

C7—C8—C9—C14 −150.9 (4)