4′ Chloro 2,2′:6′,2′′ terpyridine

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organic papers

Acta Cryst.(2006). E62, o2497–o2498 doi:10.1107/S1600536806019180 Beveset al. _C15H10ClN3

o2497

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

4

000

_-Chloro-2,2

000

_:6

000

_,2

000000

_-terpyridine

Jonathon E. Beves, Edwin C. Constable, Catherine E.

Housecroft,* Markus Neuburger and Silvia Schaffner

Department of Chemistry, University of Basel, Spitalstrasse 51, CH4056 Basel, Switzerland

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 173 K

Mean(C–C) = 0.003 A˚

Rfactor = 0.030

wRfactor = 0.032

Data-to-parameter ratio = 10.7

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

Received 26 April 2006 Accepted 23 May 2006

In the title compound, C15H10ClN3, the terpyridine unit adopts

atrans,transconformation. Molecules assemble into-stacked columns along the b axis, with an interplanar distance of 3.51 A˚ .

Comment

Despite the widespread use of ligands based on 2,20_:60_,200

-terpyridine (tpy) in coordination chemistry (Andres & Schu-bert, 2004; Baranoffet al., 2004; Constable, 1986; Hofmeier & Schubert, 2004; Thummel, 2004), few crystal structures of ligands with simple substituents have been reported. Ligands with substituents in the 40_{-position (Fallahpour, 2003) are of}

particular significance in the design of extended assemblies with controlled stereochemistry. 40_-Chloro-2,20_:60_,200

-terpyr-idine, (I) (Constable & Ward, 1990), is commonly used as a precursor to other 40_{-substituted-tpy ligands. We present here}

the crystal structure of (I).

Crystals of (I) were grown by slow cooling of a hot methanol solution of the ligand. Fig. 1 shows the structure of a molecule of (I). As expected, the three pyridine rings adopt a

trans,trans conformation. Bond distances and angles are unexceptional. The molecule is close to being planar: the angles between the least-squares planes of the pyridine rings containing atoms N1 and N2, and N2 and N3 are 8.0 (1) and 5.4 (1)_{, respectively. Molecules of (I) pack in} _-stacked

columns which run along the b axis (Fig. 2). The distance between the least-squares planes (each containing 29 atoms) of adjacent molecules is 3.51 A˚ . Atom Cl is not involved in any short intermolecular contacts. A search of the Cambridge Structural Database (CSD, Version 5.2.7; Allen, 2002; Brunoet al., 2002) for tpy-based ligands containing single atoms (e.g.

halogen) or short rigid-rod substituents at the 40_-position

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contrast to the simple stacked columns of molecules in (I), those of 2,20_:60_,200_{-terpyridine form a more complex}

arrange-ment.

Experimental

Compound (I) was prepared as previously reported (Constable & Ward, 1990) and crystals were grown by slow cooling of a hot methanol solution.

Crystal data

C15H10ClN3 Mr= 267.72

Orthorhombic,Pna21 a= 29.8317 (15) A˚

b= 3.8344 (2) A˚

c= 10.6476 (5) A˚

V= 1217.94 (11) A˚3

Z= 4

Dx= 1.460 Mg m 3

MoKradiation

= 0.30 mm1 T= 173 K Plate, colourless 0.200.170.04 mm

Data collection

Nonius KappaCCD diffractometer

’and!scans

Absorption correction: multi-scan

(DENZO/SCALEPACK;

Otwinowski & Minor, 1997)

Tmin= 0.95,Tmax= 0.99

7250 measured reflections 2554 independent reflections 1848 reflections withI> 3(I)

Rint= 0.098 max= 27.6

Refinement

Refinement onF R[F> 2(F)] = 0.030

wR(F) = 0.032

S= 0.94 1848 reflections 173 parameters

H-atom parameters constrained

w= 1/[2

(F2) + (0.02P)2] whereP= [max(Fo2,0) + 2Fc2]/3

(/)max= 0.001

max= 0.14 e A˚ 3

min=0.18 e A˚ 3

Absolute structure: Flack (1983), 1130 Friedel pairs

Flack parameter:0.04 (6)

All H atoms were treated as riding atoms, with C—H = 0.96 A˚ and Uiso(H) = 1.2Ueq(C).

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK(Otwinowski & Minor, 1997); data reduc-tion: DENZO/SCALEPACK; program(s) used to solve structure: SIR92(Altomareet al., 1994); program(s) used to refine structure: CRYSTALS(Betteridgeet al., 2003); molecular graphics:ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CRYSTALS.

We thank the Swiss National Science Foundation and the University of Basel for financial support.

References

Allen, F. H. (2002).Acta Cryst.B58, 380–388.

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

Andres, P. R. & Schubert, U. S. (2004).Adv. Mater.16, 1043–1068.

Baranoff, E., Collin, J.-P., Flamigni, L. & Sauvage, J.-P. (2004).Chem. Soc. Rev. 33, 147–155.

Bessel, C. A., See, R. F., Jameson, D. L., Churchill, M. R. & Takeuchi, K. J. (1992).J. Chem. Soc. Dalton Trans.pp. 3223–3228.

Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003).J. Appl. Cryst.36, 1487.

Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M. K., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002).Acta Cryst.B58, 389–397.

Constable, E. C. (1986).Adv. Inorg. Chem. Radiochem.30, 69–121. Constable, E. C. & Ward, M. D. (1990).J. Chem. Soc. Dalton Trans.pp. 1405–

1409.

Fallahpour, R.-A. (2003).Synthesis, pp. 155–184. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Flack, H. D. (1983).Acta Cryst.A39, 876–881.

Hofmeier, H. & Schubert, U. S. (2004).Chem. Soc. Rev.33, 373-399. Nonius (2001).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 Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

[image:2.610.67.273.73.217.2] [image:2.610.44.295.270.409.2]

Thummel, R. P. (2004).Comprehensive Coordination Chemistry II, edited by J. A. McCleverty & T. J. Meyer, Vol. 2, pp. 41–53. Oxford: Elsevier.

Figure 1

The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radius.

Figure 2

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supporting information

sup-1 Acta Cryst. (2006). E62, o2497–o2498

supporting information

Acta Cryst. (2006). E62, o2497–o2498 [https://doi.org/10.1107/S1600536806019180]

4 ′

-Chloro-2,2

′

:6

′

,2

′′

-terpyridine

Jonathon E. Beves, Edwin C. Constable, Catherine E. Housecroft, Markus Neuburger and Silvia

Schaffner

4′-Chloro-2,2′:6′,2′′-terpyridine

Crystal data

C15H10ClN3 Mr = 267.72

Orthorhombic, Pna21

Hall symbol: P 2c -2n

a = 29.8317 (15) Å

b = 3.8344 (2) Å

c = 10.6476 (5) Å

V = 1217.94 (11) Å3 Z = 4

F(000) = 552

Dx = 1.460 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3476 reflections

θ = 1–27°

µ = 0.30 mm−1 T = 173 K Plate, colourless 0.20 × 0.17 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer

Graphite monochromator

φ and ω scans

Absorption correction: multi-scan

(DENZO/SCALEPACK; Otwinowski & Minor, 1997)

Tmin = 0.95, Tmax = 0.99

7250 measured reflections 2554 independent reflections 1848 reflections with I > 3σ(I)

Rint = 0.098

θmax = 27.6°, θmin = 1.4°

h = −38→38

k = −4→4

l = −13→12

Refinement

Refinement on F

Least-squares matrix: full

R[F2_{> 2}_σ₍_F2_{)] = 0.030} wR(F2_{) = 0.032} S = 0.94 1848 reflections 173 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2₍_F2_{) + (0.02}_P₎2_]

where P = [max(Fo2_{,0) + 2}_Fc2_]/3

(Δ/σ)max = 0.001

Δρmax = 0.14 e Å−3

Δρmin = −0.18 e Å−3

Absolute structure: Flack (1983), 1130 Friedel pairs

Absolute structure parameter: −0.04 (6)

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

x y z Uiso*/Ueq

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N2 0.89799 (5) 1.0349 (4) 0.69348 (16) 0.0276 N3 0.78951 (6) 0.7575 (5) 0.58118 (17) 0.0350 C1 1.03672 (8) 1.2342 (7) 0.8905 (2) 0.0345 C2 1.05556 (8) 1.3886 (6) 0.7862 (2) 0.0342 C3 1.02932 (8) 1.4367 (6) 0.6809 (2) 0.0332 C4 0.98525 (7) 1.3210 (6) 0.68374 (19) 0.0304 C5 0.96894 (7) 1.1684 (5) 0.79145 (19) 0.0263 C6 0.92195 (7) 1.0365 (5) 0.8001 (2) 0.0262 C7 0.90514 (7) 0.9187 (6) 0.9141 (2) 0.0281 C8 0.86177 (7) 0.7951 (6) 0.9158 (2) 0.0298 C9 0.83628 (7) 0.7896 (6) 0.8088 (2) 0.0299 C10 0.85575 (7) 0.9135 (5) 0.6982 (2) 0.0275 C11 0.83026 (6) 0.9081 (5) 0.5776 (2) 0.0277 C12 0.84819 (7) 1.0452 (6) 0.4684 (2) 0.0319 C13 0.82400 (8) 1.0238 (6) 0.3580 (2) 0.0366 C14 0.78250 (8) 0.8660 (6) 0.3603 (2) 0.0375 C15 0.76683 (8) 0.7425 (7) 0.4730 (2) 0.0386

H11 1.0552 1.2019 0.9634 0.0414*

H21 1.0864 1.4613 0.7868 0.0411*

H31 1.0413 1.5476 0.6073 0.0398*

H41 0.9663 1.3470 0.6114 0.0365*

H71 0.9231 0.9232 0.9890 0.0337*

H91 0.8061 0.7035 0.8098 0.0359*

H121 0.8771 1.1543 0.4693 0.0383*

H131 0.8359 1.1169 0.2812 0.0439*

H141 0.7650 0.8431 0.2850 0.0450*

H151 0.7376 0.6381 0.4743 0.0463*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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supporting information

sup-3 Acta Cryst. (2006). E62, o2497–o2498

C14 0.0352 (12) 0.0431 (15) 0.0343 (14) 0.0094 (12) −0.0089 (11) −0.0052 (12) C15 0.0319 (12) 0.0427 (15) 0.0411 (14) 0.0011 (11) −0.0018 (11) −0.0065 (13)

Geometric parameters (Å, º)

Cl1—C8 1.743 (2) C6—C7 1.389 (3)

N1—C1 1.341 (3) C7—C8 1.378 (3)

N1—C5 1.348 (3) C7—H71 0.960

N2—C6 1.341 (3) C8—C9 1.370 (3)

N2—C10 1.344 (3) C9—C10 1.396 (3)

N3—C11 1.346 (3) C9—H91 0.960

N3—C15 1.337 (3) C10—C11 1.493 (3)

C1—C2 1.378 (3) C11—C12 1.384 (3)

C1—H11 0.960 C12—C13 1.382 (3)

C2—C3 1.380 (3) C12—H121 0.960

C2—H21 0.960 C13—C14 1.378 (3)

C3—C4 1.388 (3) C13—H131 0.960

C3—H31 0.960 C14—C15 1.373 (3)

C4—C5 1.376 (3) C14—H141 0.960

C4—H41 0.960 C15—H151 0.960

C5—C6 1.493 (3)

C1—N1—C5 117.12 (18) Cl1—C8—C7 119.28 (18)

C6—N2—C10 118.00 (18) Cl1—C8—C9 119.69 (16)

C11—N3—C15 116.8 (2) C7—C8—C9 121.0 (2)

N1—C1—C2 123.6 (2) C8—C9—C10 117.7 (2)

N1—C1—H11 118.2 C8—C9—H91 121.1

C2—C1—H11 118.2 C10—C9—H91 121.1

C1—C2—C3 118.7 (2) C9—C10—N2 122.6 (2)

C1—C2—H21 120.6 C9—C10—C11 120.59 (18)

C3—C2—H21 120.6 N2—C10—C11 116.74 (19)

C2—C3—C4 118.5 (2) C10—C11—N3 116.20 (19)

C2—C3—H31 120.8 C10—C11—C12 121.39 (18)

C4—C3—H31 120.8 N3—C11—C12 122.4 (2)

C3—C4—C5 119.3 (2) C11—C12—C13 119.4 (2)

C3—C4—H41 120.4 C11—C12—H121 120.3

C5—C4—H41 120.4 C13—C12—H121 120.3

C4—C5—N1 122.76 (18) C12—C13—C14 118.7 (2)

C4—C5—C6 121.81 (19) C12—C13—H131 120.7

N1—C5—C6 115.43 (18) C14—C13—H131 120.7

C5—C6—N2 116.74 (18) C13—C14—C15 118.2 (2)

C5—C6—C7 120.18 (19) C13—C14—H141 120.9

N2—C6—C7 123.08 (19) C15—C14—H141 120.9

C6—C7—C8 117.5 (2) C14—C15—N3 124.5 (2)

C6—C7—H71 121.2 C14—C15—H151 117.8