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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o279.
Published online 2007 December 18. doi:  10.1107/S1600536807065701
PMCID: PMC2915332

4-[4-(Methyl­sulfan­yl)phen­yl]-6-phenyl-2,2′-bipyridine

Abstract

The structure of the title compound, C23H18N2S, is revealed by X-ray diffraction to be almost planar over all four aromatic rings; the pendant rings are at angles of 10.18, 14.12 and 15.42° relative to the central pyridine ring for the 4-methylsulfanyl, 2-pyridyl and 6-phenyl rings, respectively. The 2,6-aromatic substituents are disordered over two sites in a 0.6:0.4 occupancy ratio.

Related literature

For related literature, see: Fitchett et al. (2005 [triangle]).

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Object name is e-64-0o279-scheme1.jpg

Experimental

Crystal data

  • C23H18N2S
  • M r = 354.45
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o279-efi1.jpg
  • a = 19.189 (3) Å
  • b = 5.3617 (8) Å
  • c = 17.084 (3) Å
  • β = 92.262 (9)°
  • V = 1756.3 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.19 mm−1
  • T = 93 (2) K
  • 0.45 × 0.17 × 0.04 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2007 [triangle]) T min = 0.599, T max = 0.992
  • 19871 measured reflections
  • 3118 independent reflections
  • 1442 reflections with I > 2σ(I)
  • R int = 0.121

Refinement

  • R[F 2 > 2σ(F 2)] = 0.063
  • wR(F 2) = 0.161
  • S = 0.93
  • 3118 reflections
  • 236 parameters
  • H-atom parameters constrained
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: ORTEP-3 for Windows (Version 1.08; Farrugia, 1997 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807065701/ww2105sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065701/ww2105Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the Foundation of Research Science and Technology for funding. FS also thanks the EC for funding (grant G5RD-CT-2002-00776, MWFM) and PJS also thanks the Royal Society of New Zealand for the award of a James Cook Research Fellowship.

supplementary crystallographic information

Comment

The use of Self Assemblied Monolayers (SAMs) in the fabrication of molecular devices is a rapidly expanding field. To incorporate the useful photophysical properties of iridium complexes into a SAM, ligands must be capable of attaching to a surface. The compound (1), a bipyridine based ligand, includes a protected thiol group for attachment to a gold surface and a phenyl group for cyclometallation. Typically bipyridine ligands crystallize with the pyridine N atoms in a s-trans arrangement (Fitchett et al., 2005). This is attributed to reduction of C—H/H—C interactions. Here, the pyridine ring and the phenyl ring crystallize in identical conformations, leading to disorder. If C—H/H—C interactions were the dominant force for the arrangement of the ring, one would expect the phenyl ring to adopt a different arrangement due to the additional interaction. This implies that the dominant force for the arrangement of the rings is the attractive C—H/N interaction.

Experimental

To a solution of 4-(methylsulfanyl)benzaldehyde (5 g), acetophenone (4.5 g), methanol (300 ml) and ammonia (0.81 g/ml, 50 ml) was added a sodium hydroxide solution (1.5 g in 50 ml water) with stirring. Overnight a precipitate of the condensation product formed. This was filtered, air dried and was used in the next step without further purification. This compound (5 g) was ground in a mortar and pestle with 2-acetylpyridine (2.5 g) and sodium hydroxide (0.83 g) until the mixture became a solid again. Excess ammonium hydroxide was added and the mixture dissolved in glacial acetic acid (50 ml) and was refluxed with stirring for 4 h. On cooling, the solution was poured into water (200 ml) and extracted with dichloromethane (3 x 50 ml). Chromatography on silica gel with dichloromethane/methanol (95:5) yielded the pure product (1). Single crystals suitable for X-ray diffraction formed on slow evaporation from dichloromethane solution. Yield = 2.3 g (25%). Spectroscopic data: 1H NMR (CDCl3): δ 2.54 (3H, s, CH3S), 7.35 (1H, ddd, py5'), 7.37 (2H, d, thio-ph3,5), 7.46 (1H, t, ph4), 7.53 (2H, dd, thio-ph2,6), 7.77 (2H, d, ph3,5), 7.87 (1H, td, py4'), 7.95 (1H, d, py5), 8.20 (2H, d, ph2,6), 8.63 (1H, d, py3), 8.68 (1H, d, py3'), 8.72 (1H, dd, py6'); 13C NMR (CDCl3): δ 15.5, 117.1, 118.1, 121.6, 123.9, 126.5, 127.1, 127.5, 128.7, 129.1, 135.0, 137.1, 139.4, 140.1, 148.8, 149.5, 156.0, 156.2, 157.2.

Refinement

The 2-pyridine and 6-phenyl rings are disordered in a 60/40 ratio over the two possible positions. The pyridine ring however always adopts a s-trans arrangement to the central pyridine nitrogen, presumably to minimize hydrogen/hydrogen repulsions.

Figures

Fig. 1.
The molecular structure of (1), showing displacement ellipsoids at the 50% probability level.

Crystal data

C23H18N2SF000 = 744
Mr = 354.45Dx = 1.341 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1819 reflections
a = 19.189 (3) Åθ = 2.7–25.9º
b = 5.3617 (8) ŵ = 0.19 mm1
c = 17.084 (3) ÅT = 93 (2) K
β = 92.262 (9)ºPlate, yellow
V = 1756.3 (5) Å30.45 × 0.17 × 0.04 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer3118 independent reflections
Radiation source: sealed tube1442 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.121
T = 93(2) Kθmax = 25.1º
[var phi] and ω scansθmin = 2.4º
Absorption correction: multi-scan(SADABS; Bruker, 2007)h = −22→22
Tmin = 0.599, Tmax = 0.992k = −6→6
19871 measured reflectionsl = −20→20

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.063H-atom parameters constrained
wR(F2) = 0.161  w = 1/[σ2(Fo2) + (0.0562P)2 + 0.5007P] where P = (Fo2 + 2Fc2)/3
S = 0.93(Δ/σ)max < 0.001
3118 reflectionsΔρmax = 0.50 e Å3
236 parametersΔρmin = −0.35 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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.

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

xyzUiso*/UeqOcc. (<1)
C100.7765 (2)0.5910 (7)0.4911 (2)0.0262 (10)
C110.8384 (2)0.6255 (8)0.5330 (3)0.0467 (13)
H110.87880.53330.52040.056*
C120.8411 (2)0.7978 (9)0.5941 (3)0.0575 (15)
H120.88320.82050.62450.069*
C130.7843 (2)0.9318 (8)0.6101 (2)0.0383 (11)
H130.78621.05160.65110.046*
C140.7242 (2)0.8947 (9)0.5672 (3)0.0440 (12)
H140.68390.98830.57920.053*
N150.71985 (18)0.7258 (8)0.5069 (2)0.0428 (10)0.60
C150.71985 (18)0.7258 (8)0.5069 (2)0.0428 (10)0.40
H150.67750.70460.47690.051*0.40
N200.82507 (15)0.2544 (7)0.41731 (17)0.0296 (8)
C200.7730 (2)0.4149 (8)0.4222 (2)0.0278 (10)
C210.7176 (2)0.4300 (8)0.3674 (2)0.0300 (10)
H210.68110.54710.37410.036*
C220.71595 (19)0.2711 (8)0.3022 (2)0.0269 (9)
C230.7708 (2)0.1064 (8)0.2974 (2)0.0322 (11)
H230.7720−0.00400.25400.039*
C240.8246 (2)0.0983 (8)0.3549 (2)0.0314 (10)
C300.8832 (2)−0.0776 (8)0.3508 (2)0.0306 (10)
C310.9434 (2)−0.0504 (9)0.3971 (3)0.0453 (13)
H310.94690.08560.43270.054*
C320.9981 (3)−0.2125 (10)0.3934 (3)0.0545 (14)
H321.0387−0.18960.42620.065*
C330.9939 (2)−0.4123 (9)0.3407 (3)0.0454 (13)
H331.0314−0.52610.33610.054*
C340.9338 (2)−0.4371 (9)0.2964 (3)0.0441 (12)
H340.9297−0.57510.26170.053*
N350.87914 (19)−0.2752 (8)0.2989 (2)0.0354 (10)0.40
C350.87914 (19)−0.2752 (8)0.2989 (2)0.0354 (10)0.60
H350.8389−0.29790.26550.042*0.60
C400.65707 (19)0.2792 (8)0.2432 (2)0.0283 (10)
C410.6070 (2)0.4625 (8)0.2429 (2)0.0380 (11)
H410.61180.59300.28030.046*
C420.5494 (2)0.4669 (8)0.1906 (2)0.0393 (12)
H420.51630.59810.19280.047*
C430.54081 (19)0.2767 (8)0.1349 (2)0.0302 (10)
C440.5919 (2)0.0955 (9)0.1327 (3)0.0442 (12)
H440.5880−0.03210.09430.053*
C450.6486 (2)0.0961 (8)0.1857 (3)0.0411 (12)
H450.6827−0.03180.18260.049*
S400.46881 (5)0.2541 (2)0.06834 (6)0.0347 (3)
C460.4188 (2)0.5257 (8)0.0889 (2)0.0422 (12)
H46A0.40830.52790.14460.063*
H46B0.37520.52320.05710.063*
H46C0.44560.67520.07630.063*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C100.032 (2)0.030 (2)0.016 (2)−0.001 (2)0.0034 (18)0.005 (2)
C110.048 (3)0.050 (3)0.041 (3)0.015 (2)−0.006 (2)−0.015 (3)
C120.056 (3)0.071 (4)0.044 (3)0.019 (3)−0.024 (2)−0.021 (3)
C130.052 (3)0.043 (3)0.019 (3)0.003 (2)−0.004 (2)−0.007 (2)
C140.046 (3)0.050 (3)0.037 (3)0.014 (2)0.004 (2)−0.019 (3)
N150.043 (2)0.058 (3)0.028 (2)0.007 (2)−0.0014 (17)−0.019 (2)
C150.043 (2)0.058 (3)0.028 (2)0.007 (2)−0.0014 (17)−0.019 (2)
N200.0384 (19)0.037 (2)0.0137 (18)0.003 (2)0.0057 (14)0.0044 (19)
C200.037 (2)0.034 (3)0.012 (2)0.001 (2)0.0076 (19)0.002 (2)
C210.042 (3)0.029 (3)0.019 (2)0.000 (2)0.002 (2)0.001 (2)
C220.039 (2)0.029 (2)0.013 (2)−0.002 (2)0.0067 (17)0.004 (2)
C230.048 (3)0.036 (3)0.013 (2)−0.002 (2)0.003 (2)−0.001 (2)
C240.043 (3)0.029 (3)0.022 (3)−0.002 (2)0.006 (2)0.005 (2)
C300.039 (3)0.037 (3)0.016 (2)0.003 (2)0.0086 (19)0.006 (2)
C310.056 (3)0.056 (3)0.024 (3)0.013 (3)0.001 (2)−0.003 (2)
C320.064 (3)0.071 (4)0.029 (3)0.018 (3)0.000 (2)0.007 (3)
C330.056 (3)0.046 (3)0.035 (3)0.012 (3)0.011 (2)0.013 (3)
C340.062 (3)0.040 (3)0.032 (3)0.003 (3)0.018 (3)−0.003 (2)
N350.048 (2)0.036 (2)0.023 (2)0.006 (2)0.0093 (18)0.000 (2)
C350.048 (2)0.036 (2)0.023 (2)0.006 (2)0.0093 (18)0.000 (2)
C400.039 (2)0.031 (3)0.016 (2)−0.005 (2)0.0059 (17)0.003 (2)
C410.053 (3)0.045 (3)0.016 (3)0.005 (2)−0.002 (2)−0.010 (2)
C420.055 (3)0.041 (3)0.022 (3)0.012 (2)0.001 (2)−0.007 (2)
C430.038 (2)0.029 (3)0.024 (2)−0.005 (2)0.0013 (18)0.004 (2)
C440.056 (3)0.040 (3)0.036 (3)0.006 (3)−0.008 (2)−0.011 (2)
C450.052 (3)0.034 (3)0.037 (3)0.010 (2)−0.004 (2)−0.009 (2)
S400.0459 (6)0.0359 (6)0.0222 (6)−0.0007 (6)−0.0005 (4)−0.0047 (6)
C460.049 (3)0.053 (3)0.024 (3)0.009 (2)−0.003 (2)−0.003 (2)

Geometric parameters (Å, °)

C10—N151.342 (5)C31—C321.367 (6)
C10—C111.374 (5)C31—H310.9500
C10—C201.509 (5)C32—C331.399 (6)
C11—C121.394 (6)C32—H320.9500
C11—H110.9500C33—C341.360 (6)
C12—C131.343 (6)C33—H330.9500
C12—H120.9500C34—N351.364 (5)
C13—C141.357 (5)C34—H340.9500
C13—H130.9500C40—C411.375 (5)
C14—N151.371 (5)C40—C451.393 (5)
C14—H140.9500C41—C421.392 (5)
N20—C201.324 (5)C41—H410.9500
N20—C241.355 (5)C42—C431.401 (6)
C20—C211.391 (5)C42—H420.9500
C21—C221.402 (5)C43—C441.381 (6)
C21—H210.9500C43—S401.758 (4)
C22—C231.378 (5)C44—C451.388 (6)
C22—C401.485 (5)C44—H440.9500
C23—C241.398 (5)C45—H450.9500
C23—H230.9500S40—C461.787 (4)
C24—C301.472 (5)C46—H46A0.9800
C30—C311.380 (6)C46—H46B0.9800
C30—N351.382 (5)C46—H46C0.9800
N15—C10—C11120.9 (4)C30—C31—H31118.9
N15—C10—C20118.8 (4)C31—C32—C33119.5 (5)
C11—C10—C20120.1 (4)C31—C32—H32120.3
C10—C11—C12119.0 (4)C33—C32—H32120.3
C10—C11—H11120.5C34—C33—C32117.3 (5)
C12—C11—H11120.5C34—C33—H33121.3
C13—C12—C11120.1 (4)C32—C33—H33121.3
C13—C12—H12120.0C33—C34—N35123.8 (5)
C11—C12—H12120.0C33—C34—H34118.1
C12—C13—C14119.4 (4)N35—C34—H34118.1
C12—C13—H13120.3C34—N35—C30118.9 (4)
C14—C13—H13120.3C41—C40—C45116.1 (4)
C13—C14—N15121.8 (4)C41—C40—C22122.4 (4)
C13—C14—H14119.1C45—C40—C22121.5 (4)
N15—C14—H14119.1C40—C41—C42123.4 (4)
C10—N15—C14118.8 (4)C40—C41—H41118.3
C20—N20—C24117.9 (3)C42—C41—H41118.3
N20—C20—C21123.7 (4)C41—C42—C43119.5 (4)
N20—C20—C10116.4 (3)C41—C42—H42120.2
C21—C20—C10119.9 (4)C43—C42—H42120.2
C20—C21—C22119.4 (4)C44—C43—C42117.7 (4)
C20—C21—H21120.3C44—C43—S40118.3 (3)
C22—C21—H21120.3C42—C43—S40123.9 (3)
C23—C22—C21116.4 (3)C43—C44—C45121.4 (4)
C23—C22—C40122.7 (4)C43—C44—H44119.3
C21—C22—C40120.9 (4)C45—C44—H44119.3
C22—C23—C24121.5 (4)C44—C45—C40121.8 (4)
C22—C23—H23119.3C44—C45—H45119.1
C24—C23—H23119.3C40—C45—H45119.1
N20—C24—C23121.1 (4)C43—S40—C46103.4 (2)
N20—C24—C30116.8 (4)S40—C46—H46A109.5
C23—C24—C30122.1 (4)S40—C46—H46B109.5
C31—C30—N35118.2 (4)H46A—C46—H46B109.5
C31—C30—C24121.9 (4)S40—C46—H46C109.5
N35—C30—C24119.8 (4)H46A—C46—H46C109.5
C32—C31—C30122.2 (5)H46B—C46—H46C109.5
C32—C31—H31118.9

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WW2105).

References

  • Bruker (2007). APEX2 (Version 2.1-4), SAINT (Version 7.34A) and SADABS (Version 2004/1). Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Fitchett, C. M., Richardson, C. & Steel, P. J. (2005). Org. Biomol. Chem.3, 498–502. [PubMed]
  • Sheldrick, G. M. (1990). Acta Cryst. A46, 467–473.
  • Sheldrick, G. M. (1997). SHELXL97 University of Göttingen, Germany. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

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