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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2295.
Published online 2008 November 8. doi:  10.1107/S160053680803609X
PMCID: PMC2959858

3-Phenyl-1-[2-(3-phenyl­isoquinolin-1-yl)­diselan­yl]isoquinoline

Abstract

The complete molecule of the title compound, C30H20N2Se2, is generated by a crystallographic inversion centre at the mid-point of the Se—Se bond. The dihedral angle between the isoquinoline-1-selenol group and the phenyl ring is 14.92 (2)°. The herringbone-like packing of the structure is supported by inter­molecular π–π stacking inter­actions with a shortest perpendicular distance between isoquinoline groups of 3.514 Å; the slippage between these ring systems is 0.972 Å, and the distance between the centroids of the six-membered carbon rings is 3.645 (3) Å.

Related literature

For biological properties of organoselenium compounds, see: Mugesh & Singh (2000 [triangle]). For chemopreventive agents in human cancer therapy, see: Sugie et al. (2000 [triangle]).

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Object name is e-64-o2295-scheme1.jpg

Experimental

Crystal data

  • C30H20N2Se2
  • M r = 566.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2295-efi1.jpg
  • a = 11.2441 (17) Å
  • b = 17.559 (3) Å
  • c = 13.248 (3) Å
  • β = 115.082 (2)°
  • V = 2369.0 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 3.14 mm−1
  • T = 290 (2) K
  • 0.20 × 0.14 × 0.11 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.585, T max = 0.703
  • 8668 measured reflections
  • 2207 independent reflections
  • 1516 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.102
  • S = 1.00
  • 2207 reflections
  • 158 parameters
  • H-atom parameters constrained
  • Δρmax = 0.66 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: SMART (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and CAMERON (Watkin et al., 1993 [triangle]); software used to prepare material for publication: PLATON (Spek, 2003 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680803609X/si2124sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680803609X/si2124Isup2.hkl

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

Acknowledgments

We thank the Department of Science and Technology, India, for use of the CCD facility set up under the IRHPA-DST program at IISc. We thank Professor T. N. Guru Row, IISc, Bangalore, for useful crystallographic discussions. FNK thanks DST for Fast Track Proposal funding.

supplementary crystallographic information

Comment

Organoselenium compounds are widely used in modern organic synthesis, materials synthesis, biochemistry, photography, ligand chemistry, electroconducting materials and biologically relevant properties like antibacterial, antiviral, antifungal, antiparastic and antiradiation (Mugesh & Singh, 2000 and references therein). Organoselenium compounds are less toxic and more chemopreventive in comparision with that of inorganoseleniums and natural organoseleniums. Hence, organoseleniums are considered as better candidates of chemopreventive agents for human cancers. (Sugie et al., 2000).

The structure has one half-molecule in the asymmetric unit (Z' = 1/2) with the molecule sitting on a crystallographic inversion centre, which is located in the middle of the Se–Se bond. The title compound (I) was obtained by a diselenide link, which is formed between Se1 and its symmetry equivalent at (3/4, 1/4, 1) (Fig. 1). The angle between the isoquinoline-1-selenol moiety and the phenyl ring is 14.92 (2)° indicating that the phenyl ring is twisted with respect to the isoquinoline-1-selenol backbone.

The crystal packing diagram does not have any significant weak intermolecular interactions whereas the herringbone-like packing of the structure (Fig.2) is supported by intermolecular π···π [Cg2···Cg2ii with the symmetry code ii = 5/2 - x, 1/2 - y, 2 - z.] stacking interactions with a shortest perpendicular distance between isochinoline groups of 3.514 Å, the slippage between these ring systems is 0.972 Å, the distance between the centroids of the six-membered carbon rings C4/C9 is 3.645 (3) Å. Similarly, another intermolecular π···π [Cg2···Cg3iii] stacking interaction with a shortest perpendicular distance of 3.768 Å between the two rings and the distance between the centroids of the six-membered carbon rings is 3.917 (3) Å with the symmetry code iii = 1-x,-y,-z. Cg2 and Cg3 are the centroids of C4/C9 ring and C10/C15 ring, respectively.

Experimental

A mixture of 1-chloro-3-phenylisoquinoline (1 mmol) and selenourea (1.1 mmol) in ethanol was vigorously stirred at ambient temperature for 2 hr. After completion of the reaction as indicated by TLC, solvent was removed and the reaction mixture was poured into water (10 ml) and the product was extracted using ethyl acetate (3X10 ml). The combined ethyl acetate extracts were concentrated in vacuo. The resulting crude product was directly charged onto a small silica gel column and eluted with a mixture of ethyl acetate/petroleum ether to get the final product of the diselenide title compound. Brown crystals of (I) were recrystalized from ethylacetate.

Refinement

All the H atoms in (I) were positioned geometrically and refined using a riding model with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms.

Figures

Fig. 1.
ORTEP diagram of molecule (I) with 50% probability displacement ellipsoids. The diselenide link is formed between Se1 and its symmetry equivalent at (3/4, 1/4, 1).
Fig. 2.
The crystal packing diagram of (I). The dotted lines indicate intermolecular π–π aromatic stacking interactions. All H atoms have been omitted for clarity. Cg2 and Cg3 are the centroids of the C4—C9 ring and C10—C15 ...

Crystal data

C30H20N2Se2F000 = 1128
Mr = 566.40Dx = 1.588 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 948 reflections
a = 11.2441 (17) Åθ = 2.3–24.6º
b = 17.559 (3) ŵ = 3.14 mm1
c = 13.248 (3) ÅT = 290 (2) K
β = 115.082 (2)ºBlock, brown
V = 2369.0 (8) Å30.20 × 0.14 × 0.11 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer2207 independent reflections
Radiation source: fine-focus sealed tube1516 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.040
T = 290(2) Kθmax = 25.5º
[var phi] and ω scansθmin = 2.3º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −13→13
Tmin = 0.585, Tmax = 0.703k = −21→19
8668 measured reflectionsl = −16→16

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.102  w = 1/[σ2(Fo2) + (0.0594P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2207 reflectionsΔρmax = 0.66 e Å3
158 parametersΔρmin = −0.22 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*/Ueq
Se10.85678 (4)0.23078 (2)1.05937 (3)0.0658 (2)
N10.8556 (3)0.35522 (16)0.9293 (2)0.0532 (7)
C10.9346 (4)0.3092 (2)1.0051 (3)0.0546 (9)
C20.9077 (3)0.41108 (19)0.8880 (3)0.0509 (9)
C31.0405 (4)0.4174 (2)0.9231 (3)0.0590 (10)
H31.07410.45500.89290.071*
C41.2651 (4)0.3718 (3)1.0436 (3)0.0732 (12)
H41.30180.40881.01530.088*
C51.3442 (4)0.3224 (3)1.1219 (4)0.0837 (13)
H51.43470.32511.14560.100*
C61.2919 (5)0.2680 (3)1.1666 (4)0.0815 (13)
H61.34740.23541.22180.098*
C71.1602 (5)0.2619 (2)1.1307 (3)0.0745 (12)
H71.12620.22431.16030.089*
C81.0740 (4)0.3116 (2)1.0490 (3)0.0556 (9)
C91.1271 (4)0.3676 (2)1.0047 (3)0.0562 (9)
C100.8121 (4)0.4607 (2)0.8015 (3)0.0523 (9)
C110.8492 (4)0.5283 (2)0.7693 (3)0.0617 (10)
H110.93600.54430.80560.074*
C120.7610 (4)0.5723 (2)0.6852 (3)0.0729 (12)
H120.78840.61720.66440.088*
C130.6320 (4)0.5498 (3)0.6320 (3)0.0755 (12)
H130.57240.57880.57380.091*
C140.5918 (5)0.4853 (3)0.6642 (4)0.0812 (13)
H140.50390.47110.62970.097*
C150.6803 (4)0.4402 (2)0.7479 (3)0.0678 (10)
H150.65150.39580.76860.081*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Se10.0824 (3)0.0453 (3)0.0779 (3)−0.0142 (2)0.0420 (2)0.00255 (19)
N10.0679 (19)0.0398 (17)0.0617 (18)−0.0123 (15)0.0370 (16)−0.0059 (15)
C10.071 (3)0.041 (2)0.060 (2)−0.0144 (19)0.036 (2)−0.0107 (19)
C20.066 (2)0.040 (2)0.058 (2)−0.0114 (17)0.0373 (18)−0.0113 (17)
C30.073 (3)0.055 (2)0.059 (2)−0.0138 (19)0.038 (2)−0.0005 (19)
C40.068 (3)0.085 (3)0.066 (3)−0.014 (2)0.028 (2)0.003 (2)
C50.070 (3)0.107 (4)0.068 (3)−0.009 (3)0.023 (2)−0.003 (3)
C60.084 (3)0.083 (3)0.064 (3)0.000 (3)0.018 (2)0.004 (2)
C70.089 (3)0.063 (3)0.073 (3)−0.011 (2)0.036 (3)0.002 (2)
C80.074 (3)0.047 (2)0.053 (2)−0.0104 (19)0.033 (2)−0.0098 (18)
C90.067 (2)0.056 (2)0.051 (2)−0.0148 (19)0.0311 (19)−0.0088 (18)
C100.069 (2)0.044 (2)0.057 (2)−0.0042 (18)0.040 (2)−0.0073 (17)
C110.074 (3)0.052 (2)0.076 (3)−0.0048 (19)0.048 (2)−0.003 (2)
C120.099 (3)0.055 (3)0.084 (3)0.007 (2)0.058 (3)0.012 (2)
C130.083 (3)0.079 (3)0.069 (3)0.015 (3)0.036 (3)0.005 (2)
C140.077 (3)0.087 (4)0.074 (3)−0.007 (3)0.027 (2)−0.001 (3)
C150.073 (3)0.059 (3)0.074 (3)−0.012 (2)0.034 (2)−0.006 (2)

Geometric parameters (Å, °)

Se1—C11.928 (4)C6—H60.9300
Se1—Se1i2.3439 (9)C7—C81.408 (5)
N1—C11.301 (4)C7—H70.9300
N1—C21.370 (4)C8—C91.402 (5)
C1—C81.422 (5)C10—C111.383 (5)
C2—C31.368 (5)C10—C151.392 (5)
C2—C101.478 (5)C11—C121.373 (5)
C3—C91.410 (5)C11—H110.9300
C3—H30.9300C12—C131.375 (5)
C4—C51.356 (6)C12—H120.9300
C4—C91.415 (5)C13—C141.354 (6)
C4—H40.9300C13—H130.9300
C5—C61.380 (6)C14—C151.381 (5)
C5—H50.9300C14—H140.9300
C6—C71.354 (6)C15—H150.9300
C1—Se1—Se1i92.40 (12)C9—C8—C1116.1 (3)
C1—N1—C2119.0 (3)C7—C8—C1125.2 (4)
N1—C1—C8124.9 (3)C8—C9—C3118.6 (3)
N1—C1—Se1117.5 (3)C8—C9—C4118.7 (4)
C8—C1—Se1117.6 (3)C3—C9—C4122.7 (4)
C3—C2—N1120.8 (3)C11—C10—C15117.3 (4)
C3—C2—C10123.1 (3)C11—C10—C2122.0 (3)
N1—C2—C10116.0 (3)C15—C10—C2120.7 (3)
C2—C3—C9120.6 (3)C12—C11—C10121.6 (4)
C2—C3—H3119.7C12—C11—H11119.2
C9—C3—H3119.7C10—C11—H11119.2
C5—C4—C9120.5 (4)C11—C12—C13119.8 (4)
C5—C4—H4119.7C11—C12—H12120.1
C9—C4—H4119.7C13—C12—H12120.1
C4—C5—C6120.7 (4)C14—C13—C12120.0 (4)
C4—C5—H5119.7C14—C13—H13120.0
C6—C5—H5119.7C12—C13—H13120.0
C7—C6—C5120.4 (4)C13—C14—C15120.6 (4)
C7—C6—H6119.8C13—C14—H14119.7
C5—C6—H6119.8C15—C14—H14119.7
C6—C7—C8121.0 (4)C14—C15—C10120.7 (4)
C6—C7—H7119.5C14—C15—H15119.7
C8—C7—H7119.5C10—C15—H15119.7
C9—C8—C7118.7 (4)
C2—N1—C1—C8−0.6 (5)C7—C8—C9—C40.1 (5)
C2—N1—C1—Se1−179.3 (2)C1—C8—C9—C4−178.8 (3)
Se1i—Se1—C1—N10.9 (3)C2—C3—C9—C8−0.1 (5)
Se1i—Se1—C1—C8−177.9 (3)C2—C3—C9—C4179.9 (3)
C1—N1—C2—C31.8 (5)C5—C4—C9—C80.3 (6)
C1—N1—C2—C10179.4 (3)C5—C4—C9—C3−179.7 (4)
N1—C2—C3—C9−1.5 (5)C3—C2—C10—C11−16.2 (5)
C10—C2—C3—C9−178.9 (3)N1—C2—C10—C11166.3 (3)
C9—C4—C5—C6−1.3 (7)C3—C2—C10—C15163.0 (3)
C4—C5—C6—C71.9 (7)N1—C2—C10—C15−14.5 (5)
C5—C6—C7—C8−1.5 (7)C15—C10—C11—C12−2.3 (5)
C6—C7—C8—C90.4 (6)C2—C10—C11—C12176.9 (3)
C6—C7—C8—C1179.2 (4)C10—C11—C12—C130.9 (6)
N1—C1—C8—C9−0.9 (5)C11—C12—C13—C141.5 (6)
Se1—C1—C8—C9177.8 (2)C12—C13—C14—C15−2.2 (7)
N1—C1—C8—C7−179.7 (3)C13—C14—C15—C100.7 (6)
Se1—C1—C8—C7−1.1 (5)C11—C10—C15—C141.6 (6)
C7—C8—C9—C3−179.9 (3)C2—C10—C15—C14−177.7 (3)
C1—C8—C9—C31.2 (5)

Symmetry codes: (i) −x+3/2, −y+1/2, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2124).

References

  • Bruker (2004). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Mugesh, G. & Singh, H. B. (2000). Chem. Soc. Rev.29, 347–357.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Sugie, S., Tanaka, T. & El-Bayoumy, K. (2000). J. Health. Sci.46, 422–425.
  • Watkin, D. J., Pearce, L. & Prout, C. K. (1993). CAMERON Chemical Crystallography Laboratory, University of Oxford, England.

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