Mesityl­selenenyl iodide

organic papers

o350

Structure Reports Online

ISSN 1600-5368

Mesitylselenenyl iodide

JoÈrg Jeske, Peter G. Jones,* Andreas Martens-von Salzen and Wolf-Walther du Mont

Institut fuÈr Anorganische und Analytische Chemie, Technische UniversitaÈt Braunschweig, Postfach 3329, 38023 Braunschweig, Germany

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 178 K

Mean(C±C) = 0.010 AÊ

Rfactor = 0.038

wRfactor = 0.109

Data-to-parameter ratio = 17.6

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

The title compound, C9H11ISe, displays the following

dimen-sions involving selenium: SeÐI 2.5360 (11) AÊ, SeÐC1 1.923 (6) AÊ and CÐSeÐI 100.2 (2)_{. Short Se I and I I}

contacts link the molecules into ribbons parallel to thebaxis.

Comment

We are interested in the structural chemistry of organosel-enium derivatives. The ®rst selenenyl iodide, 2,4,6-tri-tert -butylphenylselenenyl iodide, was synthesized and character-ized by X-ray structure analysis by du Montet al. (1987). It displayed crystallographic mirror symmetry, with SeÐI = 2.529 (1) AÊ, SeÐC = 1.941 (3) AÊ and CÐSeÐI = 97.5 (1)_{. A}

search of the Cambridge Structural Database (version of October 2001; Allen & Kennard, 1993) revealed no other neutral selenenyl iodides, although two structures described as such contain very short intramolecular Se N contacts of 2.242 (5) and 2.074 (6) AÊ that we would prefer to describe as genuine bonds, thus making the selenium three-coordinate (Pandaet al., 1993; Mugeshet al., 1999).

We present here the structure of mesitylselenenyl iodide, (I), which we have previously described brie¯y in a review of selenium±iodine contacts (du Montet al., 2001). The molecule, which has no crystallographically imposed symmetry, is shown in Fig. 1. The geometry at selenium is essentially the same as in the structure of du Mont et al. (1987), with SeÐI = 2.5360 (11) AÊ, SeÐC1 = 1.923 (6) AÊ and CÐSeÐI 100.2 (2)_.

The SeÐI bond is not symmetrically disposed with respect to the ring; the relevant torsion angles are ÿ99.3 (5) and 84.4 (5)_.

The molecular packing (Fig. 2) involves the following short contacts: I Iii_{and I I}iii_{3.840 (1) AÊ, and Se I}iv_{3.839 (2) AÊ}

(symmetry codes: see Table 1). The overall effect is to form a ribbon parallel to the b axis. Appreciably shorter Se I contacts were observed in the 2:1 adduct between

triisopropylphenyl) diselenide and molecular iodine [3.483 (1) AÊ; du Mont et al., 1990]. The selenenyl iodide structure of du Montet al.(1987) involves no such contacts (no Se I < 5.7 AÊ).

Experimental

Dimesityl diselenide was allowed to react with the equivalent amount of elemental iodine in dichloromethane to form the title compound. Single crystals were obtained by slow evaporation of the solution.

Crystal data C9H11ISe Mr= 325.04

Monoclinic,P21=c a= 13.964 (5) AÊ

b= 4.606 (2) AÊ

c= 16.214 (6) AÊ = 99.87 (3)

V= 1027.5 (7) AÊ3 Z= 4

Dx= 2.101 Mg mÿ3

MoKradiation Cell parameters from 50

re¯ections = 10±11.5

= 6.60 mmÿ1 T= 178 (2) K Needle, dark red 0.600.200.05 mm Data collection

NicoletP3 diffractometer !scans

Absorption correction: scan (XEMP; Siemens 1994)

Tmin= 0.590,Tmax= 0.932 5385 measured re¯ections 1811 independent re¯ections 1442 re¯ections withI> 2(I)

Rint= 0.069 max= 25.1 h=ÿ16!16

k=ÿ5!3

l=ÿ19!19 3 standard re¯ections

every 147 re¯ections intensity decay: none Re®nement

Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.038} wR(F2_{) = 0.109} S= 1.19 1811 re¯ections 103 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0519P)2

+ 0.8646P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001 max= 1.09 e AÊÿ3 min=ÿ1.32 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_). IÐSe 2.5360 (11) I Sei _{3.8393 (15)}

I Iii _{3.8398 (13)}

I Iiii _{3.8398 (13)}

SeÐC1 1.923 (6) Se Iiv _{3.8393 (15)}

SeÐI Sei _{90.13 (4)}

SeÐI Iii _{169.63 (3)}

Sei _{I I}ii _{86.00 (3)}

SeÐI Iiii _{108.72 (4)}

Sei _{I I}iii _{158.68 (2)}

Iii _{I I}iii _{73.71 (3)}

C1ÐSeÐI 100.21 (18) C1ÐSe Iiv _{163.54 (19)}

IÐSe Iiv _{90.13 (4)}

Symmetry codes: (i) x;yÿ1;z; (ii) ÿx;yÿ1

2;12ÿz; (iii) ÿx;12‡y;12ÿz; (iv)

x;1‡y;z.

H atoms at C7 and C9 were included using rigid methyl groups, and at C8 a rigid, ideally disordered methyl group with components mutually rotated by 60_{; starting positions were taken from difference}

syntheses and then allowed to rotate but not tip. Other H atoms were included, using a riding model, starting from calculated positions. The maximum features of residual electron density areca1 AÊ from the Se and I atoms and can probably be ascribed to residual absorption errors.

Data collection:P3Software(Nicolet, 1987); cell re®nement:P3

Software; data reduction:XDISK(Nicolet, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:

XP(Siemens, 1994); software used to prepare material for publica-tion:SHELXL97.

We thank the Fonds der Chemischen Industrie for ®nancial support and Mr A. Weinkauf for technical assistance.

References

Allen, F. H. & Kennard, O. (1993).Chem. Des. Autom. News,8, 1, 31±37. Mont, W.-W. du, Kubiniok, S., Peters, K. & von Schnering, H. G. (1987).

Angew. Chem. Int. Ed. Engl.26, 780±781.

Acta Cryst.(2002). E58, o350±o352 JoÈrg Jeskeet al. C₉H₁₁ISe

o351

organic papers

Figure 2

Packing diagram of the title compound. I I and Se I contacts are indicated by broken lines. H atoms have been omitted for clarity. Figure 1

organic papers

o352

Mont, W.-W. du, Martens, A., Pohl, S. & Saak, W. (1990).Inorg. Chem.29, 4847±4848.

Mont, W.-W. du, Martens-von Salzen, A., Ruthe, F., SeppaÈlaÈ, E., Mugesh, G., Devillanova, F. A., Lippolis, V. & Kuhn, N. (2001).J. Organomet. Chem.623, 14±28.

Mugesh, G., Singh, H. B. & Butcher, R. J. (1999).Tetrahedron Asymmetry,10, 237±242.

Nicolet (1987).P3Software. Nicolet Analytical X-ray Instruments, Madison, Wisconsin, USA.

Panda, A., Mugesh, G., Singh, H. B. & Butcher, R. J. (1993).Organometallics, 18, 1986±1993.

Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.

Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Siemens (1994). XEMPand XP(Version 5.03). Siemens Analytical X-ray

supporting information

sup-1 Acta Cryst. (2002). E58, o350–o352

supporting information

Acta Cryst. (2002). E58, o350–o352 [https://doi.org/10.1107/S1600536802003677]

Mesitylselenenyl iodide

J

ö

rg Jeske, Peter G. Jones, Andreas Martens-von Salzen and Wolf-Walther du Mont

mesitylselenenyl iodide

Crystal data

C9H11ISe Mr = 325.04 Monoclinic, P21/c a = 13.964 (5) Å

b = 4.606 (2) Å

c = 16.214 (6) Å

β = 99.87 (3)°

V = 1027.5 (7) Å3 Z = 4

F(000) = 608

Dx = 2.101 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 50 reflections

θ = 10–11.5°

µ = 6.60 mm−1 T = 178 K Needle, dark red 0.6 × 0.2 × 0.05 mm

Data collection

Nicolet P3 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: ψ scan (XEMP; Siemens 1994)

Tmin = 0.590, Tmax = 0.932

5385 measured reflections

1811 independent reflections 1442 reflections with I > 2σ(I)

Rint = 0.069

θmax = 25.1°, θmin = 3.6° h = −16→16

k = −5→3

l = −19→19

3 standard reflections every 147 reflections intensity decay: none

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.038} wR(F2_{) = 0.109} S = 1.19 1811 reflections 103 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) + (0.0519P)2 + 0.8646P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 1.09 e Å−3

Δρmin = −1.32 e Å−3

Special details

Experimental. mesitylselenenyl iodide

supporting information

sup-2 Acta Cryst. (2002). E58, o350–o352

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 Occ. (<1)

I 0.09448 (4) 0.21646 (10) 0.21344 (3) 0.0397 (2)

Se 0.20453 (6) 0.52063 (16) 0.13871 (4) 0.0435 (2)

C1 0.2510 (5) 0.2277 (13) 0.0709 (4) 0.0297 (14)

C2 0.1949 (5) 0.1555 (15) −0.0061 (4) 0.0317 (14)

C3 0.2325 (5) −0.0386 (15) −0.0562 (4) 0.0377 (16)

H3 0.1945 −0.0923 −0.1082 0.045*

C4 0.3240 (6) −0.1589 (16) −0.0335 (4) 0.0400 (17)

C5 0.3775 (5) −0.0832 (18) 0.0439 (5) 0.0448 (18)

H5 0.4405 −0.1639 0.0604 0.054*

C6 0.3420 (5) 0.1056 (16) 0.0975 (4) 0.0374 (15)

C7 0.0935 (5) 0.2757 (16) −0.0347 (5) 0.0427 (18)

H7A 0.0658 0.1912 −0.0890 0.064*

H7B 0.0969 0.4872 −0.0400 0.064*

H7C 0.0523 0.2262 0.0065 0.064*

C8 0.3644 (7) −0.3616 (19) −0.0916 (6) 0.063 (3)

H8A 0.4353 −0.3685 −0.0763 0.095* 0.50

H8B 0.3465 −0.2920 −0.1493 0.095* 0.50

H8C 0.3376 −0.5565 −0.0871 0.095* 0.50

H8D 0.3109 −0.4428 −0.1321 0.095* 0.50

H8E 0.3998 −0.5194 −0.0591 0.095* 0.50

H8F 0.4087 −0.2548 −0.1214 0.095* 0.50

C9 0.4026 (7) 0.174 (2) 0.1806 (5) 0.058 (2)

H9A 0.4614 0.0537 0.1887 0.087*

H9B 0.3652 0.1335 0.2252 0.087*

H9C 0.4210 0.3796 0.1823 0.087*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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sup-3 Acta Cryst. (2002). E58, o350–o352

Geometric parameters (Å, º)

I—Se 2.5360 (11) C5—H5 0.9500

I—Sei _{3.8393 (15) C6—C9 1.496 (10)}

I—Iii _{3.8398 (13) C7—H7A 0.9800}

I—Iiii _{3.8398 (13) C7—H7B 0.9800}

Se—C1 1.923 (6) C7—H7C 0.9800

Se—Iiv _{3.8393 (15) C8—H8A 0.9800}

C1—C6 1.389 (10) C8—H8B 0.9800

C1—C2 1.395 (9) C8—H8C 0.9800

C2—C3 1.371 (9) C8—H8D 0.9800

C2—C7 1.517 (10) C8—H8E 0.9800

C3—C4 1.383 (11) C8—H8F 0.9800

C3—H3 0.9500 C9—H9A 0.9800

C4—C5 1.391 (11) C9—H9B 0.9800

C4—C8 1.502 (10) C9—H9C 0.9800

C5—C6 1.380 (11)

Se—I—Sei _{90.13 (4) C1—C6—C9 122.8 (7)}

Se—I—Iii _{169.63 (3) C2—C7—H7A 109.5}

Sei_—I—Iii _{86.00 (3) C2—C7—H7B 109.5}

Se—I—Iiii _{108.72 (4) H7A—C7—H7B 109.5}

Sei_—I—Iiii _{158.68 (2) C2—C7—H7C 109.5}

Iii_—I—Iiii _{73.71 (3) H7A—C7—H7C 109.5}

C1—Se—I 100.21 (18) H7B—C7—H7C 109.5

C1—Se—Iiv _{163.54 (19) C4—C8—H8A 109.5}

I—Se—Iiv _{90.13 (4) C4—C8—H8B 109.5}

C6—C1—C2 121.7 (6) H8A—C8—H8B 109.5

C6—C1—Se 119.1 (5) C4—C8—H8C 109.5

C2—C1—Se 119.1 (5) H8A—C8—H8C 109.5

C3—C2—C1 118.1 (6) H8B—C8—H8C 109.5

C3—C2—C7 119.3 (6) C4—C8—H8D 109.5

C1—C2—C7 122.5 (6) C4—C8—H8E 109.5

C2—C3—C4 122.3 (7) H8D—C8—H8E 109.5

C2—C3—H3 118.8 C4—C8—H8F 109.5

C4—C3—H3 118.8 H8D—C8—H8F 109.5

C3—C4—C5 117.9 (7) H8E—C8—H8F 109.5

C3—C4—C8 120.7 (7) C6—C9—H9A 109.5

C5—C4—C8 121.3 (8) C6—C9—H9B 109.5

C6—C5—C4 122.1 (7) H9A—C9—H9B 109.5

C6—C5—H5 119.0 C6—C9—H9C 109.5

C4—C5—H5 119.0 H9A—C9—H9C 109.5

C5—C6—C1 117.9 (6) H9B—C9—H9C 109.5

C5—C6—C9 119.4 (7)

Sei_{—I—Se—C1 12.9 (2) Se—C1—C2—C7 −6.7 (9)}

Iii_{—I—Se—C1 −55.1 (3) C1—C2—C3—C4 −1.2 (10)}

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sup-4 Acta Cryst. (2002). E58, o350–o352

Sei_{—I—Se—I}iv _{180.0 C2—C3—C4—C5 1.6 (10)}

Iii_{—I—Se—I}iv _{112.05 (14) C2—C3—C4—C8 −177.5 (7)}

Iiii_{—I—Se—I}iv _{10.15 (3) C3—C4—C5—C6 0.0 (10)}

I—Se—C1—C6 −99.3 (5) C8—C4—C5—C6 179.2 (7)

Iiv_{—Se—C1—C6 132.6 (6) C4—C5—C6—C1 −2.0 (10)}

I—Se—C1—C2 84.4 (5) C4—C5—C6—C9 178.9 (7)

Iiv_{—Se—C1—C2 −43.7 (10) C2—C1—C6—C5 2.4 (10)}

C6—C1—C2—C3 −0.8 (10) Se—C1—C6—C5 −173.8 (5)

Se—C1—C2—C3 175.4 (5) C2—C1—C6—C9 −178.5 (7)

C6—C1—C2—C7 177.1 (6) Se—C1—C6—C9 5.3 (9)