The synthesis and crystal structure of 2-(chloro­selan­yl)pyridine 1-oxide: the first monomeric organoselenenyl chloride stabilized by an intra­molecular secondary Se⋯O inter­action

Askerov, R.K.; Matsulevich, Z.V.; Borisova, G.N.; Zalepkina, S.A.; Smirnov, V.F.; Grishina, M.M.; Dorovatovskii, P.V.; Borisov, A.V.; Khrustalev, V.N.

doi:10.1107/S2056989016018946

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Volume 72| Part 12| December 2016| Pages 1864-1866

https://doi.org/10.1107/S2056989016018946

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The synthesis and crystal structure of 2-(chloroselanyl)pyridine 1-oxide: the first monomeric organoselenenyl chloride stabilized by an intramolecular secondary Se⋯O interaction

^aDepartment of Chemistry, Baku State University, 23 Z. Khalilov St., Baku, AZ-1148, Azerbaijan, ^bR.E. Alekseev Nizhny Novgorod State Technical University, 24 Minin St., Nizhny Novgorod, 603950, Russian Federation, ^cN.I. Lobachevsky State University of Nizhny Novgorod, 23 Gagarin Prosp., Nizhny Novgorod, 603950, Russian Federation, ^dInorganic Chemistry Department, Peoples' Friendship University of Russia, 6 Miklukho-Maklay St., Moscow, 117198, Russian Federation, ^eNational Research Center "Kurchatov Institute", 1 Acad. Kurchatov Sq., Moscow, 123182, Russian Federation, and ^fX-Ray Structural Centre, A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov St., B–334, Moscow 119991, Russian Federation
^*Correspondence e-mail: vnkhrustalev@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 27 November 2016; accepted 27 November 2016; online 30 November 2016)

The title compound, C₅H₄ClNOSe, is the product of the reaction of sulfuryl chloride and 2-selanyl-1-pyridine 1-oxide in dichloromethane. The molecule has an almost planar geometry (r.m.s. deviation = 0.012 Å), and its molecular structure is stabilized by an intramolecular secondary Se⋯O interaction of 2.353 (3) Å, closing a four-membered N—C—Se⋯O ring. The title compound represents the first monomeric organoselenenyl chloride stabilized intramolecularly by an interaction of this type. The non-valent attractive Se⋯O interaction results in a substantial distortion of the geometry of the ipso-carbon atom. The endo-cyclic N—C—Se [102.1 (3)°] and exo-cyclic C—C—Se [136.9 (3)°] bond angles deviate significantly from the ideal value of 120° for an sp²-hybridized carbon atom, the former bond angle being much smaller than the latter. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming zigzag chains propagating along [010]. The chains, which stack along the a-axis direction, are linked by offset π–π interactions [intercentroid distance = 3.960 (3) Å], forming corrugated sheets parallel to the ab plane.

Keywords: crystal structure; synchrotron radiation; organoselenenyl chloride; intramolecular stabilization; secondary interactions.

CCDC reference: 1519449

1. Chemical context

Organoselenenyl halides RSeX (X = Cl, Br) play an important role in modern organic synthesis and are used as reagents for the functionalization of many classes of compounds, including organoselenium compounds with a broad spectrum of biological activities (Ranganathan et al., 2004 ; Selvakumar et al., 2010 , 2011 ; Ninomiya et al., 2011 ; Singh & Wirth, 2011 ; Zade & Singh, 2014 ; Elsherbini et al., 2016 ). An essential aspect of the chemistry of selenenyl halides is the factors responsible for the stability of these reagents (Coles, 2006 ; Mukherjee et al., 2010 ; Nakanishi et al., 2013 ; Takaluoma et al., 2015 ). Recently, we have developed a new effective method for the stabilization of heteroarenselenenyl and -tellurenyl chlorides by the transformation of them to T-shaped zwitterionic adducts with hydrochloric acid (Khrustalev et al., 2012 , 2014 , 2016 ). Moreover, we have established another stabilization method of heteroarenselenenyl and -tellurenyl chlorides by intermolecular secondary Ch⋯N (Ch = Se, Te) interactions with the formation of dimers (Borisov et al., 2010a ,b ,c ; Khrustalev et al., 2016). Herein, we report on the synthesis and structural characterization of the first monomeric 2-(chloroselanyl)pyridine 1-oxide stabilized by an intramolecular secondary Se⋯O interaction.

2. Structural commentary

The title compound, Fig. 1, is the product of the reaction of sulfuryl chloride and 2-selanyl-1-pyridine 1-oxide in dichloromethane. It has an almost planar geometry (r.m.s. deviation = 0.012 Å), and its molecular structure is stabilized by an intramolecular secondary Se1⋯O1 interaction of 2.353 (3) Å, closing the four-membered N1—C2—Se1⋯O1 ring (Fig. 1). The non-valent attractive Se1⋯O1 interaction results in the substantial distortion of the geometry of the ipso-C2 carbon atom. The endo-cyclic N1—C2—Se1 [102.1 (3)°] and exo-cyclic C3—C2—Se1 [136.9 (3)°] bond angles deviate significantly from the ideal value of 120° for an sp²-hybridized carbon atom, the former angle being much smaller than the latter. The title compound represents the first monomeric organoselenenyl chloride stabilized intramolecularly by an interaction of this type. Previously, the analogous stabilization of monomeric organoselenenyl chlorides by intramolecular secondary Se⋯S (Tiecco et al., 2006 ) and Se⋯N (Panda et al., 1999 ; Klapötke et al., 2004 ; Kulcsar et al., 2007 ; Pöllnitz et al., 2011 ) interactions have been reported.

Figure 1
The molecular structure of the title compound, with atom labelling and displacement ellipsoids drawn at the 50% probability level. The dashed line indicates the intramolecular secondary attractive Se1⋯O1 interaction.

3. Supramolecular features

In the crystal, molecules are linked by C—H⋯O hydrogen bonds (Table 1 and Fig. 2), forming zigzag chains propagating along the b-axis direction. The chains stack along the a-axis direction and are linked by offset π–π interactions, forming corrugated sheets parallel to the ab plane [Cg⋯Cg^i,ii = 3.960 (3) Å, Cg is the centroid of the N1/C2–C6 ring, interplanar distances = 3.590 (2) Å, slippages = 1.671 Å, symmetry codes: (i) x − 1, y, z; (ii) x + 1, y, z].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1ⁱ	0.95	2.34	3.101 (6)	137
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
The crystal packing of the title compound viewed along the a axis. The intramolecular secondary Se⋯O interactions and the intermolecular C—H⋯O hydrogen bonds are shown as dashed lines (see Table 1

4. Synthesis and crystallization

The synthesis of the title compound is illustrated in Fig. 3. It was synthesized according to the procedure described previously by Borisov et al. (2010a,b,c). A solution of sulfuryl chloride (0.27 g, 2 mmol) in dichloromethane (15 ml) was added to a solution of 2-selanyl-1-pyridine 1-oxide (0.35 g, 2 mmol) in dichloromethane (20 ml) at 293 K. After one h it was filtered to give the title compound (yield 0.33 g, 80%). The filtrate was evaporated in vacuo and recrystallization of the residue from dichloromethane solution gave an additional 0.06 g (15%) of the title compound. Colourless prismatic crystals of the title compound were obtained after recrystallization of the crude product from dichloromethane (m.p. 433–435 K). IR (KBr, cm⁻¹), ν 1617, 1462, 1423, 1254, 1151, 836, 748, 621. ¹H NMR (DMSO-d₆, 300 MHz, 300 K): δ = 8.28 (d, 1H, ³J = 5.9, H6); 7.52 (d, 1H, ³J = 7.3, H3); 7.43 (dd, 1H, ³J = 7.8, ³J = 7.3, H4); 7.30 (dd, 1H, ³J = 7.8, ³J = 5.9, H5). Analysis calculated for C₅H₄ClNOSe: C 24.81; H 1.93; N 6.72. Found: 24.43; H 1.83; N 6.65.

Figure 3
The synthesis of the title compound; the reaction of 2-selanyl-1-pyridine 1-oxide with sulfuryl chloride in dichloromethane.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were placed in calculated positions and refined as riding: C—H = 0.95 Å with U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₅H₄ClNOSe
M_r	208.50
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	3.9601 (8), 7.5102 (15), 22.350 (5)
β (°)	94.32 (3)
V (Å³)	662.8 (2)
Z	4
Radiation type	Synchrotron, λ = 0.96990 Å
μ (mm⁻¹)	13.68
Crystal size (mm)	0.05 × 0.03 × 0.03

Data collection
Diffractometer	Rayonix SX-165 CCD
Absorption correction	Multi-scan (SCALA; Evans, 2006 )
T_min, T_max	0.550, 0.660
No. of measured, independent and observed [I > 2σ(I)] reflections	5526, 1310, 1121
R_int	0.083
(sin θ/λ)_max (Å⁻¹)	0.636

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.175, 1.01
No. of reflections	1310
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.26, −1.58
Computer programs: Automar (MarXperts, 2015 ), iMosflm (Battye et al., 2011 ), SHELXS97 and SHELXTL (Sheldrick, 2008 ) and SHELXL2014/6 (Sheldrick, 2015 ).

Supporting information

CCDC reference: 1519449

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989016018946/su5337sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016018946/su5337Isup2.hkl

checkCIF report

Computing details top

Data collection: Automar (MarXperts, 2015); cell refinement: iMosflm (Battye et al., 2011); data reduction: iMosflm (Battye et al., 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

2-(Chloroselanyl)pyridine 1-oxide top

Crystal data top

C₅H₄ClNOSe	F(000) = 400
M_r = 208.50	D_x = 2.089 Mg m⁻³
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.96990 Å
a = 3.9601 (8) Å	Cell parameters from 600 reflections
b = 7.5102 (15) Å	θ = 5.0–35.0°
c = 22.350 (5) Å	µ = 13.68 mm⁻¹
β = 94.32 (3)°	T = 100 K
V = 662.8 (2) Å³	Prism, colourless
Z = 4	0.05 × 0.03 × 0.03 mm

Data collection top

Rayonix SX-165 CCD diffractometer	1121 reflections with I > 2σ(I)
/f scan	R_int = 0.083
Absorption correction: multi-scan (SCALA; Evans, 2006)	θ_max = 38.1°, θ_min = 5.0°
T_min = 0.550, T_max = 0.660	h = −4→4
5526 measured reflections	k = −9→9
1310 independent reflections	l = −28→28

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.074	H-atom parameters constrained
wR(F²) = 0.175	w = 1/[σ²(F_o²) + (0.06P)² + 1.6P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
1310 reflections	Δρ_max = 1.26 e Å⁻³
83 parameters	Δρ_min = −1.58 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: difference Fourier map	Extinction coefficient: 0.054 (3)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Se1	0.51523 (13)	0.26936 (7)	0.34782 (2)	0.02716 (17)
Cl1	0.4514 (3)	0.18592 (14)	0.44303 (4)	0.0331 (3)
O1	0.6571 (9)	0.4577 (4)	0.26942 (12)	0.0347 (8)
N1	0.7603 (10)	0.5643 (5)	0.31523 (14)	0.0290 (8)
C2	0.7093 (11)	0.4927 (5)	0.36941 (16)	0.0266 (9)
C3	0.7969 (12)	0.5838 (6)	0.42160 (17)	0.0301 (10)
H3	0.7578	0.5342	0.4596	0.036*
C4	0.9449 (14)	0.7515 (6)	0.4172 (2)	0.0334 (13)
H4	1.0115	0.8173	0.4524	0.040*
C5	0.9941 (12)	0.8213 (7)	0.36099 (19)	0.0343 (12)
H5	1.0906	0.9365	0.3579	0.041*
C6	0.9047 (14)	0.7257 (5)	0.3095 (2)	0.0317 (12)
H6	0.9436	0.7720	0.2710	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.0427 (4)	0.0202 (3)	0.0200 (3)	−0.00320 (19)	0.0117 (3)	−0.00209 (16)
Cl1	0.0522 (7)	0.0277 (5)	0.0208 (4)	−0.0077 (5)	0.0122 (4)	0.0037 (4)
O1	0.058 (2)	0.0284 (15)	0.0190 (12)	−0.0061 (14)	0.0139 (13)	−0.0045 (12)
N1	0.044 (2)	0.0265 (17)	0.0177 (14)	0.0022 (16)	0.0106 (13)	−0.0035 (13)
C2	0.041 (2)	0.0217 (19)	0.0183 (16)	0.0003 (18)	0.0111 (15)	−0.0008 (14)
C3	0.049 (3)	0.028 (2)	0.0144 (16)	−0.0006 (19)	0.0089 (16)	0.0008 (15)
C4	0.049 (3)	0.027 (2)	0.024 (2)	−0.0035 (19)	0.004 (2)	−0.0028 (15)
C5	0.051 (3)	0.026 (2)	0.0267 (19)	−0.002 (2)	0.0033 (19)	−0.0008 (19)
C6	0.048 (3)	0.0180 (18)	0.030 (2)	0.0009 (18)	0.009 (2)	0.0062 (15)

Geometric parameters (Å, º) top

Se1—C2	1.892 (4)	C3—H3	0.9500
Se1—Cl1	2.2506 (11)	C4—C5	1.389 (7)
O1—N1	1.339 (4)	C4—H4	0.9500
N1—C6	1.350 (6)	C5—C6	1.381 (6)
N1—C2	1.354 (5)	C5—H5	0.9500
C2—C3	1.374 (6)	C6—H6	0.9500
C3—C4	1.395 (6)

C2—Se1—Cl1	94.48 (11)	C5—C4—C3	119.6 (4)
O1—N1—C6	124.8 (3)	C5—C4—H4	120.2
O1—N1—C2	112.9 (3)	C3—C4—H4	120.2
C6—N1—C2	122.3 (4)	C6—C5—C4	120.9 (4)
N1—C2—C3	121.0 (4)	C6—C5—H5	119.6
N1—C2—Se1	102.1 (3)	C4—C5—H5	119.6
C3—C2—Se1	136.9 (3)	N1—C6—C5	118.1 (4)
C2—C3—C4	118.0 (4)	N1—C6—H6	120.9
C2—C3—H3	121.0	C5—C6—H6	120.9
C4—C3—H3	121.0

O1—N1—C2—C3	−179.4 (4)	Se1—C2—C3—C4	178.9 (4)
C6—N1—C2—C3	1.4 (7)	C2—C3—C4—C5	0.9 (7)
O1—N1—C2—Se1	0.7 (4)	C3—C4—C5—C6	−1.3 (8)
C6—N1—C2—Se1	−178.5 (4)	O1—N1—C6—C5	179.2 (4)
Cl1—Se1—C2—N1	−179.0 (3)	C2—N1—C6—C5	−1.7 (7)
Cl1—Se1—C2—C3	1.0 (5)	C4—C5—C6—N1	1.6 (8)
N1—C2—C3—C4	−1.0 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.95	2.34	3.101 (6)	137

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

Acknowledgements

The work was supported by the Ministry of Education of the Russian Federation (Agreement number 02.a03.21.0008 of June 24, 2016) and the Russian Foundation for Basic Research (Grant No. 14–03-00914).

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