4-Chloro­selanyl-3,5-diethyl-1H-pyrazol-2-ium chloride

Seredyuk, M.; Znovjyak, K.O.; Sliva, T.Y.; Haukka, M.; Fritsky, I.O.

doi:10.1107/S1600536811043790

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3083

doi:10.1107/S1600536811043790

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4-Chloroselanyl-3,5-diethyl-1H-pyrazol-2-ium chloride

Maksym Seredyuk,^a ^* Kateryna O. Znovjyak,^a Tetyana Yu. Sliva,^a Matti Haukka ^b and Igor O. Fritsky ^a

^aNational Taras Shevchenko University, Department of Chemistry, Volodymyrska Street 64, 01033 Kyiv, Ukraine, and ^bDepartment of Chemistry, University of Joensuu, PO Box 111, 80101 Joensuu, Finland
^*Correspondence e-mail: mcs@univ.kiev.ua

(Received 14 October 2011; accepted 21 October 2011; online 29 October 2011)

In the cation of the title compound, C₇H₁₂ClN₂Se⁺·Cl⁻, the ethylene groups and the Se–Cl fragment adopt a cis configuration with a C—Se—Cl angle of 96.09 (6)°. In the crystal, intermolecular N—H⋯Cl hydrogen bonds link two cations and two chlorine anions into centrosymmetric clusters. π–π interactions between the pyrazole rings [centroid–centroid distance of 3.530 (2) Å] link these clusters into columns along [001] with short intermolecular Se⋯Cl⁻ contacts of 2.995 (1) Å.

Related literature

For reviews of organoselenium chemistry, see: Krief (1995 ); Freudendahl et al. (2009 ). For structural studies of bis(1H-pyrazol-4-yl)selenides, see: Seredyuk, Fritsky et al. (2010 ). For structural studies of d-metal complexes of bis(1H-pyrazol-4-yl)selenides, see: Seredyuk et al. (2007 , 2009 ); Seredyuk, Moroz et al. (2010 ).

Experimental

Crystal data

C₇H₁₂ClN₂Se⁺·Cl⁻
M_r = 274.05
Monoclinic, P 2₁ /c
a = 8.1944 (6) Å
b = 19.3719 (10) Å
c = 7.1241 (3) Å
β = 111.025 (6)°
V = 1055.60 (10) Å³
Z = 4
Mo Kα radiation
μ = 4.01 mm⁻¹
T = 120 K
0.30 × 0.21 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008 ) T_min = 0.379, T_max = 0.699
13385 measured reflections
2423 independent reflections
2040 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.049
S = 1.04
2423 reflections
119 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1	0.82 (3)	2.22 (3)	3.0333 (19)	172 (3)
N2—H2⋯Cl1ⁱ	0.81 (3)	2.22 (3)	3.030 (2)	178 (2)
Symmetry code: (i) -x, -y, -z+3.

Data collection: COLLECT (Bruker–Nonius, 2004 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2003 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811043790/cv5179sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811043790/cv5179Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811043790/cv5179Isup3.cml

checkCIF report

Comment top

Aryl selenides are central reagents in organoselenium chemistry (Krief, 1995; Freudendahl et al., 2009). Pyrazole-based selenides are promising multidentate ligands for supramolecular frameworks and complexes of 3d-metals (Seredyuk et al., 2007; Seredyuk et al., 2009; Seredyuk, Moroz et al., 2010). As a part of our study of the bis(1H-pyrazol-4-yl)selenides (Seredyuk, Fritsky et al., 2010), we report the crystal structure of the title compound (Fig. 1).

In the title compound, between pairs of molecules of the compound strong N—H···Cl hydrogen bonds are observed with the distance N···Cl being 3.030 (2) and 3.0333 (19) Å (Table 1). The crystal packing exhibits π···π interactions between the pyrazol rings (centroid-centroid distance is 3.530 (2) Å) and short intermolecular Se···Cl^- contacts of 2.995 (1) Å.

Related literature top

For a review of organoselenium chemistry, see: Krief (1995); Freudendahl et al. (2009). For structural studies of bis(1H-pyrazol-4-yl)selenides, see: Seredyuk, Fritsky et al. (2010). For structural studies of d-metal complexes of bis(1H-pyrazol-4-yl)selenides, see: Seredyuk et al. (2007, 2009); Seredyuk, Moroz et al. (2010).

Experimental top

Mixture of 3,5-diethyl-1H-pyrazole (1.241 g, 10 mmol), selenium dioxide (1.670 g, 15 mmol) and pyridine (25 ml) was refluxed 6 h, after that pyridine was distilled off under reduced pressure. Syrup-like residue was dissolved in 20 ml of conc. HCl and put in a fridge at 4°C for one week. The obtained precipitate was filtered off and dried. In the obtained mixture, well formed orange crystals are the target compound, whereas yellowish crystals are hydrochloride of bis(3,5-diethyl-1H-pyrazol-4-yl)selenide. C₇H₁₂Cl₂N₂Se requires: C, 30.68; H, 4.41; N, 10.22. Found: C, 30.44; H, 4.54; N, 10.20.

Computing details top

Data collection: COLLECT (Bruker–Nonius, 2004); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The content of asymmetric part of the title compound showing the atomic numbering and 50% probability displacement ellipsoids. Dashed line denotes hydrogen bond.

4-Chloroselanyl-3,5-diethyl-1H-pyrazol-2-ium chloride top

Crystal data top

C₇H₁₂ClN₂Se⁺·Cl⁻	F(000) = 544
M_r = 274.05	D_x = 1.724 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3966 reflections
a = 8.1944 (6) Å	θ = 1.0–27.5°
b = 19.3719 (10) Å	µ = 4.01 mm⁻¹
c = 7.1241 (3) Å	T = 120 K
β = 111.025 (6)°	Block, orange
V = 1055.60 (10) Å³	0.30 × 0.21 × 0.10 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	2423 independent reflections
Radiation source: fine-focus sealed tube	2040 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.032
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 2.7°
ϕ scans and ω scans with κ offset	h = −10→10
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008)	k = −23→25
T_min = 0.379, T_max = 0.699	l = −9→9
13385 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0163P)² + 1.0004P] where P = (F_o² + 2F_c²)/3
2423 reflections	(Δ/σ)_max = 0.001
119 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₇H₁₂ClN₂Se⁺·Cl⁻	V = 1055.60 (10) Å³
M_r = 274.05	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1944 (6) Å	µ = 4.01 mm⁻¹
b = 19.3719 (10) Å	T = 120 K
c = 7.1241 (3) Å	0.30 × 0.21 × 0.10 mm
β = 111.025 (6)°

Data collection top

Nonius KappaCCD diffractometer	2423 independent reflections
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008)	2040 reflections with I > 2σ(I)
T_min = 0.379, T_max = 0.699	R_int = 0.032
13385 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.50 e Å⁻³
2423 reflections	Δρ_min = −0.38 e Å⁻³
119 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Se1	0.09775 (3)	0.154947 (11)	0.72449 (3)	0.01773 (7)
Cl1	−0.26973 (7)	−0.02283 (3)	1.32107 (8)	0.01820 (12)
Cl2	0.00330 (8)	0.25802 (3)	0.77369 (9)	0.02668 (14)
N1	−0.0543 (3)	0.06371 (10)	1.1409 (3)	0.0188 (4)
H1	−0.119 (4)	0.0437 (15)	1.188 (4)	0.040 (8)*
N2	0.1181 (3)	0.06797 (9)	1.2431 (3)	0.0192 (4)
H2	0.162 (3)	0.0557 (13)	1.359 (4)	0.023 (7)*
C1	0.0658 (3)	0.11191 (10)	0.9452 (3)	0.0144 (4)
C2	−0.0913 (3)	0.08920 (10)	0.9570 (3)	0.0158 (4)
C3	0.1960 (3)	0.09761 (10)	1.1294 (3)	0.0164 (4)
C4	−0.2731 (3)	0.09086 (12)	0.8111 (4)	0.0235 (5)
H4A	−0.3384	0.0512	0.8368	0.028*
H4B	−0.2718	0.0860	0.6733	0.028*
C5	−0.3658 (3)	0.15699 (13)	0.8246 (5)	0.0352 (6)
H5A	−0.3615	0.1634	0.9627	0.053*
H5B	−0.4880	0.1545	0.7333	0.053*
H5C	−0.3082	0.1960	0.7864	0.053*
C6	0.3877 (3)	0.10861 (12)	1.2043 (4)	0.0247 (5)
H6A	0.4335	0.0933	1.1001	0.030*
H6B	0.4428	0.0796	1.3251	0.030*
C7	0.4393 (3)	0.18281 (13)	1.2570 (4)	0.0353 (6)
H7A	0.3884	0.2117	1.1371	0.053*
H7B	0.5670	0.1869	1.3064	0.053*
H7C	0.3960	0.1982	1.3617	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.02534 (13)	0.01435 (11)	0.01690 (11)	−0.00085 (9)	0.01169 (9)	0.00111 (9)
Cl1	0.0180 (3)	0.0205 (3)	0.0173 (3)	0.0003 (2)	0.0077 (2)	0.0031 (2)
Cl2	0.0454 (4)	0.0144 (3)	0.0276 (3)	0.0047 (2)	0.0220 (3)	0.0042 (2)
N1	0.0212 (11)	0.0159 (9)	0.0228 (10)	−0.0016 (8)	0.0122 (9)	0.0014 (8)
N2	0.0281 (11)	0.0145 (9)	0.0156 (10)	0.0028 (8)	0.0084 (9)	0.0021 (8)
C1	0.0201 (11)	0.0097 (10)	0.0153 (10)	−0.0002 (8)	0.0086 (9)	−0.0004 (8)
C2	0.0209 (12)	0.0095 (9)	0.0194 (11)	0.0004 (8)	0.0101 (10)	−0.0010 (8)
C3	0.0218 (12)	0.0097 (10)	0.0178 (11)	0.0011 (8)	0.0072 (9)	−0.0030 (8)
C4	0.0181 (12)	0.0209 (12)	0.0307 (13)	−0.0004 (9)	0.0076 (10)	−0.0010 (10)
C5	0.0208 (12)	0.0229 (13)	0.0586 (18)	0.0025 (11)	0.0103 (12)	0.0011 (12)
C6	0.0196 (12)	0.0232 (12)	0.0276 (12)	0.0002 (10)	0.0039 (10)	−0.0023 (10)
C7	0.0311 (15)	0.0263 (13)	0.0429 (16)	−0.0088 (11)	0.0063 (13)	−0.0067 (12)

Geometric parameters (Å, º) top

Se1—C1	1.8793 (19)	C4—H4A	0.9900
Se1—Cl2	2.2144 (6)	C4—H4B	0.9900
N1—C2	1.329 (3)	C5—H5A	0.9800
N1—N2	1.339 (3)	C5—H5B	0.9800
N1—H1	0.82 (3)	C5—H5C	0.9800
N2—C3	1.328 (3)	C6—C7	1.507 (3)
N2—H2	0.81 (3)	C6—H6A	0.9900
C1—C3	1.390 (3)	C6—H6B	0.9900
C1—C2	1.391 (3)	C7—H7A	0.9800
C2—C4	1.480 (3)	C7—H7B	0.9800
C3—C6	1.482 (3)	C7—H7C	0.9800
C4—C5	1.510 (3)

C1—Se1—Cl2	96.09 (6)	C5—C4—H4B	109.2
C2—N1—N2	109.64 (18)	H4A—C4—H4B	107.9
C2—N1—H1	129 (2)	C4—C5—H5A	109.5
N2—N1—H1	121 (2)	C4—C5—H5B	109.5
C3—N2—N1	109.82 (19)	H5A—C5—H5B	109.5
C3—N2—H2	128.2 (18)	C4—C5—H5C	109.5
N1—N2—H2	121.9 (18)	H5A—C5—H5C	109.5
C3—C1—C2	107.06 (18)	H5B—C5—H5C	109.5
C3—C1—Se1	126.01 (16)	C3—C6—C7	113.1 (2)
C2—C1—Se1	126.93 (16)	C3—C6—H6A	109.0
N1—C2—C1	106.75 (19)	C7—C6—H6A	109.0
N1—C2—C4	121.10 (19)	C3—C6—H6B	109.0
C1—C2—C4	132.13 (19)	C7—C6—H6B	109.0
N2—C3—C1	106.72 (19)	H6A—C6—H6B	107.8
N2—C3—C6	121.5 (2)	C6—C7—H7A	109.5
C1—C3—C6	131.8 (2)	C6—C7—H7B	109.5
C2—C4—C5	112.1 (2)	H7A—C7—H7B	109.5
C2—C4—H4A	109.2	C6—C7—H7C	109.5
C5—C4—H4A	109.2	H7A—C7—H7C	109.5
C2—C4—H4B	109.2	H7B—C7—H7C	109.5

C2—N1—N2—C3	1.3 (2)	N1—N2—C3—C6	−179.63 (18)
Cl2—Se1—C1—C3	−101.57 (18)	C2—C1—C3—N2	0.0 (2)
Cl2—Se1—C1—C2	77.53 (18)	Se1—C1—C3—N2	179.22 (14)
N2—N1—C2—C1	−1.3 (2)	C2—C1—C3—C6	178.7 (2)
N2—N1—C2—C4	179.96 (18)	Se1—C1—C3—C6	−2.1 (3)
C3—C1—C2—N1	0.8 (2)	N1—C2—C4—C5	90.0 (3)
Se1—C1—C2—N1	−178.43 (15)	C1—C2—C4—C5	−88.4 (3)
C3—C1—C2—C4	179.4 (2)	N2—C3—C6—C7	−105.4 (3)
Se1—C1—C2—C4	0.1 (3)	C1—C3—C6—C7	76.0 (3)
N1—N2—C3—C1	−0.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.82 (3)	2.22 (3)	3.0333 (19)	172 (3)
N2—H2···Cl1ⁱ	0.81 (3)	2.22 (3)	3.030 (2)	178 (2)

Symmetry code: (i) −x, −y, −z+3.

Experimental details

Crystal data
Chemical formula	C₇H₁₂ClN₂Se⁺·Cl⁻
M_r	274.05
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	8.1944 (6), 19.3719 (10), 7.1241 (3)
β (°)	111.025 (6)
V (Å³)	1055.60 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.01
Crystal size (mm)	0.30 × 0.21 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (XPREP in SHELXTL; Sheldrick, 2008)
T_min, T_max	0.379, 0.699
No. of measured, independent and observed [I > 2σ(I)] reflections	13385, 2423, 2040
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.049, 1.04
No. of reflections	2423
No. of parameters	119
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.38

Computer programs: COLLECT (Bruker–Nonius, 2004), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR2004 (Burla et al., 2003), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.82 (3)	2.22 (3)	3.0333 (19)	172 (3)
N2—H2···Cl1ⁱ	0.81 (3)	2.22 (3)	3.030 (2)	178 (2)

Symmetry code: (i) −x, −y, −z+3.

References

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doi:10.1107/S1600536811043790

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