3-(Pyridin-4-yl­thio)­pentane-2,4-dione

Zhang, Q.-F.; Pang, J.-D.; Sun, D.-Z.; Liu, C.-H.

doi:10.1107/S1600536811011330

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o1023

doi:10.1107/S1600536811011330

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3-(Pyridin-4-ylthio)pentane-2,4-dione

Qing-Fu Zhang,^a ^* Jian-Dong Pang,^a De-Zhi Sun ^a and Cai-Hua Liu ^a

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China
^*Correspondence e-mail: zhangqingfu@foxmail.com

(Received 24 March 2011; accepted 27 March 2011; online 31 March 2011)

In the title compound, C₁₀H₁₁NO₂S, the acetylacetone group crystallizes in the keto form with all the non-hydrogen atoms in the acetylacetone group approximately co-planar with a maximum atomic deviation 0.055 (2) Å; the dihedral angle between the acetylacetone group and the pyridine ring is 85.90 (6)°. An intramolecular O—H⋯O hydrogen bond involving the acetylacetone group forms a six-membered ring.

Related literature

For applications of β-diketones and their derivatives in metallo-supramolecular chemistry, see: Aromí et al. (2008 ); Chen et al. (2003 ; 2004 ); Domasevitch et al. (2006 ); Massue et al. (2005 ); Soldatov & Ripmeester (2001 ); Tabellion et al. (2001 ); Vigato et al. (2009 ); Vreshch et al. (2003 , 2004 ); Won et al. (2007 ); Zhang et al. (2006 ).

Experimental

Crystal data

C₁₀H₁₁NO₂S
M_r = 209.26
Monoclinic, P 2₁ /c
a = 8.3273 (7) Å
b = 9.5614 (8) Å
c = 13.0681 (11) Å
β = 92.698 (1)°
V = 1039.34 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 298 K
0.35 × 0.30 × 0.28 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.907, T_max = 0.925
5011 measured reflections
1822 independent reflections
1351 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.120
S = 1.06
1822 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.88	1.58	2.427 (3)	161

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011330/zj2007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011330/zj2007Isup2.hkl

checkCIF report

Comment top

The β-diketones and their derivatives have attracted much attention in recent years, not only for their valuable intrinsic chemical and physical properties but also for their wide applications in metallo-supramolecular chemistry (Aromí & Gamez et al.,2008; Massue & Bellec et al., 2005; Soldatov & Ripmeester, 2001; Tabellion & Seidel et al., 2001; Vigato & Peruzzo et al., 2009; Chen & Fronczek et al.,2003; Chen & Fronczek et al.,2004; Domasevitch & Vreshch, et al., 2006; Vreshch & Chernega et al. 2003; Vreshch & Lysenko et al. 2004; Won & Clegg et al.,2007; Zhang & Chen et al., 2006). Among them, the N-containing bifunctional derivatives of β-diketones have been successfully applied to construct various metal-organic supramolecular complexes (Chen & Fronczek et al.,2003; Chen & Fronczek et al.,2004; Domasevitch & Vreshch, et al., 2006; Vreshch & Chernega et al. 2003; Vreshch & Lysenko et al. 2004; Won & Clegg et al.,2007; Zhang & Chen et al., 2006). We report here on the structure of an interesting nonlinear N-containing bifunctional compound, 3-(pyridin-4-ylthio)pentane-2,4-dione, which is prepared according to the previously reported methord (Won & Clegg et al.,2007).

As shown in Fig. 1, the acetylacetone group is with keto-enol tautomerism, where all the non-hydrogen atoms in the acetylacetone group are approximately co-planar with a maximum atomic deviation 0.0547 (24) Å, and the dihedral angle between the acetylacetone group and the pyridine ring is about of 85.90 (6)°. The bond angle of C3—S1—C6 is about of 105.16 (10)°, leading to a V-shaped conformation of the whole molecule. In the crystal strucutre, the intramolecular O—H···O hydrogen bonding interactions have been found in the same acetylacetone group, forming a six-membered cyclic structure. However, no intermolecular H-bonding interactions have been found in the title comound (Fig. 2).

Related literature top

For applications of β-diketones and their derivatives in metallo-supramolecular chemistry, see: Aromí et al. (2008); Chen et al. (2003; 2004); Domasevitch et al. (2006); Massue et al. (2005); Soldatov & Ripmeester (2001); Tabellion et al. (2001); Vigato et al. (2009); Vreshch et al. (2003, 2004); Won et al. (2007); Zhang et al. (2006).

Experimental top

The title compound, 3-(pyridin-4-ylthio)pentane-2,4-dione, was prepared according to the previously reported method (Won & Clegg et al.,2007). The yellow crystals of title compound suitable for X-ray crystallographic analysis were obtained by recrystallization from acetonitrile.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids.
	Fig. 2. The packing diagram of the title compound.

3-(Pyridin-4-ylthio)pentane-2,4-dione top

Crystal data top

C₁₀H₁₁NO₂S	F(000) = 440
M_r = 209.26	D_x = 1.337 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2174 reflections
a = 8.3273 (7) Å	θ = 2.5–27.3°
b = 9.5614 (8) Å	µ = 0.28 mm⁻¹
c = 13.0681 (11) Å	T = 298 K
β = 92.698 (1)°	Block, yellow
V = 1039.34 (15) Å³	0.35 × 0.30 × 0.28 mm
Z = 4

Data collection top

Siemens SMART CCD area-detector diffractometer	1822 independent reflections
Radiation source: fine-focus sealed tube	1351 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
phi and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.907, T_max = 0.925	k = −5→11
5011 measured reflections	l = −15→15

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)] = 0.038	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.0562P)² + 0.3241P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1822 reflections	Δρ_max = 0.17 e Å⁻³
130 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.136 (9)

Crystal data top

C₁₀H₁₁NO₂S	V = 1039.34 (15) Å³
M_r = 209.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3273 (7) Å	µ = 0.28 mm⁻¹
b = 9.5614 (8) Å	T = 298 K
c = 13.0681 (11) Å	0.35 × 0.30 × 0.28 mm
β = 92.698 (1)°

Data collection top

Siemens SMART CCD area-detector diffractometer	1822 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1351 reflections with I > 2σ(I)
T_min = 0.907, T_max = 0.925	R_int = 0.030
5011 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.06	Δρ_max = 0.17 e Å⁻³
1822 reflections	Δρ_min = −0.19 e Å⁻³
130 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
S1	0.87871 (8)	0.22005 (6)	0.95516 (6)	0.0688 (3)
O1	0.7336 (2)	0.60208 (19)	1.01493 (15)	0.0761 (6)
H1	0.7715	0.6213	0.9547	0.091*
O2	0.8608 (2)	0.60632 (19)	0.85162 (14)	0.0769 (6)
N1	0.4443 (3)	−0.0271 (2)	0.83293 (19)	0.0714 (6)
C1	0.6930 (4)	0.3985 (4)	1.1103 (2)	0.0863 (9)
H1A	0.7813	0.3688	1.1550	0.129*
H1B	0.6305	0.3185	1.0886	0.129*
H1C	0.6266	0.4623	1.1461	0.129*
C2	0.7557 (3)	0.4691 (3)	1.01961 (19)	0.0566 (6)
C3	0.8327 (3)	0.3980 (2)	0.94164 (17)	0.0495 (6)
C4	0.8804 (3)	0.4736 (3)	0.85562 (18)	0.0580 (6)
C5	0.9512 (4)	0.4065 (4)	0.7658 (2)	0.0890 (10)
H5A	1.0051	0.4759	0.7269	0.133*
H5B	0.8674	0.3639	0.7235	0.133*
H5C	1.0270	0.3363	0.7889	0.133*
C6	0.7057 (3)	0.1310 (2)	0.90682 (16)	0.0466 (5)
C7	0.7102 (3)	−0.0134 (2)	0.90713 (19)	0.0584 (6)
H7	0.8011	−0.0607	0.9327	0.070*
C8	0.5786 (3)	−0.0856 (3)	0.8692 (2)	0.0730 (8)
H8	0.5843	−0.1827	0.8690	0.088*
C9	0.4412 (3)	0.1119 (3)	0.8347 (2)	0.0630 (7)
H9	0.3474	0.1561	0.8107	0.076*
C10	0.5674 (3)	0.1949 (2)	0.86962 (18)	0.0542 (6)
H10	0.5591	0.2919	0.8680	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0565 (4)	0.0432 (4)	0.1043 (6)	0.0034 (3)	−0.0216 (3)	−0.0036 (3)
O1	0.0818 (13)	0.0532 (11)	0.0934 (14)	0.0072 (9)	0.0045 (10)	−0.0142 (9)
O2	0.0901 (14)	0.0563 (11)	0.0827 (13)	−0.0179 (10)	−0.0131 (10)	0.0166 (9)
N1	0.0674 (14)	0.0546 (13)	0.0923 (17)	−0.0155 (11)	0.0029 (12)	−0.0121 (11)
C1	0.090 (2)	0.095 (2)	0.0750 (19)	−0.0214 (18)	0.0168 (15)	−0.0053 (16)
C2	0.0498 (13)	0.0525 (14)	0.0668 (15)	−0.0059 (10)	−0.0058 (11)	−0.0064 (11)
C3	0.0459 (12)	0.0407 (12)	0.0610 (14)	−0.0075 (9)	−0.0053 (10)	−0.0053 (10)
C4	0.0484 (13)	0.0634 (16)	0.0614 (15)	−0.0137 (11)	−0.0080 (11)	−0.0028 (12)
C5	0.080 (2)	0.116 (3)	0.0717 (19)	−0.0176 (18)	0.0129 (15)	−0.0173 (17)
C6	0.0502 (13)	0.0403 (12)	0.0495 (12)	−0.0014 (9)	0.0039 (9)	−0.0023 (9)
C7	0.0605 (15)	0.0398 (12)	0.0751 (16)	0.0029 (10)	0.0060 (12)	0.0046 (11)
C8	0.076 (2)	0.0402 (13)	0.103 (2)	−0.0097 (13)	0.0085 (16)	−0.0015 (13)
C9	0.0570 (14)	0.0594 (16)	0.0720 (16)	−0.0022 (12)	−0.0043 (12)	−0.0048 (12)
C10	0.0577 (14)	0.0413 (12)	0.0630 (14)	−0.0010 (10)	−0.0044 (11)	−0.0041 (10)

Geometric parameters (Å, º) top

S1—C3	1.752 (2)	C4—C5	1.484 (4)
S1—C6	1.764 (2)	C5—H5A	0.9600
O1—C2	1.286 (3)	C5—H5B	0.9600
O1—H1	0.8814	C5—H5C	0.9600
O2—C4	1.280 (3)	C6—C10	1.373 (3)
N1—C8	1.318 (3)	C6—C7	1.381 (3)
N1—C9	1.330 (3)	C7—C8	1.368 (4)
C1—C2	1.480 (4)	C7—H7	0.9300
C1—H1A	0.9600	C8—H8	0.9300
C1—H1B	0.9600	C9—C10	1.378 (3)
C1—H1C	0.9600	C9—H9	0.9300
C2—C3	1.404 (3)	C10—H10	0.9300
C3—C4	1.409 (3)

C3—S1—C6	105.16 (10)	H5A—C5—H5B	109.5
C2—O1—H1	101.1	C4—C5—H5C	109.5
C8—N1—C9	115.8 (2)	H5A—C5—H5C	109.5
C2—C1—H1A	109.5	H5B—C5—H5C	109.5
C2—C1—H1B	109.5	C10—C6—C7	117.9 (2)
H1A—C1—H1B	109.5	C10—C6—S1	124.71 (17)
C2—C1—H1C	109.5	C7—C6—S1	117.38 (17)
H1A—C1—H1C	109.5	C8—C7—C6	118.8 (2)
H1B—C1—H1C	109.5	C8—C7—H7	120.6
O1—C2—C3	120.9 (2)	C6—C7—H7	120.6
O1—C2—C1	115.7 (2)	N1—C8—C7	124.6 (2)
C3—C2—C1	123.4 (2)	N1—C8—H8	117.7
C2—C3—C4	119.1 (2)	C7—C8—H8	117.7
C2—C3—S1	120.14 (18)	N1—C9—C10	124.5 (2)
C4—C3—S1	120.67 (18)	N1—C9—H9	117.7
O2—C4—C3	120.0 (2)	C10—C9—H9	117.7
O2—C4—C5	116.8 (2)	C6—C10—C9	118.4 (2)
C3—C4—C5	123.1 (3)	C6—C10—H10	120.8
C4—C5—H5A	109.5	C9—C10—H10	120.8
C4—C5—H5B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.88	1.58	2.427 (3)	161

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁NO₂S
M_r	209.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.3273 (7), 9.5614 (8), 13.0681 (11)
β (°)	92.698 (1)
V (Å³)	1039.34 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.35 × 0.30 × 0.28

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.907, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	5011, 1822, 1351
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.120, 1.06
No. of reflections	1822
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.19

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.88	1.58	2.427 (3)	161

Acknowledgements

We acknowledge financial support by the National Natural Science Foundation of China (grant No. 21001061), the Natural Science Foundation of Shandong Province (grant No. ZR2010BL020) and the Liaocheng University Funds for Young Scientists (31805).

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