Diisopropyl­ammonium 3,5,6-trichloro­pyridin-2-olate

Hu, Z.Y.; Zheng, H.; Xu, D.Q.

doi:10.1107/S1600536808002389

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o537

doi:10.1107/S1600536808002389

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Diisopropylammonium 3,5,6-trichloropyridin-2-olate

Zhi Yan Hu,^a Hui Zheng ^b and Dan Qian Xu ^b ^*

^aSchool of Science, Zhejiang Forestry University, Linan, Hangzhou 311300, People's Republic of China, and ^bState Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: zhenghui86@gmail.com

(Received 7 January 2008; accepted 22 January 2008; online 30 January 2008)

In the title salt, C₆H₁₆N⁺·C₅HCl₃NO⁻, the cation links to the anion, which is almost planar, through an N—H⋯O hydrogen bond. Intermolecular hydrogen bonds link two cations and two anions into a centrosymmetric cluster. The atoms involved in the hydrogen bonding form a planar octagonal arrangement in the crystal structure.

Related literature

For related literature, see: Fox et al. (2002 ); Baughman (1989 ); Fakhraian et al. (2004 ); Zheng, Liu, Li et al. (2006 ); Zheng, Liu, Xu et al. (2006a ,b ).

Experimental

Crystal data

C₆H₁₆N⁺·C₅HCl₃NO⁻
M_r = 299.63
Monoclinic, P 2₁ /c
a = 8.087 (3) Å
b = 11.066 (3) Å
c = 16.389 (5) Å
β = 94.540 (15)°
V = 1462.1 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 298 (1) K
0.39 × 0.18 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.794, T_max = 0.907
14096 measured reflections
3357 independent reflections
2081 reflections with F² > 2σ(F²)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.081
S = 1.04
3357 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H201⋯O1	0.96	1.94	2.8803 (15)	166
N2—H201⋯N1	0.96	2.53	3.2556 (16)	133
N2—H202⋯O1ⁱ	0.96	1.85	2.7424 (16)	152
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808002389/wk2076sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808002389/wk2076Isup2.hkl

checkCIF report

Comment top

Many compounds containing the 3,5,6-trichloro-pyridin-2-ol group have potential bioactivity (Fakhraian et al., 2004; Baughman, 1989; Fox et al., 2002). Similar compounds has been synthesized in our laboratory and some bioactive compounds have been found (Zheng et al., 2006). In a continuation of our work into structure–activity relationships (Zheng, Liu, Xu & Xu, 2006a,b), we obtained a colorless crystalline compound, (I), by mixing sodium 3,5,6-trichloropyridin-2-olate with diisopropylammonium chloride, which was crystallized from diethyl ether. In the crystal structure, there are two independent structural units. The diisopropylammonium cation has an N2—C10 distance of 1.5009 (19)Å and a C10—N2—C7 angle of 117.47 (11)° (Table 1). The 3,5,6-trichloropyridin-2-olate anion has a C1—O1 distance of 1.2716 (18) Å, which is shorter than normal C—O distance for a smallar covalent radius with Csp². The interesting feature of the crystal structure is the intermolecular hydrogen bonds N2—H201···O1 and N2—H202···O1ⁱ, which link two cations and two anions into a centrosymmetric cluster and form a planar octagon (Table 2 and Fig. 1).

Related literature top

For related literature, see: Fox et al. (2002); Baughman (1989); Fakhraian et al. (2004); Zheng et al. (2006); Zheng et al. (2006a,b).

Experimental top

Sodium 3,5,6-trichloropyridin-2-olate (2.2 g, 10 mmol) was dissolved in the distilled water (30 ml) at 370 K, cooled to room temperature, and diisopropylammonium chloride, which was generated from diisopropylamine (1.8 ml, 12 mmol) with HCl (36%) (2 ml), was added dropwise with stirring for 0.5 h. The solution was extracted with diethyl ether 2 × 15 ml. and dried over anhydrous magnesium sulfate. Suitable crystals (m.p. 442–443 K) were obtained from a diethyl ether solution.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).

Figures top

Fig. 1. The centrosymmetric hydrogen-bonded (dashed lines) cluster in (I), showing the atom-numbering scheme and 40% probability displacement ellipsoids. [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]

Diisopropylammonium 3,5,6-trichloropyridin-2-olate top

Crystal data top

C₆H₁₆N⁺·C₅HCl₃NO⁻	F(000) = 624.00
M_r = 299.63	D_x = 1.361 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 443 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71075 Å
a = 8.087 (3) Å	Cell parameters from 10937 reflections
b = 11.066 (3) Å	θ = 3.1–27.5°
c = 16.389 (5) Å	µ = 0.61 mm⁻¹
β = 94.540 (15)°	T = 298 K
V = 1462.1 (8) Å³	Block, colorless
Z = 4	0.39 × 0.18 × 0.16 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	2081 reflections with F² > 2σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.027
ω scans	θ_max = 27.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→10
T_min = 0.794, T_max = 0.907	k = −14→14
14096 measured reflections	l = −21→21
3357 independent reflections

Refinement top

Refinement on F²	w = 1/[0.0002F_o² + σ(F_o²)]/(4F_o²)
R[F² > 2σ(F²)] = 0.035	(Δ/σ)_max < 0.001
wR(F²) = 0.081	Δρ_max = 0.29 e Å⁻³
S = 1.05	Δρ_min = −0.31 e Å⁻³
3357 reflections	Extinction correction: Larson (1970), equation 22
155 parameters	Extinction coefficient: 143 (15)
H-atom parameters constrained

Crystal data top

C₆H₁₆N⁺·C₅HCl₃NO⁻	V = 1462.1 (8) Å³
M_r = 299.63	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.087 (3) Å	µ = 0.61 mm⁻¹
b = 11.066 (3) Å	T = 298 K
c = 16.389 (5) Å	0.39 × 0.18 × 0.16 mm
β = 94.540 (15)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3357 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2081 reflections with F² > 2σ(F²)
T_min = 0.794, T_max = 0.907	R_int = 0.027
14096 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	155 parameters
wR(F²) = 0.081	H-atom parameters constrained
S = 1.05	Δρ_max = 0.29 e Å⁻³
3357 reflections	Δρ_min = −0.31 e Å⁻³

Special details top

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
Cl1	0.39967 (6)	0.13293 (4)	0.40436 (3)	0.08518 (18)
Cl2	0.05102 (6)	−0.02373 (5)	0.65045 (3)	0.08680 (17)
Cl3	0.06254 (8)	0.24633 (5)	0.71793 (4)	0.1034 (2)
O1	0.36820 (13)	0.36964 (9)	0.49068 (6)	0.0604 (3)
N1	0.22849 (16)	0.29782 (11)	0.59411 (9)	0.0566 (4)
N2	0.37423 (14)	0.57219 (10)	0.60126 (6)	0.0469 (3)
C1	0.30288 (18)	0.28003 (12)	0.52456 (10)	0.0498 (4)
C2	0.30287 (19)	0.16000 (13)	0.49307 (10)	0.0529 (4)
C3	0.2269 (2)	0.06825 (13)	0.53135 (11)	0.0595 (5)
C4	0.1497 (2)	0.09140 (13)	0.60194 (10)	0.0573 (4)
C5	0.1557 (2)	0.20776 (14)	0.62985 (10)	0.0573 (5)
C6	0.5796 (2)	0.46023 (17)	0.68652 (12)	0.0771 (6)
C7	0.4207 (2)	0.53190 (13)	0.68790 (9)	0.0561 (4)
C8	0.4384 (2)	0.63777 (17)	0.74638 (11)	0.0780 (6)
C9	0.0708 (2)	0.58893 (18)	0.60955 (12)	0.0764 (6)
C10	0.2255 (2)	0.65272 (13)	0.58681 (10)	0.0570 (4)
C11	0.2132 (2)	0.69139 (17)	0.49810 (11)	0.0742 (6)
H3	0.2274	−0.0097	0.5101	0.071*
H7	0.3333	0.4784	0.7051	0.067*
H10	0.2433	0.7245	0.6214	0.068*
H61	0.6635	0.5111	0.6664	0.091*
H62	0.5625	0.3911	0.6515	0.092*
H63	0.6146	0.4340	0.7410	0.092*
H81	0.3347	0.6800	0.7466	0.093*
H82	0.4713	0.6094	0.8006	0.093*
H83	0.5216	0.6914	0.7286	0.093*
H91	−0.0234	0.6409	0.5988	0.093*
H92	0.0557	0.5167	0.5774	0.092*
H93	0.0819	0.5681	0.6666	0.093*
H111	0.1926	0.6214	0.4642	0.088*
H112	0.3152	0.7287	0.4854	0.088*
H113	0.1237	0.7479	0.4883	0.088*
H201	0.3549	0.5015	0.5680	0.056*
H202	0.4689	0.6125	0.5820	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1051 (4)	0.0724 (3)	0.0820 (3)	−0.0167 (2)	0.0323 (2)	−0.0223 (2)
Cl2	0.1076 (4)	0.0690 (3)	0.0828 (3)	−0.0353 (2)	0.0014 (2)	0.0219 (2)
Cl3	0.1362 (5)	0.0953 (4)	0.0860 (4)	−0.0262 (3)	0.0534 (3)	−0.0126 (2)
O1	0.0653 (7)	0.0426 (5)	0.0749 (7)	−0.0111 (5)	0.0165 (5)	0.0024 (5)
N1	0.0615 (8)	0.0436 (7)	0.0654 (9)	−0.0082 (6)	0.0109 (6)	−0.0044 (6)
N2	0.0512 (7)	0.0390 (6)	0.0509 (7)	−0.0053 (5)	0.0052 (5)	−0.0037 (5)
C1	0.0464 (8)	0.0419 (8)	0.0603 (10)	−0.0055 (6)	−0.0003 (7)	0.0006 (7)
C2	0.0559 (9)	0.0458 (8)	0.0570 (9)	−0.0060 (7)	0.0036 (7)	−0.0039 (7)
C3	0.0691 (10)	0.0399 (8)	0.0675 (11)	−0.0095 (7)	−0.0064 (8)	−0.0031 (7)
C4	0.0622 (10)	0.0498 (9)	0.0582 (10)	−0.0147 (7)	−0.0059 (8)	0.0108 (8)
C5	0.0611 (10)	0.0559 (9)	0.0552 (10)	−0.0084 (8)	0.0063 (8)	0.0022 (7)
C6	0.0878 (13)	0.0710 (11)	0.0703 (12)	0.0083 (10)	−0.0086 (10)	0.0142 (10)
C7	0.0666 (10)	0.0507 (8)	0.0511 (9)	−0.0089 (7)	0.0052 (7)	0.0077 (7)
C8	0.1041 (15)	0.0719 (12)	0.0562 (10)	−0.0103 (10)	−0.0058 (10)	−0.0070 (9)
C9	0.0577 (11)	0.0899 (13)	0.0834 (13)	0.0033 (9)	0.0158 (9)	−0.0142 (11)
C10	0.0581 (9)	0.0469 (8)	0.0652 (10)	0.0045 (7)	−0.0003 (8)	−0.0107 (7)
C11	0.0690 (12)	0.0679 (11)	0.0833 (13)	0.0045 (9)	−0.0092 (10)	0.0105 (10)

Geometric parameters (Å, º) top

Cl1—C2	1.7310 (17)	C6—H62	0.960
Cl2—C4	1.7297 (17)	C6—H63	0.960
Cl3—C5	1.7337 (18)	C7—C8	1.513 (2)
O1—C1	1.2716 (18)	C7—H7	0.980
N1—C1	1.345 (2)	C8—H81	0.960
N1—C5	1.318 (2)	C8—H82	0.960
N2—C7	1.5072 (18)	C8—H83	0.960
N2—C10	1.5009 (19)	C9—C10	1.508 (2)
N2—H201	0.959	C9—H91	0.960
N2—H202	0.961	C9—H92	0.960
C1—C2	1.425 (2)	C9—H93	0.960
C2—C3	1.365 (2)	C10—C11	1.511 (2)
C3—C4	1.382 (2)	C10—H10	0.980
C3—H3	0.930	C11—H111	0.960
C4—C5	1.366 (2)	C11—H112	0.960
C6—C7	1.512 (2)	C11—H113	0.960
C6—H61	0.960

C1—N1—C5	120.76 (13)	N2—C7—C8	111.82 (12)
C7—N2—C10	117.47 (11)	N2—C7—H7	108.5
C7—N2—H201	108.2	C6—C7—C8	112.20 (14)
C7—N2—H202	107.5	C6—C7—H7	108.7
C10—N2—H201	107.6	C8—C7—H7	108.6
C10—N2—H202	108.8	C7—C8—H81	109.9
H201—N2—H202	106.8	C7—C8—H82	109.8
O1—C1—N1	119.02 (13)	C7—C8—H83	108.7
O1—C1—C2	123.84 (14)	H81—C8—H82	109.5
N1—C1—C2	117.14 (13)	H81—C8—H83	109.5
Cl1—C2—C1	118.58 (12)	H82—C8—H83	109.5
Cl1—C2—C3	120.48 (12)	C10—C9—H91	109.7
C1—C2—C3	120.93 (15)	C10—C9—H92	109.0
C2—C3—C4	119.79 (14)	C10—C9—H93	109.7
C2—C3—H3	120.1	H91—C9—H92	109.5
C4—C3—H3	120.1	H91—C9—H93	109.5
Cl2—C4—C3	120.26 (12)	H92—C9—H93	109.5
Cl2—C4—C5	123.09 (13)	N2—C10—C9	110.68 (12)
C3—C4—C5	116.66 (14)	N2—C10—C11	108.09 (13)
Cl3—C5—N1	115.00 (12)	N2—C10—H10	108.1
Cl3—C5—C4	120.30 (13)	C9—C10—C11	112.20 (14)
N1—C5—C4	124.70 (15)	C9—C10—H10	108.9
C7—C6—H61	108.8	C11—C10—H10	108.8
C7—C6—H62	110.2	C10—C11—H111	108.9
C7—C6—H63	109.4	C10—C11—H112	109.8
H61—C6—H62	109.5	C10—C11—H113	109.7
H61—C6—H63	109.5	H111—C11—H112	109.5
H62—C6—H63	109.5	H111—C11—H113	109.5
N2—C7—C6	106.86 (13)	H112—C11—H113	109.5

C1—N1—C5—Cl3	−178.90 (11)	N1—C1—C2—Cl1	−179.19 (11)
C1—N1—C5—C4	0.7 (2)	N1—C1—C2—C3	1.5 (2)
C5—N1—C1—O1	178.24 (13)	Cl1—C2—C3—C4	−179.77 (12)
C5—N1—C1—C2	−1.6 (2)	C1—C2—C3—C4	−0.4 (2)
C7—N2—C10—C9	−62.42 (16)	C2—C3—C4—Cl2	179.30 (12)
C7—N2—C10—C11	174.34 (12)	C2—C3—C4—C5	−0.5 (2)
C10—N2—C7—C6	−176.04 (12)	Cl2—C4—C5—Cl3	0.2 (2)
C10—N2—C7—C8	−52.90 (18)	Cl2—C4—C5—N1	−179.41 (12)
O1—C1—C2—Cl1	1.0 (2)	C3—C4—C5—Cl3	179.98 (9)
O1—C1—C2—C3	−178.36 (14)	C3—C4—C5—N1	0.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H201···O1	0.96	1.94	2.8803 (15)	166
N2—H201···N1	0.96	2.53	3.2556 (16)	133
N2—H202···O1ⁱ	0.96	1.86	2.7424 (16)	152

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₆H₁₆N⁺·C₅HCl₃NO⁻
M_r	299.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.087 (3), 11.066 (3), 16.389 (5)
β (°)	94.540 (15)
V (Å³)	1462.1 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.39 × 0.18 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.794, 0.907
No. of measured, independent and observed [F² > 2σ(F²)] reflections	14096, 3357, 2081
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.081, 1.05
No. of reflections	3357
No. of parameters	155
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.31

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SIR97 (Altomare et al., 1999), CRYSTALS (Watkin et al., 1996), ORTEP-3 for Windows (Farrugia, 1997).

Selected geometric parameters (Å, º) top

Cl1—C2	1.7310 (17)	N2—C7	1.5072 (18)
O1—C1	1.2716 (18)	N2—C10	1.5009 (19)

C7—N2—C10	117.47 (11)	Cl2—C4—C3	120.26 (12)
O1—C1—N1	119.02 (13)	Cl3—C5—N1	115.00 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H201···O1	0.959	1.941	2.8803 (15)	165.7
N2—H201···N1	0.959	2.526	3.2556 (16)	132.9
N2—H202···O1ⁱ	0.961	1.855	2.7424 (16)	152.3

Symmetry code: (i) −x+1, −y+1, −z+1.

References

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