4-(2-Chloro­ethoxy)phthalonitrile

Huang, X.; Li, M.; Lin, X.; Chen, H.; Zhu, S.

doi:10.1107/S1600536808027141

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2337

doi:10.1107/S1600536808027141

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4-(2-Chloroethoxy)phthalonitrile

Xin Huang,^a Mingfu Li,^a Xiangmei Lin,^a Hongjun Chen ^a and Shuifang Zhu ^a ^*

^aInstitute of Animal and Plant Quarantine, Chinese Academy of Inspection and Quarantine, Beijing, 100029, People's Republic of China
^*Correspondence e-mail: zhushf@netchina.com.cn

(Received 2 August 2008; accepted 23 August 2008; online 13 November 2008)

In the title compound, C₁₀H₇ClN₂O, the O and both C atoms of the chloroethoxy group are disordered over two positions, the occupancy factor of the major disorder component refining to 0.54 (2).

Related literature

For background to the use of phthalonitriles and phthalocyanines, see: McKeown (1998 ); Leznoff & Lever (1989–1996 ); Moser & Thomas (1983 ). For related structures, see: Nesi et al. (1998 ); Dinçer et al. (2004 ); Ocak et al. (2004 ).

Experimental

Crystal data

C₁₀H₇ClN₂O
M_r = 206.63
Monoclinic, P 2₁ /c
a = 4.9021 (8) Å
b = 19.014 (3) Å
c = 10.640 (3) Å
β = 97.123 (18)°
V = 984.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 295 (2) K
0.6 × 0.2 × 0.1 mm

Data collection

Bruker P4 diffractometer
Absorption correction: none
2496 measured reflections
1741 independent reflections
890 reflections with I > 2σ(I)
R_int = 0.062
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.240
S = 1.08
1741 reflections
155 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: XSCANS (Bruker, 1997 ); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, huangx-4. DOI: 10.1107/S1600536808027141/sj2530sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027141/sj2530Isup2.hkl

checkCIF report

Comment top

Substituted phthalonitriles are generally used for preparing peripherally substituted symmetrical and unsymmetrical phthalocyanine complexes and subphthalocyanines (McKeown, 1998; Leznoff & Lever, 1989–1996). Phthalocyanines were first developed as dyes and pigments (Moser & Thomas, 1983). Over last few years, a great deal of interest has been focused on the synthesis of phthalocyanine derivatives due to their applications in fields, such as chemical sensors, electrochromism, batteries, semiconducting materials, liquid crystals, non-linear optics and photodynamic therapy (PDT) (Leznoff & Lever, 1989–1996). We report here the structure of the title phthalonitrile derivative, (I), (Fig 1).

The title compound, C₁₀H₇ClN₂O, contains a pathalonitrile ring and 2-chloroethoxy substituent in the 4-position. The oxygen and both carbon atoms of this substituent are disordered over two positions. The occupancy factor of the major disorder component refined to 0.54 (2). The C1≡N1 and C2≡N2 bond distances are both 1.138 (4) °, consistent with N≡C triple-bond character, They are also in good agreement with literature values (Nesi et al., 1998; Dinçer et al., 2004; Ocak et al., 2004).

Related literature top

For background to the use of phthalonitriles and phthalocyanines, see: McKeown (1998); Leznoff & Lever (1989–1996); Moser & Thomas (1983). For related structures, see: Nesi et al. (1998); Dinçer et al. (2004); Ocak et al. (2004).

Experimental top

2-chloroethanol (1.6 g, 20 mmol) and 3-nitrophthalonitrile (1.73 g, 10 mmol) were dissolved in dry dimethylformamide (50 ml). After stirring for 1 h at room temperature, dry fine-powdered potassium carbonate (2.76 g, 20 mmol) was added portionwise over a period of 2 h with stirring. The reaction mixture was stirred for 36 h at room temperature and poured into ice-water (300 g). The product was filtered off and washed with water until the filtrate was neutral. Recrystallization from toluene gave a white product (yield 1.6 g, 77.4%). Single crystals were obtained from ethanol at room temperature by slow evaporation. Spectroscopic analysis: IR (KBr, ν cm^-1): 2963, 2868, 2237, 2229; MS(ESI, CH₃OH): m/z =207.2 [M+H]⁺; Anal. Found: C,58.45; H, 3.72; N, 13.23%. Calcd for C₁₈H₁₆N₂O: C, 58.13; H, 3.41; N, 13.56%

Computing details top

Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS(Bruker, 1997); data reduction: XSCANS(Bruker, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, (I), showing 35% probability ellipsoids and the atom numbering scheme. For clarity only atoms of the major disorder component are shown.
	Fig. 2. The molecular packing of (I) viewed along the a axis. H atoms and atoms of the minor disorder component have been omitted.

(I) top

Crystal data top

C₁₀H₇ClN₂O	F(000) = 424
M_r = 206.63	D_x = 1.395 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 43 reflections
a = 4.9021 (8) Å	θ = 4.9–12.4°
b = 19.014 (3) Å	µ = 0.35 mm⁻¹
c = 10.640 (3) Å	T = 295 K
β = 97.123 (18)°	Prism, colorless
V = 984.1 (3) Å³	0.6 × 0.2 × 0.1 mm
Z = 4

Data collection top

Bruker P4 diffractometer	R_int = 0.062
Radiation source: fine-focus sealed tube	θ_max = 25.1°, θ_min = 2.1°
Graphite monochromator	h = −5→1
ω scans	k = −1→22
2496 measured reflections	l = −12→12
1741 independent reflections	3 standard reflections every 97 reflections
890 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.240	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.1087P)² + 0.4256P] where P = (F_o² + 2F_c²)/3
1741 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.27 e Å⁻³
3 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₀H₇ClN₂O	V = 984.1 (3) Å³
M_r = 206.63	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.9021 (8) Å	µ = 0.35 mm⁻¹
b = 19.014 (3) Å	T = 295 K
c = 10.640 (3) Å	0.6 × 0.2 × 0.1 mm
β = 97.123 (18)°

Data collection top

Bruker P4 diffractometer	R_int = 0.062
2496 measured reflections	3 standard reflections every 97 reflections
1741 independent reflections	intensity decay: none
890 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.065	3 restraints
wR(F²) = 0.240	H-atom parameters constrained
S = 1.08	Δρ_max = 0.27 e Å⁻³
1741 reflections	Δρ_min = −0.34 e Å⁻³
155 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	Occ. (<1)
Cl1	0.5427 (3)	0.44767 (7)	0.83121 (16)	0.1010 (7)
N1	0.8645 (10)	0.8557 (2)	0.4503 (5)	0.1033 (15)
N2	1.0442 (9)	0.6789 (2)	0.3064 (4)	0.0871 (13)
C1	0.7656 (10)	0.8069 (2)	0.4867 (5)	0.0759 (13)
C2	0.8952 (9)	0.6778 (2)	0.3795 (5)	0.0689 (12)
C3	0.6468 (8)	0.7433 (2)	0.5291 (4)	0.0662 (11)
C4	0.7097 (8)	0.6785 (2)	0.4738 (4)	0.0621 (11)
C5	0.5977 (8)	0.6167 (2)	0.5135 (4)	0.0707 (12)
H5A	0.6393	0.5738	0.4785	0.085*
C6	0.4228 (9)	0.6196 (2)	0.6063 (5)	0.0761 (13)
C7	0.3573 (9)	0.6827 (3)	0.6596 (4)	0.0755 (13)
H7A	0.2388	0.6837	0.7214	0.091*
C8	0.4698 (9)	0.7442 (2)	0.6201 (5)	0.0717 (12)
H8A	0.4254	0.7869	0.6553	0.086*
O1	0.297 (3)	0.5510 (8)	0.6161 (17)	0.084 (4)	0.54 (2)
C9	0.134 (4)	0.5396 (9)	0.719 (2)	0.098 (6)	0.54 (2)
H9A	0.0513	0.5837	0.7401	0.118*	0.54 (2)
H9B	−0.0127	0.5068	0.6922	0.118*	0.54 (2)
C10	0.294 (4)	0.5130 (10)	0.8277 (15)	0.101 (6)	0.54 (2)
H10A	0.1641	0.4968	0.8830	0.121*	0.54 (2)
H10B	0.3863	0.5534	0.8694	0.121*	0.54 (2)
O1'	0.352 (4)	0.5616 (10)	0.6669 (13)	0.080 (4)	0.46 (2)
C9'	0.255 (3)	0.5600 (6)	0.7816 (13)	0.059 (4)	0.46 (2)
H9C	0.0815	0.5851	0.7771	0.071*	0.46 (2)
H9D	0.3849	0.5819	0.8458	0.071*	0.46 (2)
C10'	0.2133 (14)	0.4813 (7)	0.8148 (17)	0.070 (4)	0.46 (2)
H10C	0.0970	0.4576	0.7474	0.085*	0.46 (2)
H10D	0.1318	0.4767	0.8930	0.085*	0.46 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0865 (10)	0.0857 (9)	0.1351 (14)	0.0058 (7)	0.0306 (8)	0.0097 (8)
N1	0.114 (4)	0.077 (3)	0.121 (4)	−0.011 (3)	0.024 (3)	0.005 (3)
N2	0.091 (3)	0.088 (3)	0.090 (3)	0.007 (2)	0.041 (2)	0.009 (2)
C1	0.074 (3)	0.070 (3)	0.084 (3)	−0.001 (2)	0.012 (2)	−0.008 (3)
C2	0.075 (3)	0.058 (2)	0.076 (3)	0.001 (2)	0.021 (2)	0.001 (2)
C3	0.064 (2)	0.061 (2)	0.074 (3)	0.0028 (19)	0.008 (2)	0.003 (2)
C4	0.060 (2)	0.062 (2)	0.066 (3)	0.0064 (19)	0.0145 (19)	0.003 (2)
C5	0.073 (3)	0.059 (2)	0.083 (3)	0.008 (2)	0.023 (2)	0.006 (2)
C6	0.079 (3)	0.068 (3)	0.086 (3)	0.008 (2)	0.027 (2)	0.017 (2)
C7	0.072 (3)	0.091 (3)	0.066 (3)	0.019 (2)	0.019 (2)	0.002 (2)
C8	0.070 (3)	0.070 (3)	0.076 (3)	0.009 (2)	0.010 (2)	−0.002 (2)
O1	0.115 (8)	0.067 (6)	0.083 (9)	0.010 (5)	0.062 (7)	0.012 (6)
C9	0.088 (9)	0.096 (9)	0.120 (13)	0.007 (7)	0.053 (9)	0.033 (8)
C10	0.073 (8)	0.141 (15)	0.089 (8)	0.017 (10)	0.015 (7)	0.041 (10)
O1'	0.125 (8)	0.056 (5)	0.066 (8)	−0.004 (5)	0.041 (8)	−0.004 (6)
C9'	0.046 (6)	0.063 (7)	0.071 (8)	−0.009 (5)	0.017 (6)	−0.018 (5)
C10'	0.051 (6)	0.056 (7)	0.109 (10)	−0.020 (5)	0.029 (6)	0.009 (6)

Geometric parameters (Å, º) top

Cl1—C10'	1.726 (5)	C7—H7A	0.9300
Cl1—C10	1.738 (5)	C8—H8A	0.9300
N1—C1	1.137 (6)	O1—C9	1.450 (16)
N2—C2	1.132 (5)	C9—C10	1.41 (3)
C1—C3	1.439 (6)	C9—H9A	0.9700
C2—C4	1.435 (6)	C9—H9B	0.9700
C3—C8	1.378 (6)	C10—H10A	0.9700
C3—C4	1.416 (5)	C10—H10B	0.9700
C4—C5	1.386 (6)	O1'—C9'	1.366 (5)
C5—C6	1.386 (6)	C9'—C10'	1.556 (19)
C5—H5A	0.9300	C9'—H9C	0.9700
C6—O1'	1.344 (17)	C9'—H9D	0.9700
C6—C7	1.382 (6)	C10'—H10C	0.9700
C6—O1	1.452 (15)	C10'—H10D	0.9700
C7—C8	1.381 (6)

N1—C1—C3	177.5 (5)	C10—C9—H9A	109.3
N2—C2—C4	178.3 (5)	O1—C9—H9A	109.3
C8—C3—C4	119.5 (4)	C10—C9—H9B	109.3
C8—C3—C1	121.6 (4)	O1—C9—H9B	109.3
C4—C3—C1	118.9 (4)	H9A—C9—H9B	107.9
C5—C4—C3	119.8 (4)	C9—C10—Cl1	126.4 (13)
C5—C4—C2	121.0 (4)	C9—C10—H10A	105.7
C3—C4—C2	119.2 (4)	Cl1—C10—H10A	105.7
C4—C5—C6	119.1 (4)	C9—C10—H10B	105.7
C4—C5—H5A	120.4	Cl1—C10—H10B	105.7
C6—C5—H5A	120.4	H10A—C10—H10B	106.2
O1'—C6—C7	115.4 (7)	C6—O1'—C9'	125.9 (13)
O1'—C6—C5	121.8 (8)	O1'—C9'—C10'	107.1 (12)
C7—C6—C5	121.5 (4)	O1'—C9'—H9C	110.3
C7—C6—O1	128.9 (7)	C10'—C9'—H9C	110.3
C5—C6—O1	108.7 (7)	O1'—C9'—H9D	110.3
C8—C7—C6	119.2 (4)	C10'—C9'—H9D	110.3
C8—C7—H7A	120.4	H9C—C9'—H9D	108.5
C6—C7—H7A	120.4	C9'—C10'—Cl1	103.4 (9)
C3—C8—C7	120.9 (4)	C9'—C10'—H10C	111.1
C3—C8—H8A	119.6	Cl1—C10'—H10C	111.1
C7—C8—H8A	119.6	C9'—C10'—H10D	111.1
C6—O1—C9	117.8 (11)	Cl1—C10'—H10D	111.1
C10—C9—O1	111.8 (13)	H10C—C10'—H10D	109.0

Experimental details

Crystal data
Chemical formula	C₁₀H₇ClN₂O
M_r	206.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	4.9021 (8), 19.014 (3), 10.640 (3)
β (°)	97.123 (18)
V (Å³)	984.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.6 × 0.2 × 0.1

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2496, 1741, 890
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.240, 1.08
No. of reflections	1741
No. of parameters	155
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.34

Computer programs: XSCANS (Bruker, 1997), XSCANS(Bruker, 1997), SHELXTL (Sheldrick, 2008).

Acknowledgements

We are grateful for the support of the National Key Project of Scientific and Technical Supporting Programs funded by the Ministry of Science and Technology of China during the 11th Five-Year Plan (No. 2006BAK10B06).

References

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