3-(Prop-2-yn-1-yl­oxy)phthalo­nitrile

Jan, C.Y.; Shamsudin, N.B.H.; Tan, A.L.; Young, D.J.; Tiekink, E.R.T.

doi:10.1107/S1600536813015663

organic compounds

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ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page o1074

https://doi.org/10.1107/S1600536813015663

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3-(Prop-2-yn-1-yloxy)phthalonitrile

Chin Yee Jan,^a Norzianah Binti Haji Shamsudin,^a Ai Ling Tan,^a David J. Young ^a ‡ and Edward R. T. Tiekink ^b ^*

^aFaculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link BE 1410, Negara Brunei Darussalam, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 5 June 2013; accepted 5 June 2013; online 12 June 2013)

In the title compound, C₁₁H₆N₂O {systematic name: 3-(prop-2-yn-1-yloxy)benzene-1,2-dicarbonitrile}, the 14 non-H atoms are approximately coplanar (r.m.s. deviation = 0.051 Å) with the terminal ethyne group being syn with the adjacent cyano residue. In the crystal, centrosymmetric dimers are connected by pairs of C—H⋯N interactions and these are linked into a supramolecular tape parallel to (1-30) via C—H⋯N interactions involving the same N atom as acceptor.

Related literature

For background to functionalized phthalocyanines, see: Chin et al. (2012 ). For background to the synthesis of precursor nitriles, see: Wu et al. (1998 ); Seven et al. (2009 ).

Experimental

Crystal data

C₁₁H₆N₂O
M_r = 182.18
Monoclinic, P 2₁ /n
a = 4.014 (4) Å
b = 6.833 (7) Å
c = 33.85 (3) Å
β = 90.77 (2)°
V = 928.1 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 153 K
0.30 × 0.16 × 0.08 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.974, T_max = 0.993
6610 measured reflections
1751 independent reflections
1310 reflections with I > 2σ(I)
R_int = 0.071

Refinement

R[F² > 2σ(F²)] = 0.086
wR(F²) = 0.250
S = 1.13
1751 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.28 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
C6—H6⋯N1ⁱ	0.95	2.47	3.335 (6)	151
C9—H9⋯N1ⁱⁱ	0.95	2.51	3.402 (6)	156
Symmetry codes: (i) x-1, y-1, z; (ii) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2011 ); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813015663/hg5321sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813015663/hg5321Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813015663/hg5321Isup3.cml

checkCIF report

Comment top

As part of our on-going study of functional phthalocyanines, we have previously reported the synthesis and structure (Chin et al., 2012) of precursor 4-(prop-2-ylnyloxy)phthalonitrile obtained by the S_NAr reaction of propagyl alcohol and 4-nitrophthalonitrile, facilitated by potassium carbonate in DMF following literature precedents (Wu et al., 1998; Seven et al., 2009). Despite increased steric hindrance, this method is also suitable for preparing the title compound, (I).

In (I), Fig. 1, the 14 non-hydrogen atoms lie in a plane with the r.m.s. deviation of the fitted atoms being 0.051 Å; the maximum deviations from the least-squares plane are found for the C9 [0.102 (5) Å], and N1 and C7 [each -0.073 (4) Å] atoms. The ethyne group is syn to the adjacent cyano group. In the crystal structure, centrosymmetrically pairs are connected into dimeric aggregates via C—H···N interactions and these are in turn linked into a supramolecular tape, parallel to (1 - 3 0), via C—H···N interactions with translationally related dimeric aggregates, Fig. 2 and Table 1. As the N1 atom participates in both C—H···N interactions, it is bifurcated. Chains stack along the a axis with separations of 4.014 (4) Å between the benzene rings, corresponding to the length of the a axis, and with no significant intermolecular interactions between them.

Related literature top

For background to functional phthalocyanines, see: Chin et al. (2012). For background to the synthesis of precursor nitriles, see: Wu et al. (1998); Seven et al. (2009).

Experimental top

The title compound was prepared by modification of literature procedures (Wu et al., 1998; Seven et al., 2009). Under a nitrogen atmosphere, anhydrous potassium carbonate (1.60 g, 11.6 mmol) was added in three portions at 1 h intervals to a solution of propargyl alcohol (2.16 ml, 37.4 mmol) and 3-nitrophthalonitrile (1.01 g, 5.83 mmol) in dry N,N-dimethylformamide (10 ml). After 96 h, the crude reaction mixture was poured into water (200 ml) and stirred rapidly. The brown precipitate was collected by vacuum filtration, washed with water and dried to provide 0.91 g of material that was purified by silica gel column chromatography using CH₂Cl₂ and recrystallized from CH₂Cl₂/hexane to yield 0.68 g (63.8%). M. pt: 427–429 K. IR (KBr) ν/cm^-1: 3296, 3095, 2230, 2138, 1586, 1474, 1376, 1297. ¹H NMR 400 MHz (CDCl₃) δ: 7.68 (1H, m), 7.42 (2H, m), 4.91 (2H, d, J = 2.4 Hz), 2.62 (1H, t, J = 2.4 Hz).

Structure description top

For background to functional phthalocyanines, see: Chin et al. (2012). For background to the synthesis of precursor nitriles, see: Wu et al. (1998); Seven et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the unit-cell contents of (I) in projection down the a axis. The C—H···N hydrogen bonds are shown as blue dashed lines.

3-(Prop-2-yn-1-yloxy)benzene-1,2-dicarbonitrile top

Crystal data top

C₁₁H₆N₂O	F(000) = 376
M_r = 182.18	D_x = 1.304 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2684 reflections
a = 4.014 (4) Å	θ = 2.4–28.4°
b = 6.833 (7) Å	µ = 0.09 mm⁻¹
c = 33.85 (3) Å	T = 153 K
β = 90.77 (2)°	Prism, colourless
V = 928.1 (16) Å³	0.30 × 0.16 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	1751 independent reflections
Radiation source: fine-focus sealed tube	1310 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
φ and ω scans	θ_max = 25.7°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −4→4
T_min = 0.974, T_max = 0.993	k = −8→8
6610 measured reflections	l = −40→41

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)] = 0.086	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.250	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.1092P)² + 0.8456P] where P = (F_o² + 2F_c²)/3
1751 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₁H₆N₂O	V = 928.1 (16) Å³
M_r = 182.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.014 (4) Å	µ = 0.09 mm⁻¹
b = 6.833 (7) Å	T = 153 K
c = 33.85 (3) Å	0.30 × 0.16 × 0.08 mm
β = 90.77 (2)°

Data collection top

Bruker APEXII diffractometer	1751 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1310 reflections with I > 2σ(I)
T_min = 0.974, T_max = 0.993	R_int = 0.071
6610 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.086	0 restraints
wR(F²) = 0.250	H-atom parameters constrained
S = 1.13	Δρ_max = 0.28 e Å⁻³
1751 reflections	Δρ_min = −0.31 e Å⁻³
127 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
O1	0.1024 (7)	0.3511 (3)	0.07894 (6)	0.0506 (7)
N1	0.4013 (9)	0.7927 (4)	0.10745 (9)	0.0563 (9)
N2	0.1893 (10)	0.8135 (5)	0.21998 (10)	0.0680 (11)
C1	0.0004 (8)	0.3448 (5)	0.11659 (9)	0.0392 (8)
C2	0.0883 (8)	0.5067 (5)	0.13953 (9)	0.0385 (8)
C3	0.0045 (8)	0.5137 (5)	0.17948 (9)	0.0412 (8)
C4	−0.1691 (9)	0.3613 (6)	0.19646 (11)	0.0526 (10)
H4	−0.2270	0.3655	0.2236	0.063*
C5	−0.2565 (9)	0.2033 (6)	0.17330 (11)	0.0525 (10)
H5	−0.3765	0.0984	0.1848	0.063*
C6	−0.1754 (9)	0.1927 (5)	0.13400 (11)	0.0486 (9)
H6	−0.2392	0.0818	0.1188	0.058*
C7	0.0045 (10)	0.1952 (6)	0.05273 (10)	0.0515 (10)
H7A	−0.2412	0.1905	0.0499	0.062*
H7B	0.0831	0.0678	0.0632	0.062*
C8	0.1545 (9)	0.2349 (5)	0.01494 (10)	0.0498 (9)
C9	0.2816 (12)	0.2662 (7)	−0.01551 (12)	0.0694 (13)
H9	0.3844	0.2914	−0.0401	0.083*
C10	0.2645 (8)	0.6647 (5)	0.12159 (9)	0.0404 (8)
C11	0.1051 (9)	0.6805 (6)	0.20227 (10)	0.0495 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0697 (17)	0.0452 (14)	0.0369 (13)	−0.0151 (12)	0.0050 (11)	−0.0086 (10)
N1	0.074 (2)	0.0469 (18)	0.0487 (18)	−0.0159 (16)	0.0095 (16)	−0.0035 (14)
N2	0.088 (3)	0.073 (2)	0.0424 (18)	−0.003 (2)	0.0059 (17)	−0.0152 (17)
C1	0.0385 (18)	0.0380 (17)	0.0410 (17)	−0.0019 (13)	−0.0001 (13)	0.0016 (13)
C2	0.0385 (17)	0.0362 (17)	0.0408 (17)	0.0010 (13)	0.0019 (13)	0.0024 (13)
C3	0.0407 (18)	0.0452 (19)	0.0376 (16)	0.0053 (15)	0.0020 (13)	0.0023 (14)
C4	0.053 (2)	0.063 (2)	0.0417 (18)	0.0042 (18)	0.0083 (16)	0.0119 (17)
C5	0.047 (2)	0.051 (2)	0.060 (2)	−0.0061 (17)	0.0055 (17)	0.0173 (18)
C6	0.048 (2)	0.0408 (19)	0.056 (2)	−0.0084 (15)	−0.0022 (16)	0.0037 (15)
C7	0.056 (2)	0.054 (2)	0.0438 (19)	−0.0129 (17)	−0.0041 (16)	−0.0145 (16)
C8	0.057 (2)	0.048 (2)	0.044 (2)	0.0008 (17)	−0.0083 (17)	−0.0126 (16)
C9	0.091 (3)	0.074 (3)	0.043 (2)	0.003 (2)	0.009 (2)	−0.009 (2)
C10	0.049 (2)	0.0364 (17)	0.0353 (17)	−0.0029 (15)	0.0020 (14)	−0.0048 (13)
C11	0.057 (2)	0.061 (2)	0.0313 (17)	0.0009 (18)	0.0076 (15)	−0.0044 (16)

Geometric parameters (Å, º) top

O1—C1	1.345 (4)	C4—C5	1.377 (6)
O1—C7	1.437 (4)	C4—H4	0.9500
N1—C10	1.141 (4)	C5—C6	1.376 (5)
N2—C11	1.137 (5)	C5—H5	0.9500
C1—C6	1.391 (5)	C6—H6	0.9500
C1—C2	1.394 (5)	C7—C8	1.447 (5)
C2—C3	1.399 (5)	C7—H7A	0.9900
C2—C10	1.431 (4)	C7—H7B	0.9900
C3—C4	1.382 (5)	C8—C9	1.176 (5)
C3—C11	1.431 (5)	C9—H9	0.9500

C1—O1—C7	118.5 (3)	C4—C5—H5	119.0
O1—C1—C6	126.0 (3)	C5—C6—C1	119.9 (3)
O1—C1—C2	115.1 (3)	C5—C6—H6	120.1
C6—C1—C2	118.9 (3)	C1—C6—H6	120.1
C1—C2—C3	120.2 (3)	O1—C7—C8	107.0 (3)
C1—C2—C10	119.0 (3)	O1—C7—H7A	110.3
C3—C2—C10	120.7 (3)	C8—C7—H7A	110.3
C4—C3—C2	120.3 (3)	O1—C7—H7B	110.3
C4—C3—C11	121.1 (3)	C8—C7—H7B	110.3
C2—C3—C11	118.6 (3)	H7A—C7—H7B	108.6
C5—C4—C3	118.7 (3)	C9—C8—C7	178.9 (4)
C5—C4—H4	120.7	C8—C9—H9	180.0
C3—C4—H4	120.7	N1—C10—C2	179.0 (4)
C6—C5—C4	122.0 (3)	N2—C11—C3	178.9 (4)
C6—C5—H5	119.0

C7—O1—C1—C6	4.8 (5)	C11—C3—C4—C5	−179.3 (3)
C7—O1—C1—C2	−176.3 (3)	C3—C4—C5—C6	0.2 (6)
O1—C1—C2—C3	−178.1 (3)	C4—C5—C6—C1	0.0 (6)
C6—C1—C2—C3	0.9 (5)	O1—C1—C6—C5	178.2 (3)
O1—C1—C2—C10	2.0 (4)	C2—C1—C6—C5	−0.6 (5)
C6—C1—C2—C10	−179.0 (3)	C1—O1—C7—C8	−178.3 (3)
C1—C2—C3—C4	−0.7 (5)	O1—C7—C8—C9	74 (21)
C10—C2—C3—C4	179.2 (3)	C1—C2—C10—N1	123 (21)
C1—C2—C3—C11	178.7 (3)	C3—C2—C10—N1	−57 (21)
C10—C2—C3—C11	−1.4 (5)	C4—C3—C11—N2	153 (24)
C2—C3—C4—C5	0.1 (5)	C2—C3—C11—N2	−26 (25)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N1ⁱ	0.95	2.47	3.335 (6)	151
C9—H9···N1ⁱⁱ	0.95	2.51	3.402 (6)	156

Symmetry codes: (i) x−1, y−1, z; (ii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₆N₂O
M_r	182.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	153
a, b, c (Å)	4.014 (4), 6.833 (7), 33.85 (3)
β (°)	90.77 (2)
V (Å³)	928.1 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.16 × 0.08

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.974, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	6610, 1751, 1310
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.086, 0.250, 1.13
No. of reflections	1751
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.31

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N1ⁱ	0.95	2.47	3.335 (6)	151
C9—H9···N1ⁱⁱ	0.95	2.51	3.402 (6)	156

Symmetry codes: (i) x−1, y−1, z; (ii) −x+1, −y+1, −z.

Footnotes

‡Additional correspondence author, e-mail: david.young@ubd.edu.bn.

Acknowledgements

We gratefully acknowledge Dr Zhang Wen-Hua, Institute of Materials Research and Engineering, Agency for Science, Technology and Research, Singapore, for the X-ray data collection. We also gratefully acknowledge funding from the Brunei Research Council (UBD/GSR/S&T/17), and thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM·C/HIR-MOHE/SC/03).

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