supplementary materials


hg5321 scheme

Acta Cryst. (2013). E69, o1074    [ doi:10.1107/S1600536813015663 ]

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

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

Abstract top

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.

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 SNAr 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).

Refinement top

Carbon-bound H-atoms were placed in calculated positions [C—H = 0.95–0.99 Å, Uiso(H) = 1.2Ueq(C)] and were included in the refinement in the riding model approximation.

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
[Figure 1] Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
[Figure 2] 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
C11H6N2OF(000) = 376
Mr = 182.18Dx = 1.304 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2684 reflections
a = 4.014 (4) Åθ = 2.4–28.4°
b = 6.833 (7) ŵ = 0.09 mm1
c = 33.85 (3) ÅT = 153 K
β = 90.77 (2)°Prism, colourless
V = 928.1 (16) Å30.30 × 0.16 × 0.08 mm
Z = 4
Data collection top
Bruker APEXII
diffractometer
1751 independent reflections
Radiation source: fine-focus sealed tube1310 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.071
φ and ω scansθmax = 25.7°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 44
Tmin = 0.974, Tmax = 0.993k = 88
6610 measured reflectionsl = 4041
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.086Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.250H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.1092P)2 + 0.8456P]
where P = (Fo2 + 2Fc2)/3
1751 reflections(Δ/σ)max < 0.001
127 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
C11H6N2OV = 928.1 (16) Å3
Mr = 182.18Z = 4
Monoclinic, P21/nMo Kα radiation
a = 4.014 (4) ŵ = 0.09 mm1
b = 6.833 (7) ÅT = 153 K
c = 33.85 (3) Å0.30 × 0.16 × 0.08 mm
β = 90.77 (2)°
Data collection top
Bruker APEXII
diffractometer
1310 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Rint = 0.071
Tmin = 0.974, Tmax = 0.993θmax = 25.7°
6610 measured reflectionsStandard reflections: 0
1751 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.086H-atom parameters constrained
wR(F2) = 0.250Δρmax = 0.28 e Å3
S = 1.13Δρmin = 0.31 e Å3
1751 reflectionsAbsolute structure: ?
127 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
O10.1024 (7)0.3511 (3)0.07894 (6)0.0506 (7)
N10.4013 (9)0.7927 (4)0.10745 (9)0.0563 (9)
N20.1893 (10)0.8135 (5)0.21998 (10)0.0680 (11)
C10.0004 (8)0.3448 (5)0.11659 (9)0.0392 (8)
C20.0883 (8)0.5067 (5)0.13953 (9)0.0385 (8)
C30.0045 (8)0.5137 (5)0.17948 (9)0.0412 (8)
C40.1691 (9)0.3613 (6)0.19646 (11)0.0526 (10)
H40.22700.36550.22360.063*
C50.2565 (9)0.2033 (6)0.17330 (11)0.0525 (10)
H50.37650.09840.18480.063*
C60.1754 (9)0.1927 (5)0.13400 (11)0.0486 (9)
H60.23920.08180.11880.058*
C70.0045 (10)0.1952 (6)0.05273 (10)0.0515 (10)
H7A0.24120.19050.04990.062*
H7B0.08310.06780.06320.062*
C80.1545 (9)0.2349 (5)0.01494 (10)0.0498 (9)
C90.2816 (12)0.2662 (7)0.01551 (12)0.0694 (13)
H90.38440.29140.04010.083*
C100.2645 (8)0.6647 (5)0.12159 (9)0.0404 (8)
C110.1051 (9)0.6805 (6)0.20227 (10)0.0495 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0697 (17)0.0452 (14)0.0369 (13)0.0151 (12)0.0050 (11)0.0086 (10)
N10.074 (2)0.0469 (18)0.0487 (18)0.0159 (16)0.0095 (16)0.0035 (14)
N20.088 (3)0.073 (2)0.0424 (18)0.003 (2)0.0059 (17)0.0152 (17)
C10.0385 (18)0.0380 (17)0.0410 (17)0.0019 (13)0.0001 (13)0.0016 (13)
C20.0385 (17)0.0362 (17)0.0408 (17)0.0010 (13)0.0019 (13)0.0024 (13)
C30.0407 (18)0.0452 (19)0.0376 (16)0.0053 (15)0.0020 (13)0.0023 (14)
C40.053 (2)0.063 (2)0.0417 (18)0.0042 (18)0.0083 (16)0.0119 (17)
C50.047 (2)0.051 (2)0.060 (2)0.0061 (17)0.0055 (17)0.0173 (18)
C60.048 (2)0.0408 (19)0.056 (2)0.0084 (15)0.0022 (16)0.0037 (15)
C70.056 (2)0.054 (2)0.0438 (19)0.0129 (17)0.0041 (16)0.0145 (16)
C80.057 (2)0.048 (2)0.044 (2)0.0008 (17)0.0083 (17)0.0126 (16)
C90.091 (3)0.074 (3)0.043 (2)0.003 (2)0.009 (2)0.009 (2)
C100.049 (2)0.0364 (17)0.0353 (17)0.0029 (15)0.0020 (14)0.0048 (13)
C110.057 (2)0.061 (2)0.0313 (17)0.0009 (18)0.0076 (15)0.0044 (16)
Geometric parameters (Å, º) top
O1—C11.345 (4)C4—C51.377 (6)
O1—C71.437 (4)C4—H40.9500
N1—C101.141 (4)C5—C61.376 (5)
N2—C111.137 (5)C5—H50.9500
C1—C61.391 (5)C6—H60.9500
C1—C21.394 (5)C7—C81.447 (5)
C2—C31.399 (5)C7—H7A0.9900
C2—C101.431 (4)C7—H7B0.9900
C3—C41.382 (5)C8—C91.176 (5)
C3—C111.431 (5)C9—H90.9500
C1—O1—C7118.5 (3)C4—C5—H5119.0
O1—C1—C6126.0 (3)C5—C6—C1119.9 (3)
O1—C1—C2115.1 (3)C5—C6—H6120.1
C6—C1—C2118.9 (3)C1—C6—H6120.1
C1—C2—C3120.2 (3)O1—C7—C8107.0 (3)
C1—C2—C10119.0 (3)O1—C7—H7A110.3
C3—C2—C10120.7 (3)C8—C7—H7A110.3
C4—C3—C2120.3 (3)O1—C7—H7B110.3
C4—C3—C11121.1 (3)C8—C7—H7B110.3
C2—C3—C11118.6 (3)H7A—C7—H7B108.6
C5—C4—C3118.7 (3)C9—C8—C7178.9 (4)
C5—C4—H4120.7C8—C9—H9180.0
C3—C4—H4120.7N1—C10—C2179.0 (4)
C6—C5—C4122.0 (3)N2—C11—C3178.9 (4)
C6—C5—H5119.0
C7—O1—C1—C64.8 (5)C11—C3—C4—C5179.3 (3)
C7—O1—C1—C2176.3 (3)C3—C4—C5—C60.2 (6)
O1—C1—C2—C3178.1 (3)C4—C5—C6—C10.0 (6)
C6—C1—C2—C30.9 (5)O1—C1—C6—C5178.2 (3)
O1—C1—C2—C102.0 (4)C2—C1—C6—C50.6 (5)
C6—C1—C2—C10179.0 (3)C1—O1—C7—C8178.3 (3)
C1—C2—C3—C40.7 (5)O1—C7—C8—C974 (21)
C10—C2—C3—C4179.2 (3)C1—C2—C10—N1123 (21)
C1—C2—C3—C11178.7 (3)C3—C2—C10—N157 (21)
C10—C2—C3—C111.4 (5)C4—C3—C11—N2153 (24)
C2—C3—C4—C50.1 (5)C2—C3—C11—N226 (25)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···N1i0.952.473.335 (6)151
C9—H9···N1ii0.952.513.402 (6)156
Symmetry codes: (i) x1, y1, z; (ii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC11H6N2O
Mr182.18
Crystal system, space groupMonoclinic, P21/n
Temperature (K)153
a, b, c (Å)4.014 (4), 6.833 (7), 33.85 (3)
β (°) 90.77 (2)
V3)928.1 (16)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.30 × 0.16 × 0.08
Data collection
DiffractometerBruker APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.974, 0.993
No. of measured, independent and
observed [I > 2σ(I)] reflections
6610, 1751, 1310
Rint0.071
(sin θ/λ)max1)0.610
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.086, 0.250, 1.13
No. of reflections1751
No. of parameters127
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C6—H6···N1i0.952.473.335 (6)151
C9—H9···N1ii0.952.513.402 (6)156
Symmetry codes: (i) x1, y1, z; (ii) x+1, y+1, z.
Acknowledgements top

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).

references
References top

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Bruker (2011). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Chin, Y. J., Tan, A. L., Wimmer, F. L., Mirza, A. H., Young, D. J., Ng, S. W. & Tiekink, E. R. T. (2012). Acta Cryst. E68, o2293–o2294.

Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.

Seven, O., Dindar, B. & Gultekin, B. (2009). Turk. J. Chem. 33, 123–134.

Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

Wu, Y., Tian, H., Chen, K., Liu, Y. & Zhu, D. (1998). Dyes Pigments, 37, 317–325.