Acta Cryst.(2003). E59, o1423±o1424 DOI: 10.1107/S1600536803018841 Yavuz KoÈysalet al. C17H9N3O
o1423
organic papers
Acta Crystallographica Section E
Structure Reports
Online ISSN 1600-5368
4-(8-Quinolinoxy)phthalonitrile
Yavuz KoÈysal,a* IsËõk SËamil,a
Nesuhi Akdemir,bAgÆar Erbilb
and Vickie McKeec
aDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayõs University, Kurupelit, 55139 Samsun, Turkey,bDepartment of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayõs University, Kurupelit, 55139 Samsun, Turkey, andcChemistry Department, Loughborough University, Loughborough, Leics. LE11 3TU, England
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study T= 150 K
Mean(C±C) = 0.002 AÊ Rfactor = 0.045 wRfactor = 0.115
Data-to-parameter ratio = 13.8
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, C17H9N3O, cyrstallizes with two
mol-ecules in the asymmetric unit. Both independent molmol-ecules have essentially the same geometry. The angles between the planes of the quinoline group and the phenyl ring of the phthalonitrile group in the two molecules are 84.36 (4) and 83.69 (4).
Comment
Substituted phthalonitriles have been used as starting mate-rials for phthalocyanines (McKeown, 1988). In addition to their extensive use as dyes and pigments, phthalocyanines have found widespread applications in catalysis, in optical recording, in photoconductive materials, in photodynamic therapy and as chemical sensors (Leznoff & Lever, 1993).
Fig. 1 shows a perspective view of the asymmetric unit of the title compound, (I), with the numbering scheme. The
C10ÐO1 bond distance is 1.3779 (19) AÊ in molecule A and
1.3717 (19) AÊ in moleculeB. The triple C N bond distances in moleculesAandBare in good agreement with those in a related structure in the literature (Karadaõet al., 2003). The
Received 30 July 2003 Accepted 26 August 2003 Online 30 August 2003
Figure 1
quinoline group is essentially planar. The angle between the least-squares planes C1±C9/N1 and C10±C15 is 84.36 (4) in
molecule A and 83.69 (4) in molecule B; the maximum
deviation from planarity isÿ0.041 (2) AÊ for atom C2Ain the C1A±C9A/N1Aring.
Experimental
8-Quinolinol (1.31 g, 9.03 mmol) and 4-nitrophthalonitrile (1.36 g, 7.86 mmol) were dissolved in dry dimethylformamide (40 ml). After stirring for 30 min at room temperature, dry ®ne-powdered potas-sium carbonate (3.25 g, 23.55 mmol) was added portionwise over 2 h with vigorous stirring. The reaction was stirred for 24 h at room temperature and poured into ice-water (200 g). The product was ®ltered off and washed with (5%w/w) NaOH solution and water until the ®ltrate was neutral. Recrystallization from ethanol gave a white product; yield 1.30 g (6.03%). Single crystals were obtained in ethanol at room temperature via slow evaporation. Calculated: C 75.27, H3.34, N 15.49%; found: C 75.25, H 3.30, N 15.53%. IR data (Vmax/ cmÿ1): 3060±3020 (ArÐCH), 2210 (CN), 1668, 1596, 1560, 1480, 1464, 1416, 1384, 1364, 1312, 1276, 1236, 1188, 1160, 1128, 1090, 1070, 1050, 1024, 990, 944, 880, 825, 790, 772, 736, 725, 705, 660, 640, 625, 575, 525. 1H NMR (acetone-d
6): 7.30±8.02 (m, 7H); 8.48 (d, 1H); 8.80 (d, 1H). 13C NMR (acetone-d
6): 109.03, 116.11, 116.67, 117.92, 122.08, 122.29, 123.21, 127.51, 127.79, 131.39, 136.49, 137.24, 141.80, 150.28, 151.49, 164.03.
Crystal data
C17H9N3O
Mr= 271.28
Monoclinic,P21=c
a= 12.7510 (11) AÊ
b= 14.7398 (12) AÊ
c= 15.0377 (13) AÊ
= 110.3240 (10)
V= 2650.3 (4) AÊ3
Z= 8
Dx= 1.360 Mg mÿ3
MoKradiation
Cell parameters from 22448 re¯ections
=1.70±28.70
= 0.09 mmÿ1
T= 150 (1) K Plate, colourless 0.360.270.05 mm
Data collection
Bruker SMART CCD area-detector diffractometer
'and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.941,Tmax= 10.996
21956 measured re¯ections
6214 independent re¯ections 4311 re¯ections withI> 2(I)
Rint= 0.031
max= 28.7
h=ÿ16!16
k=ÿ18!19
l=ÿ19!19
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.045
wR(F2) = 0.115
S= 1.03 6214 re¯ections 451 parameters
All H-atom parameters re®ned
w= 1/[2(F
o2) + (0.052P)2
+ 0.6288P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.51 e AÊÿ3
min=ÿ0.20 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
O1BÐC10B 1.3717 (19) O1BÐC8B 1.3990 (18) O1AÐC10A 1.3779 (19) O1AÐC8A 1.4048 (18) N1AÐC1A 1.316 (2) N1AÐC9A 1.370 (2)
C16AÐN2A 1.148 (2) N1BÐC1B 1.316 (2) N1BÐC9B 1.368 (2) C17BÐN3B 1.150 (2) C16BÐN2B 1.149 (2) C17AÐN3A 1.150 (2)
C10BÐO1BÐC8B 118.22 (12) C10AÐO1AÐC8A 117.76 (12)
H atoms were located in a difference Fourier map and re®ned independently with isotropic displacement parameters. The ®nal CÐ H distances ranged from 0.94 (2) to 1.01 (2) AÊ.
Data collection:SMART(Bruker, 1998); cell re®nement:SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL (Bruker, 1998); software used to prepare material for publication:WinGX(Farrugia, 1999) andPARST(Nardelli, 1995).
References
Bruker (1998).SMART, SAINTandSHELXTL(Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (1999).J. Appl. Cryst.32, 837±839.
Karadaõ, N., Akdemir, N., AgÆar, E., GuÈmruÈkcËuÈogÆlu, I. E. & BuÈyuÈkguÈngoÈr, O. (2003).Acta Cryst.E59, o945±o946.
Leznoff, C. C. & Lever, A. B. P. (1993). Phthalocyanines: Properties and Applications. Vol. 2. Weinheim: VCH Publishers Inc.
McKeown, N. B. (1988).Phthalocyanine Materials: Synthesis, Structure and Function. Cambridge University Press.
Nardelli, M. (1995).J. Appl. Cryst.28, 659.
Sheldrick, G. M. (1996).SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
supporting information
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Acta Cryst. (2003). E59, o1423–o1424
supporting information
Acta Cryst. (2003). E59, o1423–o1424 [doi:10.1107/S1600536803018841]
4-(8-Quinolinoxy)phthalonitrile
Yavuz K
ö
ysal, I
şı
k
Ş
amil, Nesuhi Akdemir, A
ğ
ar Erbil and Vickie McKee
S1. Comment
Substituted phthalonitriles have been used as starting materials for phthalocyanines (McKeown, 1988). In addition to
their extensive use as dyes and pigments, phthalocyanines have found widespread applications in catalysis, in optical
recording, in photoconductive materials, in photodynamic therapy and as chemical sensors (Leznoff, 1993).
Fig. 1 shows a perspective view of the asymmetric unit of the title compound, (I), with the numbering scheme. The C10
—O1 bond distance is 1.3779 (19) Å in molecule A and 1.3717 (19) Å in molecule B. The triple C≡N bond distances in
molecules A and B are in good agreement with those in a related structure in the literature (Karadaı et al., 2003). The
quinoline group is essentially planar. The angle between the least-squares planes C1–C9/N1 and C10–C15 is 84.36 (4)° in
molecule A and 83.69 (4)° in molecule B; the maximun deviation deviation from planarity being -0.041 (2) Å for C2A
atom in the C1A–C9A/N1A ring.
S2. Experimental
8-Quinolinol (1.31 g, 9.03 mmol) and 4-nitrophthalonitrile (1.36 g, 7.86 mmol) were dissolved in dry dimethylformamide
(40 ml). After stirring for 30 min at room temperature, dry fine-powdered potassium cabonate (3.25 g, 23.55 mmol) was
added portionwise over 2 h with efficent stirring. The reaction was stirred for 24 h at room temperature and poured into
ice-water (200 g). The product was filtered off and washed with (5% w/w) NaOH solution and water until the filtrate was
neutral. Recrystallizaiton from ethanol gave a white product; yield 1.30 g (6.03%). Single crystals were obtained in
ethanol at room temperature via slow evaporation. Calculated: C 75.27, H3.34, N 15.49%; found: C 75.25, H 3.30, N
15.53%. IR data (Vmax/cm-1): 3060–3020 (Ar—CH), 2210 (CN), 1668, 1596, 1560, 1480, 1464, 1416, 1384, 1364, 1312,
1276, 1236, 1188, 1160, 1128, 1090, 1070, 1050, 1024, 990, 944, 880, 825, 790, 772, 736, 725, 705, 660, 640, 625, 575,
525. 1H NMR (acetone-d
6): 7.30–8.02 (m, 7H); 8.48 (d, 1H); 8.80 (d, 1H). 13C NMR (acetone-d6): 109.03, 116.11, 116.67,
117.92, 122.08, 122.29, 123.21, 127.51, 127.79, 131.39, 136.49, 137.24, 141.80, 150.28, 151.49, 164.03.
S3. Refinement
H atoms were located in a difference Fourier map and refined independently with isotropic thermal parameters. The final
Figure 1
The structure of the title compound, showing %50 probability displacement ellipsoids and the atom-numbering scheme.
4-(8-Quinolinoxy)phthalonitrile
Crystal data C17H9N3O Mr = 271.28 Monoclinic, P21/c
Hall symbol: -P 2ybc a = 12.7510 (11) Å b = 14.7398 (12) Å c = 15.0377 (13) Å β = 110.324 (1)° V = 2650.3 (4) Å3
Z = 8
F(000) = 1120 Dx = 1.360 Mg m−3
Mo Kα radiation, λ = 0.71073 Å µ = 0.09 mm−1
T = 150 K Plate, colourless 0.36 × 0.27 × 0.05 mm
Data collection
Bruker SMART CCD area-detector diffractometer
Radiation source: sealed tube Graphite monochromator φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick 1996) Tmin = 0.941, Tmax = 0.996
21956 measured reflections 6214 independent reflections 4311 reflections with I > 2σ(I) Rint = 0.031
θmax = 28.7°, θmin = 1.7° h = −16→16
k = −18→19 l = −19→19
Refinement Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.045 wR(F2) = 0.115 S = 1.03 6214 reflections 451 parameters
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
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Acta Cryst. (2003). E59, o1423–o1424
w = 1/[σ2(F
o2) + (0.052P)2 + 0.6288P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.51 e Å−3
Δρmin = −0.20 e Å−3
Special details
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)
x y z Uiso*/Ueq
C16A 0.51506 (14) 0.92081 (11) 0.79608 (12) 0.0321 (4) N1B 0.41096 (12) 0.83712 (9) 0.28083 (10) 0.0343 (3) C9B 0.46570 (13) 0.84459 (10) 0.21739 (12) 0.0286 (3) C15B 0.24444 (14) 0.72749 (11) 0.07964 (12) 0.0310 (4) C5A 1.19999 (14) 0.82842 (13) 0.82587 (12) 0.0367 (4) N2A 0.43757 (13) 0.91940 (11) 0.81835 (12) 0.0453 (4) C8B 0.40436 (12) 0.86788 (11) 0.12188 (11) 0.0291 (3) N3B −0.09994 (14) 0.56323 (11) 0.03184 (12) 0.0456 (4) C16B −0.08082 (14) 0.79890 (11) 0.06641 (11) 0.0316 (4) C10A 0.81049 (13) 0.91006 (10) 0.80766 (11) 0.0285 (3) N2B −0.16893 (12) 0.81843 (11) 0.06417 (11) 0.0429 (4) C17A 0.48962 (14) 0.93467 (12) 0.60115 (12) 0.0340 (4) C7B 0.45435 (14) 0.87757 (13) 0.05578 (13) 0.0358 (4) C11A 0.71796 (13) 0.91426 (11) 0.83610 (12) 0.0301 (4) C17B −0.02901 (14) 0.61542 (12) 0.04582 (11) 0.0327 (4) C10B 0.21740 (12) 0.81722 (11) 0.08768 (11) 0.0272 (3) C4B 0.58294 (13) 0.83046 (11) 0.24209 (12) 0.0326 (4) C7A 1.08690 (14) 0.94396 (12) 0.86105 (12) 0.0343 (4) C5B 0.63295 (14) 0.83950 (12) 0.17202 (13) 0.0384 (4) C1A 0.95151 (16) 0.64430 (12) 0.82104 (12) 0.0369 (4) C1B 0.47268 (17) 0.81627 (13) 0.36850 (14) 0.0414 (4) N3A 0.40145 (13) 0.94165 (12) 0.54542 (12) 0.0484 (4) C6A 1.18454 (14) 0.91693 (13) 0.84374 (13) 0.0387 (4) C2A 1.04955 (17) 0.61071 (13) 0.80988 (12) 0.0415 (4) C3A 1.13241 (16) 0.66930 (13) 0.81058 (12) 0.0379 (4) C6B 0.57067 (15) 0.86318 (13) 0.08191 (14) 0.0401 (4) C2B 0.58950 (17) 0.80187 (13) 0.40044 (14) 0.0443 (5) C3B 0.64430 (16) 0.80849 (12) 0.33797 (14) 0.0403 (4)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
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Acta Cryst. (2003). E59, o1423–o1424
C9B 0.0266 (8) 0.0222 (8) 0.0372 (9) −0.0031 (6) 0.0113 (7) −0.0058 (6) C15B 0.0231 (8) 0.0341 (9) 0.0351 (9) 0.0027 (7) 0.0092 (7) −0.0041 (7) C5A 0.0260 (9) 0.0534 (12) 0.0306 (9) 0.0073 (8) 0.0097 (7) 0.0046 (8) N2A 0.0343 (8) 0.0511 (10) 0.0569 (10) 0.0004 (7) 0.0239 (8) 0.0023 (8) C8B 0.0199 (7) 0.0275 (8) 0.0376 (9) −0.0019 (6) 0.0073 (7) −0.0070 (7) N3B 0.0478 (9) 0.0424 (9) 0.0535 (10) −0.0108 (8) 0.0261 (8) −0.0038 (7) C16B 0.0304 (9) 0.0352 (9) 0.0295 (8) −0.0026 (7) 0.0109 (7) −0.0013 (7) C10A 0.0260 (8) 0.0244 (8) 0.0340 (8) 0.0003 (6) 0.0091 (7) 0.0007 (6) N2B 0.0308 (8) 0.0542 (10) 0.0465 (9) 0.0013 (7) 0.0169 (7) −0.0013 (7) C17A 0.0288 (9) 0.0357 (9) 0.0374 (9) −0.0030 (7) 0.0115 (8) 0.0084 (7) C7B 0.0295 (9) 0.0433 (10) 0.0325 (9) −0.0037 (7) 0.0082 (7) −0.0071 (8) C11A 0.0298 (8) 0.0299 (9) 0.0317 (9) 0.0018 (7) 0.0120 (7) 0.0009 (7) C17B 0.0357 (9) 0.0348 (9) 0.0313 (8) −0.0027 (8) 0.0163 (7) −0.0025 (7) C10B 0.0237 (8) 0.0309 (8) 0.0245 (7) −0.0021 (6) 0.0053 (6) −0.0032 (6) C4B 0.0254 (8) 0.0276 (8) 0.0413 (9) −0.0017 (6) 0.0071 (7) −0.0056 (7) C7A 0.0316 (9) 0.0335 (10) 0.0336 (9) 0.0039 (7) 0.0060 (7) 0.0044 (7) C5B 0.0242 (9) 0.0420 (11) 0.0495 (11) −0.0026 (7) 0.0132 (8) −0.0086 (8) C1A 0.0430 (10) 0.0370 (10) 0.0255 (8) −0.0023 (8) 0.0054 (7) 0.0001 (7) C1B 0.0518 (11) 0.0360 (10) 0.0395 (10) −0.0070 (8) 0.0196 (9) −0.0032 (8) N3A 0.0317 (8) 0.0630 (11) 0.0461 (9) −0.0035 (7) 0.0079 (7) 0.0171 (8) C6A 0.0275 (9) 0.0469 (11) 0.0390 (10) −0.0010 (8) 0.0081 (8) 0.0093 (8) C2A 0.0524 (12) 0.0366 (10) 0.0288 (9) 0.0084 (9) 0.0057 (8) −0.0047 (8) C3A 0.0387 (10) 0.0468 (11) 0.0245 (8) 0.0135 (9) 0.0061 (7) −0.0034 (7) C6B 0.0325 (9) 0.0489 (11) 0.0420 (10) −0.0046 (8) 0.0169 (8) −0.0100 (8) C2B 0.0494 (12) 0.0379 (10) 0.0360 (10) −0.0058 (8) 0.0027 (9) 0.0025 (8) C3B 0.0331 (10) 0.0321 (10) 0.0478 (11) −0.0017 (7) 0.0040 (8) −0.0011 (8)
Geometric parameters (Å, º)
O1B—C10B 1.3717 (19) C9B—C8B 1.418 (2)
O1B—C8B 1.3990 (18) C9B—C4B 1.425 (2)
O1A—C10A 1.3779 (19) C15B—C10B 1.383 (2) O1A—C8A 1.4048 (18) C15B—H8B 0.942 (18)
C4A—C3A 1.409 (2) C5A—C6A 1.360 (3)
C4A—C5A 1.414 (3) C5A—H4A 0.968 (18)
C4A—C9A 1.427 (2) C8B—C7B 1.362 (2)
C12A—C11A 1.385 (2) C17B—N3B 1.150 (2) C12A—C13A 1.406 (2) C16B—N2B 1.149 (2) C12A—C16A 1.445 (2) C10A—C11A 1.389 (2) C12B—C11B 1.385 (2) C17A—N3A 1.150 (2)
C12B—C13B 1.407 (2) C7B—C6B 1.412 (2)
C12B—C16B 1.442 (2) C7B—H6B 0.952 (19)
C11B—C10B 1.390 (2) C11A—H7A 0.971 (16)
C11B—H7B 0.991 (18) C4B—C5B 1.415 (2)
C14A—C15A 1.382 (2) C4B—C3B 1.419 (2)
C14A—C13A 1.391 (2) C7A—C6A 1.415 (2)
C14A—H9A 0.961 (18) C7A—H6A 0.978 (19)
N1A—C1A 1.316 (2) C5B—H4B 0.968 (19)
N1A—C9A 1.370 (2) C1A—C2A 1.408 (3)
C9A—C8A 1.419 (2) C1A—H1A 1.01 (2)
C13B—C14B 1.394 (2) C1B—C2B 1.413 (3)
C13B—C17B 1.438 (2) C1B—H1B 0.953 (19)
C15A—C10A 1.386 (2) C6A—H5A 0.96 (2)
C15A—H8A 0.956 (19) C2A—C3A 1.362 (3)
C8A—C7A 1.352 (2) C2A—H2A 0.99 (2)
C14B—C15B 1.388 (2) C3A—H3A 0.96 (2)
C14B—H9B 0.987 (18) C6B—H5B 0.99 (2)
C16A—N2A 1.148 (2) C2B—C3B 1.355 (3)
N1B—C1B 1.316 (2) C2B—H2B 0.94 (2)
N1B—C9B 1.368 (2) C3B—H3B 0.99 (2)
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Acta Cryst. (2003). E59, o1423–o1424
C15B—C14B—H9B 121.0 (10) C3A—C2A—C1A 119.66 (18) C13B—C14B—H9B 119.2 (10) C3A—C2A—H2A 124.6 (12) N2A—C16A—C12A 178.57 (18) C1A—C2A—H2A 115.8 (12) C1B—N1B—C9B 116.42 (15) C2A—C3A—C4A 118.97 (17) N1B—C9B—C8B 119.34 (14) C2A—C3A—H3A 122.1 (12) N1B—C9B—C4B 123.33 (15) C4A—C3A—H3A 119.0 (12) C8B—C9B—C4B 117.32 (15) C5B—C6B—C7B 120.68 (18) C10B—C15B—C14B 120.17 (15) C5B—C6B—H5B 119.6 (12) C10B—C15B—H8B 119.2 (11) C7B—C6B—H5B 119.7 (12) C14B—C15B—H8B 120.6 (11) C3B—C2B—C1B 119.34 (18) C6A—C5A—C4A 120.44 (16) C3B—C2B—H2B 121.4 (13) C6A—C5A—H4A 120.2 (11) C1B—C2B—H2B 119.2 (13) C4A—C5A—H4A 119.4 (11) C2B—C3B—C4B 119.07 (18) C7B—C8B—O1B 118.99 (15) C2B—C3B—H3B 121.5 (12) C7B—C8B—C9B 122.08 (15) C4B—C3B—H3B 119.4 (12)
