4-{4-[(E)-(2-Hy­droxy­phen­yl)imino­methyl]phen­oxy}benzene-1,2-di­carbo­nitrile

Tuncer, H.; Görgülü, A.O.; Hökelek, T.

doi:10.1107/S1600536812003649

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages o565-o566

doi:10.1107/S1600536812003649

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4-{4-[(E)-(2-Hydroxyphenyl)iminomethyl]phenoxy}benzene-1,2-dicarbonitrile

Hülya Tuncer,^a Ahmet Orhan Görgülü ^a and Tuncer Hökelek ^b ^*

^aFırat University, Department of Chemistry, 23169 Elazığ, Turkey, and ^bHacettepe University, Department of Physics, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 24 January 2012; accepted 27 January 2012; online 4 February 2012)

The asymmetric unit of the title compound, C₂₁H₁₃N₃O₂, contains two independent molecules with a similar structure. In one molecule, the central benzene ring is oriented with respect to the terminal benzene rings at 27.23 (7) and 67.96 (7)°; in the other molecule, the corresponding dihedral angles are 12.42 (7) and 64.55 (7)°. In both molecules, there is a short O—H⋯N interaction involving the OH group and the adjacent N atom. In the crystal, there are O—H⋯N hydrogen bonds, and C—H⋯O and N—H⋯O interactions linking the molecules to form a three-dimensional network. π–π stacking between the pyridine and benzene rings and between the benzene rings [centroid–centroid distances = 3.989 (2), 3.705 (2) and 3.607 (2) Å] may further stabilize the structure. A weak C—H⋯π interaction is present in the crystal.

Related literature

For the use of phthalonitriles for preparing symmetrically and unsymmetrically substituted phthalocyanine complexes, see: Leznoff & Lever (1996 ). For the widespread applications of phthalocyanines in photodynamic therapy, see: Kartal et al. (2006 ); Tüfekçi et al. (2009 ). For the fundamental optical and electronic properties of phthalocyanines, see: McKeown (1998 ). For related structures, see: Tuncer et al. (2012 ); Tüfekçi et al. (2009); Yazıcı et al. (2009 ); Kartal et al. (2006). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₁H₁₃N₃O₂
M_r = 339.34
Triclinic, $[P \overline 1]$
a = 9.842 (3) Å
b = 13.448 (4) Å
c = 14.061 (4) Å
α = 109.940 (15)°
β = 96.937 (16)°
γ = 104.182 (15)°
V = 1652.9 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.40 × 0.23 × 0.13 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.975, T_max = 0.988
28993 measured reflections
8180 independent reflections
4415 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.148
S = 1.01
8180 reflections
478 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C8–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.84	2.24	2.713 (3)	116
O1—H1⋯N2ⁱ	0.84	2.50	2.993 (3)	119
O1′—H1′⋯N1′	0.84	2.18	2.659 (3)	116
O1′—H1′⋯N3ⁱ	0.84	2.39	2.948 (3)	125
C3′—H3′⋯N3′ⁱⁱ	0.95	2.52	3.344 (4)	145
C5—H5⋯O1′ⁱⁱⁱ	0.95	2.40	3.180 (3)	139
C12—H12⋯O1^iv	0.95	2.35	3.214 (3)	151
C6′—H6′⋯Cg^v	0.95	2.93	3.785 (3)	151
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y-1, z; (iii) x, y+1, z; (iv) x+1, y, z; (v) -x+1, -y, -z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812003649/xu5458sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003649/xu5458Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812003649/xu5458Isup3.cml

checkCIF report

Comment top

Phthalonitriles are used for preparing symmetrically and unsymmetrically substituted phthalocyanine complexes (Leznoff & Lever, 1996). Phthalocyanines have been of great interest to chemists, physicists and industrial scientists. Phthalocyanines have currently been the topic of research because of their wide application fields, such as thin film fabrication, organic pigments, chemical sensors, electrochromic display devices, molecular epitaxic deposition and composites, liquid crystals, photovoltaic cells self-assembled materials. In addition to their extensive use as dyes and pigments, phthalocyanines have found widespread application, in photodynamic therapy (Kartal et al., 2006; Tüfekçi et al., 2009). The fundamental optical and electronic properties of these materials are explained and their potential in non-linear optics, optical data storage, electronic sensors, xerography, solar energy conversion, nuclear chemistry, molecular magnetism, electrochromic displays and heterogeneous catalysis is evaulated by McKeown (1998).

The structures of some phthalonitrile derivatives, C₁₃H₈N₂O₂ (Tuncer et al., 2012), C₂₁H₁₂ClN₃O (Tüfekçi et al., 2009), C₂₃H₁₇N₃O₂ (Yazıcı et al., 2009) and C₁₅H₈N₂O₂ (Kartal et al., 2006) have also been determined.

The asymmetric unit of the title compound, (Fig. 1) contains two crystallographically independent molecules, and the bond lengths are close to standard values (Allen et al., 1987).

The dihedral angles between the hydroxyphenyl rings [A (C1—C6) and A' (C1'—C6')] and the benzene [B (C8—C13), C (C14—C19) and B' (C8'—C13'), C' (C14'—C19')] rings are A/B = 27.23 (7), A/C = 41.88 (7) and A'/B' = 12.42 (7), A'/C' = 73.19 (7) °, while those between the benzene rings B, C and B', C' are B/C = 67.96 (7) and B'/C' = 64.55 (7) °.

In the crystal, intermolecular O—H···N, C—H···O and C—H···N hydrogen bonds (Table 1) link the molecules into a three-dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure. π–π Contacts between the pyridine and benzene rings and between the benzene rings, Cg1—Cg2ⁱ, Cg1—Cg6 and Cg5—Cg5ⁱⁱ [symmetry codes: (i) 1 - x, 1 - y, 1 - z, (ii) -x, -y, -z, where Cg1, Cg2, Cg5 and Cg6 are the centroids of the rings A (C1—C6), B (C8—C13), B' (C8'—C13') and C' (C14'—C19'), respectively] may further stabilize the structure, with centroid-centroid distances of 3.989 (2), 3.705 (2) and 3.607 (2) Å]. There also exists a weak C—H···π interaction (Table 1).

Related literature top

For the use of phthalonitriles for preparing symmetrically and unsymmetrically substituted phthalocyanine complexes, see: Leznoff & Lever (1996). For the widespread applications of phthalocyanines in photodynamic therapy, see: Kartal et al. (2006); Tüfekçi et al. (2009). For the fundamental optical and electronic properties of phthalocyanines, see: McKeown (1998). For related structures, see: Tuncer et al. (2012); Tüfekçi et al. (2009); Yazıcı et al. (2009); Kartal et al. (2006). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound has been prepared in two steps. In the first step; 4-hydroxybenzaldehyde (1.86 g, 15.2 mmol) and 4-nitrophthalonitrile (2.64 g, 15.2 mmol) were heated at 353 K in dry DMF (20 ml) with stirring under argon atmosphere. Then, dry fine powdered potassium carbonate (6.00 g, 43.47 mmol) was added in portions (14 × 3.1 mmol) every 10 min. The mixture was heated for a further 18 h. After cooling, the mixture was added into ice-water (200 g). The product was filtered off and washed with NaOH solution (10% w/w) and water until the filtrate was neutral. In the second step; 4-(4-formylphenoxy)benzene-1,2-dicarbonitrile (1.88 g, 7.6 mmol), the product obtained in the first step, and 2-hydroxyaniline (0.83 g, 7.6 mmol) were reacted at 333 K for 4 h in absolute ethanol (50 ml). Recrystallization from absolute ethanol gave a yellow product (yield: 1.55 g, 60%). Single crystals suitable for X-ray diffraction measurement were obtained by slow evaporation of the solution in ethanol (m.p. 433 K).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram. Hydrogen bonds are shown as dashed lines. Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.

4-{4-[(E)-(2-Hydroxyphenyl)iminomethyl]phenoxy}benzene-1,2-dicarbonitrile top

Crystal data top

C₂₁H₁₃N₃O₂	Z = 4
M_r = 339.34	F(000) = 704
Triclinic, P1	D_x = 1.364 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.842 (3) Å	Cell parameters from 4598 reflections
b = 13.448 (4) Å	θ = 2.3–23.5°
c = 14.061 (4) Å	µ = 0.09 mm⁻¹
α = 109.940 (15)°	T = 100 K
β = 96.937 (16)°	Block, yellow
γ = 104.182 (15)°	0.40 × 0.23 × 0.13 mm
V = 1652.9 (9) Å³

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	8180 independent reflections
Radiation source: fine-focus sealed tube	4415 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ϕ and ω scans	θ_max = 28.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→13
T_min = 0.975, T_max = 0.988	k = −17→17
28993 measured reflections	l = −18→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.148	w = 1/[σ²(F_o²) + (0.0581P)² + 0.3399P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
8180 reflections	Δρ_max = 0.25 e Å⁻³
478 parameters	Δρ_min = −0.26 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0067 (11)

Crystal data top

C₂₁H₁₃N₃O₂	γ = 104.182 (15)°
M_r = 339.34	V = 1652.9 (9) Å³
Triclinic, P1	Z = 4
a = 9.842 (3) Å	Mo Kα radiation
b = 13.448 (4) Å	µ = 0.09 mm⁻¹
c = 14.061 (4) Å	T = 100 K
α = 109.940 (15)°	0.40 × 0.23 × 0.13 mm
β = 96.937 (16)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	8180 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4415 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.988	R_int = 0.059
28993 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	1 restraint
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.25 e Å⁻³
8180 reflections	Δρ_min = −0.26 e Å⁻³
478 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.18465 (16)	0.42838 (13)	0.39648 (13)	0.0415 (4)
H1	0.2341	0.3847	0.3902	0.062*
O2	0.81989 (17)	0.09971 (13)	0.27981 (12)	0.0363 (4)
N1	0.4497 (2)	0.44136 (14)	0.35611 (13)	0.0307 (4)
N2	0.8274 (2)	−0.23636 (18)	0.53937 (17)	0.0523 (6)
N3	0.6366 (2)	−0.00505 (17)	0.62696 (17)	0.0470 (6)
C1	0.3989 (2)	0.53409 (17)	0.36774 (16)	0.0296 (5)
C2	0.2600 (2)	0.52160 (18)	0.38515 (16)	0.0315 (5)
C3	0.1965 (3)	0.60425 (19)	0.39298 (17)	0.0342 (6)
H3	0.1024	0.5953	0.4054	0.041*
C4	0.2708 (3)	0.69943 (19)	0.38268 (17)	0.0376 (6)
H4	0.2274	0.7563	0.3878	0.045*
C5	0.4085 (3)	0.71348 (19)	0.36498 (18)	0.0396 (6)
H5	0.4592	0.7798	0.3584	0.048*
C6	0.4720 (3)	0.63074 (18)	0.35691 (17)	0.0351 (6)
H6	0.5659	0.6400	0.3439	0.042*
C7	0.5842 (3)	0.45413 (19)	0.37209 (17)	0.0312 (5)
H7	0.655 (2)	0.5282 (18)	0.3985 (16)	0.028 (6)*
C8	0.6422 (2)	0.36070 (18)	0.35210 (16)	0.0295 (5)
C9	0.5531 (2)	0.25160 (18)	0.31442 (17)	0.0338 (5)
H9	0.4519	0.2370	0.3045	0.041*
C10	0.6099 (2)	0.16393 (19)	0.29116 (18)	0.0348 (6)
H10	0.5486	0.0894	0.2639	0.042*
C11	0.7580 (2)	0.18678 (19)	0.30826 (17)	0.0305 (5)
C12	0.8491 (2)	0.29320 (19)	0.34658 (17)	0.0339 (5)
H12	0.9503	0.3073	0.3584	0.041*
C13	0.7904 (2)	0.37987 (19)	0.36777 (17)	0.0344 (5)
H13	0.8525	0.4541	0.3936	0.041*
C14	0.8182 (2)	0.03424 (18)	0.33583 (16)	0.0290 (5)
C15	0.8887 (2)	−0.04502 (18)	0.30548 (17)	0.0334 (5)
H15	0.9354	−0.0505	0.2494	0.040*
C16	0.8912 (2)	−0.11571 (18)	0.35649 (17)	0.0345 (6)
H16	0.9389	−0.1703	0.3351	0.041*
C17	0.8244 (2)	−0.10786 (17)	0.43904 (17)	0.0300 (5)
C18	0.7555 (2)	−0.02651 (17)	0.47002 (16)	0.0285 (5)
C19	0.7513 (2)	0.04448 (17)	0.41867 (16)	0.0282 (5)
H19	0.7036	0.0991	0.4397	0.034*
C20	0.8271 (3)	−0.18017 (19)	0.49414 (19)	0.0373 (6)
C21	0.6881 (3)	−0.01535 (18)	0.55668 (18)	0.0332 (5)
O1'	0.48536 (19)	−0.14517 (14)	0.22704 (13)	0.0492 (5)
H1'	0.4479	−0.0949	0.2288	0.074*
O2'	−0.00214 (16)	0.24585 (12)	0.13213 (12)	0.0353 (4)
N1'	0.37253 (18)	−0.08750 (14)	0.07998 (14)	0.0281 (4)
N2'	0.1000 (2)	0.76703 (18)	0.15817 (17)	0.0486 (6)
N3'	−0.2416 (2)	0.60508 (18)	0.22270 (19)	0.0549 (6)
C1'	0.4335 (2)	−0.17435 (18)	0.04730 (17)	0.0304 (5)
C2'	0.4886 (2)	−0.20314 (19)	0.12727 (18)	0.0354 (6)
C3'	0.5463 (3)	−0.2899 (2)	0.1072 (2)	0.0429 (6)
H3'	0.5834	−0.3086	0.1621	0.052*
C4'	0.5493 (3)	−0.3490 (2)	0.0066 (2)	0.0422 (6)
H4'	0.5865	−0.4101	−0.0079	0.051*
C5'	0.4992 (2)	−0.3211 (2)	−0.0738 (2)	0.0402 (6)
H5'	0.5044	−0.3614	−0.1427	0.048*
C6'	0.4417 (2)	−0.23440 (19)	−0.05337 (18)	0.0364 (6)
H6'	0.4071	−0.2153	−0.1087	0.044*
C7'	0.3167 (2)	−0.05176 (18)	0.01768 (18)	0.0292 (5)
H7'	0.317 (2)	−0.0807 (17)	−0.0559 (13)	0.040 (7)*
C8'	0.2428 (2)	0.03159 (17)	0.05018 (16)	0.0263 (5)
C9'	0.2161 (2)	0.06816 (17)	0.14996 (16)	0.0293 (5)
H9'	0.2504	0.0410	0.1991	0.035*
C10'	0.1404 (2)	0.14318 (18)	0.17726 (17)	0.0309 (5)
H10'	0.1238	0.1690	0.2454	0.037*
C11'	0.0888 (2)	0.18043 (17)	0.10454 (17)	0.0293 (5)
C12'	0.1125 (2)	0.14594 (18)	0.00537 (17)	0.0333 (5)
H12'	0.0766	0.1727	−0.0436	0.040*
C13'	0.1897 (2)	0.07143 (17)	−0.02080 (17)	0.0310 (5)
H13'	0.2070	0.0469	−0.0888	0.037*
C14'	0.0287 (2)	0.34959 (17)	0.12998 (16)	0.0286 (5)
C15'	0.1547 (2)	0.40575 (18)	0.11284 (17)	0.0321 (5)
H15'	0.2274	0.3712	0.0987	0.038*
C16'	0.1749 (2)	0.51264 (18)	0.11636 (17)	0.0326 (5)
H16'	0.2608	0.5506	0.1030	0.039*
C17'	0.0709 (2)	0.56471 (17)	0.13924 (16)	0.0294 (5)
C18'	−0.0559 (2)	0.50719 (18)	0.15786 (16)	0.0291 (5)
C19'	−0.0774 (2)	0.39984 (18)	0.15198 (16)	0.0295 (5)
H19'	−0.1644	0.3605	0.1629	0.035*
C20'	0.0907 (2)	0.6771 (2)	0.14833 (17)	0.0355 (6)
C21'	−0.1606 (3)	0.56133 (19)	0.19089 (19)	0.0372 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0353 (10)	0.0367 (9)	0.0574 (11)	0.0106 (8)	0.0084 (8)	0.0249 (8)
O2	0.0479 (10)	0.0463 (10)	0.0352 (9)	0.0280 (8)	0.0222 (8)	0.0265 (8)
N1	0.0350 (11)	0.0306 (10)	0.0283 (10)	0.0125 (9)	0.0059 (8)	0.0123 (8)
N2	0.0672 (16)	0.0409 (12)	0.0511 (14)	0.0164 (12)	0.0019 (12)	0.0245 (11)
N3	0.0592 (15)	0.0501 (14)	0.0409 (13)	0.0184 (12)	0.0200 (11)	0.0246 (11)
C1	0.0345 (13)	0.0285 (12)	0.0237 (11)	0.0095 (10)	0.0015 (9)	0.0092 (9)
C2	0.0344 (13)	0.0310 (12)	0.0268 (12)	0.0073 (11)	0.0007 (10)	0.0124 (10)
C3	0.0359 (13)	0.0378 (13)	0.0296 (12)	0.0149 (11)	0.0034 (10)	0.0125 (11)
C4	0.0513 (16)	0.0330 (13)	0.0265 (12)	0.0179 (12)	−0.0017 (11)	0.0089 (10)
C5	0.0459 (15)	0.0337 (13)	0.0389 (14)	0.0082 (12)	0.0024 (11)	0.0188 (11)
C6	0.0336 (13)	0.0362 (13)	0.0344 (13)	0.0083 (11)	0.0029 (10)	0.0155 (11)
C7	0.0371 (14)	0.0294 (13)	0.0250 (12)	0.0082 (11)	0.0038 (10)	0.0105 (10)
C8	0.0331 (13)	0.0341 (13)	0.0252 (11)	0.0109 (10)	0.0080 (9)	0.0152 (10)
C9	0.0296 (13)	0.0374 (13)	0.0350 (13)	0.0111 (11)	0.0053 (10)	0.0147 (11)
C10	0.0354 (14)	0.0316 (13)	0.0385 (14)	0.0094 (11)	0.0093 (11)	0.0151 (11)
C11	0.0398 (14)	0.0383 (13)	0.0267 (12)	0.0208 (11)	0.0160 (10)	0.0197 (10)
C12	0.0281 (12)	0.0452 (14)	0.0359 (13)	0.0124 (11)	0.0113 (10)	0.0226 (11)
C13	0.0327 (13)	0.0349 (13)	0.0350 (13)	0.0066 (11)	0.0062 (10)	0.0160 (11)
C14	0.0317 (12)	0.0344 (12)	0.0253 (12)	0.0118 (10)	0.0068 (9)	0.0156 (10)
C15	0.0372 (13)	0.0386 (13)	0.0277 (12)	0.0179 (11)	0.0104 (10)	0.0113 (10)
C16	0.0395 (14)	0.0311 (12)	0.0334 (13)	0.0180 (11)	0.0055 (11)	0.0090 (10)
C17	0.0322 (12)	0.0271 (12)	0.0284 (12)	0.0073 (10)	0.0006 (10)	0.0111 (10)
C18	0.0297 (12)	0.0294 (12)	0.0244 (11)	0.0062 (10)	0.0044 (9)	0.0105 (10)
C19	0.0319 (12)	0.0293 (12)	0.0266 (12)	0.0124 (10)	0.0090 (9)	0.0117 (10)
C20	0.0418 (15)	0.0303 (13)	0.0370 (14)	0.0103 (11)	0.0020 (11)	0.0123 (11)
C21	0.0400 (14)	0.0315 (13)	0.0314 (13)	0.0114 (11)	0.0073 (11)	0.0160 (11)
O1'	0.0714 (13)	0.0581 (11)	0.0373 (10)	0.0373 (10)	0.0189 (9)	0.0272 (9)
O2'	0.0333 (9)	0.0301 (9)	0.0484 (10)	0.0135 (7)	0.0155 (7)	0.0175 (8)
N1'	0.0276 (10)	0.0278 (10)	0.0324 (10)	0.0103 (8)	0.0067 (8)	0.0143 (8)
N2'	0.0527 (14)	0.0440 (13)	0.0553 (14)	0.0165 (11)	0.0085 (11)	0.0265 (11)
N3'	0.0510 (14)	0.0489 (14)	0.0791 (18)	0.0283 (12)	0.0234 (13)	0.0299 (13)
C1'	0.0257 (12)	0.0319 (12)	0.0361 (13)	0.0086 (10)	0.0071 (10)	0.0160 (11)
C2'	0.0382 (14)	0.0411 (14)	0.0343 (14)	0.0165 (12)	0.0145 (11)	0.0184 (11)
C3'	0.0486 (16)	0.0497 (15)	0.0513 (16)	0.0271 (13)	0.0208 (13)	0.0327 (13)
C4'	0.0396 (15)	0.0397 (14)	0.0575 (17)	0.0180 (12)	0.0202 (13)	0.0238 (13)
C5'	0.0368 (14)	0.0396 (14)	0.0420 (15)	0.0158 (12)	0.0111 (11)	0.0094 (12)
C6'	0.0341 (13)	0.0390 (14)	0.0348 (13)	0.0137 (11)	0.0045 (10)	0.0119 (11)
C7'	0.0280 (12)	0.0303 (12)	0.0284 (12)	0.0081 (10)	0.0057 (10)	0.0110 (10)
C8'	0.0235 (11)	0.0253 (11)	0.0279 (12)	0.0052 (9)	0.0026 (9)	0.0104 (9)
C9'	0.0276 (12)	0.0340 (12)	0.0275 (12)	0.0087 (10)	0.0040 (9)	0.0147 (10)
C10'	0.0288 (12)	0.0334 (12)	0.0290 (12)	0.0086 (10)	0.0079 (10)	0.0105 (10)
C11'	0.0253 (12)	0.0253 (11)	0.0356 (13)	0.0088 (10)	0.0067 (10)	0.0088 (10)
C12'	0.0363 (13)	0.0334 (13)	0.0311 (13)	0.0116 (11)	0.0032 (10)	0.0144 (10)
C13'	0.0359 (13)	0.0300 (12)	0.0271 (12)	0.0122 (10)	0.0067 (10)	0.0097 (10)
C14'	0.0308 (12)	0.0263 (12)	0.0274 (12)	0.0090 (10)	0.0034 (9)	0.0095 (9)
C15'	0.0291 (13)	0.0331 (13)	0.0332 (13)	0.0117 (10)	0.0074 (10)	0.0101 (10)
C16'	0.0322 (13)	0.0334 (13)	0.0305 (12)	0.0071 (11)	0.0088 (10)	0.0116 (10)
C17'	0.0338 (13)	0.0309 (12)	0.0246 (11)	0.0107 (10)	0.0049 (9)	0.0119 (10)
C18'	0.0298 (12)	0.0322 (12)	0.0264 (12)	0.0124 (10)	0.0026 (9)	0.0117 (10)
C19'	0.0253 (12)	0.0317 (12)	0.0304 (12)	0.0079 (10)	0.0053 (9)	0.0116 (10)
C20'	0.0397 (14)	0.0377 (14)	0.0321 (13)	0.0133 (11)	0.0052 (10)	0.0171 (11)
C21'	0.0366 (14)	0.0345 (13)	0.0455 (15)	0.0155 (12)	0.0092 (11)	0.0183 (12)

Geometric parameters (Å, º) top

O1—C2	1.362 (3)	O1'—C2'	1.362 (3)
O1—H1	0.8400	O1'—H1'	0.8400
O2—C11	1.411 (2)	O2'—C14'	1.365 (3)
O2—C14	1.366 (2)	O2'—C11'	1.401 (2)
N1—C1	1.420 (3)	N1'—C1'	1.407 (3)
N1—C7	1.274 (3)	N1'—C7'	1.265 (3)
N2—C20	1.142 (3)	C1'—C6'	1.393 (3)
C1—C2	1.398 (3)	C2'—C1'	1.400 (3)
C1—C6	1.390 (3)	C3'—C2'	1.379 (3)
C3—C2	1.382 (3)	C3'—H3'	0.9500
C3—H3	0.9500	C4'—C3'	1.374 (3)
C4—C3	1.374 (3)	C4'—C5'	1.381 (3)
C4—H4	0.9500	C4'—H4'	0.9500
C5—C4	1.387 (3)	C5'—C6'	1.377 (3)
C5—H5	0.9500	C5'—H5'	0.9500
C6—C5	1.383 (3)	C6'—H6'	0.9500
C6—H6	0.9500	C7'—C8'	1.457 (3)
C7—H7	0.98 (2)	C7'—H7'	0.974 (16)
C8—C7	1.461 (3)	C8'—C9'	1.401 (3)
C8—C9	1.389 (3)	C8'—C13'	1.390 (3)
C9—C10	1.383 (3)	C9'—C10'	1.376 (3)
C9—H9	0.9500	C9'—H9'	0.9500
C10—H10	0.9500	C10'—C11'	1.379 (3)
C11—C12	1.368 (3)	C10'—H10'	0.9500
C11—C10	1.386 (3)	C11'—C12'	1.380 (3)
C12—C13	1.384 (3)	C12'—H12'	0.9500
C12—H12	0.9500	C13'—C12'	1.381 (3)
C13—C8	1.393 (3)	C13'—H13'	0.9500
C13—H13	0.9500	C14'—C15'	1.379 (3)
C14—C15	1.387 (3)	C14'—C19'	1.387 (3)
C15—C16	1.375 (3)	C15'—C16'	1.385 (3)
C15—H15	0.9500	C15'—H15'	0.9500
C16—H16	0.9500	C16'—C17'	1.385 (3)
C17—C16	1.388 (3)	C16'—H16'	0.9500
C18—C17	1.398 (3)	C17'—C18'	1.402 (3)
C18—C19	1.384 (3)	C17'—C20'	1.434 (3)
C18—C21	1.437 (3)	C18'—C19'	1.379 (3)
C19—C14	1.389 (3)	C18'—C21'	1.436 (3)
C19—H19	0.9500	C19'—H19'	0.9500
C20—C17	1.438 (3)	C20'—N2'	1.148 (3)
C21—N3	1.147 (3)	C21'—N3'	1.148 (3)

C2—O1—H1	109.5	C2'—O1'—H1'	109.5
C14—O2—C11	120.14 (16)	C14'—O2'—C11'	121.23 (17)
C7—N1—C1	120.25 (19)	C7'—N1'—C1'	122.54 (19)
C2—C1—N1	115.60 (19)	C2'—C1'—N1'	114.24 (19)
C6—C1—N1	125.4 (2)	C6'—C1'—N1'	127.7 (2)
C6—C1—C2	118.8 (2)	C6'—C1'—C2'	118.0 (2)
O1—C2—C1	120.78 (19)	O1'—C2'—C1'	119.9 (2)
O1—C2—C3	118.4 (2)	O1'—C2'—C3'	118.8 (2)
C3—C2—C1	120.8 (2)	C3'—C2'—C1'	121.3 (2)
C2—C3—H3	120.3	C2'—C3'—H3'	120.5
C4—C3—C2	119.4 (2)	C4'—C3'—C2'	119.1 (2)
C4—C3—H3	120.3	C4'—C3'—H3'	120.5
C3—C4—C5	120.7 (2)	C3'—C4'—C5'	121.2 (2)
C3—C4—H4	119.6	C3'—C4'—H4'	119.4
C5—C4—H4	119.6	C5'—C4'—H4'	119.4
C4—C5—H5	120.1	C4'—C5'—H5'	120.2
C6—C5—C4	119.9 (2)	C6'—C5'—C4'	119.5 (2)
C6—C5—H5	120.1	C6'—C5'—H5'	120.2
C1—C6—H6	119.9	C1'—C6'—H6'	119.5
C5—C6—C1	120.3 (2)	C5'—C6'—C1'	120.9 (2)
C5—C6—H6	119.9	C5'—C6'—H6'	119.5
N1—C7—C8	122.6 (2)	N1'—C7'—C8'	122.4 (2)
N1—C7—H7	121.4 (12)	N1'—C7'—H7'	121.7 (13)
C8—C7—H7	116.0 (12)	C8'—C7'—H7'	115.8 (13)
C9—C8—C7	121.7 (2)	C9'—C8'—C7'	121.56 (19)
C9—C8—C13	118.4 (2)	C13'—C8'—C7'	119.66 (19)
C13—C8—C7	119.9 (2)	C13'—C8'—C9'	118.66 (19)
C8—C9—H9	119.6	C8'—C9'—H9'	119.8
C10—C9—C8	120.8 (2)	C10'—C9'—C8'	120.5 (2)
C10—C9—H9	119.6	C10'—C9'—H9'	119.8
C9—C10—C11	118.8 (2)	C9'—C10'—C11'	119.2 (2)
C9—C10—H10	120.6	C9'—C10'—H10'	120.4
C11—C10—H10	120.6	C11'—C10'—H10'	120.4
C10—C11—O2	120.6 (2)	C10'—C11'—O2'	116.81 (19)
C12—C11—O2	117.4 (2)	C10'—C11'—C12'	122.0 (2)
C12—C11—C10	121.9 (2)	C12'—C11'—O2'	120.9 (2)
C11—C12—C13	118.5 (2)	C11'—C12'—C13'	118.3 (2)
C11—C12—H12	120.8	C11'—C12'—H12'	120.9
C13—C12—H12	120.8	C13'—C12'—H12'	120.9
C8—C13—H13	119.3	C8'—C13'—H13'	119.3
C12—C13—C8	121.5 (2)	C12'—C13'—C8'	121.4 (2)
C12—C13—H13	119.3	C12'—C13'—H13'	119.3
O2—C14—C15	115.88 (19)	O2'—C14'—C15'	125.50 (19)
O2—C14—C19	123.40 (19)	O2'—C14'—C19'	113.92 (19)
C15—C14—C19	120.7 (2)	C15'—C14'—C19'	120.5 (2)
C14—C15—H15	120.0	C14'—C15'—C16'	119.8 (2)
C16—C15—C14	120.1 (2)	C14'—C15'—H15'	120.1
C16—C15—H15	120.0	C16'—C15'—H15'	120.1
C15—C16—C17	120.4 (2)	C15'—C16'—C17'	120.5 (2)
C15—C16—H16	119.8	C15'—C16'—H16'	119.7
C17—C16—H16	119.8	C17'—C16'—H16'	119.7
C16—C17—C18	119.0 (2)	C16'—C17'—C18'	119.0 (2)
C16—C17—C20	121.3 (2)	C16'—C17'—C20'	122.2 (2)
C18—C17—C20	119.7 (2)	C18'—C17'—C20'	118.8 (2)
C19—C18—C17	121.0 (2)	C17'—C18'—C21'	120.8 (2)
C17—C18—C21	120.0 (2)	C19'—C18'—C17'	120.43 (19)
C19—C18—C21	118.97 (19)	C19'—C18'—C21'	118.6 (2)
C14—C19—H19	120.6	C14'—C19'—H19'	120.2
C18—C19—C14	118.72 (19)	C18'—C19'—C14'	119.6 (2)
C18—C19—H19	120.6	C18'—C19'—H19'	120.2
N2—C20—C17	178.4 (3)	N2'—C20'—C17'	176.1 (3)
N3—C21—C18	178.8 (3)	N3'—C21'—C18'	176.3 (3)

C14—O2—C11—C10	−72.6 (3)	C14'—O2'—C11'—C10'	123.8 (2)
C14—O2—C11—C12	111.6 (2)	C14'—O2'—C11'—C12'	−62.8 (3)
C11—O2—C14—C15	−176.49 (19)	C11'—O2'—C14'—C15'	−7.5 (3)
C11—O2—C14—C19	3.3 (3)	C11'—O2'—C14'—C19'	175.44 (18)
C7—N1—C1—C2	−158.2 (2)	C7'—N1'—C1'—C2'	−179.4 (2)
C7—N1—C1—C6	26.0 (3)	C7'—N1'—C1'—C6'	−0.9 (3)
C1—N1—C7—C8	−174.19 (19)	C1'—N1'—C7'—C8'	174.67 (19)
N1—C1—C2—O1	4.0 (3)	N1'—C1'—C6'—C5'	−176.9 (2)
N1—C1—C2—C3	−177.04 (19)	C2'—C1'—C6'—C5'	1.5 (3)
C6—C1—C2—O1	−179.83 (19)	O1'—C2'—C1'—N1'	−2.7 (3)
C6—C1—C2—C3	−0.9 (3)	O1'—C2'—C1'—C6'	178.7 (2)
N1—C1—C6—C5	176.8 (2)	C3'—C2'—C1'—N1'	177.1 (2)
C2—C1—C6—C5	1.0 (3)	C3'—C2'—C1'—C6'	−1.5 (3)
C4—C3—C2—O1	179.47 (19)	C4'—C3'—C2'—O1'	179.7 (2)
C4—C3—C2—C1	0.5 (3)	C4'—C3'—C2'—C1'	−0.1 (4)
C5—C4—C3—C2	−0.2 (3)	C5'—C4'—C3'—C2'	1.7 (4)
C6—C5—C4—C3	0.4 (3)	C3'—C4'—C5'—C6'	−1.7 (4)
C1—C6—C5—C4	−0.8 (3)	C4'—C5'—C6'—C1'	0.1 (4)
C9—C8—C7—N1	−0.2 (3)	N1'—C7'—C8'—C9'	−7.0 (3)
C13—C8—C7—N1	177.8 (2)	N1'—C7'—C8'—C13'	176.9 (2)
C7—C8—C9—C10	176.8 (2)	C7'—C8'—C9'—C10'	−177.02 (19)
C13—C8—C9—C10	−1.2 (3)	C13'—C8'—C9'—C10'	−0.9 (3)
C8—C9—C10—C11	1.4 (3)	C7'—C8'—C13'—C12'	176.5 (2)
O2—C11—C10—C9	−176.21 (19)	C9'—C8'—C13'—C12'	0.3 (3)
C12—C11—C10—C9	−0.5 (3)	C8'—C9'—C10'—C11'	1.2 (3)
O2—C11—C12—C13	175.25 (19)	C9'—C10'—C11'—O2'	172.43 (18)
C10—C11—C12—C13	−0.6 (3)	C9'—C10'—C11'—C12'	−0.9 (3)
C11—C12—C13—C8	0.8 (3)	O2'—C11'—C12'—C13'	−172.77 (19)
C12—C13—C8—C7	−178.0 (2)	C10'—C11'—C12'—C13'	0.3 (3)
C12—C13—C8—C9	0.1 (3)	C8'—C13'—C12'—C11'	0.0 (3)
O2—C14—C15—C16	−179.2 (2)	O2'—C14'—C15'—C16'	−177.6 (2)
C19—C14—C15—C16	1.0 (3)	C19'—C14'—C15'—C16'	−0.8 (3)
C14—C15—C16—C17	−0.5 (3)	O2'—C14'—C19'—C18'	176.48 (18)
C18—C17—C16—C15	−0.5 (3)	C15'—C14'—C19'—C18'	−0.7 (3)
C20—C17—C16—C15	−179.3 (2)	C14'—C15'—C16'—C17'	1.4 (3)
C19—C18—C17—C16	1.0 (3)	C15'—C16'—C17'—C18'	−0.6 (3)
C19—C18—C17—C20	179.9 (2)	C15'—C16'—C17'—C20'	177.1 (2)
C21—C18—C17—C16	−178.7 (2)	C16'—C17'—C18'—C19'	−0.9 (3)
C21—C18—C17—C20	0.1 (3)	C16'—C17'—C18'—C21'	174.4 (2)
C17—C18—C19—C14	−0.6 (3)	C20'—C17'—C18'—C19'	−178.65 (19)
C21—C18—C19—C14	179.2 (2)	C20'—C17'—C18'—C21'	−3.3 (3)
C18—C19—C14—O2	179.77 (19)	C17'—C18'—C19'—C14'	1.6 (3)
C18—C19—C14—C15	−0.4 (3)	C21'—C18'—C19'—C14'	−173.8 (2)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C8-ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84	2.24	2.713 (3)	116
O1—H1···N2ⁱ	0.84	2.50	2.993 (3)	119
O1′—H1′···N1′	0.84	2.18	2.659 (3)	116
O1′—H1′···N3ⁱ	0.84	2.39	2.948 (3)	125
C3′—H3′···N3′ⁱⁱ	0.95	2.52	3.344 (4)	145
C5—H5···O1′ⁱⁱⁱ	0.95	2.40	3.180 (3)	139
C12—H12···O1^iv	0.95	2.35	3.214 (3)	151
C6′—H6′···Cg^v	0.95	2.93	3.785 (3)	151

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

Experimental details

Crystal data
Chemical formula	C₂₁H₁₃N₃O₂
M_r	339.34
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.842 (3), 13.448 (4), 14.061 (4)
α, β, γ (°)	109.940 (15), 96.937 (16), 104.182 (15)
V (Å³)	1652.9 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.23 × 0.13

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.975, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	28993, 8180, 4415
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.148, 1.01
No. of reflections	8180
No. of parameters	478
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.26

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C8-ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84	2.24	2.713 (3)	116
O1—H1···N2ⁱ	0.84	2.50	2.993 (3)	119
O1'—H1'···N1'	0.84	2.18	2.659 (3)	116
O1'—H1'···N3ⁱ	0.84	2.39	2.948 (3)	125
C3'—H3'···N3'ⁱⁱ	0.95	2.52	3.344 (4)	145
C5—H5···O1'ⁱⁱⁱ	0.95	2.40	3.180 (3)	139
C12—H12···O1^iv	0.95	2.35	3.214 (3)	151
C6'—H6'···Cg^v	0.95	2.93	3.785 (3)	151

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

Acknowledgements

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of the X-ray diffractometer.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages o565-o566

doi:10.1107/S1600536812003649

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-{4-[(E)-(2-Hy­dr­oxy­phen­yl)imino­methyl]phen­­oxy}benzene-1,2-di­carbo­nitrile

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-{4-[(E)-(2-Hydroxyphenyl)iminomethyl]phenoxy}benzene-1,2-dicarbonitrile