2-{(E)-[(2Z)-2-(1,2-Di-hydro-phthalazin-1-yl-idene)hydrazinyl-idene]meth-yl}phenol.

The title compound, C15H12N4O, adopts an E conformation with respect to the azomethine bond and crystallizes in its hydrazinyl-idene tautomeric form. The dihedral angle between the ring systems is 15.98 (7)°. The phenol O-H group forms an intra-molecular O-H⋯N hydrogen bond. In the crystal, pairs of N-H⋯N and C-H⋯O hydrogen bonds link neighbouring mol-ecules into centrosymmetric dimers. These dimers are inter-connected by means of three types of π-π stacking inter-actions. One, with a centroid-centroid distance of 3.577 (1) Å [inter-planar separation = 3.4673 (6) Å], connects adjacent mol-ecules into centrosymmetric dimers. The other two inter-actions, on the outward facing sides of the dimers, are between phenol rings of neighboring mol-ecules [centroid-centroid separation = 3.7907 (13) Å and inter-planar separation = 3.5071 (8) Å], and between phthalazin units [centroid-centroid separation = 3.6001 (12) Å and inter-planar separation = 3.4891 (7) Å]. In combination, the π-π inter-actions lead to the formation of infinite layers with mol-ecules stacked along [0-11]. These layers are, in turn, connected with neighbouring layers through the N-H⋯N and C-H⋯O hydrogen bonds, yielding a three-dimensional supra-molecular architecture.

Related literature

For biological properties of phthalazine and its derivatives, see: Awadallah et al. (2012 ▶); Minami et al. (1985 ▶); Zhang et al. (2010 ▶); Bian et al. (2013 ▶). For applications of 1-phthalazinyl hydrazones in optoelectronics, see: Caruso et al. (2005 ▶). For the synthesis of related compounds, see: El-Sherif et al. (2012 ▶). For related structures and background references, see: Shafiq et al. (2013 ▶).

Experimental

Crystal data

C15H12N4O

M = 264.29

Triclinic,

a = 6.8028 (12) Å

b = 8.4263 (13) Å

c = 11.868 (2) Å

α = 89.774 (9)°

β = 83.113 (9)°

γ = 70.356 (8)°

V = 635.62 (19) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.978, T max = 0.982

3781 measured reflections

2204 independent reflections

1623 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.117

S = 1.03

2204 reflections

175 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.16 e Å−3

Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); 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, 2010 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813024203/zl2563sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813024203/zl2563Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813024203/zl2563Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H12N4O	Z = 2
Mr = 264.29	F(000) = 276
Triclinic, P1	Dx = 1.381 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8028 (12) Å	Cell parameters from 1437 reflections
b = 8.4263 (13) Å	θ = 2.6–27.4°
c = 11.868 (2) Å	µ = 0.09 mm−1
α = 89.774 (9)°	T = 296 K
β = 83.113 (9)°	Block, colorless
γ = 70.356 (8)°	0.25 × 0.20 × 0.20 mm
V = 635.62 (19) Å3

Bruker Kappa APEXII CCD diffractometer	2204 independent reflections
Radiation source: fine-focus sealed tube	1623 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 8.33 pixels mm-1	θmax = 25.1°, θmin = 3.2°
ω and φ scan	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −10→10
Tmin = 0.978, Tmax = 0.982	l = −13→14
3781 measured reflections

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)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.117	w = 1/[σ2(Fo2) + (0.0527P)2 + 0.1254P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2204 reflections	Δρmax = 0.16 e Å−3
175 parameters	Δρmin = −0.17 e Å−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (4)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.8932 (2)	0.3936 (2)	0.68867 (13)	0.0707 (5)
N1	0.55508 (10)	0.56322 (8)	0.82756 (6)	0.0369 (4)
H1B	0.6902	0.5244	0.8219	0.044*	0.20 (3)
H1A	0.8225	0.4602	0.7435	0.044*	0.80 (3)
N2	0.43095 (10)	0.68017 (8)	0.91179 (6)	0.0365 (4)
N3	0.74379 (10)	0.62960 (8)	0.99606 (6)	0.0393 (4)
N4	0.85914 (10)	0.66505 (8)	1.07304 (6)	0.0438 (4)
C3	0.72100 (10)	0.18492 (8)	0.47512 (6)	0.0661 (6)
H3	0.7802	0.1108	0.4127	0.079*
C2	0.8484 (3)	0.2362 (3)	0.53623 (17)	0.0630 (6)
H2	0.9931	0.1976	0.5147	0.076*
C1	0.7630 (3)	0.3452 (2)	0.62990 (15)	0.0455 (5)
C6	0.5458 (3)	0.40421 (19)	0.66211 (14)	0.0361 (4)
C7	0.4493 (3)	0.51830 (19)	0.75881 (14)	0.0356 (4)
H7	0.3032	0.5616	0.7722	0.043*
C8	0.5352 (2)	0.71106 (18)	0.98897 (14)	0.0322 (4)
C9	0.4266 (2)	0.84219 (18)	1.07626 (13)	0.0323 (4)
C10	0.2102 (3)	0.9273 (2)	1.08475 (15)	0.0430 (4)
H10	0.1302	0.8972	1.0359	0.052*
C11	0.1156 (3)	1.0551 (2)	1.16484 (16)	0.0504 (5)
H11	−0.0286	1.1118	1.1698	0.060*
C12	0.2321 (3)	1.1010 (2)	1.23860 (16)	0.0517 (5)
H12	0.1664	1.1892	1.2919	0.062*
C5	0.4208 (3)	0.3510 (2)	0.59677 (15)	0.0472 (5)
H5	0.2755	0.3907	0.6161	0.057*
C4	0.5070 (4)	0.2413 (3)	0.50468 (17)	0.0602 (6)
H4	0.4214	0.2057	0.4628	0.072*
C15	0.7637 (3)	0.7886 (2)	1.14463 (15)	0.0428 (4)
H15	0.8421	0.8171	1.1951	0.051*
C14	0.5434 (3)	0.88579 (19)	1.15182 (14)	0.0363 (4)
C13	0.4441 (3)	1.0164 (2)	1.23294 (16)	0.0462 (5)
H13	0.5219	1.0461	1.2832	0.055*
H3'	0.811 (3)	0.5389 (17)	0.9514 (14)	0.058 (6)*

	U11	U22	U33	U12	U13	U23
O1	0.0336 (7)	0.1084 (12)	0.0615 (10)	−0.0118 (7)	−0.0082 (7)	−0.0239 (9)
N1	0.0332 (8)	0.0376 (8)	0.0384 (8)	−0.0096 (6)	−0.0060 (6)	−0.0029 (6)
N2	0.0320 (7)	0.0349 (7)	0.0394 (8)	−0.0067 (6)	−0.0056 (6)	−0.0064 (6)
N3	0.0299 (7)	0.0406 (8)	0.0448 (9)	−0.0073 (6)	−0.0079 (6)	−0.0070 (7)
N4	0.0335 (8)	0.0498 (9)	0.0486 (9)	−0.0121 (7)	−0.0126 (7)	−0.0038 (7)
C3	0.0787 (16)	0.0594 (13)	0.0451 (12)	−0.0035 (11)	−0.0081 (11)	−0.0165 (10)
C2	0.0452 (11)	0.0717 (14)	0.0509 (13)	0.0066 (10)	−0.0017 (9)	−0.0110 (10)
C1	0.0381 (10)	0.0508 (11)	0.0408 (10)	−0.0046 (8)	−0.0090 (8)	−0.0008 (8)
C6	0.0391 (9)	0.0337 (9)	0.0342 (9)	−0.0098 (7)	−0.0067 (7)	0.0018 (7)
C7	0.0307 (8)	0.0368 (9)	0.0388 (10)	−0.0101 (7)	−0.0059 (7)	0.0008 (7)
C8	0.0291 (8)	0.0307 (8)	0.0370 (9)	−0.0097 (7)	−0.0056 (7)	0.0025 (7)
C9	0.0338 (9)	0.0295 (8)	0.0343 (9)	−0.0112 (7)	−0.0057 (7)	0.0041 (7)
C10	0.0344 (9)	0.0438 (10)	0.0486 (11)	−0.0085 (8)	−0.0110 (8)	−0.0025 (8)
C11	0.0394 (10)	0.0477 (11)	0.0534 (12)	−0.0015 (8)	−0.0038 (9)	−0.0080 (9)
C12	0.0587 (12)	0.0429 (10)	0.0470 (12)	−0.0101 (9)	−0.0015 (9)	−0.0102 (9)
C5	0.0475 (11)	0.0526 (11)	0.0445 (11)	−0.0197 (9)	−0.0087 (9)	−0.0034 (9)
C4	0.0703 (14)	0.0607 (13)	0.0509 (13)	−0.0217 (11)	−0.0128 (11)	−0.0132 (10)
C15	0.0368 (10)	0.0492 (10)	0.0469 (11)	−0.0172 (8)	−0.0141 (8)	−0.0013 (8)
C14	0.0392 (9)	0.0364 (9)	0.0368 (10)	−0.0159 (7)	−0.0090 (8)	0.0036 (7)
C13	0.0520 (11)	0.0456 (10)	0.0431 (11)	−0.0171 (9)	−0.0121 (9)	−0.0059 (8)

O1—C1	1.353 (2)	C7—H7	0.9300
O1—H1A	0.8460	C8—C9	1.455 (2)
N1—C7	1.2861 (16)	C9—C14	1.393 (2)
N1—N2	1.3891	C9—C10	1.395 (2)
N1—H1B	0.8600	C10—C11	1.368 (2)
N2—C8	1.3008 (16)	C10—H10	0.9300
N3—C8	1.3654 (16)	C11—C12	1.385 (2)
N3—N4	1.3680	C11—H11	0.9300
N3—H3'	0.886 (9)	C12—C13	1.371 (3)
N4—C15	1.2834 (18)	C12—H12	0.9300
C3—C2	1.367 (2)	C5—C4	1.372 (3)
C3—C4	1.372 (2)	C5—H5	0.9300
C3—H3	0.9300	C4—H4	0.9300
C2—C1	1.383 (3)	C15—C14	1.439 (2)
C2—H2	0.9300	C15—H15	0.9300
C1—C6	1.396 (2)	C14—C13	1.395 (2)
C6—C5	1.394 (2)	C13—H13	0.9300
C6—C7	1.441 (2)
C1—O1—H1A	109.9	C14—C9—C10	119.33 (15)
C7—N1—N2	113.77 (8)	C14—C9—C8	118.79 (14)
C7—N1—H1B	123.1	C10—C9—C8	121.87 (14)
N2—N1—H1B	123.1	C11—C10—C9	120.02 (16)
C8—N2—N1	113.87 (7)	C11—C10—H10	120.0
C8—N3—N4	126.36 (7)	C9—C10—H10	120.0
C8—N3—H3'	118.5 (12)	C10—C11—C12	120.77 (17)
N4—N3—H3'	114.9 (12)	C10—C11—H11	119.6
C15—N4—N3	117.14 (8)	C12—C11—H11	119.6
C2—C3—C4	120.90 (12)	C13—C12—C11	119.97 (16)
C2—C3—H3	119.6	C13—C12—H12	120.0
C4—C3—H3	119.5	C11—C12—H12	120.0
C3—C2—C1	120.24 (17)	C4—C5—C6	121.54 (18)
C3—C2—H2	119.9	C4—C5—H5	119.2
C1—C2—H2	119.9	C6—C5—H5	119.2
O1—C1—C2	118.85 (17)	C3—C4—C5	119.22 (16)
O1—C1—C6	121.08 (15)	C3—C4—H4	120.4
C2—C1—C6	120.06 (17)	C5—C4—H4	120.4
C5—C6—C1	118.02 (16)	N4—C15—C14	124.22 (14)
C5—C6—C7	119.84 (16)	N4—C15—H15	117.9
C1—C6—C7	122.14 (15)	C14—C15—H15	117.9
N1—C7—C6	123.25 (14)	C9—C14—C13	119.80 (15)
N1—C7—H7	118.4	C9—C14—C15	117.65 (15)
C6—C7—H7	118.4	C13—C14—C15	122.52 (15)
N2—C8—N3	125.28 (13)	C12—C13—C14	120.10 (16)
N2—C8—C9	119.19 (13)	C12—C13—H13	120.0
N3—C8—C9	115.53 (12)	C14—C13—H13	120.0
C7—N1—N2—C8	172.44 (12)	N3—C8—C9—C10	−175.18 (14)
C8—N3—N4—C15	−1.23 (12)	C14—C9—C10—C11	1.6 (3)
C4—C3—C2—C1	0.6 (3)	C8—C9—C10—C11	−177.04 (16)
C3—C2—C1—O1	179.96 (16)	C9—C10—C11—C12	−0.3 (3)
C3—C2—C1—C6	−0.4 (3)	C10—C11—C12—C13	−1.0 (3)
O1—C1—C6—C5	179.15 (16)	C1—C6—C5—C4	1.2 (3)
C2—C1—C6—C5	−0.5 (3)	C7—C6—C5—C4	−179.45 (17)
O1—C1—C6—C7	−0.1 (3)	C2—C3—C4—C5	0.1 (3)
C2—C1—C6—C7	−179.82 (17)	C6—C5—C4—C3	−1.1 (3)
N2—N1—C7—C6	177.11 (12)	N3—N4—C15—C14	2.9 (2)
C5—C6—C7—N1	174.86 (14)	C10—C9—C14—C13	−1.6 (2)
C1—C6—C7—N1	−5.9 (2)	C8—C9—C14—C13	177.10 (15)
N1—N2—C8—N3	−5.34 (17)	C10—C9—C14—C15	176.45 (15)
N1—N2—C8—C9	174.60 (10)	C8—C9—C14—C15	−4.8 (2)
N4—N3—C8—N2	176.70 (9)	N4—C15—C14—C9	0.2 (2)
N4—N3—C8—C9	−3.25 (16)	N4—C15—C14—C13	178.22 (15)
N2—C8—C9—C14	−173.79 (13)	C11—C12—C13—C14	1.0 (3)
N3—C8—C9—C14	6.2 (2)	C9—C14—C13—C12	0.3 (3)
N2—C8—C9—C10	4.9 (2)	C15—C14—C13—C12	−177.65 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3′···N4i	0.89 (1)	2.31 (1)	3.0181 (14)	137 (2)
O1—H1A···N1	0.85	1.89	2.6362 (15)	147
C15—H15···O1i	0.93	2.59	3.224 (3)	125

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3′⋯N4i	0.89 (1)	2.31 (1)	3.0181 (14)	137 (2)
O1—H1A⋯N1	0.85	1.89	2.6362 (15)	147
C15—H15⋯O1i	0.93	2.59	3.224 (3)	125

Symmetry code: (i) .