An ortho-rhom-bic polymorph of 5-[(4-methyl-phen-yl)diazen-yl]salicylaldehyde.

The title compound, C(14)H(12)N(2)O(2), is an ortho-rhom-bic polymorph of the previously reported monoclinic form [Bakir et al. (2005 ▶). Acta Cryst. E61, o1611-o1613]. The dihedral angle between the aromatic rings is 4.32 (13)°. The mol-ecular structures of the two polymorphs, including short intra-molecular O-H⋯O hydrogen bonds between the the hydr-oxy and keto groups, are quite similar but their crystal packings are distinct. Unlike the monoclinic form, in which centrosymmetrically related hydr-oxy and keto groups form {⋯H⋯O}(2) synthons via weak O-H⋯O contacts, leading to dimeric aggregates, in the ortho-rhom-bic form, the hydrogen bonding between these groups leads to the formation of supra-molecular chains orientated along the a axis.

Related literature

For the structure of the monoclinic polymorph, see: Bakir et al. (2005 ▶). For background and motivation for the synthesis of the title compound, see: Basu Baul et al. (2005 ▶). For the synthesis, see: Sarma et al. (1993 ▶).

Experimental

Crystal data

C14H12N2O2

M = 240.26

Orthorhombic,

a = 6.016 (4) Å

b = 14.299 (9) Å

c = 26.878 (17) Å

V = 2312 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.09 mm−1

T = 98 K

0.25 × 0.18 × 0.15 mm

Data collection

Rigaku Saturn724 diffractometer

Absorption correction: none

12587 measured reflections

2032 independent reflections

1774 reflections with I > 2σ(I)

R int = 0.082

Refinement

R[F 2 > 2σ(F 2)] = 0.081

wR(F 2) = 0.208

S = 1.14

2032 reflections

167 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.32 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809046868/hb5215sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809046868/hb5215Isup2.hkl

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

C14H12N2O2	F(000) = 1008
Mr = 240.26	Dx = 1.380 Mg m−3
Orthorhombic, Pbna	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2b	Cell parameters from 8423 reflections
a = 6.016 (4) Å	θ = 3.0–40.5°
b = 14.299 (9) Å	µ = 0.09 mm−1
c = 26.878 (17) Å	T = 98 K
V = 2312 (3) Å3	Prism, orange
Z = 8	0.25 × 0.18 × 0.15 mm

Rigaku Saturn724 diffractometer	1774 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.082
graphite	θmax = 25.0°, θmin = 2.9°
Detector resolution: 28.5714 pixels mm-1	h = −5→7
ω scans	k = −17→17
12587 measured reflections	l = −31→31
2032 independent reflections

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)] = 0.081	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.208	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.0971P)2 + 2.61P] where P = (Fo2 + 2Fc2)/3
2032 reflections	(Δ/σ)max < 0.001
167 parameters	Δρmax = 0.40 e Å−3
1 restraint	Δρmin = −0.32 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.5504 (3)	0.03566 (15)	0.16786 (7)	0.0290 (5)
H1O	0.4957	0.0411	0.1965	0.043*
O2	0.2044 (3)	0.07693 (15)	0.22794 (7)	0.0340 (6)
N1	−0.0156 (4)	0.13491 (16)	0.01161 (7)	0.0245 (6)
N2	0.0617 (4)	0.12120 (16)	−0.03149 (8)	0.0251 (6)
C1	0.4095 (4)	0.0603 (2)	0.13084 (9)	0.0248 (6)
C2	0.1931 (4)	0.09462 (19)	0.13980 (9)	0.0242 (6)
C3	0.0583 (4)	0.12043 (19)	0.09890 (9)	0.0239 (6)
H3	−0.0864	0.1446	0.1047	0.029*
C4	0.1341 (4)	0.11101 (18)	0.05081 (9)	0.0226 (6)
C5	0.3522 (5)	0.07589 (19)	0.04248 (9)	0.0250 (6)
H5	0.4058	0.0698	0.0094	0.030*
C6	0.4862 (4)	0.0508 (2)	0.08146 (9)	0.0252 (6)
H6	0.6309	0.0269	0.0753	0.030*
C7	0.1029 (5)	0.1000 (2)	0.18997 (10)	0.0285 (7)
H7	−0.0444	0.1228	0.1938	0.034*
C8	−0.0859 (4)	0.14457 (19)	−0.07115 (9)	0.0239 (6)
C9	−0.0071 (5)	0.12717 (19)	−0.11890 (9)	0.0263 (7)
H9	0.1367	0.1010	−0.1234	0.032*
C10	−0.1380 (5)	0.1479 (2)	−0.16010 (10)	0.0276 (7)
H10	−0.0824	0.1359	−0.1926	0.033*
C11	−0.3501 (5)	0.18602 (19)	−0.15435 (9)	0.0265 (7)
C12	−0.4272 (5)	0.20340 (19)	−0.10605 (9)	0.0262 (6)
H12	−0.5709	0.2297	−0.1015	0.031*
C13	−0.2985 (5)	0.18306 (19)	−0.06474 (10)	0.0256 (6)
H13	−0.3537	0.1951	−0.0323	0.031*
C14	−0.4928 (5)	0.2058 (2)	−0.19935 (10)	0.0341 (7)
H14A	−0.4410	0.2631	−0.2156	0.051*
H14B	−0.6477	0.2137	−0.1889	0.051*
H14C	−0.4823	0.1533	−0.2227	0.051*

	U11	U22	U33	U12	U13	U23
O1	0.0230 (11)	0.0436 (13)	0.0203 (10)	0.0040 (9)	−0.0026 (7)	−0.0010 (8)
O2	0.0260 (11)	0.0533 (14)	0.0227 (10)	0.0007 (9)	−0.0016 (8)	0.0003 (9)
N1	0.0246 (12)	0.0289 (13)	0.0202 (12)	0.0002 (10)	−0.0018 (9)	0.0010 (9)
N2	0.0238 (12)	0.0293 (13)	0.0221 (12)	−0.0007 (10)	−0.0029 (10)	0.0001 (9)
C1	0.0214 (14)	0.0306 (15)	0.0224 (13)	−0.0030 (11)	−0.0023 (10)	−0.0018 (11)
C2	0.0223 (13)	0.0280 (15)	0.0222 (13)	−0.0001 (11)	0.0021 (11)	−0.0006 (10)
C3	0.0197 (13)	0.0282 (14)	0.0239 (14)	0.0017 (11)	−0.0011 (11)	−0.0012 (10)
C4	0.0212 (14)	0.0248 (14)	0.0217 (13)	−0.0024 (10)	−0.0033 (11)	0.0005 (10)
C5	0.0242 (14)	0.0306 (15)	0.0203 (12)	−0.0003 (11)	0.0014 (11)	−0.0021 (11)
C6	0.0191 (13)	0.0312 (15)	0.0252 (13)	0.0002 (11)	0.0008 (11)	−0.0021 (11)
C7	0.0240 (14)	0.0362 (16)	0.0255 (14)	0.0008 (12)	0.0011 (12)	−0.0004 (11)
C8	0.0231 (14)	0.0267 (15)	0.0219 (13)	−0.0015 (11)	−0.0026 (11)	0.0001 (10)
C9	0.0241 (14)	0.0298 (15)	0.0251 (14)	−0.0025 (11)	−0.0012 (11)	0.0007 (11)
C10	0.0273 (14)	0.0350 (16)	0.0204 (13)	−0.0023 (12)	0.0020 (11)	−0.0014 (11)
C11	0.0279 (15)	0.0258 (15)	0.0258 (14)	−0.0033 (11)	−0.0034 (12)	0.0009 (11)
C12	0.0223 (14)	0.0277 (15)	0.0285 (14)	−0.0005 (11)	−0.0004 (11)	0.0007 (11)
C13	0.0278 (15)	0.0256 (15)	0.0234 (13)	−0.0016 (11)	0.0002 (11)	0.0009 (10)
C14	0.0369 (16)	0.0407 (18)	0.0248 (14)	0.0037 (14)	−0.0051 (12)	0.0033 (12)

O1—C1	1.353 (3)	C7—H7	0.9500
O1—H1O	0.8400	C8—C9	1.391 (4)
O2—C7	1.234 (3)	C8—C13	1.403 (4)
N1—N2	1.264 (3)	C9—C10	1.391 (4)
N1—C4	1.428 (3)	C9—H9	0.9500
N2—C8	1.427 (3)	C10—C11	1.396 (4)
C1—C6	1.411 (4)	C10—H10	0.9500
C1—C2	1.413 (4)	C11—C12	1.401 (4)
C2—C3	1.415 (4)	C11—C14	1.510 (4)
C2—C7	1.455 (4)	C12—C13	1.385 (4)
C3—C4	1.377 (4)	C12—H12	0.9500
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.423 (4)	C14—H14A	0.9800
C5—C6	1.370 (4)	C14—H14B	0.9800
C5—H5	0.9500	C14—H14C	0.9800
C6—H6	0.9500
C1—O1—H1O	113.8	C9—C8—C13	119.6 (2)
N2—N1—C4	114.0 (2)	C9—C8—N2	115.8 (2)
N1—N2—C8	114.8 (2)	C13—C8—N2	124.6 (2)
O1—C1—C6	117.5 (2)	C8—C9—C10	120.2 (3)
O1—C1—C2	122.8 (2)	C8—C9—H9	119.9
C6—C1—C2	119.7 (2)	C10—C9—H9	119.9
C1—C2—C3	119.1 (2)	C9—C10—C11	120.8 (2)
C1—C2—C7	121.3 (2)	C9—C10—H10	119.6
C3—C2—C7	119.5 (2)	C11—C10—H10	119.6
C4—C3—C2	120.9 (2)	C10—C11—C12	118.3 (2)
C4—C3—H3	119.5	C10—C11—C14	120.3 (2)
C2—C3—H3	119.5	C12—C11—C14	121.4 (3)
C3—C4—C5	119.2 (2)	C13—C12—C11	121.4 (3)
C3—C4—N1	117.4 (2)	C13—C12—H12	119.3
C5—C4—N1	123.4 (2)	C11—C12—H12	119.3
C6—C5—C4	121.0 (2)	C12—C13—C8	119.6 (2)
C6—C5—H5	119.5	C12—C13—H13	120.2
C4—C5—H5	119.5	C8—C13—H13	120.2
C5—C6—C1	120.1 (2)	C11—C14—H14A	109.5
C5—C6—H6	119.9	C11—C14—H14B	109.5
C1—C6—H6	119.9	H14A—C14—H14B	109.5
O2—C7—C2	124.6 (3)	C11—C14—H14C	109.5
O2—C7—H7	117.7	H14A—C14—H14C	109.5
C2—C7—H7	117.7	H14B—C14—H14C	109.5
C4—N1—N2—C8	179.9 (2)	C2—C1—C6—C5	0.8 (4)
O1—C1—C2—C3	178.8 (2)	C1—C2—C7—O2	0.9 (5)
C6—C1—C2—C3	−1.1 (4)	C3—C2—C7—O2	178.1 (3)
O1—C1—C2—C7	−4.0 (4)	N1—N2—C8—C9	−178.0 (2)
C6—C1—C2—C7	176.1 (3)	N1—N2—C8—C13	2.2 (4)
C1—C2—C3—C4	1.1 (4)	C13—C8—C9—C10	0.1 (4)
C7—C2—C3—C4	−176.2 (3)	N2—C8—C9—C10	−179.8 (2)
C2—C3—C4—C5	−0.8 (4)	C8—C9—C10—C11	−0.2 (4)
C2—C3—C4—N1	177.4 (2)	C9—C10—C11—C12	0.3 (4)
N2—N1—C4—C3	−177.4 (2)	C9—C10—C11—C14	−178.4 (3)
N2—N1—C4—C5	0.7 (4)	C10—C11—C12—C13	−0.4 (4)
C3—C4—C5—C6	0.6 (4)	C14—C11—C12—C13	178.3 (3)
N1—C4—C5—C6	−177.6 (3)	C11—C12—C13—C8	0.2 (4)
C4—C5—C6—C1	−0.6 (4)	C9—C8—C13—C12	−0.1 (4)
O1—C1—C6—C5	−179.0 (2)	N2—C8—C13—C12	179.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O2	0.84	2.01	2.700 (3)	139
O1—H1o···O2i	0.84	2.44	3.008 (3)	125

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯O2	0.84	2.01	2.700 (3)	139
O1—H1o⋯O2i	0.84	2.44	3.008 (3)	125

Symmetry code: (i) .