An ortho­rhom­bic polymorph of 5-[(4-methyl­phen­yl)diazen­yl]salicylaldehyde

Basu Baul, T.S.; Kundu, S.; Arman, H.D.; Tiekink, E.R.T.

doi:10.1107/S1600536809046868

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3061

doi:10.1107/S1600536809046868

Open

access

An orthorhombic polymorph of 5-[(4-methylphenyl)diazenyl]salicylaldehyde

Tushar S. Basu Baul,^a ‡ Sajal Kundu,^a Hadi D. Arman ^b and Edward R. T. Tiekink ^c ^*

^aDepartment of Chemistry, North-Eastern Hill University, NEHU Permanent Campus, Umshing, Shillong 793 022, India, ^bDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 5 November 2009; accepted 6 November 2009; online 11 November 2009)

The title compound, C₁₄H₁₂N₂O₂, is an orthorhombic 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 molecular structures of the two polymorphs, including short intramolecular O—H⋯O hydrogen bonds between the the hydroxy and keto groups, are quite similar but their crystal packings are distinct. Unlike the monoclinic form, in which centrosymmetrically related hydroxy and keto groups form {⋯H⋯O}₂ synthons via weak O—H⋯O contacts, leading to dimeric aggregates, in the orthorhombic form, the hydrogen bonding between these groups leads to the formation of supramolecular 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_r = 240.26
Orthorhombic, P b n a
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[F² > 2σ(F²)] = 0.081
wR(F²) = 0.208
S = 1.14
2032 reflections
167 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.32 e Å⁻³

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) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

The title compound, (I), was isolated during on-going studies into the biological activities of their organotin complexes (Basu Baul et al., 2005). The structure of (I) represents an orthorhombic polymorph of a previously reported monoclinic form (Bakir et al., 2005). The molecular structure of (I), Fig. 1, closely resembles that of the monoclinic form, with comparable geometric parameters being equal within experimental error. The overall molecule of (I) is planar as seen in the values of the C1/C2/C3/O2, C5/C4/N1/N2 and C9/C8/N2/N1 torsion angles of 0.9 (4), 0.7 (4) and -178.0 (2) °, respectively. In each of the polymorphs, a short intramolecular O–H···O hydrogen bond is formed between the hydroxyl and keto groups, Table 1. The key difference between the polymorphs rests with the nature of the weaker O–H···O intermolecular interactions formed between these groups. Thus, in the previously reported monoclinic form, the crystal structure comprises the packing of centrosymmetric dimers linked by a four-membered {···H···O}₂ synthon. By contrast, in (I) the intermolecular hydrogen bonding between these groups leads to 1-D supramolecular chains aligned along the a direction, Table 1 and Fig. 2. The crystal structure comprises packing of these chains as illustrated in Fig. 3.

Related literature top

Experimental top

Compound (I) was prepared by reacting p-tolyldiazonium chloride with o-hydroxybenzaldehyde using a previously reported method (Sarma et al., 1993). Orange crystals were obtained by slow evaporation of a methanol solution of (I); m.pt. 421–423 K.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 2. Supramolecular chain formation along the a axis in (I) mediated by O–H···O hydrogen bonds (orange dashed lines).
	Fig. 3. View in projection down the a axis of the crystal packing in (I), highlighting the stacking of supramolecular chains. The O–H···O hydrogen bonds are highlighted as orange dashed lines.

5-[(4-methylphenyl)diazenyl]salicylaldehyde top

Crystal data top

C₁₄H₁₂N₂O₂	F(000) = 1008
M_r = 240.26	D_x = 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

Data collection top

Rigaku Saturn724 diffractometer	1774 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.082
Graphite monochromator	θ_max = 25.0°, θ_min = 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 top

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(F_o²) + (0.0971P)² + 2.61P] where P = (F_o² + 2F_c²)/3
2032 reflections	(Δ/σ)_max < 0.001
167 parameters	Δρ_max = 0.40 e Å⁻³
1 restraint	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₄H₁₂N₂O₂	V = 2312 (3) Å³
M_r = 240.26	Z = 8
Orthorhombic, Pbna	Mo Kα radiation
a = 6.016 (4) Å	µ = 0.09 mm⁻¹
b = 14.299 (9) Å	T = 98 K
c = 26.878 (17) Å	0.25 × 0.18 × 0.15 mm

Data collection top

Rigaku Saturn724 diffractometer	1774 reflections with I > 2σ(I)
12587 measured reflections	R_int = 0.082
2032 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.081	1 restraint
wR(F²) = 0.208	H-atom parameters constrained
S = 1.14	Δρ_max = 0.40 e Å⁻³
2032 reflections	Δρ_min = −0.32 e Å⁻³
167 parameters

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) x+1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₂O₂
M_r	240.26
Crystal system, space group	Orthorhombic, Pbna
Temperature (K)	98
a, b, c (Å)	6.016 (4), 14.299 (9), 26.878 (17)
V (Å³)	2312 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.18 × 0.15

Data collection
Diffractometer	Rigaku Saturn724 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12587, 2032, 1774
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.081, 0.208, 1.14
No. of reflections	2032
No. of parameters	167
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.32

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006).

Hydrogen-bond geometry (Å, º) top

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) x+1/2, y, −z+1/2.

Footnotes

‡Additional correspondence author, e-mail: basubaul@hotmail.com.

Acknowledgements

The financial support of the Department of Science & Technology, New Delhi, India (grant No. SR/S1/IC-03/2005, TSBB) and the University Grants Commission, New Delhi, India, through SAP–DSA (Phase-III), is gratefully acknowledged.

References

Bakir, M., Harewood, G. R., Holder, A., Hassan, I., Dasgupta, T. P., Maragh, P. & Singh-Wilmot, M. (2005). Acta Cryst. E61, o1611–o1613. Web of Science CSD CrossRef IUCr Journals Google Scholar
Basu Baul, T. S., Singh, K. S., Holčapek, M., Jirásko, R., Linden, A., Song, X., Zapata, A. & Eng, G. (2005). Appl. Organomet. Chem. 19, 935–944. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sarma, K., Basu Baul, T. S., Basaiawmoit, W. L. & Saran, R. (1993). Spectrochim. Acta Part A, 49, 1027. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar