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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3061.
Published online 2009 November 11. doi:  10.1107/S1600536809046868
PMCID: PMC2971774

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

Abstract

The title compound, C14H12N2O2, is an ortho­rhom­bic polymorph of the previously reported monoclinic form [Bakir et al. (2005 [triangle]). 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 [triangle]). For background and motivation for the synthesis of the title compound, see: Basu Baul et al. (2005 [triangle]). For the synthesis, see: Sarma et al. (1993 [triangle]).

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Object name is e-65-o3061-scheme1.jpg

Experimental

Crystal data

  • C14H12N2O2
  • M r = 240.26
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3061-efi1.jpg
  • 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 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Acknowledgments

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.

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.95–0.98 Å) and were included in the refinement in the riding model approximation with Uiso(H) set to 1.2–1.5Ueq(C). The O–bound H-atom was located in a difference Fourier map and was refined with an O–H restraint of 0.840±0.001 Å, and with Uiso(H) = 1.5Ueq(O).

Figures

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.

Crystal data

C14H12N2O2F(000) = 1008
Mr = 240.26Dx = 1.380 Mg m3
Orthorhombic, PbnaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2bCell parameters from 8423 reflections
a = 6.016 (4) Åθ = 3.0–40.5°
b = 14.299 (9) ŵ = 0.09 mm1
c = 26.878 (17) ÅT = 98 K
V = 2312 (3) Å3Prism, orange
Z = 80.25 × 0.18 × 0.15 mm

Data collection

Rigaku Saturn724 diffractometer1774 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.082
graphiteθmax = 25.0°, θmin = 2.9°
Detector resolution: 28.5714 pixels mm-1h = −5→7
ω scansk = −17→17
12587 measured reflectionsl = −31→31
2032 independent reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.081Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.208H-atom parameters constrained
S = 1.14w = 1/[σ2(Fo2) + (0.0971P)2 + 2.61P] where P = (Fo2 + 2Fc2)/3
2032 reflections(Δ/σ)max < 0.001
167 parametersΔρmax = 0.40 e Å3
1 restraintΔρmin = −0.32 e Å3

Special details

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)

xyzUiso*/Ueq
O10.5504 (3)0.03566 (15)0.16786 (7)0.0290 (5)
H1O0.49570.04110.19650.043*
O20.2044 (3)0.07693 (15)0.22794 (7)0.0340 (6)
N1−0.0156 (4)0.13491 (16)0.01161 (7)0.0245 (6)
N20.0617 (4)0.12120 (16)−0.03149 (8)0.0251 (6)
C10.4095 (4)0.0603 (2)0.13084 (9)0.0248 (6)
C20.1931 (4)0.09462 (19)0.13980 (9)0.0242 (6)
C30.0583 (4)0.12043 (19)0.09890 (9)0.0239 (6)
H3−0.08640.14460.10470.029*
C40.1341 (4)0.11101 (18)0.05081 (9)0.0226 (6)
C50.3522 (5)0.07589 (19)0.04248 (9)0.0250 (6)
H50.40580.06980.00940.030*
C60.4862 (4)0.0508 (2)0.08146 (9)0.0252 (6)
H60.63090.02690.07530.030*
C70.1029 (5)0.1000 (2)0.18997 (10)0.0285 (7)
H7−0.04440.12280.19380.034*
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)
H90.13670.1010−0.12340.032*
C10−0.1380 (5)0.1479 (2)−0.16010 (10)0.0276 (7)
H10−0.08240.1359−0.19260.033*
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)
H12−0.57090.2297−0.10150.031*
C13−0.2985 (5)0.18306 (19)−0.06474 (10)0.0256 (6)
H13−0.35370.1951−0.03230.031*
C14−0.4928 (5)0.2058 (2)−0.19935 (10)0.0341 (7)
H14A−0.44100.2631−0.21560.051*
H14B−0.64770.2137−0.18890.051*
H14C−0.48230.1533−0.22270.051*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0230 (11)0.0436 (13)0.0203 (10)0.0040 (9)−0.0026 (7)−0.0010 (8)
O20.0260 (11)0.0533 (14)0.0227 (10)0.0007 (9)−0.0016 (8)0.0003 (9)
N10.0246 (12)0.0289 (13)0.0202 (12)0.0002 (10)−0.0018 (9)0.0010 (9)
N20.0238 (12)0.0293 (13)0.0221 (12)−0.0007 (10)−0.0029 (10)0.0001 (9)
C10.0214 (14)0.0306 (15)0.0224 (13)−0.0030 (11)−0.0023 (10)−0.0018 (11)
C20.0223 (13)0.0280 (15)0.0222 (13)−0.0001 (11)0.0021 (11)−0.0006 (10)
C30.0197 (13)0.0282 (14)0.0239 (14)0.0017 (11)−0.0011 (11)−0.0012 (10)
C40.0212 (14)0.0248 (14)0.0217 (13)−0.0024 (10)−0.0033 (11)0.0005 (10)
C50.0242 (14)0.0306 (15)0.0203 (12)−0.0003 (11)0.0014 (11)−0.0021 (11)
C60.0191 (13)0.0312 (15)0.0252 (13)0.0002 (11)0.0008 (11)−0.0021 (11)
C70.0240 (14)0.0362 (16)0.0255 (14)0.0008 (12)0.0011 (12)−0.0004 (11)
C80.0231 (14)0.0267 (15)0.0219 (13)−0.0015 (11)−0.0026 (11)0.0001 (10)
C90.0241 (14)0.0298 (15)0.0251 (14)−0.0025 (11)−0.0012 (11)0.0007 (11)
C100.0273 (14)0.0350 (16)0.0204 (13)−0.0023 (12)0.0020 (11)−0.0014 (11)
C110.0279 (15)0.0258 (15)0.0258 (14)−0.0033 (11)−0.0034 (12)0.0009 (11)
C120.0223 (14)0.0277 (15)0.0285 (14)−0.0005 (11)−0.0004 (11)0.0007 (11)
C130.0278 (15)0.0256 (15)0.0234 (13)−0.0016 (11)0.0002 (11)0.0009 (10)
C140.0369 (16)0.0407 (18)0.0248 (14)0.0037 (14)−0.0051 (12)0.0033 (12)

Geometric parameters (Å, °)

O1—C11.353 (3)C7—H70.9500
O1—H1O0.8400C8—C91.391 (4)
O2—C71.234 (3)C8—C131.403 (4)
N1—N21.264 (3)C9—C101.391 (4)
N1—C41.428 (3)C9—H90.9500
N2—C81.427 (3)C10—C111.396 (4)
C1—C61.411 (4)C10—H100.9500
C1—C21.413 (4)C11—C121.401 (4)
C2—C31.415 (4)C11—C141.510 (4)
C2—C71.455 (4)C12—C131.385 (4)
C3—C41.377 (4)C12—H120.9500
C3—H30.9500C13—H130.9500
C4—C51.423 (4)C14—H14A0.9800
C5—C61.370 (4)C14—H14B0.9800
C5—H50.9500C14—H14C0.9800
C6—H60.9500
C1—O1—H1O113.8C9—C8—C13119.6 (2)
N2—N1—C4114.0 (2)C9—C8—N2115.8 (2)
N1—N2—C8114.8 (2)C13—C8—N2124.6 (2)
O1—C1—C6117.5 (2)C8—C9—C10120.2 (3)
O1—C1—C2122.8 (2)C8—C9—H9119.9
C6—C1—C2119.7 (2)C10—C9—H9119.9
C1—C2—C3119.1 (2)C9—C10—C11120.8 (2)
C1—C2—C7121.3 (2)C9—C10—H10119.6
C3—C2—C7119.5 (2)C11—C10—H10119.6
C4—C3—C2120.9 (2)C10—C11—C12118.3 (2)
C4—C3—H3119.5C10—C11—C14120.3 (2)
C2—C3—H3119.5C12—C11—C14121.4 (3)
C3—C4—C5119.2 (2)C13—C12—C11121.4 (3)
C3—C4—N1117.4 (2)C13—C12—H12119.3
C5—C4—N1123.4 (2)C11—C12—H12119.3
C6—C5—C4121.0 (2)C12—C13—C8119.6 (2)
C6—C5—H5119.5C12—C13—H13120.2
C4—C5—H5119.5C8—C13—H13120.2
C5—C6—C1120.1 (2)C11—C14—H14A109.5
C5—C6—H6119.9C11—C14—H14B109.5
C1—C6—H6119.9H14A—C14—H14B109.5
O2—C7—C2124.6 (3)C11—C14—H14C109.5
O2—C7—H7117.7H14A—C14—H14C109.5
C2—C7—H7117.7H14B—C14—H14C109.5
C4—N1—N2—C8179.9 (2)C2—C1—C6—C50.8 (4)
O1—C1—C2—C3178.8 (2)C1—C2—C7—O20.9 (5)
C6—C1—C2—C3−1.1 (4)C3—C2—C7—O2178.1 (3)
O1—C1—C2—C7−4.0 (4)N1—N2—C8—C9−178.0 (2)
C6—C1—C2—C7176.1 (3)N1—N2—C8—C132.2 (4)
C1—C2—C3—C41.1 (4)C13—C8—C9—C100.1 (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—N1177.4 (2)C9—C10—C11—C120.3 (4)
N2—N1—C4—C3−177.4 (2)C9—C10—C11—C14−178.4 (3)
N2—N1—C4—C50.7 (4)C10—C11—C12—C13−0.4 (4)
C3—C4—C5—C60.6 (4)C14—C11—C12—C13178.3 (3)
N1—C4—C5—C6−177.6 (3)C11—C12—C13—C80.2 (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—C12179.7 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1o···O20.842.012.700 (3)139
O1—H1o···O2i0.842.443.008 (3)125

Symmetry codes: (i) x+1/2, y, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5215).

References

  • Bakir, M., Harewood, G. R., Holder, A., Hassan, I., Dasgupta, T. P., Maragh, P. & Singh-Wilmot, M. (2005). Acta Cryst. E61, o1611–o1613.
  • 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.
  • Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
  • Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sarma, K., Basu Baul, T. S., Basaiawmoit, W. L. & Saran, R. (1993). Spectrochim. Acta Part A, 49, 1027.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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