4-Methyl-7-(salicylideneamino)coumarin

Aazam, E.S.; Fawazy, A.; Hitchcock, P.B.

doi:10.1107/S1600536806034519

organic compounds

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ISSN: 2056-9890

Volume 62| Part 10| October 2006| Pages o4285-o4287

https://doi.org/10.1107/S1600536806034519

4-Methyl-7-(salicylideneamino)coumarin

Elham S. Aazam,^a ^* Amel Fawazy ^a and Peter B. Hitchcock ^b

^aDepartment of Chemistry, University of King Abdulaziz, PO Box 6171, Jeddah 21442, Saudi Arabia, and ^bThe Chemistry Laboratory, School of Chemistry, Physics and Environmental Science, University of Sussex, Brighton BN1 9QJ, England
^*Correspondence e-mail: eazam@kaau.edu.sa

(Received 21 July 2006; accepted 28 August 2006; online 6 September 2006)

The title compound, C₁₇H₁₃NO₃, consists of a methyl-substituted coumarin group fused to a 2-hydroxyphenyl ring via an azomethine linkage. The coumarin and benzene ring planes form a dihedral angle of 24.0 (1)°. Intramolecular O—H⋯N hydrogen bonding is present and the crystal structure includes intermolecular C—H⋯O interactions.

Comment

Coumarin derivatives are used as fluorescent dyes for synthetic fibres and daylight fluorescent pigments. The absorption spectrum of the title compound, (I), is comparable to that of azomethine dyes such as 6-substituted derivatives of 2Hchromen-2-one (Kachkovski et al., 2004 ). We report here the crystal structure of (I) (Fig. 1).

Planar molecules of Schiff bases are usually stabilized by intermolecular π–π interactions (Wozniak et al. 2000 ). However, (I) is not planar [the dihedral angle between the coumarin and benzene ring planes is 24.0 (1)°], indicating an absence of π–π coupling. Compound (I) shows no photochromic effect in the solid state at ambient temperature, which is attributed to the presence of an intramolecular O—H⋯N hydrogen bond. Such an interaction is considered to be vital for determining lightfastness properties (that is, retention of colour strength over time under exposure to sunlight) by providing electronic protection of the chromophore towards photochemical degradation (Chang et al., 2003 ).

Adjacent molecules of (I) are linked via intermolecular C—H⋯O interactions (Fig. 2) between the carbonyl atom O3 and two C—H groups (C13—H13 and C7—H7) from a neighbouring molecule [C13⋯O3ⁱ = 3.5565 (16) Å and C13—H13⋯O3ⁱ = 165°, and C7⋯O3ⁱ = 3.2733 (15) Å and C7—H7⋯O3ⁱ = 146°; symmetry code: (i) 1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z]. Similar interactions are present in 7-methoxy-3-(salicylideneamino)coumarin, which is a planar molecule (Khoo et al., 2000 ).

Figure 1
The molecular structure of (I), showing displacement ellipsoids at the 50% probability level for non-H atoms.

Figure 2
View of the unit-cell contents of (I), showing intramolecular O—H⋯N hydrogen bonds and intermolecular C—H⋯O interactions as dashed lines.

Experimental

Salicylaldehyde (1.22 ml, 10 mmol) dissolved in 15 ml absolute ethanol was added to a warm stirred solution of 7-amino-4-methylcoumarin (1.75 g, 10 mmol) in absolute ethanol (15 ml), and the mixture was refluxed for 1 h. The resulting yellow–orange precipitate was removed, washed with ethanol followed by diethyl ether and then dried in vacuo. Suitable single crystals were grown by slow evaporation from either chloroform/methanol (1:1) or 10–15 ml ethanol (yield 85%, m.p 459–460 K). ¹H NMR (400 MHz, DMSO-d⁶, 298 K, TMS): δ 6.28 (1H, s, H15), 7.41–7.45 (2H, m, H9,H10), 7.64 (1H, d, H13), 7.00–7.26 (4H, m, aromatic), 2.46 (3H, s, H17A–C), 8.65 (1H, s, H7), 12.79 (1H, s, H1); ¹³C NMR (100.6 MHz, DMSO-d⁶, 298 K, TMS): δ 108.75–160.16 (aromatic C), 18.79 (C17), 164 (C16), 154 (C7). UV/Vis (ethanol, λ, nm): 210, 229, 269, 285, 350. Elemental analysis found: C 73.11, H 4.69, N 5.02%; calculated: C 72.78, H 4.55, N 5.11%. IR (ν, cm⁻¹): 3459 (O—H), 1718 (C=O), 1639 (C=N), 1570 (C=C), 1215 (C—O).

Crystal data

C₁₇H₁₃NO₃
M_r = 279.28
Monoclinic, P 2₁ /c
a = 8.7209 (3) Å
b = 9.9919 (3) Å
c = 15.3906 (4) Å
β = 97.853 (2)°
V = 1328.53 (7) Å³
Z = 4
D_x = 1.396 Mg m⁻³
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 173 (2) K
Prism, orange
0.25 × 0.2 × 0.2 mm

Data collection

Nonius KappaCCD diffractometer
ω and φ scans
Absorption correction: none
12760 measured reflections
2600 independent reflections
2213 reflections with I > 2σ(I)
R_int = 0.033
θ_max = 26.0°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.099
S = 1.02
2600 reflections
195 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0498P)² + 0.3959P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.21 e Å⁻³

H atoms bound to C atoms were placed in calculated positions and allowed to ride during subsequent refinement, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for Csp², and C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for the methyl group. The methyl group was allowed to rotate about its local threefold axis. Atom H1 of the hydroxyl group was located in a Fourier map and refined freely with an isotropic displacement parameter; the refined O—H distance is 0.92 (2) Å.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806034519/bi2044sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806034519/bi2044Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

4-Methyl-7-(salicylideneamino)coumarin top

Crystal data top

C₁₇H₁₃NO₃	F(000) = 584
M_r = 279.28	D_x = 1.396 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7644 reflections
a = 8.7209 (3) Å	θ = 3.4–26.0°
b = 9.9919 (3) Å	µ = 0.10 mm⁻¹
c = 15.3906 (4) Å	T = 173 K
β = 97.853 (2)°	Prism, orange
V = 1328.53 (7) Å³	0.25 × 0.2 × 0.2 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	2213 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590	R_int = 0.033
Graphite monochromator	θ_max = 26.0°, θ_min = 3.5°
Detector resolution: 9 pixels mm^-1	h = −10→10
ω and φ scans	k = −12→9
12760 measured reflections	l = −18→18
2600 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0498P)² + 0.3959P] where P = (F_o² + 2F_c²)/3
2600 reflections	(Δ/σ)_max < 0.001
195 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.96556 (10)	−0.13858 (10)	0.67129 (6)	0.0321 (2)
H1	0.934 (2)	−0.069 (2)	0.6335 (13)	0.068 (6)*
O2	0.60263 (10)	0.21112 (9)	0.27394 (5)	0.0286 (2)
O3	0.51133 (12)	0.30134 (10)	0.14659 (6)	0.0422 (3)
N1	0.80250 (12)	−0.00876 (10)	0.54404 (7)	0.0270 (3)
C1	0.73582 (14)	−0.22881 (12)	0.58642 (8)	0.0233 (3)
C2	0.86395 (14)	−0.23980 (13)	0.65290 (8)	0.0251 (3)
C3	0.88635 (15)	−0.35761 (13)	0.70148 (9)	0.0300 (3)
H3	0.9725	−0.3655	0.7462	0.036*
C4	0.78415 (16)	−0.46272 (13)	0.68494 (9)	0.0322 (3)
H4	0.801	−0.5427	0.7183	0.039*
C5	0.65646 (16)	−0.45341 (13)	0.62004 (9)	0.0310 (3)
H5	0.5861	−0.5261	0.6093	0.037*
C6	0.63358 (15)	−0.33729 (12)	0.57154 (8)	0.0272 (3)
H6	0.5468	−0.3307	0.5272	0.033*
C7	0.70922 (14)	−0.10920 (12)	0.53335 (8)	0.0250 (3)
H7	0.6211	−0.1047	0.4897	0.03*
C8	0.77850 (14)	0.10553 (12)	0.48957 (8)	0.0257 (3)
C9	0.84691 (16)	0.22489 (14)	0.52279 (8)	0.0322 (3)
H9	0.9039	0.2264	0.58	0.039*
C10	0.83234 (16)	0.34013 (13)	0.47339 (8)	0.0302 (3)
H10	0.8783	0.4205	0.4974	0.036*
C11	0.75108 (14)	0.34116 (12)	0.38847 (8)	0.0242 (3)
C12	0.68437 (14)	0.22046 (12)	0.35694 (8)	0.0233 (3)
C13	0.69678 (14)	0.10337 (12)	0.40544 (8)	0.0250 (3)
H13	0.6503	0.023	0.3817	0.03*
C14	0.73364 (14)	0.45777 (12)	0.33190 (8)	0.0250 (3)
C15	0.65366 (14)	0.44444 (13)	0.25094 (8)	0.0282 (3)
H15	0.6425	0.5206	0.2136	0.034*
C16	0.58430 (15)	0.32011 (13)	0.21838 (8)	0.0293 (3)
C17	0.80358 (16)	0.58880 (13)	0.36292 (9)	0.0323 (3)
H17A	0.9165	0.5835	0.3664	0.048*
H17B	0.7758	0.6093	0.4211	0.048*
H17C	0.7644	0.6595	0.3216	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0291 (5)	0.0327 (5)	0.0317 (5)	−0.0064 (4)	−0.0055 (4)	0.0040 (4)
O2	0.0346 (5)	0.0253 (5)	0.0230 (5)	−0.0008 (4)	−0.0057 (4)	0.0015 (4)
O3	0.0530 (7)	0.0380 (6)	0.0300 (5)	−0.0041 (5)	−0.0139 (5)	0.0056 (4)
N1	0.0311 (6)	0.0259 (6)	0.0232 (5)	−0.0020 (4)	0.0007 (4)	0.0025 (4)
C1	0.0247 (6)	0.0245 (6)	0.0213 (6)	0.0005 (5)	0.0049 (5)	−0.0011 (5)
C2	0.0237 (6)	0.0270 (6)	0.0250 (6)	−0.0003 (5)	0.0054 (5)	−0.0005 (5)
C3	0.0284 (7)	0.0330 (7)	0.0282 (7)	0.0048 (5)	0.0023 (5)	0.0050 (5)
C4	0.0373 (7)	0.0257 (7)	0.0353 (7)	0.0053 (5)	0.0113 (6)	0.0071 (6)
C5	0.0325 (7)	0.0255 (6)	0.0365 (8)	−0.0033 (5)	0.0102 (6)	−0.0015 (6)
C6	0.0262 (6)	0.0291 (7)	0.0262 (6)	−0.0014 (5)	0.0032 (5)	−0.0030 (5)
C7	0.0264 (6)	0.0276 (6)	0.0204 (6)	0.0003 (5)	0.0005 (5)	0.0002 (5)
C8	0.0269 (6)	0.0262 (6)	0.0236 (6)	−0.0010 (5)	0.0024 (5)	0.0029 (5)
C9	0.0387 (8)	0.0331 (7)	0.0227 (6)	−0.0088 (6)	−0.0037 (5)	0.0011 (5)
C10	0.0362 (7)	0.0270 (7)	0.0265 (7)	−0.0085 (5)	0.0006 (5)	−0.0019 (5)
C11	0.0249 (6)	0.0245 (6)	0.0239 (6)	−0.0007 (5)	0.0054 (5)	−0.0004 (5)
C12	0.0234 (6)	0.0263 (6)	0.0197 (6)	0.0012 (5)	0.0011 (5)	−0.0005 (5)
C13	0.0275 (6)	0.0224 (6)	0.0245 (6)	−0.0014 (5)	0.0017 (5)	−0.0012 (5)
C14	0.0241 (6)	0.0243 (6)	0.0278 (7)	0.0018 (5)	0.0079 (5)	0.0015 (5)
C15	0.0294 (7)	0.0259 (6)	0.0293 (7)	0.0017 (5)	0.0038 (5)	0.0054 (5)
C16	0.0313 (7)	0.0290 (7)	0.0262 (7)	0.0024 (5)	−0.0004 (5)	0.0048 (5)
C17	0.0408 (8)	0.0252 (7)	0.0314 (7)	−0.0030 (6)	0.0068 (6)	0.0013 (5)

Geometric parameters (Å, º) top

O1—C2	1.3489 (15)	C7—H7	0.95
O1—H1	0.92 (2)	C8—C13	1.3902 (17)
O2—C12	1.3784 (14)	C8—C9	1.3987 (18)
O2—C16	1.3804 (15)	C9—C10	1.3761 (18)
O3—C16	1.2119 (15)	C9—H9	0.95
N1—C7	1.2882 (16)	C10—C11	1.3990 (18)
N1—C8	1.4152 (15)	C10—H10	0.95
C1—C6	1.4024 (17)	C11—C12	1.3969 (17)
C1—C2	1.4124 (17)	C11—C14	1.4500 (17)
C1—C7	1.4483 (17)	C12—C13	1.3841 (17)
C2—C3	1.3940 (18)	C13—H13	0.95
C3—C4	1.3785 (19)	C14—C15	1.3488 (18)
C3—H3	0.95	C14—C17	1.4947 (17)
C4—C5	1.394 (2)	C15—C16	1.4413 (18)
C4—H4	0.95	C15—H15	0.95
C5—C6	1.3793 (18)	C17—H17A	0.98
C5—H5	0.95	C17—H17B	0.98
C6—H6	0.95	C17—H17C	0.98

C2—O1—H1	107.5 (12)	C8—C9—H9	119.7
C12—O2—C16	121.47 (10)	C9—C10—C11	121.27 (12)
C7—N1—C8	120.88 (10)	C9—C10—H10	119.4
C6—C1—C2	118.73 (11)	C11—C10—H10	119.4
C6—C1—C7	119.76 (11)	C12—C11—C10	116.87 (11)
C2—C1—C7	121.51 (11)	C12—C11—C14	118.73 (11)
O1—C2—C3	118.73 (11)	C10—C11—C14	124.40 (11)
O1—C2—C1	121.71 (11)	O2—C12—C13	115.79 (10)
C3—C2—C1	119.55 (11)	O2—C12—C11	121.24 (10)
C4—C3—C2	120.31 (12)	C13—C12—C11	122.98 (11)
C4—C3—H3	119.8	C12—C13—C8	118.78 (11)
C2—C3—H3	119.8	C12—C13—H13	120.6
C3—C4—C5	120.97 (12)	C8—C13—H13	120.6
C3—C4—H4	119.5	C15—C14—C11	118.29 (11)
C5—C4—H4	119.5	C15—C14—C17	121.23 (11)
C6—C5—C4	119.10 (12)	C11—C14—C17	120.48 (11)
C6—C5—H5	120.4	C14—C15—C16	123.08 (11)
C4—C5—H5	120.4	C14—C15—H15	118.5
C5—C6—C1	121.34 (12)	C16—C15—H15	118.5
C5—C6—H6	119.3	O3—C16—O2	116.39 (11)
C1—C6—H6	119.3	O3—C16—C15	126.41 (12)
N1—C7—C1	121.41 (11)	O2—C16—C15	117.19 (11)
N1—C7—H7	119.3	C14—C17—H17A	109.5
C1—C7—H7	119.3	C14—C17—H17B	109.5
C13—C8—C9	119.50 (11)	H17A—C17—H17B	109.5
C13—C8—N1	123.69 (11)	C14—C17—H17C	109.5
C9—C8—N1	116.77 (11)	H17A—C17—H17C	109.5
C10—C9—C8	120.59 (12)	H17B—C17—H17C	109.5
C10—C9—H9	119.7

C6—C1—C2—O1	−179.16 (11)	C16—O2—C12—C13	−178.79 (11)
C7—C1—C2—O1	1.41 (18)	C16—O2—C12—C11	0.50 (17)
C6—C1—C2—C3	0.41 (17)	C10—C11—C12—O2	−179.69 (11)
C7—C1—C2—C3	−179.01 (11)	C14—C11—C12—O2	−0.29 (18)
O1—C2—C3—C4	179.50 (12)	C10—C11—C12—C13	−0.45 (19)
C1—C2—C3—C4	−0.09 (19)	C14—C11—C12—C13	178.95 (11)
C2—C3—C4—C5	−0.4 (2)	O2—C12—C13—C8	179.63 (11)
C3—C4—C5—C6	0.5 (2)	C11—C12—C13—C8	0.35 (19)
C4—C5—C6—C1	−0.14 (19)	C9—C8—C13—C12	−0.51 (19)
C2—C1—C6—C5	−0.30 (18)	N1—C8—C13—C12	−178.09 (11)
C7—C1—C6—C5	179.13 (11)	C12—C11—C14—C15	−0.11 (17)
C8—N1—C7—C1	177.58 (11)	C10—C11—C14—C15	179.24 (12)
C6—C1—C7—N1	−178.58 (12)	C12—C11—C14—C17	−179.81 (11)
C2—C1—C7—N1	0.84 (18)	C10—C11—C14—C17	−0.46 (19)
C7—N1—C8—C13	−24.41 (19)	C11—C14—C15—C16	0.33 (19)
C7—N1—C8—C9	157.94 (12)	C17—C14—C15—C16	−179.98 (12)
C13—C8—C9—C10	0.8 (2)	C12—O2—C16—O3	179.55 (11)
N1—C8—C9—C10	178.54 (12)	C12—O2—C16—C15	−0.29 (17)
C8—C9—C10—C11	−0.9 (2)	C14—C15—C16—O3	−179.95 (13)
C9—C10—C11—C12	0.73 (19)	C14—C15—C16—O2	−0.13 (19)
C9—C10—C11—C14	−178.64 (12)

Acknowledgements

The authors gratefully acknowledge the Ministry of Higher Education in Saudi Arabia and the Institute of Research and Consultation at King Abdulaziz University for financial support (grant No. 426/501).

References

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Volume 62| Part 10| October 2006| Pages o4285-o4287

https://doi.org/10.1107/S1600536806034519

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

4-Methyl-7-(salicyl­idene­amino)coumarin

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-Methyl-7-(salicylideneamino)coumarin