4-Hy­droxy-3-[(E)-3-phenyl­prop-2-eno­yl]-2H-chromen-2-one

In the title mol­ecule, C₁₈H₁₂O₄, the phenyl ring is twisted by 23.2 (1)° from the mean plane of the chromene system. In the crystal, weak inter­molecular C-H...O hydrogen bonds link mol­ecules into zigzag chains extending in the [010] direction. An intra­molecular O-H...O hydrogen bond is also present.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.069
• wR factor = 0.300
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT939_ALERT_3_B Large Value of Not (SHELXL) Weight Optimized S .     322.46

Alert level C
DIFMN02_ALERT_2_C  The minimum difference density is < -0.1*ZMAX*0.75
            _refine_diff_density_min given =     -0.686
            Test value =     -0.600
DIFMN03_ALERT_1_C  The minimum difference density is < -0.1*ZMAX*0.75
            The relevant atom site should be identified.
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.300
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         47 Perc.
PLAT084_ALERT_2_C High wR2 Value .................................       0.30
PLAT098_ALERT_2_C Large Reported Min.  (Negative) Residual Density      -0.69 eA-3
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0059 Ang
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2
PLAT918_ALERT_3_C Reflection(s) # with I(obs) much smaller I(calc)         11

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT Unusually Large.       0.16
PLAT153_ALERT_1_G The su's on the Cell Axes   are Equal ..........    0.00050 Ang.
PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 =          3
PLAT195_ALERT_1_G Missing _cell_measurement_theta_max   datum ....          ?
PLAT196_ALERT_1_G Missing _cell_measurement_theta_min   datum ....          ?

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   9 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

In continuation of our structural and biological studies of coumarin derivatives (Mechi et al., 2009; Hamdi et al., 2010), we present the crystal structure of the title compound (I) - a new chalcone of the coumarin.

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in related structures (Mechi et al., 2009; Asad et al., 2010). The presence of α, β-unsaturated ketone is indicated by the short O2–C10 and C11–C12 bond lengths of 1.289 (5)Å and 1.327 (5) Å, respectively, and the O2–C10–C11 and C10–C11–C12 bond angles of 118.2 (4) ° and 121.8 (4) °, respectively. The structure exhibits intramolecular hydrogen bonding between the hydroxyl oxygen and the ketonic oxygen in the coumarin group (Table 1). The chromen-2-one is twisted out of the plane of the phenyl ring (C13– C14) at 23.2 (1) °. The linkage between the coumarin system and phenyl ring is quite conjugated with bond lengths C10–C11 = 1.457 (5) Å, C11–C12 = 1.327 (5) Å, and C12–C13 = 1.440 (5) Å, suggesting that all non-hydrogen atoms between the electron-donors and acceptors are highly conjugated, leading to a π-bridge for the charge transfer from phenyl ring to coumarin system. Similar geometry has been observed in coumarin chalcone analogues (Mechi et al., 2009; Sun & Cui, 2008). Consequently, the C10–O2 = 1.289 (5) Å is elongated as compared with its mean value found in 3-acetyl-4hydroxycoumarin (1.253 Å) (Traven et al., 2000) owing to the localization of the hydroxyl hydrogen (H2) between the O2 ketonic oxygen and the hydroxyl oxygen O1. The O1–H2 distance (0.99 (7) Å) in (I) is shorter than that in related compounds - C₁₈H₁₀O₇ (1.22 (7) Å) (Mechi et al., 2009) and C₁₈H₁₀Cl₂O₄ (1.27 (2) Å) (Asad et al., 2010). It should be noted that the C9–O4 bond length (1.198 (5) Å) is less than that (1.210 Å) observed in 3-acetyl-4hydroxycoumarin (Traven et al., 2000). It was concluded that it was a substantial difference for stabilizing the H atom of the hydroxyl group when we changed the nature of the substituted R group (from H to Cl and to OCH3).

In the crystal structure, weak intermolecular C– H···O hydrogen bonds (Table 1) link molecules into zigzag chains extended in [010].

Related literature

For related structures, see: Traven et al. (2000); Sun & Cui (2008); Mechi et al. (2009); Hamdi et al. (2010); Asad et al. (2010). For the synthesis of coumarin chalcone, see: Claisen & Claparede (1881).

S2. Experimental

The new chalcone (I) was synthesized using the Claisen Schmidt reaction (Claisen & Claparede, 1881), by the condensation of 3-acetyl-4hydroxycoumarin (1g, 4.9 mmol) and aromatic benzaldehyde (6.4 mmol, 0.5 ml) in chloroform (5 ml) in the presence of one drop of piperidine. The mixture was refluxed in a water bath for 2 h. After cooling at room temperature, a yellow solid was obtained in good yield, filtered, washed with ethanol, and dried in air. Yellow block-shaped single crystals of the title compound, suitable for X-ray structure determination, were recrystalized by slow evaporation of dichloromethane (CH₂Cl₂) at room temperature after several days. Yield: 1.1 g (80%). mp= 499K. IR: ν 3468 (OH), 1690(s) (>C=O), 1578 (C= C), 1272(s) (sym) (C-O-C); 1HNMR: δppm: 7.4-8.1 (m, 10H, Ar-H+ Hethyl), 16.1(s,1H,OH). 13C NMR (ppm): 192.6(CO); 181.56 (C2); 160.22 (C9); 100.8 (C8), 116.32-147.368 (C arom); 124.39 (Cethyl1), 154.79 (Cethyl2),

S3. Refinement

H2 atom was located on a difference map and refined isotropically. The remaining H atoms were positioned geometrically (C–H 0.93 Å) and refined using a riding model, with U_iso(H) = 1.2 U_eq(C).

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids and the atomic numbering. Dashed line denotes hydrogen bond.

4-Hydroxy-3-[(E)-3-phenylprop-2-enoyl]-2H-chromen-2-one

Crystal data

C18H12O4	F(000) = 608
Mr = 292.28	Dx = 1.435 Mg m^−3
Monoclinic, P21/c	Melting point: 489 K
Hall symbol: -P2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.8040 (5) Å	Cell parameters from 203 reflections
b = 3.8860 (5) Å	µ = 0.10 mm^−1
c = 29.7190 (5) Å	T = 296 K
β = 97.164 (5)°	Plate, yellow
V = 1352.58 (18) Å^3	0.3 × 0.14 × 0.06 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2983 independent reflections
Radiation source: fine-focus sealed tube	1404 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
ϕ and ω scans	θmax = 27.2°, θmin = 1.4°
Absorption correction: numerical (SADABS; Bruker, 2003)	h = −15→14
Tmin = 0.861, Tmax = 0.865	k = −4→4
11154 measured reflections	l = −38→37

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.300	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.1616P)^2] where P = (Fo^2 + 2Fc^2)/3
2983 reflections	(Δ/σ)max < 0.001
203 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.69 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.0403 (2)	0.2994 (9)	0.14926 (11)	0.0562 (9)
O2	0.0632 (2)	0.0415 (9)	0.07711 (9)	0.0559 (9)
C1	0.1298 (4)	0.5245 (10)	0.23674 (14)	0.0449 (11)
H1	0.0526	0.5667	0.2281	0.054*
C2	0.1481 (3)	0.2566 (10)	0.16162 (13)	0.0372 (9)
C10	0.1719 (3)	0.0080 (10)	0.08756 (13)	0.0403 (10)
C3	0.1795 (4)	0.6154 (11)	0.27952 (14)	0.0531 (12)
H3	0.1357	0.7162	0.2999	0.064*
C14	0.1811 (4)	−0.5082 (11)	−0.06124 (13)	0.0473 (11)
H12	0.1031	−0.5413	−0.0610	0.057*
C12	0.1891 (4)	−0.2364 (10)	0.01330 (13)	0.0418 (10)
H6	0.1098	−0.2428	0.0093	0.050*
C7	0.1950 (3)	0.3694 (9)	0.20651 (12)	0.0362 (9)
C8	0.2206 (3)	0.1046 (10)	0.13289 (12)	0.0363 (9)
C15	0.2328 (4)	−0.6146 (11)	−0.09835 (14)	0.0546 (13)
H11	0.1895	−0.7214	−0.1227	0.065*
C11	0.2385 (4)	−0.1217 (10)	0.05304 (13)	0.0421 (10)
H7	0.3177	−0.1241	0.0590	0.050*
C4	0.2948 (4)	0.5566 (11)	0.29212 (14)	0.0532 (12)
H4	0.3282	0.6208	0.3209	0.064*
C6	0.3095 (3)	0.3138 (10)	0.22020 (12)	0.0379 (9)
C9	0.3401 (4)	0.0457 (11)	0.14931 (13)	0.0445 (10)
C16	0.3483 (4)	−0.5624 (11)	−0.09925 (14)	0.0536 (12)
H10	0.3824	−0.6308	−0.1244	0.064*
C5	0.3595 (4)	0.4068 (11)	0.26304 (14)	0.0507 (11)
H5	0.4368	0.3669	0.2718	0.061*
O3	0.3791 (2)	0.1608 (8)	0.19242 (9)	0.0485 (8)
C17	0.4132 (4)	−0.4082 (12)	−0.06275 (15)	0.0538 (12)
H9	0.4912	−0.3759	−0.0630	0.065*
O4	0.4098 (3)	−0.0973 (11)	0.12993 (11)	0.0753 (12)
C18	0.3610 (4)	−0.3021 (11)	−0.02576 (13)	0.0471 (11)
H8	0.4046	−0.1954	−0.0015	0.057*
C13	0.2453 (4)	−0.3519 (10)	−0.02429 (13)	0.0386 (9)
H2	0.022 (6)	0.181 (17)	0.120 (2)	0.13 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0409 (18)	0.085 (2)	0.0422 (18)	0.0068 (16)	0.0031 (14)	−0.0133 (17)
O2	0.0428 (18)	0.083 (2)	0.0404 (17)	0.0022 (16)	−0.0005 (14)	−0.0144 (16)
C1	0.056 (3)	0.040 (2)	0.041 (2)	0.0013 (19)	0.017 (2)	0.0005 (18)
C2	0.040 (2)	0.038 (2)	0.034 (2)	−0.0007 (17)	0.0080 (17)	0.0014 (17)
C10	0.045 (2)	0.040 (2)	0.037 (2)	−0.0008 (18)	0.0070 (19)	0.0017 (18)
C3	0.086 (4)	0.044 (2)	0.034 (2)	−0.002 (2)	0.021 (2)	−0.0042 (18)
C14	0.053 (3)	0.049 (2)	0.038 (2)	0.005 (2)	0.001 (2)	0.0004 (19)
C12	0.048 (2)	0.044 (2)	0.034 (2)	0.0010 (19)	0.0072 (19)	−0.0007 (18)
C7	0.045 (2)	0.036 (2)	0.028 (2)	−0.0032 (17)	0.0103 (17)	0.0047 (16)
C8	0.042 (2)	0.038 (2)	0.029 (2)	−0.0014 (17)	0.0038 (17)	0.0021 (16)
C15	0.084 (4)	0.047 (3)	0.030 (2)	0.011 (2)	0.001 (2)	−0.0057 (19)
C11	0.046 (2)	0.047 (2)	0.033 (2)	0.0025 (19)	0.0059 (18)	−0.0005 (18)
C4	0.076 (3)	0.050 (3)	0.032 (2)	−0.010 (2)	0.000 (2)	−0.0010 (19)
C6	0.043 (2)	0.041 (2)	0.030 (2)	−0.0036 (18)	0.0080 (17)	0.0012 (17)
C9	0.043 (2)	0.056 (3)	0.034 (2)	0.008 (2)	0.0060 (19)	−0.0003 (19)
C16	0.078 (4)	0.052 (3)	0.034 (2)	0.018 (2)	0.016 (2)	0.003 (2)
C5	0.055 (3)	0.055 (3)	0.041 (2)	−0.009 (2)	−0.002 (2)	0.000 (2)
O3	0.0369 (16)	0.072 (2)	0.0357 (16)	0.0048 (15)	0.0014 (12)	−0.0042 (14)
C17	0.060 (3)	0.056 (3)	0.047 (3)	0.007 (2)	0.014 (2)	0.003 (2)
O4	0.053 (2)	0.123 (3)	0.050 (2)	0.032 (2)	0.0068 (17)	−0.021 (2)
C18	0.060 (3)	0.047 (2)	0.033 (2)	0.001 (2)	0.005 (2)	0.0004 (18)
C13	0.052 (2)	0.035 (2)	0.029 (2)	0.0043 (18)	0.0049 (18)	0.0029 (16)

Geometric parameters (Å, º)

O1—C2	1.290 (5)	C7—C6	1.379 (5)
O1—H2	0.99 (7)	C8—C9	1.452 (5)
O2—C10	1.289 (5)	C15—C16	1.383 (7)
C1—C3	1.378 (6)	C15—H11	0.9300
C1—C7	1.391 (5)	C11—H7	0.9300
C1—H1	0.9300	C4—C5	1.354 (6)
C2—C8	1.411 (5)	C4—H4	0.9300
C2—C7	1.447 (5)	C6—O3	1.371 (4)
C10—C8	1.447 (5)	C6—C5	1.383 (5)
C10—C11	1.457 (5)	C9—O4	1.198 (5)
C3—C4	1.385 (7)	C9—O3	1.381 (5)
C3—H3	0.9300	C16—C17	1.384 (6)
C14—C15	1.388 (6)	C16—H10	0.9300
C14—C13	1.394 (6)	C5—H5	0.9300
C14—H12	0.9300	C17—C18	1.388 (6)
C12—C11	1.327 (5)	C17—H9	0.9300
C12—C13	1.440 (5)	C18—C13	1.385 (6)
C12—H6	0.9300	C18—H8	0.9300
C2—O1—H2	107 (4)	C12—C11—C10	121.8 (4)
C3—C1—C7	120.0 (4)	C12—C11—H7	119.1
C3—C1—H1	120.0	C10—C11—H7	119.1
C7—C1—H1	120.0	C5—C4—C3	120.8 (4)
O1—C2—C8	122.2 (4)	C5—C4—H4	119.6
O1—C2—C7	118.3 (3)	C3—C4—H4	119.6
C8—C2—C7	119.5 (4)	O3—C6—C7	122.0 (3)
O2—C10—C8	117.8 (4)	O3—C6—C5	116.7 (4)
O2—C10—C11	118.2 (4)	C7—C6—C5	121.4 (4)
C8—C10—C11	124.0 (4)	O4—C9—O3	115.3 (4)
C1—C3—C4	119.9 (4)	O4—C9—C8	127.5 (4)
C1—C3—H3	120.1	O3—C9—C8	117.3 (3)
C4—C3—H3	120.1	C15—C16—C17	120.0 (4)
C15—C14—C13	120.4 (4)	C15—C16—H10	120.0
C15—C14—H12	119.8	C17—C16—H10	120.0
C13—C14—H12	119.8	C4—C5—C6	119.4 (4)
C11—C12—C13	127.0 (4)	C4—C5—H5	120.3
C11—C12—H6	116.5	C6—C5—H5	120.3
C13—C12—H6	116.5	C6—O3—C9	122.9 (3)
C6—C7—C1	118.6 (4)	C16—C17—C18	119.5 (5)
C6—C7—C2	118.2 (3)	C16—C17—H9	120.3
C1—C7—C2	123.2 (4)	C18—C17—H9	120.3
C2—C8—C10	118.1 (4)	C13—C18—C17	121.4 (4)
C2—C8—C9	120.0 (3)	C13—C18—H8	119.3
C10—C8—C9	121.9 (3)	C17—C18—H8	119.3
C16—C15—C14	120.3 (4)	C18—C13—C14	118.5 (4)
C16—C15—H11	119.9	C18—C13—C12	122.1 (4)
C14—C15—H11	119.9	C14—C13—C12	119.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3^i	0.93	2.57	3.350 (5)	142
O1—H2···O2	0.99 (7)	1.51 (7)	2.413 (4)	149 (6)

Symmetry code: (i) −x+1, y+1/2, −z+1/2.