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Acta Cryst. (2009). E65, o1259    [ doi:10.1107/S1600536809016559 ]

1,1'-(2-Thienylmethylene)di-2-naphthol ethyl acetate solvate

Y. Zhang, Y. H. Li, M. M. Zhao, D. H. Wu and R. Yang

Abstract top

In the title compound, C25H18O2S·C4H8O2, there are intermolecular O-H...O hydrogen bonds between the main molecule and the solvent molecule. The thiophene ring is oriented at dihedral angles of 70.87 (7) and 75.36 (4)° with respect to the mean planes of the two naphthyl ring systems.

Comment top

The molten reaction of 2-naphthol, thiophene-2-carbaldehyde and 1-p-tolylethanamine at 120°C did not yield a Betti-type product, but the title bisnaphthol compound. Bisnaphthols are usually referred to as a diverse group of synthetic compounds containing two naphthol units which are connected by an aldehyde group. They have synthetic, medicinal and industrial value (Handique & Barauh et al. 2002). Here we report the synthesis and crystal structure of the title compound. The asymmetric unit of the compound contains an ethyl acetate solvent molecule (Fig. 1). The bond lengths and angles are within normal ranges (Allen et al. 1987).

Rings of the two naphthols and thiophene are, of course, planar. The dihedral angles between rings A (C2–C6/C11) and B (C6–C11), and between rings C (C12–C16/C21) and D (C16–C21), are 0.87 (4) and 1.57 (3), respectively. The orientation of ring E (C22–C25/S1) with respect to the mean planes of the two naphthyl groups containing rings A and B, and C and D, may be described by the dihedral angles of 70.87 (7) and 75.36 (4), respectively. The dihedral angle between the mean planes of the two naphthyl groups is 75.36 (4).

As can be seen from the packing diagram (Fig. 2), intermolecular O—H···O hydrogen bonds (Table 1) link the molecules. Dipole–dipole and van der Waals interactions are also effective in the molecular packing.

Related literature top

For the properties of bisnaphthols, see: Handique & Barauh et al. (2002). For bond-length data, see: Allen et al. (1987).

Experimental top

Thiophene-2-carbaldehyde (1.68 g, 0.015 mol) and 1-p-tolylethanamine (2.025 g, 0.015 mol) was added to 2-naphthol (2.16 g, 0.015 mol) without solvent under nitrogen. The temperature was raised to 120°C in one hour gradually and the mixture was stirred at this temperature for 10 h. The system was treated with 20 ml of ethanol 95% and cooled. The precipitate was filtered and washed with a small amount of ethanol 95%. The title compound was isolated using column chromatography (petroleum ether:ethyl acetate 2:1). Single crystals suitable for X-ray diffraction analysis were obtained from slow evaporation of ethyl acetate solution.

Refinement top

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.91–0.96 Å and Uiso(H) = 1.3–1.5Ueq(C).

Computing details top

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

Figures top
[Figure 1] Fig. 1. Perspective structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The crystal packing of the title compound viewed along the c axis showing hydrogen bondings network.
1,1'-(2-Thienylmethylene)di-2-naphthol ethyl acetate solvate top
Crystal data top
C25H18O2S·C4H8O2F000 = 992
Mr = 470.57Dx = 1.295 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4944 reflections
a = 13.425 (3) Åθ = 2.4–27.2º
b = 21.613 (4) ŵ = 0.17 mm−1
c = 8.417 (2) ÅT = 291 K
β = 98.808 (15)ºPrism, colourless
V = 2413.4 (9) Å30.40 × 0.27 × 0.25 mm
Z = 4
Data collection top
Rigaku SCXmini
diffractometer		5314 independent reflections
Radiation source: fine-focus sealed tube4010 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.047
Detector resolution: 13.6612 pixels mm-1θmax = 27.1º
T = 291 Kθmin = 3.1º
CCD Profile fitting scansh = −17→17
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		k = −27→27
Tmin = 0.95, Tmax = 0.96l = −10→10
23800 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.063H-atom parameters constrained
wR(F2) = 0.158  w = 1/[σ2(Fo2) + (0.0651P)2 + 1.3572P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
5314 reflectionsΔρmax = 0.19 e Å−3
309 parametersΔρmin = −0.31 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C25H18O2S·C4H8O2V = 2413.4 (9) Å3
Mr = 470.57Z = 4
Monoclinic, P21/cMo Kα
a = 13.425 (3) ŵ = 0.17 mm−1
b = 21.613 (4) ÅT = 291 K
c = 8.417 (2) Å0.40 × 0.27 × 0.25 mm
β = 98.808 (15)º
Data collection top
Rigaku SCXmini
diffractometer		5314 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		4010 reflections with I > 2σ(I)
Tmin = 0.95, Tmax = 0.96Rint = 0.047
23800 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.063309 parameters
wR(F2) = 0.158H-atom parameters constrained
S = 1.00Δρmax = 0.19 e Å−3
5314 reflectionsΔρmin = −0.31 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
xyzUiso*/Ueq
C10.31470 (16)0.04909 (9)0.4961 (3)0.0371 (5)
H10.38020.02920.49570.045*
C20.33844 (16)0.10811 (9)0.5991 (3)0.0376 (5)
C30.28873 (17)0.16412 (10)0.5686 (3)0.0451 (5)
C40.3180 (2)0.21791 (11)0.6593 (3)0.0573 (7)
H40.28410.25500.63360.069*
C50.3952 (2)0.21569 (12)0.7836 (3)0.0591 (7)
H50.41350.25130.84290.071*
C60.44799 (18)0.16039 (11)0.8243 (3)0.0480 (6)
C70.5277 (2)0.15747 (14)0.9552 (3)0.0618 (7)
H70.54370.19251.01800.074*
C80.5814 (2)0.10479 (15)0.9913 (3)0.0652 (8)
H80.63500.10431.07570.078*
C90.55585 (19)0.05109 (13)0.9008 (3)0.0568 (7)
H90.59280.01500.92520.068*
C100.47685 (17)0.05134 (11)0.7766 (3)0.0458 (5)
H100.45980.01490.72040.055*
C110.42030 (16)0.10589 (10)0.7312 (3)0.0404 (5)
C120.25054 (15)0.00026 (9)0.5662 (2)0.0361 (4)
C130.16002 (16)0.01613 (10)0.6138 (3)0.0414 (5)
C140.09914 (18)−0.02789 (11)0.6780 (3)0.0488 (6)
H140.0391−0.01550.71080.059*
C150.12767 (18)−0.08802 (12)0.6921 (3)0.0501 (6)
H150.0871−0.11640.73500.060*
C160.21813 (17)−0.10821 (10)0.6425 (3)0.0428 (5)
C170.2476 (2)−0.17108 (11)0.6544 (3)0.0579 (7)
H170.2070−0.19950.69720.070*
C180.3338 (2)−0.19076 (12)0.6049 (4)0.0650 (8)
H180.3524−0.23220.61540.078*
C190.3948 (2)−0.14842 (12)0.5376 (4)0.0596 (7)
H190.4534−0.16200.50220.072*
C200.36867 (17)−0.08722 (11)0.5238 (3)0.0464 (5)
H200.4100−0.06010.47810.056*
C210.28040 (16)−0.06379 (10)0.5769 (2)0.0370 (5)
C220.27474 (17)0.06136 (10)0.3198 (3)0.0399 (5)
C230.18677 (18)0.04016 (11)0.2295 (3)0.0476 (5)
H230.13950.01540.26930.057*
C240.1777 (2)0.06118 (15)0.0666 (3)0.0673 (8)
H240.12300.0516−0.01130.081*
C250.2557 (2)0.09609 (14)0.0369 (3)0.0647 (7)
H250.26090.1133−0.06280.078*
C260.8122 (2)0.13551 (18)0.8359 (4)0.0821 (10)
H26B0.79990.09280.85800.123*
H26C0.75650.15160.76230.123*
H26D0.81950.15870.93430.123*
C270.9068 (2)0.14072 (14)0.7629 (3)0.0598 (7)
C281.0195 (3)0.20912 (15)0.6570 (5)0.0830 (10)
H28B1.01310.18880.55310.100*
H28C1.07750.19190.72560.100*
C291.0330 (3)0.27622 (15)0.6379 (5)0.0852 (10)
H29B1.09270.28360.59090.128*
H29C1.03940.29590.74120.128*
H29D0.97560.29280.56910.128*
O10.20776 (13)0.17382 (8)0.4507 (2)0.0556 (4)
H1A0.18190.13730.40770.106 (13)*
O20.12727 (13)0.07581 (8)0.5945 (2)0.0564 (5)
H2A0.06500.08330.62070.110 (13)*
O30.95846 (15)0.09760 (9)0.7375 (3)0.0736 (6)
O40.92817 (15)0.19908 (10)0.7291 (3)0.0728 (6)
S10.34342 (5)0.10506 (3)0.20365 (8)0.0582 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0354 (10)0.0330 (10)0.0441 (11)−0.0001 (8)0.0099 (9)0.0002 (9)
C20.0368 (11)0.0338 (10)0.0439 (11)−0.0041 (9)0.0115 (9)−0.0015 (9)
C30.0457 (12)0.0382 (12)0.0525 (13)−0.0019 (10)0.0114 (11)−0.0021 (10)
C40.0652 (16)0.0334 (12)0.0756 (18)−0.0004 (11)0.0181 (14)−0.0056 (12)
C50.0699 (17)0.0439 (14)0.0657 (17)−0.0144 (13)0.0177 (14)−0.0156 (12)
C60.0495 (13)0.0497 (14)0.0467 (13)−0.0158 (11)0.0139 (11)−0.0050 (10)
C70.0661 (17)0.0686 (18)0.0509 (15)−0.0277 (15)0.0096 (13)−0.0073 (13)
C80.0548 (16)0.089 (2)0.0490 (15)−0.0225 (16)−0.0012 (12)0.0039 (15)
C90.0466 (14)0.0697 (17)0.0529 (15)−0.0025 (13)0.0039 (11)0.0125 (13)
C100.0427 (12)0.0473 (13)0.0485 (13)−0.0057 (10)0.0105 (10)0.0026 (10)
C110.0379 (11)0.0434 (12)0.0424 (11)−0.0086 (9)0.0139 (9)0.0000 (9)
C120.0358 (10)0.0355 (11)0.0378 (10)−0.0043 (9)0.0079 (9)0.0002 (8)
C130.0385 (11)0.0391 (11)0.0472 (12)−0.0004 (9)0.0084 (9)−0.0015 (9)
C140.0410 (12)0.0518 (14)0.0574 (14)−0.0047 (10)0.0194 (11)−0.0018 (11)
C150.0462 (13)0.0488 (13)0.0575 (14)−0.0121 (11)0.0154 (11)0.0029 (11)
C160.0429 (12)0.0394 (12)0.0461 (12)−0.0058 (10)0.0064 (10)0.0028 (9)
C170.0620 (16)0.0381 (12)0.0753 (18)−0.0091 (12)0.0155 (14)0.0069 (12)
C180.0685 (18)0.0359 (13)0.093 (2)0.0037 (12)0.0205 (16)0.0043 (13)
C190.0568 (15)0.0453 (14)0.0800 (19)0.0068 (12)0.0210 (14)−0.0009 (13)
C200.0437 (12)0.0396 (12)0.0577 (14)0.0004 (10)0.0132 (11)0.0014 (10)
C210.0366 (10)0.0363 (10)0.0374 (11)−0.0032 (9)0.0035 (9)0.0003 (9)
C220.0438 (12)0.0347 (10)0.0433 (12)−0.0017 (9)0.0131 (9)−0.0018 (9)
C230.0494 (13)0.0544 (14)0.0393 (12)−0.0096 (11)0.0078 (10)−0.0001 (10)
C240.0680 (18)0.086 (2)0.0461 (14)−0.0053 (16)0.0021 (13)−0.0025 (14)
C250.081 (2)0.0704 (18)0.0453 (14)0.0063 (15)0.0185 (14)0.0104 (13)
C260.0555 (17)0.102 (3)0.093 (2)0.0005 (17)0.0272 (16)−0.024 (2)
C270.0524 (15)0.0723 (19)0.0556 (16)0.0040 (14)0.0108 (12)−0.0122 (14)
C280.086 (2)0.072 (2)0.101 (3)0.0128 (18)0.047 (2)0.0006 (18)
C290.084 (2)0.075 (2)0.097 (3)0.0114 (18)0.015 (2)−0.0006 (19)
O10.0534 (10)0.0441 (10)0.0672 (11)0.0089 (8)0.0028 (9)−0.0003 (8)
O20.0460 (9)0.0431 (9)0.0851 (13)0.0081 (7)0.0265 (9)0.0043 (9)
O30.0633 (12)0.0669 (13)0.0975 (16)0.0098 (10)0.0340 (12)−0.0031 (11)
O40.0678 (13)0.0683 (13)0.0873 (15)0.0129 (10)0.0281 (11)−0.0074 (11)
S10.0638 (4)0.0544 (4)0.0600 (4)−0.0099 (3)0.0212 (3)0.0090 (3)
Geometric parameters (Å, °) top
C1—C221.522 (3)C17—C181.357 (4)
C1—C121.536 (3)C17—H170.9300
C1—C21.548 (3)C18—C191.404 (4)
C1—H10.9800C18—H180.9300
C2—C31.387 (3)C19—C201.369 (3)
C2—C111.439 (3)C19—H190.9300
C3—O11.371 (3)C20—C211.422 (3)
C3—C41.413 (3)C20—H200.9300
C4—C51.357 (4)C22—C231.381 (3)
C4—H40.9300C22—S11.725 (2)
C5—C61.405 (4)C23—C241.431 (4)
C5—H50.9300C23—H230.9300
C6—C71.415 (4)C24—C251.344 (4)
C6—C111.432 (3)C24—H240.9300
C7—C81.357 (4)C25—S11.699 (3)
C7—H70.9300C25—H250.9300
C8—C91.402 (4)C26—C271.497 (4)
C8—H80.9300C26—H26B0.9600
C9—C101.370 (3)C26—H26C0.9600
C9—H90.9300C26—H26D0.9600
C10—C111.422 (3)C27—O31.201 (3)
C10—H100.9300C27—O41.334 (4)
C12—C131.380 (3)C28—O41.465 (4)
C12—C211.440 (3)C28—C291.473 (4)
C13—O21.364 (3)C28—H28B0.9700
C13—C141.414 (3)C28—H28C0.9700
C14—C151.355 (3)C29—H29B0.9600
C14—H140.9300C29—H29C0.9600
C15—C161.412 (3)C29—H29D0.9600
C15—H150.9300O1—H1A0.9136
C16—C171.415 (3)O2—H2A0.9116
C16—C211.437 (3)
C22—C1—C12111.05 (17)C18—C17—H17119.3
C22—C1—C2114.47 (17)C16—C17—H17119.3
C12—C1—C2115.52 (17)C17—C18—C19119.8 (2)
C22—C1—H1104.8C17—C18—H18120.1
C12—C1—H1104.8C19—C18—H18120.1
C2—C1—H1104.8C20—C19—C18120.4 (2)
C3—C2—C11117.4 (2)C20—C19—H19119.8
C3—C2—C1124.3 (2)C18—C19—H19119.8
C11—C2—C1118.19 (18)C19—C20—C21122.2 (2)
O1—C3—C2125.0 (2)C19—C20—H20118.9
O1—C3—C4112.9 (2)C21—C20—H20118.9
C2—C3—C4122.1 (2)C20—C21—C16116.4 (2)
C5—C4—C3120.3 (2)C20—C21—C12124.04 (19)
C5—C4—H4119.9C16—C21—C12119.56 (19)
C3—C4—H4119.9C23—C22—C1128.5 (2)
C4—C5—C6121.0 (2)C23—C22—S1110.84 (17)
C4—C5—H5119.5C1—C22—S1120.59 (16)
C6—C5—H5119.5C22—C23—C24111.2 (2)
C5—C6—C7121.4 (2)C22—C23—H23124.4
C5—C6—C11119.2 (2)C24—C23—H23124.4
C7—C6—C11119.4 (2)C25—C24—C23113.7 (3)
C8—C7—C6121.6 (3)C25—C24—H24123.2
C8—C7—H7119.2C23—C24—H24123.2
C6—C7—H7119.2C24—C25—S1111.8 (2)
C7—C8—C9119.7 (3)C24—C25—H25124.1
C7—C8—H8120.1S1—C25—H25124.1
C9—C8—H8120.1C27—C26—H26B109.5
C10—C9—C8120.5 (3)C27—C26—H26C109.5
C10—C9—H9119.7H26B—C26—H26C109.5
C8—C9—H9119.7C27—C26—H26D109.5
C9—C10—C11121.8 (2)H26B—C26—H26D109.5
C9—C10—H10119.1H26C—C26—H26D109.5
C11—C10—H10119.1O3—C27—O4123.1 (3)
C10—C11—C6116.9 (2)O3—C27—C26124.4 (3)
C10—C11—C2123.2 (2)O4—C27—C26112.5 (3)
C6—C11—C2119.9 (2)O4—C28—C29108.4 (3)
C13—C12—C21118.02 (18)O4—C28—H28B110.0
C13—C12—C1120.75 (18)C29—C28—H28B110.0
C21—C12—C1121.17 (18)O4—C28—H28C110.0
O2—C13—C12118.84 (19)C29—C28—H28C110.0
O2—C13—C14119.1 (2)H28B—C28—H28C108.4
C12—C13—C14122.0 (2)C28—C29—H29B109.5
C15—C14—C13120.4 (2)C28—C29—H29C109.5
C15—C14—H14119.8H29B—C29—H29C109.5
C13—C14—H14119.8C28—C29—H29D109.5
C14—C15—C16121.0 (2)H29B—C29—H29D109.5
C14—C15—H15119.5H29C—C29—H29D109.5
C16—C15—H15119.5C3—O1—H1A111.5
C15—C16—C17121.3 (2)C13—O2—H2A115.5
C15—C16—C21119.0 (2)C27—O4—C28116.7 (2)
C17—C16—C21119.7 (2)C25—S1—C2292.43 (13)
C18—C17—C16121.4 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O3i0.911.882.764 (3)163
Symmetry codes: (i) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O3i0.911.882.764 (3)163
Symmetry codes: (i) x−1, y, z.
Acknowledgements top

This work was supported by a Start-up Grant (No. 4007041028) and a Science Technology Grant (No. KJ2009375) from Southeast University to YHL.

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Bruker (2000). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Handique, J. G. & Barauh, J. B. (2002). React. Funct. Polym. A, 52, 163–188.

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.