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Acta Crystallogr Sect E Struct Rep Online

Acta Cryst. E

Acta Crystallographica Section E: Structure Reports Online

1600-5368

International Union of Crystallography

21201891

2960860

rk2073

10.1107/S1600536808003012

ACSEBH

S1600536808003012

Organic Papers

8-Hydroxy-8-phenyl-2,3,7,8-tetrahydro-6H-1,4-dioxino[2,3-f]isoindol-6-one

C₁₆H₁₃NO₄

Tafeenko

Viktor A.

aAslanov

Leonid A.

a*Khasanov

Mahmud I.

aMochalov

Sergei S.

aaChemistry Department, Moscow State University, 119991 Moscow, Russian Federation

Correspondence e-mail: aslanov@struct.chem.msu.ru

0132008

0622008

64Pt 3

e080300

o548o548291220072812008

2008

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

A full version of this article is available from Crystallography Journals Online.

In the title compound, C₁₆H₁₃NO₄, the indole system is essentially planar, whereas the dioxane ring adopts a twist conformation. The molecules are linked into chains by —O— H⋯O=C— hydrogen bonds and these chains are linked into rods by means of N—H⋯O hydrogen bonds. Exept for weak C—H⋯O interactions between the rods, no other intermolecular contacts of interest are present.

Related literature

For details of the appropriate nitrile hydrolysis, see: Moorthy & Singhal (2005 ▶).

Experimental<sec id="sec2.1.1"><title>Crystal data

C₁₆H₁₃NO₄

M _r = 283.27

Monoclinic,

a = 8.6001 (17) Å

b = 27.005 (5) Å

c = 5.7221 (5) Å

β = 92.602 (10)°

V = 1327.6 (4) Å³

Z = 4

Cu Kα radiation

μ = 0.85 mm⁻¹

T = 291 (2) K

0.08 × 0.06 × 0.04 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: none

2892 measured reflections

2653 independent reflections

1784 reflections with I > 2σ(I)

R _int = 0.025

2 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.054

wR(F ²) = 0.147

S = 1.05

2653 reflections

192 parameters

H-atom parameters constrained

Δρ_max = 0.23 e Å⁻³

Δρ_min = −0.24 e Å⁻³

Data collection: <italic>CAD-4 Software</italic> (Enraf–Nonius, 1989<xref ref-type="bibr" rid="bb2"> ▶</xref>); cell refinement: <italic>CAD-4 Software</italic>; data reduction: <italic>XCAD4</italic> (Harms & Wocadlo, 1995<xref ref-type="bibr" rid="bb4"> ▶</xref>); program(s) used to solve structure: <italic>SHELXS97</italic> (Sheldrick, 2008<xref ref-type="bibr" rid="bb6"> ▶</xref>); program(s) used to refine structure: <italic>SHELXL97</italic> (Sheldrick, 2008<xref ref-type="bibr" rid="bb6"> ▶</xref>); molecular graphics: <italic>DIAMOND</italic> (Brandenburg, 2000<xref ref-type="bibr" rid="bb1"> ▶</xref>); software used to prepare material for publication: <italic>WinGX</italic> (Farrugia, 1999<xref ref-type="bibr" rid="bb3"> ▶</xref>).</sec></sec><sec sec-type="supplementary-material"><title>Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808003012/rk2073sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808003012/rk2073Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2073).

supplementary crystallographic information Comment

To investigate mechanisms of intra- and intermolecular reactions of ortho-substituted benzenes we intended to synthesize novel ortho-acyl-substituted benzamides by hydrolysis (Moorthy & Singhal, 2005) of appropriate nitriles. In the case of hydrolysis of 7-benzoyl-2,3-dihydro-1,4-benzodioxine-6-carbonitrile (1) the compound 7-benzoyl-2,3-dihydro-1,4-benzodioxine-6-carboxamide (2) was expected to be produced (Fig. 1). Both the elemental analysis and mass spectroscopic data (M+ 283) of the compound we obtained, were in good agreement with structure (2), but ¹H NMR data were not. Although 13 protons were identified in the ¹H NMR spectrum, an expected signal for the NH₂ group was absent. In addition, two single signals were detected in the ¹H NMR spectrum, each corresponding to one proton of large difference in chemical shift (6.70 and 9.02). To determine the structure of the compound, we carried out an X-ray crystallographic analysis, which revealed that hydrolysis of (1), under the conditions specified by Moorthy & Singhal, did not produce the expected compound (2); instead the product was an isomer of compound (2), viz. 8-hydroxy-8-phenyl-2,3,7,8-tetrahydro-6H-[1,4]dioxino [2,3-f]isoindol-6-one, (3) (Fig. 1).

The dihedral angle between the planes defined by the atoms C5/C9/C10/C11/C12/C13 (plane 1) and C8/N7/C6/C10/C11 (plane 2) (Fig. 2) is 1.64 (9)°. The 6-membered dioxane ring adopts a twist conformation, with atoms C3 and C2 displaced out of plane 1 by 0.375 (4) and -0.273 (3) Å, respectively, compared with displacements of -0.012 (3) and 0.010 (3) Å for O4 and O1, respectively (Fig. 2). The torsion angle O2—C8—C14—C19 has rather a small value [16.7 (3)°]. This results from the intramolecular hydrogen bond C19—H19···O2. The packing motif, as shown in Fig.3, can be described as follows: molecules are linked by hydrogen bonds in head-to-tail fashion through oxy- and keto-groups to form infinite chains. The two adjacent chains are linked by N7—H7···O2ⁱⁱ hydrogen bonds, forming infinite rods running along the c axis. Neighbouring rods interact via centrosymmetric C5—H5···O4ⁱⁱⁱ hydrogen bonds. Symmetry codes are listed in Table 1.

Experimental

A mixture of (1) (1 g, 0.0038 mol), concentrated sulfuric acid (1 ml) and trifluoroacetic acid (4 ml) was boiled under reflux. with stirring, for 5 h. The solution was then poured into ice-water (75 ml). The resulting white precipitate was filtered off, washed with water and recrystallized from acetone.

FiguresFig. 1.

Hydrolysis of (1) did not produce the expected compound, (2) but rather an isomer of (2), viz. compound (3).

Fig. 2.

The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. The dashed line indicates an intramolecular hydrogen bond.

Fig. 3.

The packing motif of the crystal structure. Hydrogen atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity. Symmetry codes: (i) x, y, z + 1; (ii) x, -y + 3/2, z - 1/2; (iii) -x, -y + 1, -z + 1.

Crystal data

C₁₆H₁₃NO₄	F₀₀₀ = 592
M_r = 283.27	D_x = 1.417 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 485–486 K
Hall symbol: -P 2ybc	Cu Kα radiation λ = 1.54184 Å
a = 8.6001 (17) Å	Cell parameters from 25 reflections
b = 27.005 (5) Å	θ = 26–42º
c = 5.7221 (5) Å	µ = 0.85 mm⁻¹
β = 92.602 (10)º	T = 291 (2) K
V = 1327.6 (4) Å³	Prism, colorless
Z = 4	0.08 × 0.06 × 0.04 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	R_int = 0.025
Radiation source: fine-focus sealed tube	θ_max = 73.9º
Monochromator: graphite	θ_min = 3.3º
T = 291(2) K	h = −10→10
Non–profiled ω scans	k = 0→32
Absorption correction: none	l = 0→7
2892 measured reflections	2 standard reflections
2653 independent reflections	every 120 min
1784 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.054	w = 1/[σ²(F_o²) + (0.061P)² + 0.4104P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.147	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.23 e Å⁻³
2653 reflections	Δρ_min = −0.24 e Å⁻³
192 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0051 (6)
Secondary atom site location: difference Fourier map

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 (Å2)

	x	y	z	U_iso*/U_eq
O1	0.3338 (2)	0.50617 (7)	1.1457 (3)	0.0654 (5)
O2	0.3093 (2)	0.70474 (6)	0.9980 (3)	0.0549 (5)
H2	0.2370	0.6906	1.0585	0.082*
O3	0.1250 (2)	0.65694 (7)	0.3005 (3)	0.0568 (5)
O4	0.1351 (3)	0.48070 (7)	0.7532 (4)	0.0737 (6)
N7	0.2877 (2)	0.68919 (8)	0.5922 (3)	0.0498 (5)
H7	0.2972	0.7182	0.5321	0.060*
C2	0.2445 (4)	0.46150 (12)	1.1374 (6)	0.0810 (10)
H2A	0.1463	0.4671	1.2100	0.097*
H2B	0.3003	0.4360	1.2259	0.097*
C3	0.2138 (5)	0.44427 (12)	0.8942 (7)	0.0878 (11)
H3A	0.3117	0.4361	0.8260	0.105*
H3B	0.1510	0.4144	0.8956	0.105*
C5	0.1581 (3)	0.56216 (9)	0.6119 (4)	0.0536 (6)
H5	0.0937	0.5541	0.4826	0.064*
C6	0.2011 (3)	0.65333 (9)	0.4881 (4)	0.0467 (6)
C8	0.3642 (3)	0.67510 (9)	0.8154 (4)	0.0455 (6)
C9	0.3521 (3)	0.58711 (9)	1.0021 (4)	0.0498 (6)
H9	0.4163	0.5955	1.1313	0.060*
C10	0.2183 (3)	0.60935 (9)	0.6404 (4)	0.0467 (6)
C11	0.3138 (3)	0.62151 (9)	0.8321 (4)	0.0446 (5)
C12	0.1965 (3)	0.52745 (10)	0.7811 (5)	0.0542 (6)
C13	0.2925 (3)	0.53960 (9)	0.9759 (4)	0.0510 (6)
C14	0.5399 (3)	0.68000 (9)	0.8127 (4)	0.0458 (6)
C15	0.6197 (3)	0.66247 (10)	0.6231 (4)	0.0555 (6)
H15	0.5636	0.6499	0.4937	0.067*
C16	0.7790 (3)	0.66338 (11)	0.6228 (5)	0.0645 (7)
H16	0.8301	0.6514	0.4946	0.077*
C17	0.8631 (4)	0.68214 (12)	0.8136 (5)	0.0683 (8)
H17	0.9712	0.6829	0.8143	0.082*
C18	0.7876 (3)	0.69959 (11)	1.0011 (5)	0.0678 (8)
H18	0.8449	0.7121	1.1297	0.081*
C19	0.6268 (3)	0.69889 (10)	1.0022 (4)	0.0561 (7)
H19	0.5767	0.7112	1.1307	0.067*

Atomic displacement parameters (Å2)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0765 (13)	0.0525 (11)	0.0666 (12)	−0.0020 (9)	−0.0039 (10)	0.0182 (9)
O2	0.0654 (12)	0.0516 (10)	0.0488 (10)	−0.0046 (8)	0.0138 (8)	−0.0083 (8)
O3	0.0575 (11)	0.0718 (12)	0.0406 (9)	−0.0020 (9)	−0.0038 (8)	0.0054 (8)
O4	0.0847 (15)	0.0480 (11)	0.0870 (15)	−0.0136 (10)	−0.0131 (12)	0.0040 (10)
N7	0.0603 (13)	0.0463 (11)	0.0421 (10)	−0.0032 (9)	−0.0049 (9)	0.0071 (9)
C2	0.097 (3)	0.0529 (18)	0.093 (2)	−0.0106 (16)	0.0003 (19)	0.0230 (17)
C3	0.107 (3)	0.0513 (18)	0.104 (3)	−0.0006 (18)	−0.011 (2)	0.0065 (18)
C5	0.0578 (15)	0.0547 (15)	0.0480 (13)	−0.0073 (12)	−0.0020 (11)	−0.0051 (12)
C6	0.0464 (13)	0.0567 (15)	0.0371 (11)	0.0029 (11)	0.0021 (10)	0.0008 (10)
C8	0.0575 (14)	0.0446 (13)	0.0343 (11)	−0.0017 (11)	−0.0001 (10)	−0.0005 (9)
C9	0.0564 (14)	0.0511 (14)	0.0417 (12)	−0.0030 (11)	−0.0005 (10)	0.0034 (11)
C10	0.0512 (13)	0.0500 (14)	0.0388 (11)	−0.0035 (11)	0.0017 (10)	−0.0004 (10)
C11	0.0505 (13)	0.0459 (13)	0.0373 (12)	−0.0014 (10)	0.0022 (10)	0.0010 (10)
C12	0.0608 (16)	0.0454 (14)	0.0565 (15)	−0.0078 (12)	0.0027 (12)	−0.0041 (12)
C13	0.0556 (14)	0.0469 (14)	0.0506 (13)	−0.0001 (11)	0.0042 (11)	0.0074 (11)
C14	0.0567 (14)	0.0436 (13)	0.0370 (11)	−0.0025 (11)	0.0011 (10)	0.0021 (10)
C15	0.0610 (16)	0.0649 (17)	0.0407 (12)	−0.0025 (13)	0.0027 (11)	−0.0039 (12)
C16	0.0606 (16)	0.074 (2)	0.0594 (17)	0.0007 (14)	0.0109 (13)	−0.0030 (15)
C17	0.0570 (16)	0.076 (2)	0.0716 (19)	−0.0002 (14)	0.0011 (14)	0.0022 (16)
C18	0.0635 (18)	0.076 (2)	0.0624 (17)	−0.0039 (15)	−0.0152 (14)	−0.0050 (15)
C19	0.0672 (17)	0.0599 (16)	0.0404 (12)	0.0001 (13)	−0.0040 (11)	−0.0032 (11)

Geometric parameters (Å, °)

O1—C13	1.362 (3)	C8—C11	1.515 (3)
O1—C2	1.430 (4)	C8—C14	1.518 (3)
O2—C8	1.415 (3)	C9—C11	1.374 (3)
O2—H2	0.8200	C9—C13	1.387 (3)
O3—C6	1.236 (3)	C9—H9	0.9300
O4—C12	1.375 (3)	C10—C11	1.380 (3)
O4—C3	1.424 (4)	C12—C13	1.396 (3)
N7—C6	1.344 (3)	C14—C19	1.386 (3)
N7—C8	1.460 (3)	C14—C15	1.393 (3)
N7—H7	0.8600	C15—C16	1.370 (4)
C2—C3	1.480 (5)	C15—H15	0.9300
C2—H2A	0.9700	C16—C17	1.378 (4)
C2—H2B	0.9700	C16—H16	0.9300
C3—H3A	0.9700	C17—C18	1.363 (4)
C3—H3B	0.9700	C17—H17	0.9300
C5—C12	1.376 (4)	C18—C19	1.384 (4)
C5—C10	1.382 (3)	C18—H18	0.9300
C5—H5	0.9300	C19—H19	0.9300
C6—C10	1.477 (3)

C13—O1—C2	114.4 (2)	C13—C9—H9	120.9
C8—O2—H2	109.5	C11—C10—C5	121.3 (2)
C12—O4—C3	113.5 (2)	C11—C10—C6	108.5 (2)
C6—N7—C8	114.7 (2)	C5—C10—C6	130.2 (2)
C6—N7—H7	122.6	C9—C11—C10	121.1 (2)
C8—N7—H7	122.6	C9—C11—C8	129.1 (2)
O1—C2—C3	111.7 (3)	C10—C11—C8	109.8 (2)
O1—C2—H2A	109.3	O4—C12—C5	117.7 (2)
C3—C2—H2A	109.3	O4—C12—C13	121.2 (2)
O1—C2—H2B	109.3	C5—C12—C13	121.0 (2)
C3—C2—H2B	109.3	O1—C13—C9	116.9 (2)
H2A—C2—H2B	107.9	O1—C13—C12	122.7 (2)
O4—C3—C2	112.1 (3)	C9—C13—C12	120.4 (2)
O4—C3—H3A	109.2	C19—C14—C15	117.8 (2)
C2—C3—H3A	109.2	C19—C14—C8	121.7 (2)
O4—C3—H3B	109.2	C15—C14—C8	120.3 (2)
C2—C3—H3B	109.2	C16—C15—C14	121.5 (3)
H3A—C3—H3B	107.9	C16—C15—H15	119.2
C12—C5—C10	117.9 (2)	C14—C15—H15	119.2
C12—C5—H5	121.0	C15—C16—C17	119.6 (3)
C10—C5—H5	121.0	C15—C16—H16	120.2
O3—C6—N7	126.1 (2)	C17—C16—H16	120.2
O3—C6—C10	127.7 (2)	C18—C17—C16	119.9 (3)
N7—C6—C10	106.23 (19)	C18—C17—H17	120.0
O2—C8—N7	110.3 (2)	C16—C17—H17	120.0
O2—C8—C11	112.82 (19)	C17—C18—C19	120.7 (3)
N7—C8—C11	100.69 (18)	C17—C18—H18	119.7
O2—C8—C14	108.89 (19)	C19—C18—H18	119.7
N7—C8—C14	112.20 (19)	C18—C19—C14	120.4 (3)
C11—C8—C14	111.8 (2)	C18—C19—H19	119.8
C11—C9—C13	118.2 (2)	C14—C19—H19	119.8
C11—C9—H9	120.9

C13—O1—C2—C3	40.4 (4)	C3—O4—C12—C5	162.9 (3)
C12—O4—C3—C2	45.2 (4)	C3—O4—C12—C13	−18.1 (4)
O1—C2—C3—O4	−57.6 (4)	C10—C5—C12—O4	179.4 (2)
C8—N7—C6—O3	179.2 (2)	C10—C5—C12—C13	0.3 (4)
C8—N7—C6—C10	−1.7 (3)	C2—O1—C13—C9	167.3 (3)
C6—N7—C8—O2	−117.5 (2)	C2—O1—C13—C12	−13.5 (4)
C6—N7—C8—C11	1.8 (3)	C11—C9—C13—O1	179.3 (2)
C6—N7—C8—C14	120.9 (2)	C11—C9—C13—C12	0.1 (4)
C12—C5—C10—C11	−0.1 (4)	O4—C12—C13—O1	1.5 (4)
C12—C5—C10—C6	178.4 (3)	C5—C12—C13—O1	−179.5 (2)
O3—C6—C10—C11	179.9 (2)	O4—C12—C13—C9	−179.3 (2)
N7—C6—C10—C11	0.8 (3)	C5—C12—C13—C9	−0.4 (4)
O3—C6—C10—C5	1.3 (4)	O2—C8—C14—C19	16.7 (3)
N7—C6—C10—C5	−177.8 (3)	N7—C8—C14—C19	139.1 (2)
C13—C9—C11—C10	0.2 (4)	C11—C8—C14—C19	−108.6 (3)
C13—C9—C11—C8	−178.9 (2)	O2—C8—C14—C15	−167.4 (2)
C5—C10—C11—C9	−0.2 (4)	N7—C8—C14—C15	−45.1 (3)
C6—C10—C11—C9	−178.9 (2)	C11—C8—C14—C15	67.2 (3)
C5—C10—C11—C8	179.0 (2)	C19—C14—C15—C16	0.5 (4)
C6—C10—C11—C8	0.3 (3)	C8—C14—C15—C16	−175.6 (2)
O2—C8—C11—C9	−64.5 (3)	C14—C15—C16—C17	−0.2 (4)
N7—C8—C11—C9	178.0 (2)	C15—C16—C17—C18	0.1 (5)
C14—C8—C11—C9	58.6 (3)	C16—C17—C18—C19	−0.3 (5)
O2—C8—C11—C10	116.3 (2)	C17—C18—C19—C14	0.5 (5)
N7—C8—C11—C10	−1.2 (3)	C15—C14—C19—C18	−0.6 (4)
C14—C8—C11—C10	−120.5 (2)	C8—C14—C19—C18	175.3 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3ⁱ	0.82	1.95	2.725 (3)	158
N7—H7···O2ⁱⁱ	0.86	2.09	2.922 (3)	161
C5—H5···O4ⁱⁱⁱ	0.93	2.52	3.404 (3)	160
C19—H19···O2	0.93	2.40	2.734 (4)	101

Symmetry codes: (i) x, y, z+1; (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z+1.

References

Brandenburg, K. (2000). DIAMOND Release 2.1d. Crystal Impact GbR, Bonn, Germany.

Enraf–Nonius (1989). CAD-4 Software. Version 5.0. Enraf–Nonius, Delft, The Netherlands.

Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.

Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.

Moorthy, J. N. & Singhal, N. (2005). J. Org. Chem.70, 1926–1929.

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

Table 1Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3ⁱ	0.82	1.95	2.725 (3)	158
N7—H7⋯O2ⁱⁱ	0.86	2.09	2.922 (3)	161
C5—H5⋯O4ⁱⁱⁱ	0.93	2.52	3.404 (3)	160
C19—H19⋯O2	0.93	2.40	2.734 (4)	101

Symmetry codes: (i) ; (ii) ; (iii) .