3′-(3-Hy­droxy­phen­yl)-4-methyl­spiro­[benzo[e][1,4]diazepine-3,2′-oxirane]-2,5(1H,4H)-dione

Liu, J.-L.; Hu, Z.-Y.; Xu, Q.-Y.

doi:10.1107/S1600536811022161

organic compounds

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Volume 67| Part 7| July 2011| Page o1670

doi:10.1107/S1600536811022161

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3′-(3-Hydroxyphenyl)-4-methylspiro[benzo[e][1,4]diazepine-3,2′-oxirane]-2,5(1H,4H)-dione

Jun-Liang Liu,^a Zhi-Yu Hu ^a and Qing-Yan Xu ^a ^*

^aLaboratory of Microbial Pharmaceutical Engineering, School of Life Sciences, Xiamen University, Xiamen 361005, People's Republic of China
^*Correspondence e-mail: xuqingyan@xmu.edu.cn

(Received 31 May 2011; accepted 8 June 2011; online 18 June 2011)

In the title compound, C₁₇H₁₄N₂O₄, the seven-membered ring adopts a boat conformation, and the two benzene rings make a dihedral angle of 45.22 (5)°. The crystal packing is stabilized by intermolecular N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For the biological activity of the title compound, see: Birkinshaw et al. (1963 ); Cutler et al. (1984 ); Heguy, et al. (1998 ). For the biosynthesis of cyclopenol, see: Nover & Luckner (1969 ).

Experimental

Crystal data

C₁₇H₁₄N₂O₄
M_r = 310.30
Monoclinic, P 2₁
a = 7.0066 (2) Å
b = 11.6160 (4) Å
c = 9.1568 (2) Å
β = 108.157 (1)°
V = 708.15 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 193 K
0.55 × 0.32 × 0.22 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
6890 measured reflections
1701 independent reflections
1627 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.107
S = 0.99
1701 reflections
208 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.13	2.893 (2)	148
O4—H4A⋯O1ⁱⁱ	0.82	1.95	2.7689 (17)	173
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811022161/xu5236sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022161/xu5236Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811022161/xu5236Isup3.cml

checkCIF report

Comment top

The title compund named cyclopenol is an benzodiazepine metabolite produced by a number of Penicllium species. Cyclopenol isolated from Penicillium cyclopium Westling (Birkinshaw et al., 1963). It display intermediate in the biosynthesis of viridicatins, inhibitors of the TNF-α-induced replication of human HIV (Nover & Luckner, 1969; Heguy, et al., 1998). It is of ecological significance due to its phytotoxic and antimicrobial properties (Cutler, et al., 1984). In our study, we determined the crystal structure of the title compound. The seven membered ring adopts a boat conformation. The crystal packing is stabilized by intermolecular N—H···O and O—H···O hydrogen bondings (Table 1).

Related literature top

For the biological activity of the title compound, see: Birkinshaw et al. (1963); Cutler et al. (1984); Heguy, et al. (1998). For the biosynthesis of cyclopenol, see: Nover & Luckner (1969).

Experimental top

The fungal F00734 was cultured using half sea-water Potato Dextrose Agar medium at 28 degrees celsius for 14 days. The fermentation (10 liters) was extracted with ethyl acetate (EtOAc). The EtOAc extract (5.0 g) which was subjected to column chromatography over RP-18, eluted with Methanol-H₂O (30%, 50%, 70%, 100%; V/V) to yield 10 fractions. Fraction 5, eluted with methanol was further puried by Sephadex LH-20 chromatography. Then merged the components 1–15 tubes eluted with acetone, and further purified by silica-gel column chromatography to afford the title compound 1 (140.0 mg). F00734 is an high-yield strain of cyclopenol (2.8%).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with 50% probability ellipsoids.
	Fig. 2. Partial packing diagram of the title compound, viewed along the a axis.

3'-(3-Hydroxyphenyl)-4-methylspiro[benzo[e][1,4]diazepine-3,2'- oxirane]-2,5(1H,4H)-dione top

Crystal data top

C₁₇H₁₄N₂O₄	F(000) = 324
M_r = 310.30	D_x = 1.455 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1484 reflections
a = 7.0066 (2) Å	θ = 1.9–27.5°
b = 11.6160 (4) Å	µ = 0.11 mm⁻¹
c = 9.1568 (2) Å	T = 193 K
β = 108.157 (1)°	Block, colourless
V = 708.15 (4) Å³	0.55 × 0.32 × 0.22 mm
Z = 2

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1627 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
ϕ and ω scans	h = −8→9
6890 measured reflections	k = −15→15
1701 independent reflections	l = −11→11

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
1701 reflections	(Δ/σ)_max = 0.009
208 parameters	Δρ_max = 0.21 e Å⁻³
1 restraint	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₇H₁₄N₂O₄	V = 708.15 (4) Å³
M_r = 310.30	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.0066 (2) Å	µ = 0.11 mm⁻¹
b = 11.6160 (4) Å	T = 193 K
c = 9.1568 (2) Å	0.55 × 0.32 × 0.22 mm
β = 108.157 (1)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1627 reflections with I > 2σ(I)
6890 measured reflections	R_int = 0.021
1701 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	1 restraint
wR(F²) = 0.107	H-atom parameters constrained
S = 0.99	Δρ_max = 0.21 e Å⁻³
1701 reflections	Δρ_min = −0.24 e Å⁻³
208 parameters

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
O2	0.4377 (2)	0.08072 (14)	0.31423 (17)	0.0269 (3)
O3	0.4521 (2)	0.40192 (14)	0.02123 (17)	0.0227 (3)
O1	0.6694 (2)	0.51497 (15)	0.29249 (19)	0.0291 (4)
O4	−0.0361 (2)	0.06229 (14)	−0.25108 (18)	0.0271 (4)
H4A	0.0758	0.0542	−0.2604	0.041*
N2	0.4837 (2)	0.24388 (15)	0.19567 (18)	0.0184 (3)
N1	0.4887 (2)	0.42631 (15)	0.42617 (18)	0.0205 (4)
H1	0.5578	0.4610	0.5087	0.025*
C8	0.3244 (3)	0.35791 (17)	0.4353 (2)	0.0186 (4)
C9	0.2804 (3)	0.24831 (18)	0.3691 (2)	0.0186 (4)
C7	0.2100 (3)	0.40240 (19)	0.5227 (2)	0.0216 (4)
H7	0.2433	0.4733	0.5712	0.026*
C4	0.1162 (3)	0.18798 (19)	0.3878 (2)	0.0236 (4)
H4	0.0858	0.1152	0.3445	0.028*
C3	0.4063 (3)	0.18510 (18)	0.2913 (2)	0.0192 (4)
C12	0.1144 (3)	0.22949 (19)	−0.1034 (2)	0.0212 (4)
H12	0.2423	0.1976	−0.0787	0.025*
C10	0.6209 (3)	0.1863 (2)	0.1253 (2)	0.0257 (4)
H10A	0.6350	0.1068	0.1554	0.038*
H10B	0.7499	0.2231	0.1592	0.038*
H10C	0.5671	0.1915	0.0154	0.038*
C16	−0.1031 (3)	0.3876 (2)	−0.0884 (2)	0.0241 (4)
H16	−0.1207	0.4607	−0.0531	0.029*
C11	0.0875 (3)	0.33865 (18)	−0.0492 (2)	0.0201 (4)
C14	−0.2433 (3)	0.21769 (19)	−0.2334 (2)	0.0234 (4)
H14	−0.3541	0.1771	−0.2941	0.028*
C6	0.0469 (3)	0.3415 (2)	0.5378 (2)	0.0247 (4)
H6	−0.0307	0.3725	0.5941	0.030*
C13	−0.0508 (3)	0.16860 (19)	−0.1948 (2)	0.0208 (4)
C17	0.2579 (3)	0.40891 (18)	0.0485 (2)	0.0198 (4)
H17	0.2200	0.4869	0.0695	0.024*
C15	−0.2672 (3)	0.3264 (2)	−0.1808 (2)	0.0252 (4)
H15	−0.3946	0.3592	−0.2075	0.030*
C2	0.4422 (3)	0.36451 (16)	0.1645 (2)	0.0180 (4)
C5	−0.0007 (3)	0.2341 (2)	0.4688 (2)	0.0267 (5)
H5	−0.1113	0.1937	0.4774	0.032*
C1	0.5463 (3)	0.44186 (18)	0.2995 (2)	0.0195 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0382 (8)	0.0157 (7)	0.0268 (7)	0.0038 (6)	0.0100 (6)	0.0041 (6)
O3	0.0288 (7)	0.0214 (7)	0.0222 (7)	0.0002 (5)	0.0139 (5)	0.0024 (6)
O1	0.0309 (8)	0.0236 (8)	0.0359 (8)	−0.0097 (6)	0.0149 (6)	−0.0027 (7)
O4	0.0268 (7)	0.0222 (8)	0.0341 (8)	−0.0028 (6)	0.0121 (6)	−0.0060 (6)
N2	0.0227 (7)	0.0155 (8)	0.0180 (7)	0.0029 (6)	0.0077 (6)	0.0006 (7)
N1	0.0236 (8)	0.0174 (8)	0.0189 (8)	−0.0052 (6)	0.0044 (6)	−0.0034 (6)
C8	0.0194 (9)	0.0184 (9)	0.0169 (8)	−0.0022 (7)	0.0042 (7)	0.0015 (7)
C9	0.0225 (8)	0.0181 (9)	0.0144 (8)	0.0006 (7)	0.0046 (7)	0.0022 (7)
C7	0.0273 (9)	0.0183 (9)	0.0180 (8)	0.0001 (7)	0.0052 (7)	−0.0012 (7)
C4	0.0251 (9)	0.0204 (10)	0.0234 (9)	−0.0063 (8)	0.0050 (7)	0.0004 (8)
C3	0.0220 (9)	0.0140 (9)	0.0188 (8)	0.0025 (7)	0.0021 (6)	0.0016 (7)
C12	0.0234 (9)	0.0216 (10)	0.0186 (8)	0.0041 (7)	0.0065 (7)	0.0022 (7)
C10	0.0248 (10)	0.0251 (11)	0.0290 (9)	0.0094 (8)	0.0113 (7)	−0.0007 (8)
C16	0.0289 (10)	0.0229 (10)	0.0216 (9)	0.0058 (8)	0.0096 (8)	0.0013 (8)
C11	0.0256 (9)	0.0208 (10)	0.0149 (8)	0.0012 (7)	0.0076 (7)	0.0007 (7)
C14	0.0204 (9)	0.0291 (12)	0.0213 (9)	−0.0014 (7)	0.0071 (7)	0.0018 (8)
C6	0.0277 (10)	0.0291 (11)	0.0202 (9)	0.0014 (8)	0.0117 (8)	0.0027 (8)
C13	0.0265 (9)	0.0187 (9)	0.0195 (8)	−0.0010 (8)	0.0105 (7)	0.0000 (7)
C17	0.0263 (10)	0.0163 (9)	0.0178 (8)	0.0017 (7)	0.0085 (7)	0.0028 (7)
C15	0.0234 (10)	0.0300 (12)	0.0230 (10)	0.0054 (8)	0.0082 (8)	0.0030 (8)
C2	0.0220 (9)	0.0143 (9)	0.0193 (8)	0.0005 (7)	0.0087 (7)	0.0016 (7)
C5	0.0263 (10)	0.0300 (12)	0.0252 (10)	−0.0084 (9)	0.0101 (8)	0.0025 (9)
C1	0.0200 (8)	0.0149 (9)	0.0238 (9)	0.0001 (6)	0.0069 (7)	−0.0002 (7)

Geometric parameters (Å, º) top

O2—C3	1.238 (3)	C12—C13	1.392 (3)
O3—C2	1.405 (2)	C12—C11	1.396 (3)
O3—C17	1.461 (2)	C12—H12	0.9300
O1—C1	1.226 (3)	C10—H10A	0.9600
O4—C13	1.354 (3)	C10—H10B	0.9600
O4—H4A	0.8200	C10—H10C	0.9600
N2—C3	1.350 (3)	C16—C15	1.392 (3)
N2—C2	1.441 (2)	C16—C11	1.392 (3)
N2—C10	1.474 (2)	C16—H16	0.9300
N1—C1	1.354 (3)	C11—C17	1.492 (3)
N1—C8	1.422 (2)	C14—C15	1.380 (3)
N1—H1	0.8600	C14—C13	1.404 (3)
C8—C7	1.397 (3)	C14—H14	0.9300
C8—C9	1.402 (3)	C6—C5	1.391 (3)
C9—C4	1.403 (3)	C6—H6	0.9300
C9—C3	1.489 (3)	C17—C2	1.486 (3)
C7—C6	1.387 (3)	C17—H17	0.9800
C7—H7	0.9300	C15—H15	0.9300
C4—C5	1.373 (3)	C2—C1	1.518 (3)
C4—H4	0.9300	C5—H5	0.9300

C2—O3—C17	62.43 (12)	C11—C16—H16	120.2
C13—O4—H4A	109.5	C16—C11—C12	120.29 (19)
C3—N2—C2	121.51 (17)	C16—C11—C17	117.10 (18)
C3—N2—C10	120.16 (17)	C12—C11—C17	122.59 (17)
C2—N2—C10	118.28 (17)	C15—C14—C13	119.7 (2)
C1—N1—C8	125.99 (16)	C15—C14—H14	120.1
C1—N1—H1	117.0	C13—C14—H14	120.1
C8—N1—H1	117.0	C7—C6—C5	119.99 (19)
C7—C8—C9	119.68 (18)	C7—C6—H6	120.0
C7—C8—N1	116.53 (18)	C5—C6—H6	120.0
C9—C8—N1	123.70 (17)	O4—C13—C12	122.98 (18)
C4—C9—C8	118.62 (18)	O4—C13—C14	117.11 (18)
C4—C9—C3	116.31 (19)	C12—C13—C14	119.9 (2)
C8—C9—C3	124.83 (17)	O3—C17—C2	56.95 (11)
C6—C7—C8	120.4 (2)	O3—C17—C11	118.78 (16)
C6—C7—H7	119.8	C2—C17—C11	126.41 (18)
C8—C7—H7	119.8	O3—C17—H17	114.1
C5—C4—C9	121.4 (2)	C2—C17—H17	114.1
C5—C4—H4	119.3	C11—C17—H17	114.1
C9—C4—H4	119.3	C14—C15—C16	120.80 (18)
O2—C3—N2	121.27 (19)	C14—C15—H15	119.6
O2—C3—C9	120.14 (19)	C16—C15—H15	119.6
N2—C3—C9	118.58 (18)	O3—C2—N2	114.81 (16)
C13—C12—C11	119.76 (18)	O3—C2—C17	60.63 (12)
C13—C12—H12	120.1	N2—C2—C17	123.77 (17)
C11—C12—H12	120.1	O3—C2—C1	115.22 (16)
N2—C10—H10A	109.5	N2—C2—C1	113.46 (16)
N2—C10—H10B	109.5	C17—C2—C1	117.85 (17)
H10A—C10—H10B	109.5	C4—C5—C6	119.79 (19)
N2—C10—H10C	109.5	C4—C5—H5	120.1
H10A—C10—H10C	109.5	C6—C5—H5	120.1
H10B—C10—H10C	109.5	O1—C1—N1	122.65 (19)
C15—C16—C11	119.5 (2)	O1—C1—C2	122.34 (19)
C15—C16—H16	120.2	N1—C1—C2	114.97 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.13	2.893 (2)	148
O4—H4A···O1ⁱⁱ	0.82	1.95	2.7689 (17)	173

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

Experimental details

Crystal data
Chemical formula	C₁₇H₁₄N₂O₄
M_r	310.30
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	193
a, b, c (Å)	7.0066 (2), 11.6160 (4), 9.1568 (2)
β (°)	108.157 (1)
V (Å³)	708.15 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.55 × 0.32 × 0.22

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6890, 1701, 1627
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.107, 0.99
No. of reflections	1701
No. of parameters	208
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.24

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.13	2.893 (2)	148
O4—H4A···O1ⁱⁱ	0.82	1.95	2.7689 (17)	173

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

Acknowledgements

The authors thank the Fundamental Research Funds for the Central Universities, China, for financial support (grant No. 2010121092).

References

Birkinshaw, J. H., Luckner, M., Mohammed, Y. S., Mothes, K. & Stickings, C. E. (1963). Biochem. J. 89, 196–202. PubMed CAS Web of Science Google Scholar
Bruker (2007). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cutler, H. G., Crumley, F. G., Cox, R. H., Wells, J. & Cole, R. J. (1984). Plant Cell Physiol. 25, 257–263. CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Heguy, A., Cai, P., Meyn, P., Houck, D., Russo, S., Michitsch, R., Pearce, C. & Katz, B. (1998). Antivir. Chem. Chemother. 9, 149–155. Web of Science CAS PubMed Google Scholar
Nover, L. & Luckner, M. (1969). Eur. J. Biochem. 10, 268–273. CrossRef CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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

3′-(3-Hy­dr­oxy­phen­yl)-4-methyl­spiro­[benzo[e][1,4]diazepine-3,2′-oxirane]-2,5(1H,4H)-dione

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

3′-(3-Hydroxyphenyl)-4-methylspiro[benzo[e][1,4]diazepine-3,2′-oxirane]-2,5(1H,4H)-dione