(E)-2,4,7-Trichloro-3-hydr-oxy-8-meth-oxy-1,9-dimethyl-6-(1-methyl-1-propen-yl)-11H-dibenzo[b,e][1,4]dioxepin-11-one monohydrate (nidulin monohydrate).

In the title compound, C(20)H(17)Cl(3)O(5)·H(2)O, the nidulin mol-ecule consists of three rings, the folded central dioxepin-11-one ring being fused on both sides to phenyl rings. The mol-ecular structure is stabilized by intra-molecular O-H⋯Cl and C-H⋯Cl hydrogen bonds that generate S(6) ring motifs. The crystal structure is stabilized by inter-molecular O-H⋯O and O-H⋯(O,O) hydrogen bonds mediated by two inversion-related water mol-ecules, generating R(4) (2)(8) ring and C(2) (2)(4) chain motifs. Weak inter-molecular Cl⋯O halogen bonds are also present with Cl⋯O distances of 3.071 (1) and 3.182 (2) Å.

Related literature

For the structure and synthesis of nidulin, see: Beach & Richards (1961 ▶, 1963 ▶); Bycroft & Roberts (1963 ▶). For the crystal structure of anhydrous nidulin, see: McMillan (1964 ▶). For related structures, see: Brassy et al. (1977 ▶); Connolly et al. (1984 ▶); Kawahara et al. (1988 ▶); Blaser & Stoeckli-Evans (1991 ▶); Xu et al. (2000 ▶); Lang et al. (2007 ▶). For the graph-set description of hydrogen-bond patterns, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C20H17Cl3O5·H2O

M = 461.70

Monoclinic,

a = 7.7706 (4) Å

b = 11.0374 (5) Å

c = 23.9428 (10) Å

β = 96.707 (2)°

V = 2039.45 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.49 mm−1

T = 298 K

0.44 × 0.28 × 0.26 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.817, T max = 0.846

11735 measured reflections

5969 independent reflections

4193 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.118

S = 1.02

5969 reflections

276 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.34 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al. 2006 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809036277/sj2646sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036277/sj2646Isup2.hkl

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

C20H17Cl3O5·H2O	F(000) = 952
Mr = 461.70	Dx = 1.504 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4256 reflections
a = 7.7706 (4) Å	θ = 2.6–30.1°
b = 11.0374 (5) Å	µ = 0.49 mm−1
c = 23.9428 (10) Å	T = 298 K
β = 96.707 (2)°	Rod, colourless
V = 2039.45 (16) Å3	0.44 × 0.28 × 0.26 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	5969 independent reflections
Radiation source: fine-focus sealed tube	4193 reflections with I > 2σ(I)
graphite	Rint = 0.022
φ and ω scans	θmax = 30.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→8
Tmin = 0.817, Tmax = 0.846	k = −8→15
11735 measured reflections	l = −30→34

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0513P)2 + 0.801P] where P = (Fo2 + 2Fc2)/3
5969 reflections	(Δ/σ)max < 0.001
276 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	1.19555 (8)	1.09399 (5)	0.19154 (2)	0.04719 (16)
Cl2	1.27489 (9)	1.13429 (5)	−0.02688 (2)	0.04800 (16)
Cl3	0.51380 (6)	0.74321 (5)	0.19233 (2)	0.04035 (13)
C1	1.2062 (2)	0.84575 (16)	0.07006 (7)	0.0260 (3)
C2	1.1823 (2)	0.90311 (15)	0.12065 (7)	0.0242 (3)
C3	1.2058 (2)	1.02676 (17)	0.12732 (8)	0.0294 (4)
C4	1.2405 (2)	1.09852 (17)	0.08192 (8)	0.0318 (4)
C5	1.2461 (2)	1.04181 (17)	0.02995 (8)	0.0312 (4)
C6	1.2317 (2)	0.91718 (16)	0.02277 (8)	0.0279 (4)
C7	1.0090 (2)	0.66126 (15)	0.12272 (7)	0.0254 (3)
C8	0.8747 (2)	0.57758 (16)	0.11380 (8)	0.0292 (4)
C9	0.7239 (2)	0.60330 (17)	0.13765 (8)	0.0298 (4)
C10	0.7088 (2)	0.71040 (16)	0.16780 (7)	0.0269 (4)
C11	0.8453 (2)	0.79319 (15)	0.17737 (7)	0.0234 (3)
C12	0.9971 (2)	0.76342 (15)	0.15515 (7)	0.0238 (3)
C13	1.2414 (2)	0.71340 (17)	0.06833 (8)	0.0291 (4)
C14	1.2365 (3)	0.8636 (2)	−0.03500 (8)	0.0418 (5)
H143	1.1706	0.9138	−0.0624	0.063*
H141	1.1876	0.7837	−0.0361	0.063*
H142	1.3543	0.8594	−0.0432	0.063*
C15	0.8942 (3)	0.46381 (19)	0.08076 (10)	0.0446 (5)
H152	0.8695	0.4809	0.0413	0.067*
H151	0.8147	0.4036	0.0913	0.067*
H153	1.0106	0.4342	0.0886	0.067*
C16	0.5569 (4)	0.4478 (2)	0.17417 (12)	0.0629 (7)
H162	0.6588	0.4005	0.1852	0.094*
H163	0.4611	0.3948	0.1630	0.094*
H161	0.5310	0.4967	0.2053	0.094*
C17	0.8290 (2)	0.91073 (16)	0.20689 (8)	0.0282 (4)
C18	0.9100 (4)	0.9166 (2)	0.26682 (9)	0.0496 (6)
H181	0.9067	0.9985	0.2801	0.074*
H183	1.0282	0.8899	0.2691	0.074*
H182	0.8471	0.8652	0.2896	0.074*
C19	0.7478 (3)	1.00046 (18)	0.17871 (9)	0.0404 (5)
H19	0.7012	0.9828	0.1421	0.061*
C20	0.7211 (4)	1.1273 (2)	0.19822 (13)	0.0623 (7)
H201	0.7663	1.1347	0.2371	0.093*
H202	0.5995	1.1457	0.1938	0.093*
H203	0.7803	1.1829	0.1762	0.093*
O1	1.3465 (2)	0.67026 (14)	0.04114 (6)	0.0449 (4)
O2	1.16197 (17)	0.63383 (11)	0.10058 (6)	0.0321 (3)
O3	1.14180 (15)	0.83871 (11)	0.16655 (5)	0.0265 (3)
O4	1.2591 (3)	1.21752 (13)	0.09119 (7)	0.0519 (4)
H4	1.2950	1.2497	0.0639	0.078*
O5	0.58658 (19)	0.52480 (13)	0.12786 (6)	0.0418 (4)
O1W	0.3826 (3)	0.38791 (17)	0.02997 (9)	0.0617 (6)
H1W1	0.465 (5)	0.372 (3)	0.0093 (15)	0.089 (12)*
H2W1	0.396 (4)	0.449 (3)	0.0451 (14)	0.076 (11)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0688 (4)	0.0363 (3)	0.0391 (3)	−0.0159 (2)	0.0170 (3)	−0.0148 (2)
Cl2	0.0726 (4)	0.0353 (3)	0.0363 (3)	−0.0106 (3)	0.0073 (3)	0.0068 (2)
Cl3	0.0276 (2)	0.0440 (3)	0.0510 (3)	−0.0006 (2)	0.0115 (2)	0.0000 (2)
C1	0.0256 (8)	0.0231 (8)	0.0295 (9)	−0.0007 (6)	0.0044 (7)	−0.0032 (7)
C2	0.0215 (8)	0.0244 (8)	0.0268 (8)	−0.0018 (6)	0.0036 (6)	−0.0019 (6)
C3	0.0320 (9)	0.0270 (9)	0.0300 (9)	−0.0050 (7)	0.0075 (7)	−0.0073 (7)
C4	0.0348 (10)	0.0239 (9)	0.0374 (10)	−0.0070 (7)	0.0067 (8)	−0.0026 (7)
C5	0.0324 (10)	0.0303 (9)	0.0307 (9)	−0.0045 (7)	0.0032 (8)	0.0034 (7)
C6	0.0287 (9)	0.0279 (9)	0.0272 (9)	−0.0019 (7)	0.0029 (7)	−0.0027 (7)
C7	0.0272 (8)	0.0207 (8)	0.0288 (9)	0.0032 (6)	0.0057 (7)	0.0012 (6)
C8	0.0366 (10)	0.0209 (8)	0.0293 (9)	−0.0009 (7)	0.0008 (7)	−0.0009 (7)
C9	0.0305 (9)	0.0259 (9)	0.0318 (9)	−0.0064 (7)	−0.0017 (7)	0.0018 (7)
C10	0.0241 (8)	0.0279 (9)	0.0288 (9)	−0.0004 (7)	0.0038 (7)	0.0031 (7)
C11	0.0253 (8)	0.0226 (8)	0.0225 (8)	0.0009 (6)	0.0039 (6)	0.0010 (6)
C12	0.0244 (8)	0.0210 (8)	0.0259 (8)	−0.0024 (6)	0.0026 (6)	0.0014 (6)
C13	0.0320 (9)	0.0258 (9)	0.0304 (9)	0.0013 (7)	0.0079 (7)	−0.0029 (7)
C14	0.0591 (14)	0.0368 (11)	0.0298 (10)	−0.0036 (10)	0.0063 (9)	−0.0035 (8)
C15	0.0521 (13)	0.0299 (11)	0.0529 (13)	−0.0047 (9)	0.0107 (11)	−0.0136 (9)
C16	0.0649 (17)	0.0448 (14)	0.0782 (19)	−0.0249 (12)	0.0053 (14)	0.0144 (13)
C17	0.0316 (9)	0.0261 (9)	0.0281 (9)	−0.0019 (7)	0.0095 (7)	−0.0044 (7)
C18	0.0693 (16)	0.0460 (13)	0.0322 (11)	−0.0012 (11)	0.0007 (11)	−0.0094 (9)
C19	0.0502 (12)	0.0298 (10)	0.0430 (12)	0.0058 (9)	0.0126 (10)	−0.0050 (8)
C20	0.0777 (19)	0.0327 (12)	0.0809 (19)	0.0149 (12)	0.0276 (16)	−0.0084 (12)
O1	0.0545 (9)	0.0367 (8)	0.0484 (9)	0.0107 (7)	0.0267 (8)	−0.0013 (7)
O2	0.0348 (7)	0.0214 (6)	0.0423 (8)	0.0042 (5)	0.0132 (6)	−0.0001 (5)
O3	0.0264 (6)	0.0274 (6)	0.0260 (6)	−0.0053 (5)	0.0044 (5)	−0.0020 (5)
O4	0.0855 (13)	0.0249 (7)	0.0483 (9)	−0.0148 (8)	0.0211 (9)	−0.0054 (6)
O5	0.0374 (8)	0.0385 (8)	0.0482 (9)	−0.0166 (6)	−0.0003 (7)	−0.0030 (7)
O1W	0.0887 (15)	0.0334 (9)	0.0700 (13)	−0.0188 (9)	0.0389 (12)	−0.0100 (9)

Cl1—C3	1.7175 (18)	C13—O2	1.364 (2)
Cl2—C5	1.7361 (19)	C14—H143	0.9600
Cl3—C10	1.7261 (18)	C14—H141	0.9600
C1—C2	1.398 (2)	C14—H142	0.9600
C1—C6	1.412 (2)	C15—H152	0.9600
C1—C13	1.488 (2)	C15—H151	0.9600
C2—O3	1.376 (2)	C15—H153	0.9600
C2—C3	1.384 (2)	C16—O5	1.437 (3)
C3—C4	1.397 (3)	C16—H162	0.9600
C4—O4	1.337 (2)	C16—H163	0.9600
C4—C5	1.398 (3)	C16—H161	0.9600
C5—C6	1.389 (3)	C17—C19	1.317 (3)
C6—C14	1.509 (3)	C17—C18	1.499 (3)
C7—C12	1.378 (2)	C18—H181	0.9600
C7—O2	1.390 (2)	C18—H183	0.9600
C7—C8	1.391 (3)	C18—H182	0.9600
C8—C9	1.391 (3)	C19—C20	1.498 (3)
C8—C15	1.501 (3)	C19—H19	0.9300
C9—O5	1.373 (2)	C20—H201	0.9600
C9—C10	1.397 (3)	C20—H202	0.9600
C10—C11	1.399 (2)	C20—H203	0.9600
C11—C12	1.389 (2)	O4—H4	0.8200
C11—C17	1.490 (2)	O1W—H1W1	0.87 (4)
C12—O3	1.399 (2)	O1W—H2W1	0.77 (3)
C13—O1	1.201 (2)
C2—C1—C6	119.13 (16)	C6—C14—H141	109.5
C2—C1—C13	120.81 (16)	H143—C14—H141	109.5
C6—C1—C13	118.85 (16)	C6—C14—H142	109.5
O3—C2—C3	117.18 (15)	H143—C14—H142	109.5
O3—C2—C1	121.60 (15)	H141—C14—H142	109.5
C3—C2—C1	121.16 (16)	C8—C15—H152	109.5
C2—C3—C4	120.29 (16)	C8—C15—H151	109.5
C2—C3—Cl1	120.68 (14)	H152—C15—H151	109.5
C4—C3—Cl1	119.03 (14)	C8—C15—H153	109.5
O4—C4—C3	117.05 (17)	H152—C15—H153	109.5
O4—C4—C5	125.00 (17)	H151—C15—H153	109.5
C3—C4—C5	117.89 (16)	O5—C16—H162	109.5
C6—C5—C4	122.89 (17)	O5—C16—H163	109.5
C6—C5—Cl2	120.08 (15)	H162—C16—H163	109.5
C4—C5—Cl2	117.03 (14)	O5—C16—H161	109.5
C5—C6—C1	118.06 (16)	H162—C16—H161	109.5
C5—C6—C14	119.41 (17)	H163—C16—H161	109.5
C1—C6—C14	122.48 (16)	C19—C17—C11	118.29 (17)
C12—C7—O2	120.62 (15)	C19—C17—C18	125.47 (19)
C12—C7—C8	122.10 (16)	C11—C17—C18	116.24 (17)
O2—C7—C8	117.15 (15)	C17—C18—H181	109.5
C7—C8—C9	117.01 (16)	C17—C18—H183	109.5
C7—C8—C15	121.09 (18)	H181—C18—H183	109.5
C9—C8—C15	121.90 (17)	C17—C18—H182	109.5
O5—C9—C8	118.43 (17)	H181—C18—H182	109.5
O5—C9—C10	120.75 (17)	H183—C18—H182	109.5
C8—C9—C10	120.69 (16)	C17—C19—C20	128.2 (2)
C9—C10—C11	121.96 (16)	C17—C19—H19	115.9
C9—C10—Cl3	118.92 (14)	C20—C19—H19	115.9
C11—C10—Cl3	119.10 (14)	C19—C20—H201	109.5
C12—C11—C10	116.40 (15)	C19—C20—H202	109.5
C12—C11—C17	120.72 (15)	H201—C20—H202	109.5
C10—C11—C17	122.79 (15)	C19—C20—H203	109.5
C7—C12—C11	121.66 (16)	H201—C20—H203	109.5
C7—C12—O3	119.40 (15)	H202—C20—H203	109.5
C11—C12—O3	118.93 (15)	C13—O2—C7	122.63 (14)
O1—C13—O2	115.66 (17)	C2—O3—C12	113.85 (13)
O1—C13—C1	122.90 (17)	C4—O4—H4	109.5
O2—C13—C1	121.33 (15)	C9—O5—C16	115.65 (17)
C6—C14—H143	109.5	H1W1—O1W—H2W1	112 (3)
C6—C1—C2—O3	174.18 (15)	O5—C9—C10—Cl3	−0.4 (2)
C13—C1—C2—O3	−18.5 (3)	C8—C9—C10—Cl3	175.49 (14)
C6—C1—C2—C3	−8.7 (3)	C9—C10—C11—C12	0.1 (3)
C13—C1—C2—C3	158.65 (17)	Cl3—C10—C11—C12	−178.12 (13)
O3—C2—C3—C4	−177.53 (16)	C9—C10—C11—C17	176.83 (17)
C1—C2—C3—C4	5.2 (3)	Cl3—C10—C11—C17	−1.4 (2)
O3—C2—C3—Cl1	3.3 (2)	O2—C7—C12—C11	179.51 (15)
C1—C2—C3—Cl1	−173.97 (14)	C8—C7—C12—C11	−4.8 (3)
C2—C3—C4—O4	178.96 (18)	O2—C7—C12—O3	−1.1 (2)
Cl1—C3—C4—O4	−1.9 (3)	C8—C7—C12—O3	174.52 (16)
C2—C3—C4—C5	1.6 (3)	C10—C11—C12—C7	3.6 (3)
Cl1—C3—C4—C5	−179.24 (15)	C17—C11—C12—C7	−173.18 (16)
O4—C4—C5—C6	177.9 (2)	C10—C11—C12—O3	−175.78 (15)
C3—C4—C5—C6	−5.0 (3)	C17—C11—C12—O3	7.4 (2)
O4—C4—C5—Cl2	−1.4 (3)	C2—C1—C13—O1	−138.3 (2)
C3—C4—C5—Cl2	175.76 (15)	C6—C1—C13—O1	29.0 (3)
C4—C5—C6—C1	1.5 (3)	C2—C1—C13—O2	37.8 (3)
Cl2—C5—C6—C1	−179.23 (14)	C6—C1—C13—O2	−154.90 (17)
C4—C5—C6—C14	179.14 (19)	C12—C11—C17—C19	98.9 (2)
Cl2—C5—C6—C14	−1.6 (3)	C10—C11—C17—C19	−77.7 (2)
C2—C1—C6—C5	5.2 (3)	C12—C11—C17—C18	−80.3 (2)
C13—C1—C6—C5	−162.32 (17)	C10—C11—C17—C18	103.1 (2)
C2—C1—C6—C14	−172.29 (18)	C11—C17—C19—C20	−177.4 (2)
C13—C1—C6—C14	20.1 (3)	C18—C17—C19—C20	1.7 (4)
C12—C7—C8—C9	2.1 (3)	O1—C13—O2—C7	−162.93 (18)
O2—C7—C8—C9	177.87 (16)	C1—C13—O2—C7	20.7 (3)
C12—C7—C8—C15	−176.85 (18)	C12—C7—O2—C13	−54.8 (2)
O2—C7—C8—C15	−1.0 (3)	C8—C7—O2—C13	129.38 (18)
C7—C8—C9—O5	177.59 (16)	C3—C2—O3—C12	129.37 (17)
C15—C8—C9—O5	−3.5 (3)	C1—C2—O3—C12	−53.4 (2)
C7—C8—C9—C10	1.6 (3)	C7—C12—O3—C2	70.77 (19)
C15—C8—C9—C10	−179.45 (19)	C11—C12—O3—C2	−109.84 (17)
O5—C9—C10—C11	−178.63 (16)	C8—C9—O5—C16	105.3 (2)
C8—C9—C10—C11	−2.8 (3)	C10—C9—O5—C16	−78.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W1···O5	0.77 (3)	2.47 (3)	3.069 (3)	135 (3)
O1W—H1W1···O1i	0.87 (4)	2.06 (4)	2.929 (3)	177 (3)
O1W—H2W1···O1ii	0.77 (3)	2.47 (4)	3.143 (2)	147 (3)
O4—H4···O1Wiii	0.82	1.89	2.634 (2)	150
O4—H4···Cl2	0.82	2.51	2.9885 (16)	119
C16—H161···Cl3	0.96	2.74	3.311 (3)	119

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W1⋯O5	0.77 (3)	2.47 (3)	3.069 (3)	135 (3)
O1W—H1W1⋯O1i	0.87 (4)	2.06 (4)	2.929 (3)	177 (3)
O1W—H2W1⋯O1ii	0.77 (3)	2.47 (4)	3.143 (2)	147 (3)
O4—H4⋯O1Wiii	0.82	1.89	2.634 (2)	150
O4—H4⋯Cl2	0.82	2.51	2.9885 (16)	119
C16—H161⋯Cl3	0.96	2.74	3.311 (3)	119

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