Benzyl 5-hy-droxy-4-oxapenta-cyclo-[5.4.1.0.0.0]dodecane-3-carboxyl-ate.

The title compound, C(19)H(18)O(4), exhibits a long C-C bond [1.575 (2) Å] in the cage structure. In the crystal, pairs of O-H⋯O hydrogen bonds link the mol-ecules into centrosymmetric dimers. C-H⋯O inter-actions also occur.

Related literature

For examples of PCU cage structures that exhibit C—C bond lengths that deviate from the normal value, see: Flippen-Anderson et al. (1991) ▶; Linden et al. (2005 ▶). For similar structures, see: Kruger et al. (2005 ▶, 2006 ▶); Karpoormath et al. (2010 ▶).

Experimental

Crystal data

C19H18O4

M = 310.33

Monoclinic,

a = 6.5254 (2) Å

b = 12.8995 (2) Å

c = 16.9772 (5) Å

β = 95.243 (1)°

V = 1423.07 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 173 K

0.34 × 0.22 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer

6925 measured reflections

3540 independent reflections

2930 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.119

S = 1.06

3540 reflections

212 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.24 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009) ▶; software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009020/is2678sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009020/is2678Isup2.hkl

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

C19H18O4	F(000) = 656
Mr = 310.33	Dx = 1.448 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6932 reflections
a = 6.5254 (2) Å	θ = 2.4–28.3°
b = 12.8995 (2) Å	µ = 0.10 mm−1
c = 16.9772 (5) Å	T = 173 K
β = 95.243 (1)°	Block, colourless
V = 1423.07 (6) Å3	0.34 × 0.22 × 0.16 mm
Z = 4

Nonius KappaCCD diffractometer	2930 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
graphite	θmax = 28.3°, θmin = 3.1°
1.2° φ and ω scans	h = −8→8
6925 measured reflections	k = −17→17
3540 independent reflections	l = −22→22

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0463P)2 + 0.932P] where P = (Fo2 + 2Fc2)/3
3540 reflections	(Δ/σ)max < 0.001
212 parameters	Δρmax = 0.47 e Å−3
1 restraint	Δρmin = −0.24 e Å−3

Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 35 mm; combination of φ and ω scans of 1.2°, 30 s per °, 2 iterations.X-ray single-crystal intensity data were collected on a Nonius Kappa-CCD diffractometer using graphite monochromated Mo Kα radiation (l = 0.71073 Å). Temperature was controlled by an Oxford Cryostream cooling system (Oxford Cryostat). The strategy for the data collections was evaluated using the Bruker Nonius "Collect" program (Nonius, 2000). Data were scaled and reduced using DENZO-SMN software (Otwinowski & Minor, 1997). The structure was solved by direct methods and refined employing full-matrix least-squares with the program SHELXL97 (Sheldrick, 2008) refining on F2. The molecular graphics were rendered using OLEX2 (Dolomove et al., 2009). All non-hydrogen atoms were refined anisotropically.

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
O1	0.74558 (16)	0.46393 (9)	0.05935 (6)	0.0284 (3)
H1	0.695 (4)	0.448 (2)	0.0053 (8)	0.073 (8)*
O2	0.45389 (15)	0.54964 (8)	0.09726 (6)	0.0223 (2)
O3	0.06298 (17)	0.60878 (9)	0.22148 (6)	0.0297 (3)
O4	0.10540 (16)	0.65377 (8)	0.09589 (6)	0.0260 (2)
C1	0.5554 (3)	0.33580 (14)	0.29940 (9)	0.0311 (4)
H1A	0.6449	0.3717	0.3411	0.037*
H1B	0.5203	0.2656	0.3174	0.037*
C2	0.2721 (2)	0.33660 (12)	0.19839 (9)	0.0279 (3)
H2	0.1596	0.2865	0.2073	0.034*
C3	0.2365 (2)	0.41085 (12)	0.12688 (9)	0.0246 (3)
H3	0.1021	0.4065	0.0937	0.029*
C4	0.3155 (2)	0.52032 (11)	0.15444 (8)	0.0208 (3)
C5	0.4540 (2)	0.49471 (12)	0.23047 (9)	0.0244 (3)
H5	0.4826	0.5553	0.2666	0.029*
C6	0.3646 (2)	0.39964 (13)	0.27044 (9)	0.0276 (3)
H6	0.2680	0.4154	0.3113	0.033*
C7	0.4690 (2)	0.29226 (12)	0.16299 (9)	0.0278 (3)
H7	0.4703	0.2164	0.1510	0.033*
C8	0.4308 (2)	0.36722 (12)	0.09197 (9)	0.0250 (3)
H8	0.4127	0.3363	0.0378	0.030*
C9	0.5850 (2)	0.45678 (11)	0.10606 (8)	0.0213 (3)
C10	0.6490 (2)	0.45031 (12)	0.19510 (8)	0.0241 (3)
H10	0.7798	0.4876	0.2125	0.029*
C11	0.6469 (2)	0.33477 (13)	0.21925 (9)	0.0284 (3)
H11	0.7810	0.2975	0.2183	0.034*
C12	0.1500 (2)	0.59911 (11)	0.16209 (8)	0.0226 (3)
C13	−0.0640 (2)	0.72567 (13)	0.09816 (9)	0.0286 (3)
H13A	−0.0465	0.7671	0.1474	0.034*
H13B	−0.1952	0.6870	0.0976	0.034*
C14	−0.0697 (2)	0.79630 (12)	0.02758 (9)	0.0250 (3)
C15	0.0895 (3)	0.80217 (13)	−0.02124 (10)	0.0309 (4)
H15	0.2077	0.7596	−0.0111	0.037*
C16	0.0759 (3)	0.87050 (14)	−0.08503 (10)	0.0350 (4)
H16	0.1843	0.8737	−0.1187	0.042*
C17	−0.0945 (3)	0.93378 (14)	−0.09964 (10)	0.0347 (4)
H17	−0.1025	0.9807	−0.1429	0.042*
C18	−0.2529 (3)	0.92858 (13)	−0.05118 (10)	0.0336 (4)
H18	−0.3697	0.9722	−0.0610	0.040*
C19	−0.2416 (3)	0.85979 (13)	0.01181 (10)	0.0296 (3)
H19	−0.3520	0.8559	0.0445	0.035*

	U11	U22	U33	U12	U13	U23
O1	0.0213 (5)	0.0420 (7)	0.0227 (5)	0.0026 (5)	0.0060 (4)	0.0028 (5)
O2	0.0218 (5)	0.0248 (5)	0.0209 (5)	0.0011 (4)	0.0052 (4)	0.0030 (4)
O3	0.0329 (6)	0.0344 (6)	0.0232 (5)	0.0061 (5)	0.0094 (4)	0.0017 (4)
O4	0.0295 (6)	0.0265 (5)	0.0225 (5)	0.0075 (4)	0.0054 (4)	0.0035 (4)
C1	0.0347 (8)	0.0332 (9)	0.0252 (8)	0.0010 (7)	0.0016 (6)	0.0059 (6)
C2	0.0250 (7)	0.0262 (8)	0.0328 (8)	−0.0035 (6)	0.0032 (6)	0.0046 (6)
C3	0.0198 (7)	0.0242 (7)	0.0294 (8)	−0.0018 (6)	0.0010 (6)	−0.0003 (6)
C4	0.0203 (6)	0.0243 (7)	0.0183 (6)	−0.0006 (5)	0.0045 (5)	0.0019 (5)
C5	0.0253 (7)	0.0283 (8)	0.0197 (7)	0.0000 (6)	0.0020 (5)	−0.0005 (6)
C6	0.0307 (8)	0.0303 (8)	0.0227 (7)	0.0045 (6)	0.0071 (6)	0.0054 (6)
C7	0.0303 (8)	0.0230 (7)	0.0304 (8)	0.0009 (6)	0.0042 (6)	0.0002 (6)
C8	0.0230 (7)	0.0248 (7)	0.0269 (7)	0.0018 (6)	−0.0002 (6)	−0.0027 (6)
C9	0.0188 (6)	0.0254 (7)	0.0200 (7)	0.0020 (5)	0.0025 (5)	0.0013 (5)
C10	0.0206 (7)	0.0309 (8)	0.0205 (7)	−0.0015 (6)	0.0005 (5)	0.0013 (6)
C11	0.0253 (7)	0.0331 (8)	0.0263 (8)	0.0033 (6)	−0.0002 (6)	0.0058 (6)
C12	0.0240 (7)	0.0227 (7)	0.0211 (7)	−0.0022 (5)	0.0021 (5)	0.0004 (5)
C13	0.0293 (8)	0.0292 (8)	0.0278 (8)	0.0089 (6)	0.0061 (6)	0.0030 (6)
C14	0.0298 (8)	0.0223 (7)	0.0224 (7)	0.0014 (6)	0.0001 (6)	−0.0028 (6)
C15	0.0325 (8)	0.0296 (8)	0.0310 (8)	0.0041 (7)	0.0047 (7)	0.0038 (6)
C16	0.0420 (10)	0.0348 (9)	0.0290 (8)	0.0017 (7)	0.0077 (7)	0.0036 (7)
C17	0.0498 (10)	0.0285 (8)	0.0250 (8)	0.0022 (7)	−0.0008 (7)	0.0035 (6)
C18	0.0402 (9)	0.0291 (8)	0.0305 (8)	0.0082 (7)	−0.0030 (7)	0.0000 (7)
C19	0.0318 (8)	0.0291 (8)	0.0277 (8)	0.0048 (6)	0.0024 (6)	−0.0019 (6)

O1—C9	1.3740 (17)	C7—C11	1.536 (2)
O1—H1	0.969 (10)	C7—C8	1.548 (2)
O2—C4	1.4355 (16)	C7—H7	1.0000
O2—C9	1.4715 (17)	C8—C9	1.536 (2)
O3—C12	1.2081 (18)	C8—H8	1.0000
O4—C12	1.3362 (18)	C9—C10	1.533 (2)
O4—C13	1.4463 (18)	C10—C11	1.546 (2)
C1—C11	1.535 (2)	C10—H10	1.0000
C1—C6	1.536 (2)	C11—H11	1.0000
C1—H1A	0.9900	C13—C14	1.503 (2)
C1—H1B	0.9900	C13—H13A	0.9900
C2—C6	1.545 (2)	C13—H13B	0.9900
C2—C3	1.547 (2)	C14—C15	1.389 (2)
C2—C7	1.575 (2)	C14—C19	1.395 (2)
C2—H2	1.0000	C15—C16	1.393 (2)
C3—C8	1.553 (2)	C15—H15	0.9500
C3—C4	1.560 (2)	C16—C17	1.384 (3)
C3—H3	1.0000	C16—H16	0.9500
C4—C12	1.497 (2)	C17—C18	1.380 (3)
C4—C5	1.542 (2)	C17—H17	0.9500
C5—C6	1.542 (2)	C18—C19	1.386 (2)
C5—C10	1.565 (2)	C18—H18	0.9500
C5—H5	1.0000	C19—H19	0.9500
C6—H6	1.0000
C9—O1—H1	108.6 (16)	C9—C8—H8	117.7
C4—O2—C9	96.46 (10)	C7—C8—H8	117.7
C12—O4—C13	115.11 (11)	C3—C8—H8	117.7
C11—C1—C6	95.19 (12)	O1—C9—O2	110.72 (11)
C11—C1—H1A	112.7	O1—C9—C10	114.78 (12)
C6—C1—H1A	112.7	O2—C9—C10	104.35 (11)
C11—C1—H1B	112.7	O1—C9—C8	118.94 (12)
C6—C1—H1B	112.7	O2—C9—C8	103.29 (11)
H1A—C1—H1B	110.2	C10—C9—C8	103.19 (12)
C6—C2—C3	108.38 (13)	C9—C10—C11	107.80 (12)
C6—C2—C7	102.71 (12)	C9—C10—C5	101.56 (11)
C3—C2—C7	89.69 (11)	C11—C10—C5	102.95 (12)
C6—C2—H2	117.3	C9—C10—H10	114.4
C3—C2—H2	117.3	C11—C10—H10	114.4
C7—C2—H2	117.3	C5—C10—H10	114.4
C2—C3—C8	90.34 (11)	C1—C11—C7	102.77 (13)
C2—C3—C4	107.64 (12)	C1—C11—C10	103.90 (13)
C8—C3—C4	100.58 (11)	C7—C11—C10	101.75 (12)
C2—C3—H3	118.0	C1—C11—H11	115.5
C8—C3—H3	118.0	C7—C11—H11	115.5
C4—C3—H3	118.0	C10—C11—H11	115.5
O2—C4—C12	112.52 (11)	O3—C12—O4	124.37 (14)
O2—C4—C5	105.42 (11)	O3—C12—C4	122.71 (13)
C12—C4—C5	116.41 (12)	O4—C12—C4	112.88 (12)
O2—C4—C3	104.28 (11)	O4—C13—C14	109.31 (12)
C12—C4—C3	114.78 (12)	O4—C13—H13A	109.8
C5—C4—C3	102.09 (12)	C14—C13—H13A	109.8
C6—C5—C4	108.82 (12)	O4—C13—H13B	109.8
C6—C5—C10	103.38 (12)	C14—C13—H13B	109.8
C4—C5—C10	101.08 (11)	H13A—C13—H13B	108.3
C6—C5—H5	114.1	C15—C14—C19	119.06 (15)
C4—C5—H5	114.1	C15—C14—C13	122.93 (14)
C10—C5—H5	114.1	C19—C14—C13	118.01 (14)
C1—C6—C5	103.84 (12)	C14—C15—C16	120.05 (16)
C1—C6—C2	102.58 (13)	C14—C15—H15	120.0
C5—C6—C2	101.90 (12)	C16—C15—H15	120.0
C1—C6—H6	115.5	C17—C16—C15	120.37 (16)
C5—C6—H6	115.5	C17—C16—H16	119.8
C2—C6—H6	115.5	C15—C16—H16	119.8
C11—C7—C8	108.68 (13)	C18—C17—C16	119.86 (16)
C11—C7—C2	103.28 (12)	C18—C17—H17	120.1
C8—C7—C2	89.51 (11)	C16—C17—H17	120.1
C11—C7—H7	117.1	C17—C18—C19	120.08 (16)
C8—C7—H7	117.1	C17—C18—H18	120.0
C2—C7—H7	117.1	C19—C18—H18	120.0
C9—C8—C7	106.97 (12)	C18—C19—C14	120.57 (16)
C9—C8—C3	102.35 (11)	C18—C19—H19	119.7
C7—C8—C3	90.47 (11)	C14—C19—H19	119.7
C6—C2—C3—C8	103.26 (13)	C3—C8—C9—O1	−156.62 (12)
C7—C2—C3—C8	−0.05 (11)	C7—C8—C9—O2	−127.86 (12)
C6—C2—C3—C4	2.05 (16)	C3—C8—C9—O2	−33.53 (13)
C7—C2—C3—C4	−101.26 (12)	C7—C8—C9—C10	−19.38 (14)
C9—O2—C4—C12	−179.39 (12)	C3—C8—C9—C10	74.95 (13)
C9—O2—C4—C5	52.74 (13)	O1—C9—C10—C11	−97.66 (15)
C9—O2—C4—C3	−54.38 (12)	O2—C9—C10—C11	140.99 (12)
C2—C3—C4—O2	127.36 (12)	C8—C9—C10—C11	33.31 (14)
C8—C3—C4—O2	33.59 (13)	O1—C9—C10—C5	154.53 (13)
C2—C3—C4—C12	−109.09 (14)	O2—C9—C10—C5	33.17 (14)
C8—C3—C4—C12	157.15 (12)	C8—C9—C10—C5	−74.51 (13)
C2—C3—C4—C5	17.78 (14)	C6—C5—C10—C9	111.60 (13)
C8—C3—C4—C5	−75.99 (13)	C4—C5—C10—C9	−1.00 (14)
O2—C4—C5—C6	−140.89 (12)	C6—C5—C10—C11	0.06 (14)
C12—C4—C5—C6	93.62 (15)	C4—C5—C10—C11	−112.55 (12)
C3—C4—C5—C6	−32.18 (14)	C6—C1—C11—C7	−53.88 (14)
O2—C4—C5—C10	−32.49 (14)	C6—C1—C11—C10	51.86 (14)
C12—C4—C5—C10	−157.98 (12)	C8—C7—C11—C1	127.80 (13)
C3—C4—C5—C10	76.22 (13)	C2—C7—C11—C1	33.76 (15)
C11—C1—C6—C5	−51.77 (14)	C8—C7—C11—C10	20.41 (15)
C11—C1—C6—C2	54.05 (14)	C2—C7—C11—C10	−73.63 (14)
C4—C5—C6—C1	139.75 (13)	C9—C10—C11—C1	−139.89 (12)
C10—C5—C6—C1	32.92 (14)	C5—C10—C11—C1	−33.04 (14)
C4—C5—C6—C2	33.42 (15)	C9—C10—C11—C7	−33.39 (15)
C10—C5—C6—C2	−73.42 (13)	C5—C10—C11—C7	73.46 (13)
C3—C2—C6—C1	−128.27 (13)	C13—O4—C12—O3	−2.0 (2)
C7—C2—C6—C1	−34.31 (14)	C13—O4—C12—C4	175.61 (12)
C3—C2—C6—C5	−20.96 (15)	O2—C4—C12—O3	−154.75 (14)
C7—C2—C6—C5	73.00 (14)	C5—C4—C12—O3	−32.9 (2)
C6—C2—C7—C11	0.35 (15)	C3—C4—C12—O3	86.21 (18)
C3—C2—C7—C11	109.13 (12)	O2—C4—C12—O4	27.56 (17)
C6—C2—C7—C8	−108.74 (12)	C5—C4—C12—O4	149.38 (13)
C3—C2—C7—C8	0.05 (11)	C3—C4—C12—O4	−91.48 (15)
C11—C7—C8—C9	−0.84 (16)	C12—O4—C13—C14	168.61 (13)
C2—C7—C8—C9	103.02 (12)	O4—C13—C14—C15	−11.6 (2)
C11—C7—C8—C3	−103.91 (13)	O4—C13—C14—C19	169.54 (13)
C2—C7—C8—C3	−0.05 (11)	C19—C14—C15—C16	−0.2 (2)
C2—C3—C8—C9	−107.44 (12)	C13—C14—C15—C16	−178.99 (16)
C4—C3—C8—C9	0.58 (14)	C14—C15—C16—C17	0.8 (3)
C2—C3—C8—C7	0.05 (12)	C15—C16—C17—C18	−0.6 (3)
C4—C3—C8—C7	108.07 (12)	C16—C17—C18—C19	−0.3 (3)
C4—O2—C9—O1	−177.16 (11)	C17—C18—C19—C14	0.9 (3)
C4—O2—C9—C10	−53.15 (12)	C15—C14—C19—C18	−0.6 (2)
C4—O2—C9—C8	54.46 (12)	C13—C14—C19—C18	178.21 (15)
C7—C8—C9—O1	109.05 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2i	0.97 (2)	1.91 (2)	2.8561 (16)	164 (2)
C3—H3···O1ii	1.00	2.46	3.3716 (18)	151
C10—H10···O3iii	1.00	2.41	3.3840 (19)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2i	0.97 (2)	1.91 (2)	2.8561 (16)	164 (2)
C3—H3⋯O1ii	1.00	2.46	3.3716 (18)	151
C10—H10⋯O3iii	1.00	2.41	3.3840 (19)	163

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