1,7-Dimethyl-penta-cyclo-[5.4.0.0.0.0]undecane-8,11-dione.

The structure of the title compound, C(13)H(14)O(2), a penta-cyclo-undecane cage derivative, exhibits unusual Csp(3)-Csp(3) single-bond lengths ranging from 1.505 (3) to 1.607 (2) Å and strained bond angles as small as 88.7 (1)° and as large as 121.0 (2)°. In this meso compound, an inter-nal non-crystallographic mirror plane exists, bis-ecting the mol-ecule. In the crystal, weak C-H⋯O hydrogen bonds link the mol-ecules into an infinite spiral about a twofold screw axis along the [100] direction.

Related literature

For related literature and examples of PCU cage structures exhibiting C—C bond lengths that deviate from the norm, see: Flippen-Anderson et al. (1991 ▶); Bott et al. (1998 ▶); Linden et al. (2005 ▶); Kruger et al. (2006 ▶). For the crystal packing of analogous PCU cage structures, see: Kruger et al. (2006 ▶); Boyle et al. (2007a ▶,b ▶). For the synthesis, see: Mehta et al. (1981 ▶). For hydrogen bonding, see: Desiraju et al. (1999 ▶).

Experimental

Crystal data

C13H14O2

M = 202.24

Orthorhombic,

a = 7.7914 (2) Å

b = 8.2149 (3) Å

c = 15.4830 (5) Å

V = 991.00 (5) Å3

Z = 4

Cu Kα radiation

μ = 0.72 mm−1

T = 173 K

0.32 × 0.25 × 0.21 mm

Data collection

Bruker Kappa DUO APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.702, T max = 0.753

4922 measured reflections

1055 independent reflections

1044 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.090

S = 1.06

1055 reflections

137 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.18 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810025055/hb5509sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025055/hb5509Isup2.hkl

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

C13H14O2	Dx = 1.356 Mg m−3
Mr = 202.24	Melting point: 382 K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4922 reflections
a = 7.7914 (2) Å	θ = 5.7–68.4°
b = 8.2149 (3) Å	µ = 0.72 mm−1
c = 15.4830 (5) Å	T = 173 K
V = 991.00 (5) Å3	Prism, colourless
Z = 4	0.32 × 0.25 × 0.21 mm
F(000) = 432

Bruker Kappa DUO APEXII diffractometer	1055 independent reflections
Radiation source: fine-focus sealed tube	1044 reflections with I > 2σ(I)
graphite	Rint = 0.020
0.5° φ scans and ω scans	θmax = 68.4°, θmin = 5.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −9→9
Tmin = 0.702, Tmax = 0.753	k = −9→9
4922 measured reflections	l = −18→13

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033	H-atom parameters constrained
wR(F2) = 0.090	w = 1/[σ2(Fo2) + (0.0627P)2 + 0.1901P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
1055 reflections	Δρmax = 0.21 e Å−3
137 parameters	Δρmin = −0.18 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraints	Extinction coefficient: 0.0178 (18)
Primary atom site location: structure-invariant direct methods

Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 30 mm; combination of φ and ω scans of 0.5°, 40 s per °, 2 iterations.

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	0.7584 (2)	0.32372 (19)	0.54950 (9)	0.0395 (4)
C1	0.4669 (2)	0.6969 (2)	0.36778 (12)	0.0255 (4)
H1A	0.4395	0.7912	0.4051	0.031*
H1B	0.3858	0.6915	0.3187	0.031*
O2	1.05692 (19)	0.5921 (2)	0.41443 (11)	0.0381 (4)
C2	0.4768 (2)	0.5374 (2)	0.41804 (11)	0.0233 (4)
H2	0.3674	0.5019	0.4461	0.028*
C3	0.6306 (2)	0.5612 (2)	0.47985 (11)	0.0232 (4)
H3	0.5988	0.6088	0.5371	0.028*
C4	0.7082 (2)	0.3924 (2)	0.48546 (12)	0.0251 (4)
C5	0.7092 (2)	0.3279 (2)	0.39345 (12)	0.0229 (4)
C6	0.5531 (2)	0.4167 (2)	0.35149 (12)	0.0231 (4)
H6	0.4697	0.3474	0.3190	0.028*
C7	0.6546 (2)	0.6948 (2)	0.33893 (11)	0.0224 (4)
H7	0.6912	0.7889	0.3023	0.027*
C8	0.7553 (2)	0.6726 (2)	0.42436 (12)	0.0229 (4)
H8	0.7872	0.7772	0.4532	0.027*
C9	0.9079 (2)	0.5714 (2)	0.39604 (12)	0.0248 (4)
C10	0.8361 (2)	0.4397 (2)	0.33708 (11)	0.0231 (4)
C11	0.6756 (2)	0.5243 (2)	0.29697 (11)	0.0230 (4)
H11	0.6630	0.5181	0.2328	0.028*
C12	0.7267 (3)	0.1443 (2)	0.38573 (13)	0.0316 (5)
H12A	0.7260	0.1133	0.3246	0.047*
H12B	0.6306	0.0915	0.4154	0.047*
H12C	0.8350	0.1096	0.4122	0.047*
C13	0.9672 (3)	0.3567 (3)	0.28080 (13)	0.0334 (5)
H13A	0.9104	0.2740	0.2452	0.050*
H13B	1.0541	0.3046	0.3172	0.050*
H13C	1.0223	0.4374	0.2433	0.050*

	U11	U22	U33	U12	U13	U23
O1	0.0546 (10)	0.0372 (8)	0.0267 (7)	0.0111 (8)	−0.0061 (7)	0.0058 (6)
C1	0.0229 (9)	0.0265 (9)	0.0269 (9)	0.0046 (7)	−0.0001 (7)	0.0022 (8)
O2	0.0216 (7)	0.0364 (8)	0.0564 (10)	−0.0003 (6)	−0.0065 (7)	−0.0079 (7)
C2	0.0193 (8)	0.0247 (9)	0.0259 (8)	0.0007 (7)	0.0027 (7)	0.0016 (7)
C3	0.0255 (8)	0.0245 (9)	0.0195 (8)	0.0020 (8)	0.0024 (7)	−0.0010 (7)
C4	0.0250 (8)	0.0264 (9)	0.0240 (8)	0.0009 (8)	0.0010 (7)	0.0017 (7)
C5	0.0237 (9)	0.0195 (9)	0.0256 (9)	−0.0004 (7)	0.0012 (7)	−0.0011 (7)
C6	0.0218 (8)	0.0240 (9)	0.0235 (8)	−0.0016 (8)	−0.0017 (7)	−0.0019 (7)
C7	0.0231 (9)	0.0208 (8)	0.0232 (8)	−0.0001 (8)	−0.0001 (7)	0.0032 (7)
C8	0.0227 (8)	0.0201 (8)	0.0257 (9)	−0.0009 (8)	−0.0029 (8)	−0.0014 (7)
C9	0.0224 (9)	0.0241 (9)	0.0280 (9)	−0.0012 (8)	0.0004 (7)	0.0030 (7)
C10	0.0215 (9)	0.0240 (9)	0.0237 (8)	0.0016 (8)	0.0023 (7)	−0.0003 (7)
C11	0.0236 (9)	0.0255 (9)	0.0200 (8)	0.0001 (8)	−0.0001 (7)	−0.0013 (7)
C12	0.0421 (11)	0.0204 (9)	0.0324 (9)	0.0009 (9)	0.0015 (9)	−0.0011 (7)
C13	0.0315 (11)	0.0344 (11)	0.0344 (9)	0.0057 (9)	0.0092 (9)	−0.0020 (9)

O1—C4	1.206 (2)	C6—H6	1.0000
C1—C2	1.525 (3)	C7—C8	1.549 (2)
C1—C7	1.529 (2)	C7—C11	1.553 (3)
C1—H1A	0.9900	C7—H7	1.0000
C1—H1B	0.9900	C8—C9	1.515 (3)
O2—C9	1.207 (3)	C8—H8	1.0000
C2—C3	1.546 (2)	C9—C10	1.523 (3)
C2—C6	1.549 (2)	C10—C13	1.505 (3)
C2—H2	1.0000	C10—C11	1.560 (2)
C3—C4	1.515 (3)	C11—H11	1.0000
C3—C8	1.587 (2)	C12—H12A	0.9800
C3—H3	1.0000	C12—H12B	0.9800
C4—C5	1.520 (2)	C12—H12C	0.9800
C5—C12	1.519 (2)	C13—H13A	0.9800
C5—C6	1.560 (2)	C13—H13B	0.9800
C5—C10	1.607 (2)	C13—H13C	0.9800
C6—C11	1.551 (3)
C2—C1—C7	95.26 (14)	C1—C7—H7	115.5
C2—C1—H1A	112.7	C8—C7—H7	115.5
C7—C1—H1A	112.7	C11—C7—H7	115.5
C2—C1—H1B	112.7	C9—C8—C7	102.44 (14)
C7—C1—H1B	112.7	C9—C8—C3	108.72 (15)
H1A—C1—H1B	110.2	C7—C8—C3	102.71 (14)
C1—C2—C3	104.26 (15)	C9—C8—H8	113.9
C1—C2—C6	103.29 (14)	C7—C8—H8	113.9
C3—C2—C6	101.25 (14)	C3—C8—H8	113.9
C1—C2—H2	115.4	O2—C9—C8	127.53 (19)
C3—C2—H2	115.4	O2—C9—C10	126.49 (19)
C6—C2—H2	115.4	C8—C9—C10	105.96 (15)
C4—C3—C2	103.24 (14)	C13—C10—C9	114.82 (16)
C4—C3—C8	108.33 (14)	C13—C10—C11	121.02 (15)
C2—C3—C8	102.26 (13)	C9—C10—C11	102.51 (14)
C4—C3—H3	114.0	C13—C10—C5	118.23 (16)
C2—C3—H3	114.0	C9—C10—C5	107.86 (14)
C8—C3—H3	114.0	C11—C10—C5	88.69 (13)
O1—C4—C3	127.20 (18)	C6—C11—C7	102.81 (13)
O1—C4—C5	127.29 (18)	C6—C11—C10	91.31 (13)
C3—C4—C5	105.51 (15)	C7—C11—C10	108.66 (14)
C12—C5—C4	114.86 (16)	C6—C11—H11	116.8
C12—C5—C6	120.11 (16)	C7—C11—H11	116.8
C4—C5—C6	102.91 (15)	C10—C11—H11	116.8
C12—C5—C10	117.97 (16)	C5—C12—H12A	109.5
C4—C5—C10	108.24 (14)	C5—C12—H12B	109.5
C6—C5—C10	89.23 (13)	H12A—C12—H12B	109.5
C2—C6—C11	103.48 (14)	C5—C12—H12C	109.5
C2—C6—C5	108.76 (14)	H12A—C12—H12C	109.5
C11—C6—C5	90.77 (13)	H12B—C12—H12C	109.5
C2—C6—H6	116.8	C10—C13—H13A	109.5
C11—C6—H6	116.8	C10—C13—H13B	109.5
C5—C6—H6	116.8	H13A—C13—H13B	109.5
C1—C7—C8	103.67 (14)	C10—C13—H13C	109.5
C1—C7—C11	103.47 (15)	H13A—C13—H13C	109.5
C8—C7—C11	101.38 (14)	H13B—C13—H13C	109.5
C7—C1—C2—C3	52.94 (15)	C2—C3—C8—C7	−0.35 (17)
C7—C1—C2—C6	−52.54 (16)	C7—C8—C9—O2	134.3 (2)
C1—C2—C3—C4	−145.63 (14)	C3—C8—C9—O2	−117.5 (2)
C6—C2—C3—C4	−38.63 (17)	C7—C8—C9—C10	−44.16 (18)
C1—C2—C3—C8	−33.19 (16)	C3—C8—C9—C10	64.06 (18)
C6—C2—C3—C8	73.81 (15)	O2—C9—C10—C13	−15.9 (3)
C2—C3—C4—O1	−136.5 (2)	C8—C9—C10—C13	162.55 (16)
C8—C3—C4—O1	115.6 (2)	O2—C9—C10—C11	−149.1 (2)
C2—C3—C4—C5	43.41 (18)	C8—C9—C10—C11	29.38 (17)
C8—C3—C4—C5	−64.51 (17)	O2—C9—C10—C5	118.2 (2)
O1—C4—C5—C12	18.7 (3)	C8—C9—C10—C5	−63.30 (18)
C3—C4—C5—C12	−161.21 (16)	C12—C5—C10—C13	−0.9 (3)
O1—C4—C5—C6	151.1 (2)	C4—C5—C10—C13	131.62 (18)
C3—C4—C5—C6	−28.88 (18)	C6—C5—C10—C13	−125.04 (17)
O1—C4—C5—C10	−115.4 (2)	C12—C5—C10—C9	−133.26 (18)
C3—C4—C5—C10	64.62 (18)	C4—C5—C10—C9	−0.7 (2)
C1—C2—C6—C11	33.43 (17)	C6—C5—C10—C9	102.62 (16)
C3—C2—C6—C11	−74.33 (16)	C12—C5—C10—C11	124.02 (18)
C1—C2—C6—C5	128.94 (15)	C4—C5—C10—C11	−103.44 (15)
C3—C2—C6—C5	21.18 (17)	C6—C5—C10—C11	−0.10 (12)
C12—C5—C6—C2	133.27 (18)	C2—C6—C11—C7	−0.07 (17)
C4—C5—C6—C2	4.12 (18)	C5—C6—C11—C7	−109.58 (14)
C10—C5—C6—C2	−104.42 (15)	C2—C6—C11—C10	109.40 (14)
C12—C5—C6—C11	−122.20 (18)	C5—C6—C11—C10	−0.10 (12)
C4—C5—C6—C11	108.64 (14)	C1—C7—C11—C6	−33.26 (17)
C10—C5—C6—C11	0.10 (12)	C8—C7—C11—C6	73.97 (16)
C2—C1—C7—C8	−52.87 (16)	C1—C7—C11—C10	−129.09 (15)
C2—C1—C7—C11	52.62 (15)	C8—C7—C11—C10	−21.86 (17)
C1—C7—C8—C9	146.37 (15)	C13—C10—C11—C6	122.67 (18)
C11—C7—C8—C9	39.30 (17)	C9—C10—C11—C6	−107.91 (14)
C1—C7—C8—C3	33.62 (18)	C5—C10—C11—C6	0.10 (12)
C11—C7—C8—C3	−73.44 (16)	C13—C10—C11—C7	−133.34 (17)
C4—C3—C8—C9	0.2 (2)	C9—C10—C11—C7	−3.91 (17)
C2—C3—C8—C9	−108.38 (15)	C5—C10—C11—C7	104.10 (14)
C4—C3—C8—C7	108.24 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2i	1.00	2.58	3.303 (2)	129
C3—H3···O2ii	1.00	2.59	3.335 (2)	131

Table 1

Selected bond lengths (Å)

C1—C2	1.525 (3)
C1—C7	1.529 (2)
C2—C3	1.546 (2)
C2—C6	1.549 (2)
C3—C4	1.515 (3)
C3—C8	1.587 (2)
C4—C5	1.520 (2)
C5—C12	1.519 (2)
C5—C6	1.560 (2)
C5—C10	1.607 (2)
C6—C11	1.551 (3)
C7—C8	1.549 (2)
C7—C11	1.553 (3)
C8—C9	1.515 (3)
C9—C10	1.523 (3)
C10—C13	1.505 (3)
C10—C11	1.560 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2i	1.00	2.58	3.303 (2)	129
C3—H3⋯O2ii	1.00	2.59	3.335 (2)	131

Symmetry codes: (i) ; (ii) .