8,11-Dihydroxy­penta­cyclo­undecane-8,11-lactam

The title mol­ecule, C₁₂H₁₃NO₃, is a penta­cyclo­undecane cage derivative that exhibits C—C bond lengths deviating from the normal values. Neighbouring mol­ecules inter­act via N—H...O and O—H...O hydrogen bonds, forming two-dimensional hydrogen-bonded sheets.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C)= 0.002 Å
• R factor = 0.039
• wR factor = 0.107
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

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S1. Comment

The present study is part of an ongoing investigation of the chemical reactivity and solid-state structures of polycyclic pentacycloundecane (PCU) cage derivatives.

The title compound, (I), was first synthesized by Martins et al. (1993). It forms a hydrate (1:1) complex with water, and the crystal structure of the hydrate was reported by Kruger et al. (1996). The crystal structure of the lactam hydrate was, however, disordered and more accurate data about the structure of the lactam was required for our computational studies. The crystal structure of pure lactam without water is reported here.

The molecule of (I) consists of a large apolar (lipophilic) hydrocarbon skeleton and more polar dihydroxy and lactam parts (Fig. 1). A number of publications have focused on the molecular geometries of PCU cage derivatives (Flippen-Anderson et al., 1991; Linden et al., 2005; Kruger et al., 2005), and it has been reported that these compounds exhibit C—C bond lengths deviating from the normal value of 1.54 Å.

In (I), the C9—C10 [1.5719 (15) Å] bond, as well as the bonds constituting the cyclobutane ring, C1—C2 [1.5588 (17) Å], C2—C6 [1.5738 (16) Å], C6—C7 [1.5655 (17) Å] and C7—C1 [1.5654 (15) Å], are longer than expected, while the bonds involving atoms C4 and C11 (Table 1) are shorter than expected. On the other hand, the C8—C12 [1.5189 (16) Å] bond is very short.

In the crystal structure of (I), molecules are arranged to form a bilayer consisting of alternating lipophilic and polar layers. The lipophilic layer contains the PCU cage groups, while the hydroxy, ketone and amino groups constitute the polar layer. In the polar layer, a complex intermolecular hydrogen-bonding network, involving atoms N, O2 and O3 as hydrogen-bond donors and atoms O1 and O2 as hydrogen-bond acceptors, is formed (Table 2). These interactions result in two-dimensional hydrogen-bonded sheets of molecules (Fig. 2).

S2. Experimental

The PCU lactam was synthesized as described by Martins et al. (1993) and recrystalized from dioxane.

S3. Refinement

Atoms H1H, H2H and H3H were located in a difference map and refined isotropically [N—H = 0.924 (17) Å and O—H = 0.83 (2) and 0.89 (2) Å]. The remaining H atoms were positioned geometrically [C—H = 1.00 (CH) and 0.99 Å (CH₂)] and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Mercury (Bruno et al., 2002) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures

	Fig. 1. An ORTEP-3 (Farrugia, 1997) drawing of the title compound, (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I), viewed down the b axis. The dashed lines denote hydrogen bonds.

8,11-Dihydroxypentacycloundecane-8,11-lactam

Crystal data

C12H13NO3	F(000) = 928
Mr = 219.23	Dx = 1.543 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 957 reflections
a = 22.0040 (11) Å	θ = 3.0–28.3°
b = 6.3299 (3) Å	µ = 0.11 mm^−1
c = 13.6153 (7) Å	T = 173 K
β = 95.426 (3)°	Block, colourless
V = 1887.88 (16) Å^3	0.38 × 0.29 × 0.29 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer	1973 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 28.3°, θmin = 1.9°
ϕ and ω scans	h = −26→29
7588 measured reflections	k = −7→8
2354 independent reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0585P)^2 + 0.9852P] where P = (Fo^2 + 2Fc^2)/3
2354 reflections	(Δ/σ)max < 0.001
157 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
N	0.43856 (5)	0.30382 (17)	−0.00885 (7)	0.0169 (2)
O1	0.48796 (4)	0.44217 (14)	−0.13557 (6)	0.0197 (2)
O2	0.42018 (5)	0.20134 (16)	−0.27049 (6)	0.0226 (2)
O3	0.38821 (4)	0.15590 (16)	0.11695 (6)	0.0219 (2)
C1	0.41021 (5)	−0.07299 (19)	−0.02310 (8)	0.0172 (2)
C2	0.34818 (6)	−0.1881 (2)	−0.04946 (9)	0.0194 (3)
C3	0.29673 (5)	−0.0259 (2)	−0.03722 (8)	0.0184 (3)
C4	0.25715 (6)	−0.0377 (2)	−0.13638 (9)	0.0228 (3)
C5	0.31036 (6)	−0.0020 (2)	−0.19988 (8)	0.0187 (3)
C6	0.35769 (6)	−0.1703 (2)	−0.16228 (8)	0.0192 (3)
C7	0.41998 (5)	−0.05508 (19)	−0.13520 (8)	0.0174 (2)
C8	0.40947 (5)	0.17571 (19)	−0.16976 (8)	0.0159 (2)
C9	0.34104 (5)	0.20274 (19)	−0.15607 (8)	0.0156 (2)
C10	0.33154 (5)	0.18463 (19)	−0.04339 (8)	0.0155 (2)
C11	0.39365 (5)	0.14539 (19)	0.01531 (8)	0.0155 (2)
C12	0.44940 (5)	0.32326 (18)	−0.10356 (8)	0.0156 (2)
H1	0.4419	−0.1538	0.0189	0.021*
H1H	0.4618 (7)	0.377 (3)	0.0400 (12)	0.023 (4)*
H2H	0.4456 (9)	0.296 (3)	−0.2752 (14)	0.039 (5)*
H2	0.3434	−0.3328	−0.0217	0.023*
H3	0.2744	−0.0444	0.0228	0.022*
H3H	0.4041 (10)	0.041 (4)	0.1458 (15)	0.053 (6)*
H4A	0.2375	−0.1773	−0.1480	0.027*
H4B	0.2262	0.0759	−0.1442	0.027*
H5	0.2992	−0.0005	−0.2728	0.022*
H6	0.3586	−0.3048	−0.2007	0.023*
H7	0.4571	−0.1265	−0.1565	0.021*
H9	0.3231	0.3344	−0.1873	0.019*
H10	0.3091	0.3079	−0.0183	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N	0.0183 (5)	0.0205 (5)	0.0115 (4)	−0.0037 (4)	−0.0002 (4)	−0.0018 (4)
O1	0.0213 (4)	0.0221 (5)	0.0160 (4)	−0.0064 (4)	0.0032 (3)	−0.0011 (3)
O2	0.0293 (5)	0.0279 (5)	0.0111 (4)	−0.0112 (4)	0.0040 (3)	−0.0021 (3)
O3	0.0289 (5)	0.0264 (5)	0.0109 (4)	0.0004 (4)	0.0035 (3)	0.0018 (3)
C1	0.0182 (6)	0.0172 (6)	0.0161 (5)	0.0029 (4)	0.0004 (4)	0.0030 (4)
C2	0.0228 (6)	0.0151 (6)	0.0202 (5)	−0.0013 (5)	0.0019 (4)	0.0029 (4)
C3	0.0175 (6)	0.0204 (6)	0.0175 (5)	−0.0027 (5)	0.0027 (4)	0.0007 (4)
C4	0.0192 (6)	0.0266 (7)	0.0221 (6)	−0.0054 (5)	0.0001 (5)	0.0006 (5)
C5	0.0204 (6)	0.0192 (6)	0.0159 (5)	−0.0041 (5)	−0.0019 (4)	−0.0009 (4)
C6	0.0240 (6)	0.0154 (6)	0.0184 (5)	−0.0027 (5)	0.0029 (4)	−0.0023 (4)
C7	0.0186 (6)	0.0168 (6)	0.0169 (5)	0.0011 (4)	0.0025 (4)	−0.0015 (4)
C8	0.0191 (6)	0.0182 (6)	0.0106 (5)	−0.0029 (4)	0.0019 (4)	−0.0006 (4)
C9	0.0165 (5)	0.0160 (6)	0.0139 (5)	−0.0004 (4)	−0.0012 (4)	0.0019 (4)
C10	0.0159 (5)	0.0162 (6)	0.0145 (5)	0.0015 (4)	0.0018 (4)	0.0010 (4)
C11	0.0172 (5)	0.0183 (6)	0.0111 (5)	−0.0003 (4)	0.0020 (4)	0.0008 (4)
C12	0.0159 (5)	0.0163 (6)	0.0142 (5)	0.0007 (4)	0.0003 (4)	−0.0008 (4)

Geometric parameters (Å, º)

C12—O1	1.2435 (14)	C9—H9	1.0000
C12—N	1.3389 (14)	C5—C4	1.5365 (17)
C12—C8	1.5189 (16)	C5—C6	1.5430 (18)
C8—O2	1.4226 (12)	C5—H5	1.0000
C8—C9	1.5442 (16)	C6—C2	1.5738 (16)
C8—C7	1.5455 (17)	C6—H6	1.0000
C7—C1	1.5654 (15)	C2—C3	1.5489 (17)
C7—C6	1.5655 (17)	C2—H2	1.0000
C7—H7	1.0000	C3—C4	1.5376 (17)
C1—C11	1.5341 (17)	C3—C10	1.5431 (16)
C1—C2	1.5588 (17)	C3—H3	1.0000
C1—H1	1.0000	C10—H10	1.0000
C11—O3	1.4019 (13)	C4—H4A	0.9900
C11—N	1.4670 (15)	C4—H4B	0.9900
C11—C10	1.5368 (16)	N—H1H	0.924 (17)
C9—C5	1.5539 (16)	O2—H2H	0.83 (2)
C9—C10	1.5719 (15)	O3—H3H	0.89 (2)
O1—C12—N	125.64 (11)	C6—C5—H5	115.5
O1—C12—C8	122.67 (10)	C9—C5—H5	115.5
N—C12—C8	111.67 (10)	C5—C6—C7	107.76 (10)
O2—C8—C12	111.27 (9)	C5—C6—C2	103.03 (9)
O2—C8—C9	110.85 (9)	C7—C6—C2	89.86 (9)
C12—C8—C9	112.09 (9)	C5—C6—H6	117.4
O2—C8—C7	111.58 (9)	C7—C6—H6	117.4
C12—C8—C7	109.82 (9)	C2—C6—H6	117.4
C9—C8—C7	100.81 (9)	C3—C2—C1	107.37 (10)
C8—C7—C1	109.57 (9)	C3—C2—C6	102.92 (9)
C8—C7—C6	105.43 (9)	C1—C2—C6	89.82 (9)
C1—C7—C6	89.89 (8)	C3—C2—H2	117.5
C8—C7—H7	116.2	C1—C2—H2	117.5
C1—C7—H7	116.2	C6—C2—H2	117.5
C6—C7—H7	116.2	C4—C3—C10	103.71 (10)
C11—C1—C2	105.57 (9)	C4—C3—C2	103.44 (10)
C11—C1—C7	109.03 (9)	C10—C3—C2	101.24 (9)
C2—C1—C7	90.42 (8)	C4—C3—H3	115.5
C11—C1—H1	116.2	C10—C3—H3	115.5
C2—C1—H1	116.2	C2—C3—H3	115.5
C7—C1—H1	116.2	C11—C10—C3	104.70 (9)
O3—C11—N	108.13 (9)	C11—C10—C9	109.00 (9)
O3—C11—C1	115.12 (9)	C3—C10—C9	103.22 (9)
N—C11—C1	110.65 (9)	C11—C10—H10	113.1
O3—C11—C10	110.55 (9)	C3—C10—H10	113.1
N—C11—C10	110.96 (9)	C9—C10—H10	113.1
C1—C11—C10	101.34 (9)	C5—C4—C3	95.08 (9)
C8—C9—C5	104.74 (9)	C5—C4—H4A	112.7
C8—C9—C10	109.33 (9)	C3—C4—H4A	112.7
C5—C9—C10	102.75 (9)	C5—C4—H4B	112.7
C8—C9—H9	113.1	C3—C4—H4B	112.7
C5—C9—H9	113.1	H4A—C4—H4B	110.2
C10—C9—H9	113.1	C12—N—C11	117.64 (9)
C4—C5—C6	103.77 (10)	C12—N—H1H	120.7 (10)
C4—C5—C9	103.49 (10)	C11—N—H1H	121.3 (10)
C6—C5—C9	101.14 (9)	C8—O2—H2H	109.4 (13)
C4—C5—H5	115.5	C11—O3—H3H	109.3 (13)
O1—C12—C8—O2	−2.99 (16)	C8—C7—C6—C2	−110.38 (9)
N—C12—C8—O2	178.49 (10)	C1—C7—C6—C2	−0.07 (9)
O1—C12—C8—C9	−127.76 (11)	C11—C1—C2—C3	6.35 (11)
N—C12—C8—C9	53.72 (13)	C7—C1—C2—C3	−103.56 (9)
O1—C12—C8—C7	121.05 (12)	C11—C1—C2—C6	109.84 (9)
N—C12—C8—C7	−57.46 (13)	C7—C1—C2—C6	−0.07 (9)
O2—C8—C7—C1	177.74 (9)	C5—C6—C2—C3	−0.34 (11)
C12—C8—C7—C1	53.87 (12)	C7—C6—C2—C3	107.87 (10)
C9—C8—C7—C1	−64.54 (11)	C5—C6—C2—C1	−108.14 (10)
O2—C8—C7—C6	−86.75 (11)	C7—C6—C2—C1	0.07 (9)
C12—C8—C7—C6	149.38 (9)	C1—C2—C3—C4	127.60 (10)
C9—C8—C7—C6	30.97 (10)	C6—C2—C3—C4	33.68 (11)
C8—C7—C1—C11	−0.21 (13)	C1—C2—C3—C10	20.39 (11)
C6—C7—C1—C11	−106.58 (10)	C6—C2—C3—C10	−73.54 (10)
C8—C7—C1—C2	106.44 (10)	O3—C11—C10—C3	−77.83 (11)
C6—C7—C1—C2	0.07 (9)	N—C11—C10—C3	162.21 (9)
C2—C1—C11—O3	88.74 (11)	C1—C11—C10—C3	44.69 (10)
C7—C1—C11—O3	−175.28 (9)	O3—C11—C10—C9	172.28 (9)
C2—C1—C11—N	−148.30 (9)	N—C11—C10—C9	52.31 (12)
C7—C1—C11—N	−52.32 (12)	C1—C11—C10—C9	−65.20 (11)
C2—C1—C11—C10	−30.56 (10)	C4—C3—C10—C11	−147.28 (10)
C7—C1—C11—C10	65.42 (11)	C2—C3—C10—C11	−40.28 (11)
O2—C8—C9—C5	73.28 (11)	C4—C3—C10—C9	−33.25 (11)
C12—C8—C9—C5	−161.72 (9)	C2—C3—C10—C9	73.75 (10)
C7—C8—C9—C5	−44.98 (10)	C8—C9—C10—C11	−0.16 (13)
O2—C8—C9—C10	−177.20 (9)	C5—C9—C10—C11	110.69 (10)
C12—C8—C9—C10	−52.19 (12)	C8—C9—C10—C3	−111.04 (10)
C7—C8—C9—C10	64.55 (10)	C5—C9—C10—C3	−0.19 (11)
C8—C9—C5—C4	147.81 (9)	C6—C5—C4—C3	52.63 (11)
C10—C9—C5—C4	33.57 (11)	C9—C5—C4—C3	−52.64 (11)
C8—C9—C5—C6	40.56 (10)	C10—C3—C4—C5	52.64 (11)
C10—C9—C5—C6	−73.68 (10)	C2—C3—C4—C5	−52.70 (11)
C4—C5—C6—C7	−127.27 (10)	O1—C12—N—C11	−176.38 (11)
C9—C5—C6—C7	−20.23 (11)	C8—C12—N—C11	2.08 (15)
C4—C5—C6—C2	−33.17 (11)	O3—C11—N—C12	−178.36 (10)
C9—C5—C6—C2	73.87 (10)	C1—C11—N—C12	54.71 (13)
C8—C7—C6—C5	−6.73 (11)	C10—C11—N—C12	−56.96 (13)
C1—C7—C6—C5	103.57 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H1H···O1^i	0.924 (17)	1.988 (17)	2.9094 (13)	174.4 (15)
O2—H2H···O1^ii	0.83 (2)	2.19 (2)	2.9214 (13)	147.2 (17)
O2—H2H···O1	0.83 (2)	2.237 (19)	2.7213 (12)	117.7 (16)
O3—H3H···O2^iii	0.89 (2)	1.92 (2)	2.7844 (13)	164.4 (19)

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