8-Amino-11-hydroxy­penta­cyclo­undecane-8,11-lactam

The title compound, C₁₂H₁₄N₂O₂, is a δ-lactam derived from the penta­cyclo­undecane skeleton. The compound displays C—C bond lengths that deviate from the normal value, ranging from very short [1.5154 (17) Å] to long [1.5691 (18) Å]. The mol­ecules are arranged in a bilayer conformation consisting of a hydro­phobic cage moiety and a polar lactam region. These polar lactam regions are linked by N—H...O and O—H...O inter­molecular hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.041
• wR factor = 0.113
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTY03_ALERT_1_C  The _exptl_absorpt_correction_type has been given as none.
            However values have been given for Tmin and Tmax. Remove
            these if an absorption correction has not been applied.
  From the CIF: _exptl_absorpt_correction_T_min   0.953
  From the CIF: _exptl_absorpt_correction_T_max   0.988
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2NA   ...          ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C1     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C3     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C5     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C7     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C9     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C10    = ...          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   6 ALERT level G = General alerts; check

   8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The structure of the title compound(I) was obtained as part of an investigation into the biological activity of cage compound derivatives. The 8,11-dihydroxy-pentacycloundecane-8, 11-lactam has been previously reported (Martins et al., 1993) as has the crystal structure of the dihydroxy derivative (Kruger, et al., 1996; Kruger et al., 2006).

It has been reported earlier that the molecular structure of pentacylcloundecane derivatives exhibit C—C single bond lengths that deviate from the normal value of 1.54 Å (for example Flippen-Anderson et al., 1991; Kruger et al., 2005). The C9—C10 bond is typically longer than expected in most derivatives whereas the C11—C12 is commonly shorter.

In (I) longer than normal bonds include C9—C10(1.569 Å), C2—C6 (1.569 Å), C1—C2 (1.560 Å) and C1—C7 (1.558 Å). The bonds involving the bridge atom C4 are shorter than normal with C11—C12 being the shortest at 1.5144 Å). Fig. 1 shows the molecular geometry and labeling scheme employed.

In the crystal structure the molecules are arranged in a bilayer conformation involving the hydrophobic cage moiety and the polar lactam region. This is typical for these types of molecules (Kruger et al., 2006). Intermolecular hydrogen bonding is observed in the polar lactam region. This complex hydrogen bonding network involves atoms N, O1 and O2 as hydrogen bond donors and O2 as a hydrogen bond acceptor. Fig. 2 shows the packing and intermolecular hydrogen bonding.

Related literature

Related structures: Flippen-Anderson et al. (1991); Kruger et al. (1996, 2005, 2006); Martins et al. (1993, 1994).

S2. Experimental

To an ice-cooled solution of 25% ammonia (15 cm³), dione (1 g) was added followed by the addition of NH₄Cl (0.4 g) and NaCN (0.4 g). The mixture was left to stir in a sealed vessel immersed in an ice-water bath for 6hrs. The resulting white precipitate was filtered and washed with acetone (2 x 15 ml) and the product (0.75 g) was recrystallized from methanol to yield crystals suitable for crystallography (Martins et al., 1994).

S3. Refinement

With the exception of those involved in H-bonding, all hydrogen atoms were first located in the difference map then positioned geometrically and allowed to ride on their respective parent atoms. Hydrogen atoms attached to O or N were placed using the Fourier difference map and allowed to refine freely.

Computing details

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

Figures

	Fig. 1. Molecular structure of (I) showing the atomic numbering scheme and displacement ellipsoids at the 50% probability level
	Fig. 2. Packing diagram of (I), illustrating the layered structure and hydrogen bond interactions. Hydrogen atoms have been omitted.

8-Amino-11-hydroxypentacycloundecane-8,11-lactam

Crystal data

C12H14N2O2	F(000) = 464
Mr = 218.25	Dx = 1.451 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1018 reflections
a = 12.8324 (6) Å	θ = 3.2–28.2°
b = 7.3821 (4) Å	µ = 0.10 mm^−1
c = 10.8437 (5) Å	T = 223 K
β = 103.449 (3)°	Plate, colourless
V = 999.05 (9) Å^3	0.48 × 0.27 × 0.12 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	1955 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.049
Graphite monochromator	θmax = 28.0°, θmin = 1.6°
φ and ω scans	h = −16→16
13512 measured reflections	k = −7→9
2418 independent reflections	l = −14→14

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0602P)^2 + 0.324P] where P = (Fo^2 + 2Fc^2)/3
2418 reflections	(Δ/σ)max < 0.001
161 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.22 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
C1	0.66746 (11)	1.11198 (17)	0.07351 (12)	0.0232 (3)
H1	0.6108	1.1929	0.0255	0.028*
C2	0.78494 (11)	1.16318 (18)	0.07122 (14)	0.0279 (3)
H2	0.7957	1.2741	0.0244	0.033*
C3	0.85446 (11)	1.14034 (19)	0.20586 (14)	0.0287 (3)
H3	0.8766	1.2543	0.2528	0.034*
C4	0.94594 (12)	1.0186 (2)	0.18706 (17)	0.0373 (4)
H4A	0.9909	0.9751	0.2674	0.045*
H4B	0.9904	1.0762	0.1360	0.045*
C5	0.87304 (11)	0.87066 (19)	0.11453 (15)	0.0300 (3)
H5	0.9102	0.7658	0.0872	0.036*
C6	0.79718 (12)	0.97639 (18)	0.00700 (13)	0.0288 (3)
H6	0.8154	0.9789	−0.0768	0.035*
C7	0.68036 (11)	0.92648 (17)	0.01022 (12)	0.0244 (3)
H7	0.6307	0.9033	−0.0729	0.029*
C8	0.68967 (10)	0.77508 (16)	0.10950 (12)	0.0213 (3)
C9	0.79613 (10)	0.82542 (17)	0.20091 (12)	0.0236 (3)
H9	0.8238	0.7285	0.2630	0.028*
C10	0.78383 (10)	1.01202 (17)	0.26537 (12)	0.0223 (3)
H10	0.8058	1.0075	0.3591	0.027*
C11	0.66954 (10)	1.08606 (16)	0.21535 (12)	0.0194 (3)
C12	0.58789 (10)	0.94538 (16)	0.23194 (12)	0.0203 (3)
N1	0.60055 (9)	0.79045 (14)	0.17415 (11)	0.0233 (2)
N2	0.69531 (11)	0.59827 (16)	0.05535 (13)	0.0303 (3)
O1	0.66090 (8)	1.25102 (12)	0.27785 (10)	0.0265 (2)
O2	0.51744 (7)	0.97022 (13)	0.29291 (9)	0.0264 (2)
H1N	0.5586 (15)	0.694 (2)	0.1800 (17)	0.035 (4)*
H2NB	0.6332 (15)	0.572 (2)	−0.0045 (18)	0.037 (5)*
H2NA	0.7070 (14)	0.517 (3)	0.1203 (18)	0.038 (5)*
H1O	0.5986 (17)	1.305 (3)	0.2435 (19)	0.043 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0274 (7)	0.0182 (6)	0.0244 (6)	0.0013 (5)	0.0068 (5)	0.0023 (5)
C2	0.0322 (7)	0.0195 (6)	0.0368 (7)	−0.0002 (5)	0.0178 (6)	0.0037 (5)
C3	0.0215 (6)	0.0260 (6)	0.0399 (8)	−0.0037 (5)	0.0098 (6)	−0.0062 (6)
C4	0.0226 (7)	0.0350 (8)	0.0563 (10)	0.0003 (6)	0.0134 (7)	−0.0055 (7)
C5	0.0251 (7)	0.0234 (6)	0.0447 (8)	0.0040 (5)	0.0151 (6)	−0.0018 (6)
C6	0.0363 (8)	0.0257 (6)	0.0293 (7)	−0.0013 (5)	0.0176 (6)	0.0000 (5)
C7	0.0324 (7)	0.0215 (6)	0.0200 (6)	−0.0004 (5)	0.0073 (5)	−0.0010 (5)
C8	0.0257 (6)	0.0164 (5)	0.0241 (6)	0.0001 (4)	0.0104 (5)	−0.0025 (5)
C9	0.0234 (6)	0.0197 (6)	0.0281 (6)	0.0048 (5)	0.0066 (5)	0.0006 (5)
C10	0.0194 (6)	0.0223 (6)	0.0246 (6)	0.0017 (5)	0.0034 (5)	−0.0028 (5)
C11	0.0199 (6)	0.0165 (5)	0.0220 (6)	0.0004 (4)	0.0052 (5)	−0.0026 (4)
C12	0.0193 (6)	0.0200 (6)	0.0214 (6)	0.0014 (4)	0.0044 (5)	0.0003 (5)
N1	0.0243 (6)	0.0183 (5)	0.0297 (6)	−0.0029 (4)	0.0114 (4)	−0.0021 (4)
N2	0.0388 (7)	0.0189 (5)	0.0365 (7)	−0.0012 (5)	0.0155 (6)	−0.0059 (5)
O1	0.0246 (5)	0.0202 (4)	0.0349 (5)	0.0009 (4)	0.0075 (4)	−0.0095 (4)
O2	0.0234 (5)	0.0251 (5)	0.0340 (5)	0.0003 (4)	0.0136 (4)	−0.0019 (4)

Geometric parameters (Å, º)

C1—C11	1.5440 (17)	C7—C8	1.5370 (17)
C1—C7	1.5577 (17)	C7—H7	0.9900
C1—C2	1.5601 (18)	C8—N2	1.4400 (15)
C1—H1	0.9900	C8—N1	1.4782 (16)
C2—C3	1.533 (2)	C8—C9	1.5353 (18)
C2—C6	1.5691 (18)	C9—C10	1.5692 (17)
C2—H2	0.9900	C9—H9	0.9900
C3—C4	1.5293 (19)	C10—C11	1.5406 (17)
C3—C10	1.5516 (18)	C10—H10	0.9900
C3—H3	0.9900	C11—O1	1.4104 (14)
C4—C5	1.531 (2)	C11—C12	1.5154 (17)
C4—H4A	0.9800	C12—O2	1.2514 (15)
C4—H4B	0.9800	C12—N1	1.3321 (16)
C5—C6	1.546 (2)	N1—H1N	0.903 (19)
C5—C9	1.5469 (18)	N2—H2NB	0.92 (2)
C5—H5	0.9900	N2—H2NA	0.913 (19)
C6—C7	1.5520 (19)	O1—H1O	0.89 (2)
C6—H6	0.9900
C11—C1—C7	110.55 (10)	C6—C7—C1	90.19 (10)
C11—C1—C2	104.65 (11)	C8—C7—H7	116.2
C7—C1—C2	90.22 (10)	C6—C7—H7	116.2
C11—C1—H1	116.1	C1—C7—H7	116.2
C7—C1—H1	116.1	N2—C8—N1	112.38 (10)
C2—C1—H1	116.1	N2—C8—C9	111.17 (11)
C3—C2—C1	107.98 (10)	N1—C8—C9	110.22 (10)
C3—C2—C6	103.29 (11)	N2—C8—C7	112.12 (11)
C1—C2—C6	89.48 (10)	N1—C8—C7	109.49 (10)
C3—C2—H2	117.3	C9—C8—C7	100.88 (10)
C1—C2—H2	117.3	C8—C9—C5	104.99 (11)
C6—C2—H2	117.3	C8—C9—C10	109.48 (10)
C4—C3—C2	103.44 (12)	C5—C9—C10	102.98 (10)
C4—C3—C10	103.73 (11)	C8—C9—H9	112.9
C2—C3—C10	101.33 (10)	C5—C9—H9	112.9
C4—C3—H3	115.5	C10—C9—H9	112.9
C2—C3—H3	115.5	C11—C10—C3	103.73 (10)
C10—C3—H3	115.5	C11—C10—C9	109.92 (10)
C3—C4—C5	95.24 (11)	C3—C10—C9	102.80 (10)
C3—C4—H4A	112.7	C11—C10—H10	113.2
C5—C4—H4A	112.7	C3—C10—H10	113.2
C3—C4—H4B	112.7	C9—C10—H10	113.2
C5—C4—H4B	112.7	O1—C11—C12	113.63 (10)
H4A—C4—H4B	110.2	O1—C11—C10	108.17 (10)
C4—C5—C6	103.29 (12)	C12—C11—C10	110.06 (10)
C4—C5—C9	104.04 (12)	O1—C11—C1	112.74 (10)
C6—C5—C9	100.79 (10)	C12—C11—C1	110.54 (10)
C4—C5—H5	115.6	C10—C11—C1	100.91 (10)
C6—C5—H5	115.6	O2—C12—N1	123.82 (11)
C9—C5—H5	115.6	O2—C12—C11	124.52 (11)
C5—C6—C7	107.78 (10)	N1—C12—C11	111.66 (10)
C5—C6—C2	102.67 (11)	C12—N1—C8	118.78 (10)
C7—C6—C2	90.10 (10)	C12—N1—H1N	120.2 (11)
C5—C6—H6	117.4	C8—N1—H1N	120.8 (11)
C7—C6—H6	117.4	C8—N2—H2NB	111.0 (11)
C2—C6—H6	117.4	C8—N2—H2NA	107.4 (11)
C8—C7—C6	105.68 (11)	H2NB—N2—H2NA	111.4 (16)
C8—C7—C1	109.24 (10)	C11—O1—H1O	110.2 (13)
C11—C1—C2—C3	7.72 (13)	N1—C8—C9—C10	−50.48 (13)
C7—C1—C2—C3	−103.61 (11)	C7—C8—C9—C10	65.17 (12)
C11—C1—C2—C6	111.54 (10)	C4—C5—C9—C8	147.14 (11)
C7—C1—C2—C6	0.21 (10)	C6—C5—C9—C8	40.36 (12)
C1—C2—C3—C4	127.45 (11)	C4—C5—C9—C10	32.56 (13)
C6—C2—C3—C4	33.62 (12)	C6—C5—C9—C10	−74.22 (12)
C1—C2—C3—C10	20.19 (13)	C4—C3—C10—C11	−148.27 (11)
C6—C2—C3—C10	−73.65 (11)	C2—C3—C10—C11	−41.23 (12)
C2—C3—C4—C5	−53.01 (13)	C4—C3—C10—C9	−33.73 (13)
C10—C3—C4—C5	52.43 (14)	C2—C3—C10—C9	73.30 (11)
C3—C4—C5—C6	52.83 (13)	C8—C9—C10—C11	−0.65 (14)
C3—C4—C5—C9	−52.09 (13)	C5—C9—C10—C11	110.63 (11)
C4—C5—C6—C7	−127.61 (11)	C8—C9—C10—C3	−110.60 (11)
C9—C5—C6—C7	−20.22 (13)	C5—C9—C10—C3	0.68 (13)
C4—C5—C6—C2	−33.37 (12)	C3—C10—C11—O1	−72.18 (12)
C9—C5—C6—C2	74.02 (12)	C9—C10—C11—O1	178.48 (9)
C3—C2—C6—C5	−0.11 (12)	C3—C10—C11—C12	163.14 (10)
C1—C2—C6—C5	−108.47 (11)	C9—C10—C11—C12	53.80 (13)
C3—C2—C6—C7	108.15 (11)	C3—C10—C11—C1	46.35 (11)
C1—C2—C6—C7	−0.21 (10)	C9—C10—C11—C1	−62.99 (12)
C5—C6—C7—C8	−6.51 (13)	C7—C1—C11—O1	178.46 (10)
C2—C6—C7—C8	−109.86 (10)	C2—C1—C11—O1	82.59 (12)
C5—C6—C7—C1	103.56 (11)	C7—C1—C11—C12	−53.13 (13)
C2—C6—C7—C1	0.21 (10)	C2—C1—C11—C12	−149.01 (10)
C11—C1—C7—C8	0.73 (14)	C7—C1—C11—C10	63.30 (12)
C2—C1—C7—C8	106.49 (11)	C2—C1—C11—C10	−32.57 (11)
C11—C1—C7—C6	−105.97 (11)	O1—C11—C12—O2	1.13 (17)
C2—C1—C7—C6	−0.21 (10)	C10—C11—C12—O2	122.61 (13)
C6—C7—C8—N2	−87.67 (13)	C1—C11—C12—O2	−126.79 (13)
C1—C7—C8—N2	176.49 (11)	O1—C11—C12—N1	−178.45 (10)
C6—C7—C8—N1	146.88 (10)	C10—C11—C12—N1	−56.97 (13)
C1—C7—C8—N1	51.05 (13)	C1—C11—C12—N1	53.63 (14)
C6—C7—C8—C9	30.69 (12)	O2—C12—N1—C8	−177.47 (12)
C1—C7—C8—C9	−65.15 (12)	C11—C12—N1—C8	2.12 (16)
N2—C8—C9—C5	74.27 (12)	N2—C8—N1—C12	178.00 (12)
N1—C8—C9—C5	−160.44 (10)	C9—C8—N1—C12	53.40 (15)
C7—C8—C9—C5	−44.79 (11)	C7—C8—N1—C12	−56.71 (15)
N2—C8—C9—C10	−175.77 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^i	0.903 (19)	1.976 (19)	2.8741 (14)	172.9 (17)
N2—H2NB···O2^ii	0.92 (2)	2.37 (2)	3.2469 (18)	158.6 (15)
O1—H1O···O2^iii	0.89 (2)	1.90 (2)	2.7619 (14)	163.2 (19)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+1, y+1/2, −z+1/2.