1-Hydroxymethyl-3,12-dioxa-14-aza­tetracyclo[9.2.1.0^4,14.0^5,10]tetradecane

In the title fused-ring compound, C₁₂H₁₃NO₃, the two five-membered C₃NO rings both approximate to envelope conformations with C atoms in the flap positions. The OH group of the pendant CH₂OH unit is disordered over two positions in a 0.528 (5):0.472 (5) ratio. One of the OH groups participates in an O—H...N hydrogen bond, generating centrosymmetric dimers in the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in main residue
• R factor = 0.098
• wR factor = 0.287
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.95

Alert level C
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.287
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT084_ALERT_2_C High R2 Value ..................................       0.29
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C4     -   C5      ..       5.31 su
PLAT301_ALERT_3_C Main Residue  Disorder .........................       6.00 Perc.
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7

Alert level G
PLAT793_ALERT_2_G Check the Absolute Configuration of C1     .....          R
PLAT793_ALERT_2_G Check the Absolute Configuration of C8     .....          S

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

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

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S1. Comment

As part of our ongoing studies of fused-ring systems (Tai et al., 2003) we now report the synthesis and structure of the title compound, (I).

The C1/C2/C7/C8/N1 ring is almost planar (r.m.s. deviation from the mean plane = 0.004Å). The C1/O1/C9/C10/N1 ring is a twisted envelope with C9 in the flap position. The C8/O2/C11/C10/N1 ring is a well defined envelope, with C11 deviating by 0.504 (7)Å from the mean plane of the other four atoms. The molecule of (I) is chiral, with C1 and C8 having R and S configurations respectively, in the arbitrarily chosen asymmetric molecule, but crystal symmetry generates a racemic mixture.

The pendant -CH₂OH group is disordered over two orientations in almost equal proportions. One of the orientations participates in an intermolecular O-H···N hydrogen bond (Table 1), leading to inversion dimers in the crystal.

Related literature

For related literature, see: Tai et al. (2003).

S2. Experimental

Ortho-phthaladehyde (5 mmol) was added to a solution of trihydroxymethyl aminomethane (5 mmol) in 10 ml of ethanol. The mixture was continuously stirred for 2 h at refluxing temperature, evaporating some ethanol, then, upon cooling, the solid product was collected by filtration and dried in vacuo (yield 58%). Colourless blocks of (I) were obtained by evaporation from a methanol solution after 10 days.

S3. Refinement

The H atoms were placed geometrically (C—H = 0.93–0.96 Å, O—H = 0.82 Å) and refined as riding with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of (I) showing 50% displacement ellipsoids for the non-hydrogen atoms. Only one orientation of the disordered -CH2OH group is shown.

1-hydroxymethyl-3,12-dioxa-14-azatetracyclo[9.2.1.0^4,14.0^5,10]tetradecane

Crystal data

C12H13NO3	F(000) = 464
Mr = 219.23	Dx = 1.397 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1373 reflections
a = 6.5045 (9) Å	θ = 3.0–23.3°
b = 7.1799 (10) Å	µ = 0.10 mm^−1
c = 22.394 (2) Å	T = 298 K
β = 94.516 (2)°	Block, colourless
V = 1042.6 (2) Å^3	0.40 × 0.21 × 0.12 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	1936 independent reflections
Radiation source: fine-focus sealed tube	1172 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
ω scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→7
Tmin = 0.961, Tmax = 0.988	k = −7→8
5012 measured reflections	l = −27→21

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.098	H-atom parameters constrained
wR(F^2) = 0.287	w = 1/[σ^2(Fo^2) + (0.1727P)^2 + 0.3664P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1936 reflections	Δρmax = 0.39 e Å^−3
150 parameters	Δρmin = −0.30 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.079 (19)

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	Occ. (<1)
N1	0.3226 (5)	0.5287 (5)	0.42690 (14)	0.0367 (9)
O1	0.4295 (5)	0.6752 (5)	0.34186 (13)	0.0486 (10)
O2	−0.0354 (5)	0.5594 (5)	0.42167 (15)	0.0511 (10)
O3	0.4817 (11)	0.7928 (9)	0.5164 (3)	0.0524 (13)	0.528 (5)
H3	0.5091	0.6856	0.5269	0.079*	0.528 (5)
O3'	0.2177 (12)	0.9609 (10)	0.5081 (3)	0.0524 (13)	0.472 (5)
H3'	0.2718	1.0454	0.4903	0.079*	0.472 (5)
C1	0.4333 (7)	0.5026 (6)	0.37325 (18)	0.0378 (11)
H1	0.5753	0.4617	0.3837	0.045*
C2	0.3133 (7)	0.3565 (7)	0.33750 (19)	0.0403 (11)
C3	0.3589 (8)	0.2725 (7)	0.2844 (2)	0.0494 (13)
H3A	0.4819	0.2969	0.2673	0.059*
C4	0.2158 (9)	0.1520 (7)	0.2581 (2)	0.0547 (14)
H4	0.2433	0.0914	0.2229	0.066*
C5	0.0313 (10)	0.1188 (8)	0.2829 (3)	0.0650 (16)
H5	−0.0665	0.0418	0.2629	0.078*
C6	−0.0101 (8)	0.1980 (7)	0.3367 (2)	0.0523 (13)
H6	−0.1303	0.1699	0.3547	0.063*
C7	0.1354 (7)	0.3223 (6)	0.36316 (19)	0.0409 (11)
C8	0.1283 (7)	0.4262 (6)	0.42126 (19)	0.0402 (11)
H8	0.1217	0.3386	0.4546	0.048*
C9	0.4143 (8)	0.8132 (7)	0.3856 (2)	0.0495 (13)
H9A	0.3567	0.9270	0.3679	0.059*
H9B	0.5484	0.8405	0.4057	0.059*
C10	0.2694 (7)	0.7288 (6)	0.42937 (19)	0.0399 (11)
C11	0.0471 (7)	0.7326 (7)	0.4034 (2)	0.0474 (12)
H11A	−0.0266	0.8366	0.4193	0.057*
H11B	0.0395	0.7421	0.3601	0.057*
C12	0.2945 (8)	0.8000 (9)	0.4924 (2)	0.0586 (15)
H12A	0.2476	0.9282	0.4928	0.070*	0.528 (5)
H12B	0.2068	0.7277	0.5167	0.070*	0.528 (5)
H12C	0.2323	0.7085	0.5173	0.070*	0.472 (5)
H12D	0.4410	0.8004	0.5045	0.070*	0.472 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.037 (2)	0.035 (2)	0.0380 (19)	0.0013 (16)	0.0021 (14)	0.0041 (15)
O1	0.067 (2)	0.0364 (19)	0.0437 (18)	−0.0037 (16)	0.0156 (15)	0.0067 (13)
O2	0.0313 (17)	0.047 (2)	0.076 (2)	−0.0037 (14)	0.0062 (14)	−0.0088 (16)
O3	0.065 (3)	0.031 (3)	0.059 (3)	0.001 (2)	−0.008 (2)	−0.008 (2)
O3'	0.065 (3)	0.031 (3)	0.059 (3)	0.001 (2)	−0.008 (2)	−0.008 (2)
C1	0.038 (2)	0.031 (2)	0.043 (2)	−0.0015 (18)	0.0019 (17)	0.0038 (18)
C2	0.040 (2)	0.037 (2)	0.044 (2)	0.0015 (19)	0.0009 (18)	0.0023 (19)
C3	0.059 (3)	0.043 (3)	0.045 (3)	0.009 (2)	−0.001 (2)	0.000 (2)
C4	0.066 (4)	0.038 (3)	0.058 (3)	0.010 (3)	−0.003 (2)	−0.010 (2)
C5	0.080 (4)	0.041 (3)	0.070 (4)	−0.006 (3)	−0.023 (3)	−0.012 (3)
C6	0.048 (3)	0.039 (3)	0.069 (3)	−0.007 (2)	−0.004 (2)	0.000 (2)
C7	0.042 (3)	0.029 (2)	0.050 (3)	0.0015 (19)	−0.0026 (19)	−0.0014 (18)
C8	0.041 (2)	0.034 (3)	0.045 (2)	−0.0039 (19)	0.0032 (18)	0.0006 (18)
C9	0.053 (3)	0.032 (3)	0.064 (3)	−0.011 (2)	0.006 (2)	0.000 (2)
C10	0.036 (2)	0.030 (2)	0.053 (3)	−0.0043 (18)	0.0030 (18)	−0.0027 (19)
C11	0.045 (3)	0.033 (3)	0.063 (3)	0.004 (2)	0.000 (2)	−0.006 (2)
C12	0.046 (3)	0.057 (4)	0.074 (3)	−0.014 (2)	0.012 (2)	−0.020 (3)

Geometric parameters (Å, º)

N1—C8	1.460 (6)	C4—H4	0.9300
N1—C1	1.461 (6)	C5—C6	1.379 (8)
N1—C10	1.480 (6)	C5—H5	0.9300
O1—C9	1.402 (6)	C6—C7	1.398 (7)
O1—C1	1.424 (5)	C6—H6	0.9300
O2—C11	1.427 (6)	C7—C8	1.504 (6)
O2—C8	1.431 (5)	C8—H8	0.9800
O3—C12	1.293 (8)	C9—C10	1.537 (7)
O3—H3	0.8200	C9—H9A	0.9700
O3—H12D	0.3646	C9—H9B	0.9700
O3'—C12	1.317 (10)	C10—C12	1.498 (7)
O3'—H3'	0.8200	C10—C11	1.516 (6)
C1—C2	1.501 (6)	C11—H11A	0.9700
C1—H1	0.9800	C11—H11B	0.9700
C2—C7	1.355 (7)	C12—H12A	0.9700
C2—C3	1.386 (7)	C12—H12B	0.9700
C3—C4	1.370 (8)	C12—H12C	0.9700
C3—H3A	0.9300	C12—H12D	0.9700
C4—C5	1.382 (9)
C8—N1—C1	110.1 (3)	C7—C8—H8	110.3
C8—N1—C10	106.8 (3)	O1—C9—C10	104.3 (4)
C1—N1—C10	106.7 (3)	O1—C9—H9A	110.9
C9—O1—C1	105.7 (3)	C10—C9—H9A	110.9
C11—O2—C8	106.4 (3)	O1—C9—H9B	110.9
C12—O3—H3	109.5	C10—C9—H9B	110.9
H3—O3—H12D	118.6	H9A—C9—H9B	108.9
C12—O3'—H3'	109.5	N1—C10—C12	111.0 (4)
O1—C1—N1	107.7 (3)	N1—C10—C11	102.8 (3)
O1—C1—C2	110.9 (3)	C12—C10—C11	112.7 (4)
N1—C1—C2	105.0 (4)	N1—C10—C9	101.7 (4)
O1—C1—H1	111.0	C12—C10—C9	116.1 (4)
N1—C1—H1	111.0	C11—C10—C9	111.2 (4)
C2—C1—H1	111.0	O2—C11—C10	104.1 (4)
C7—C2—C3	122.2 (5)	O2—C11—H11A	110.9
C7—C2—C1	109.1 (4)	C10—C11—H11A	110.9
C3—C2—C1	128.6 (4)	O2—C11—H11B	110.9
C4—C3—C2	117.4 (5)	C10—C11—H11B	110.9
C4—C3—H3A	121.3	H11A—C11—H11B	109.0
C2—C3—H3A	121.3	O3—C12—O3'	106.8 (5)
C3—C4—C5	121.2 (5)	O3—C12—C10	114.0 (5)
C3—C4—H4	119.4	O3'—C12—C10	122.3 (6)
C5—C4—H4	119.4	O3—C12—H12A	108.7
C6—C5—C4	121.0 (5)	C10—C12—H12A	108.7
C6—C5—H5	119.5	O3—C12—H12B	108.7
C4—C5—H5	119.5	C10—C12—H12B	108.7
C5—C6—C7	117.5 (5)	H12A—C12—H12B	107.6
C5—C6—H6	121.2	O3—C12—H12C	99.0
C7—C6—H6	121.2	O3'—C12—H12C	104.9
C2—C7—C6	120.5 (4)	C10—C12—H12C	106.9
C2—C7—C8	111.3 (4)	H12A—C12—H12C	119.4
C6—C7—C8	128.1 (4)	O3'—C12—H12D	107.9
O2—C8—N1	107.6 (4)	C10—C12—H12D	107.2
O2—C8—C7	114.2 (3)	H12A—C12—H12D	107.3
N1—C8—C7	103.9 (3)	H12B—C12—H12D	116.9
O2—C8—H8	110.3	H12C—C12—H12D	106.7
N1—C8—H8	110.3
C9—O1—C1—N1	27.5 (4)	C10—N1—C8—C7	120.2 (4)
C9—O1—C1—C2	141.9 (4)	C2—C7—C8—O2	117.6 (4)
C8—N1—C1—O1	110.3 (4)	C6—C7—C8—O2	−65.0 (6)
C10—N1—C1—O1	−5.3 (4)	C2—C7—C8—N1	0.7 (5)
C8—N1—C1—C2	−8.0 (5)	C6—C7—C8—N1	178.1 (5)
C10—N1—C1—C2	−123.5 (4)	C1—O1—C9—C10	−37.8 (5)
O1—C1—C2—C7	−107.7 (4)	C8—N1—C10—C12	101.6 (4)
N1—C1—C2—C7	8.4 (5)	C1—N1—C10—C12	−140.7 (4)
O1—C1—C2—C3	68.2 (6)	C8—N1—C10—C11	−19.1 (4)
N1—C1—C2—C3	−175.7 (4)	C1—N1—C10—C11	98.6 (4)
C7—C2—C3—C4	0.2 (7)	C8—N1—C10—C9	−134.3 (3)
C1—C2—C3—C4	−175.2 (5)	C1—N1—C10—C9	−16.6 (4)
C2—C3—C4—C5	1.3 (8)	O1—C9—C10—N1	33.4 (4)
C3—C4—C5—C6	−3.6 (9)	O1—C9—C10—C12	154.0 (4)
C4—C5—C6—C7	4.1 (8)	O1—C9—C10—C11	−75.4 (5)
C3—C2—C7—C6	0.4 (7)	C8—O2—C11—C10	−34.6 (4)
C1—C2—C7—C6	176.7 (4)	N1—C10—C11—O2	32.8 (4)
C3—C2—C7—C8	178.1 (4)	C12—C10—C11—O2	−86.7 (5)
C1—C2—C7—C8	−5.7 (5)	C9—C10—C11—O2	140.9 (4)
C5—C6—C7—C2	−2.5 (7)	N1—C10—C12—O3	63.2 (6)
C5—C6—C7—C8	−179.8 (5)	C11—C10—C12—O3	177.9 (5)
C11—O2—C8—N1	22.8 (4)	C9—C10—C12—O3	−52.2 (7)
C11—O2—C8—C7	−92.0 (4)	N1—C10—C12—O3'	−165.7 (6)
C1—N1—C8—O2	−116.7 (4)	C11—C10—C12—O3'	−51.1 (7)
C10—N1—C8—O2	−1.2 (4)	C9—C10—C12—O3'	78.8 (7)
C1—N1—C8—C7	4.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N1^i	0.82	2.11	2.882 (7)	156

Symmetry code: (i) −x+1, −y+1, −z+1.