1-Hydroxymethyl-3,12-dioxa-14-aza­tetracyclo[9.2.1.04,14.05,10]tetradecane

Tai, X.-S.; Feng, Y.-M.; Kong, F.-Y.

doi:10.1107/S1600536808007976

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o757

doi:10.1107/S1600536808007976

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

Xi-Shi Tai,^a ^* Yi-Min Feng ^a and Fan-Yuan Kong ^a

^aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: taixishi@lzu.edu.cn

(Received 15 March 2008; accepted 24 March 2008; online 29 March 2008)

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.

Related literature

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

Experimental

Crystal data

C₁₂H₁₃NO₃
M_r = 219.23
Monoclinic, P 2₁ /c
a = 6.5045 (9) Å
b = 7.1799 (10) Å
c = 22.394 (2) Å
β = 94.516 (2)°
V = 1042.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 (2) K
0.40 × 0.21 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.961, T_max = 0.988
5012 measured reflections
1936 independent reflections
1172 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.098
wR(F²) = 0.287
S = 1.03
1936 reflections
150 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯N1ⁱ	0.82	2.11	2.882 (7)	156
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808007976/hb2709sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808007976/hb2709Isup2.hkl

checkCIF report

Comment top

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 top

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

Experimental top

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.

Computing details top

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 top

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 top

Crystal data top

C₁₂H₁₃NO₃	F(000) = 464
M_r = 219.23	D_x = 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) Å³	0.40 × 0.21 × 0.12 mm
Z = 4

Data collection top

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

Refinement top

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)] = 0.098	H-atom parameters constrained
wR(F²) = 0.287	w = 1/[σ²(F_o²) + (0.1727P)² + 0.3664P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
1936 reflections	Δρ_max = 0.39 e Å⁻³
150 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.079 (19)

Crystal data top

C₁₂H₁₃NO₃	V = 1042.6 (2) Å³
M_r = 219.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.5045 (9) Å	µ = 0.10 mm⁻¹
b = 7.1799 (10) Å	T = 298 K
c = 22.394 (2) Å	0.40 × 0.21 × 0.12 mm
β = 94.516 (2)°

Data collection top

Bruker SMART CCD diffractometer	1936 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1172 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.988	R_int = 0.073
5012 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.098	0 restraints
wR(F²) = 0.287	H-atom parameters constrained
S = 1.03	Δρ_max = 0.39 e Å⁻³
1936 reflections	Δρ_min = −0.30 e Å⁻³
150 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

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) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N1ⁱ	0.82	2.11	2.882 (7)	156

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃NO₃
M_r	219.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	6.5045 (9), 7.1799 (10), 22.394 (2)
β (°)	94.516 (2)
V (Å³)	1042.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.40 × 0.21 × 0.12

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.961, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	5012, 1936, 1172
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.098, 0.287, 1.03
No. of reflections	1936
No. of parameters	150
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.30

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N1ⁱ	0.82	2.11	2.882 (7)	156

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The authors thank the National Natural Science Foundation of China (20671073), the National Natural Science Foundation of Shandong, the Science and Technology Foundation of Weifang and Weifang University for research grants.

References

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tai, X. S., Yin, X. H., Liu, D. B., Tan, M. Y. & Yu, K. B. (2003). Chem. Res. Chinese Univ. 19, 434–436. CAS Google Scholar