Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003294/ya6011sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003294/ya6011Isup2.hkl |
CCDC reference: 159872
A methanol (5 ml) solution of 5-hexyloxy-2-methoxytropone (0.327 g, 1.38 mmol) and aqueous ammonia (28%, 2 ml) was heated at 373 K for 12 h in a sealed tube. The mixture was extracted with chloroform (50 ml). The extract was dried over MgSO4 and distilled in vacuo and the residue was chromatographed on a silica-gel column (hexane–ethyl acetate, 1:1 v/v) to give the title compound (I) (0.166 g, 54%). Single crystals of (I) were obtained by recrystallization from ethyl acetate.
H atoms bonded to C atoms were included in the refinement at calculated positions as riding models, with C—H set to 0.93 Å for aromatic, 0.96 Å for for CH3 and 0.97 Å for CH2. The H atoms of the NH2 group were located in the difference synthesis and subsequently included in the refinement in an isotropic approximation.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal_GX (Hall & du Boulay, 1995); software used to prepare material for publication: SHELXL97.
C13H19NO2 | F(000) = 480 |
Mr = 221.29 | Dx = 1.133 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
a = 10.7540 (4) Å | Cell parameters from 25 reflections |
b = 13.9616 (5) Å | θ = 10.7–18.2° |
c = 8.9464 (4) Å | µ = 0.08 mm−1 |
β = 104.9458 (12)° | T = 296 K |
V = 1297.80 (9) Å3 | Prism, yellow |
Z = 4 | 0.40 × 0.37 × 0.17 mm |
Enraf-Nonius CAD-4 diffractometer | 1461 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 28.0°, θmin = 2.8° |
ω–2θ scans | h = −14→0 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→18 |
Tmin = 0.987, Tmax = 1.000 | l = −11→11 |
3274 measured reflections | 3 standard reflections every 120 min |
3113 independent reflections | intensity decay: 3.1% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.071 | Hydrogen site location: mixed |
wR(F2) = 0.244 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.1195P)2 + 0.2445P] where P = (Fo2 + 2Fc2)/3 |
3113 reflections | (Δ/σ)max < 0.001 |
153 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C13H19NO2 | V = 1297.80 (9) Å3 |
Mr = 221.29 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 10.7540 (4) Å | µ = 0.08 mm−1 |
b = 13.9616 (5) Å | T = 296 K |
c = 8.9464 (4) Å | 0.40 × 0.37 × 0.17 mm |
β = 104.9458 (12)° |
Enraf-Nonius CAD-4 diffractometer | 1461 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.019 |
Tmin = 0.987, Tmax = 1.000 | 3 standard reflections every 120 min |
3274 measured reflections | intensity decay: 3.1% |
3113 independent reflections |
R[F2 > 2σ(F2)] = 0.071 | 0 restraints |
wR(F2) = 0.244 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.48 e Å−3 |
3113 reflections | Δρmin = −0.27 e Å−3 |
153 parameters |
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 | ||
N1 | 0.6758 (3) | 0.2549 (2) | 1.0734 (4) | 0.0696 (8) | |
O1 | 0.90866 (18) | 0.22072 (15) | 1.0657 (3) | 0.0748 (7) | |
O2 | 0.6451 (2) | −0.08804 (15) | 0.6873 (3) | 0.0768 (7) | |
C1 | 0.8277 (2) | 0.1644 (2) | 0.9862 (3) | 0.0562 (7) | |
C2 | 0.6924 (2) | 0.17955 (19) | 0.9878 (3) | 0.0517 (7) | |
C3 | 0.5876 (2) | 0.1245 (2) | 0.9134 (3) | 0.0621 (8) | |
H3 | 0.5096 | 0.1462 | 0.9271 | 0.074* | |
C4 | 0.5768 (3) | 0.0433 (2) | 0.8225 (4) | 0.0627 (8) | |
H4 | 0.4939 | 0.0189 | 0.7879 | 0.075* | |
C5 | 0.6701 (3) | −0.0069 (2) | 0.7755 (3) | 0.0596 (7) | |
C6 | 0.8015 (3) | 0.0179 (2) | 0.8111 (4) | 0.0670 (8) | |
H6 | 0.8520 | −0.0218 | 0.7674 | 0.080* | |
C7 | 0.8660 (3) | 0.0901 (2) | 0.8986 (4) | 0.0654 (8) | |
H7 | 0.9532 | 0.0914 | 0.9024 | 0.079* | |
C8 | 0.5158 (3) | −0.1230 (2) | 0.6366 (4) | 0.0666 (8) | |
H8A | 0.4608 | −0.0751 | 0.5741 | 0.080* | |
H8B | 0.4826 | −0.1376 | 0.7251 | 0.080* | |
C9 | 0.5181 (3) | −0.2115 (2) | 0.5434 (4) | 0.0788 (10) | |
H9A | 0.5518 | −0.1953 | 0.4559 | 0.095* | |
H9B | 0.5767 | −0.2573 | 0.6066 | 0.095* | |
C10 | 0.3908 (4) | −0.2577 (3) | 0.4852 (5) | 0.0970 (12) | |
H10A | 0.3322 | −0.2129 | 0.4197 | 0.116* | |
H10B | 0.3562 | −0.2736 | 0.5720 | 0.116* | |
C11 | 0.3995 (5) | −0.3487 (4) | 0.3933 (6) | 0.1266 (17) | |
H11A | 0.4273 | −0.3301 | 0.3025 | 0.152* | |
H11B | 0.4670 | −0.3884 | 0.4562 | 0.152* | |
C12 | 0.2905 (6) | −0.4054 (4) | 0.3438 (7) | 0.151 (2) | |
H12A | 0.2236 | −0.3670 | 0.2770 | 0.182* | |
H12B | 0.2606 | −0.4228 | 0.4336 | 0.182* | |
C13 | 0.3053 (5) | −0.4937 (4) | 0.2606 (7) | 0.143 (2) | |
H13A | 0.2244 | −0.5267 | 0.2310 | 0.215* | |
H13B | 0.3684 | −0.5341 | 0.3268 | 0.215* | |
H13C | 0.3330 | −0.4778 | 0.1699 | 0.215* | |
H1 | 0.596 (4) | 0.268 (2) | 1.075 (4) | 0.084 (10)* | |
H2 | 0.741 (4) | 0.285 (2) | 1.124 (4) | 0.078 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0368 (13) | 0.0711 (17) | 0.100 (2) | −0.0032 (12) | 0.0167 (13) | −0.0172 (15) |
O1 | 0.0379 (10) | 0.0833 (15) | 0.1048 (16) | −0.0130 (10) | 0.0213 (11) | −0.0149 (12) |
O2 | 0.0557 (12) | 0.0769 (14) | 0.0984 (16) | −0.0052 (10) | 0.0212 (11) | −0.0224 (12) |
C1 | 0.0367 (13) | 0.0620 (17) | 0.0714 (17) | −0.0038 (12) | 0.0167 (12) | 0.0066 (14) |
C2 | 0.0346 (12) | 0.0544 (16) | 0.0662 (16) | 0.0015 (11) | 0.0130 (11) | 0.0055 (13) |
C3 | 0.0328 (12) | 0.0688 (19) | 0.0841 (19) | 0.0034 (12) | 0.0142 (12) | −0.0021 (16) |
C4 | 0.0365 (13) | 0.0683 (18) | 0.0814 (19) | −0.0024 (12) | 0.0116 (12) | −0.0046 (16) |
C5 | 0.0489 (15) | 0.0612 (17) | 0.0693 (17) | −0.0011 (13) | 0.0165 (13) | −0.0028 (14) |
C6 | 0.0456 (15) | 0.076 (2) | 0.084 (2) | 0.0038 (14) | 0.0261 (14) | −0.0062 (17) |
C7 | 0.0365 (13) | 0.077 (2) | 0.088 (2) | −0.0013 (13) | 0.0257 (14) | −0.0048 (17) |
C8 | 0.0575 (17) | 0.0671 (19) | 0.0730 (19) | −0.0061 (14) | 0.0127 (14) | −0.0007 (15) |
C9 | 0.080 (2) | 0.075 (2) | 0.084 (2) | −0.0099 (17) | 0.0251 (18) | −0.0159 (18) |
C10 | 0.105 (3) | 0.097 (3) | 0.092 (3) | −0.036 (2) | 0.030 (2) | −0.026 (2) |
C11 | 0.124 (4) | 0.137 (4) | 0.127 (4) | −0.045 (3) | 0.047 (3) | −0.054 (3) |
C12 | 0.124 (4) | 0.163 (5) | 0.190 (5) | −0.051 (4) | 0.082 (4) | −0.087 (4) |
C13 | 0.118 (4) | 0.132 (4) | 0.190 (5) | −0.029 (3) | 0.056 (4) | −0.089 (4) |
N1—C2 | 1.340 (4) | C8—H8A | 0.9700 |
N1—H1 | 0.89 (4) | C8—H8B | 0.9700 |
N1—H2 | 0.84 (4) | C9—C10 | 1.481 (5) |
O1—C1 | 1.250 (3) | C9—H9A | 0.9700 |
O2—C5 | 1.367 (3) | C9—H9B | 0.9700 |
O2—C8 | 1.433 (3) | C10—C11 | 1.530 (5) |
C1—C2 | 1.474 (3) | C10—H10A | 0.9700 |
C1—C7 | 1.423 (4) | C10—H10B | 0.9700 |
C2—C3 | 1.385 (4) | C11—C12 | 1.390 (6) |
C3—C4 | 1.382 (4) | C11—H11A | 0.9700 |
C3—H3 | 0.9300 | C11—H11B | 0.9700 |
C4—C5 | 1.376 (4) | C12—C13 | 1.469 (6) |
C4—H4 | 0.9300 | C12—H12A | 0.9700 |
C5—C6 | 1.409 (4) | C12—H12B | 0.9700 |
C6—C7 | 1.353 (4) | C13—H13A | 0.9600 |
C6—H6 | 0.9300 | C13—H13B | 0.9600 |
C7—H7 | 0.9300 | C13—H13C | 0.9600 |
C8—C9 | 1.495 (4) | ||
C2—N1—H1 | 116 (2) | C10—C9—C8 | 114.1 (3) |
C2—N1—H2 | 119 (2) | C10—C9—H9A | 108.7 |
H1—N1—H2 | 124 (3) | C8—C9—H9A | 108.7 |
C5—O2—C8 | 119.7 (2) | C10—C9—H9B | 108.7 |
O1—C1—C7 | 120.9 (2) | C8—C9—H9B | 108.7 |
O1—C1—C2 | 116.6 (3) | H9A—C9—H9B | 107.6 |
C7—C1—C2 | 122.5 (2) | C9—C10—C11 | 111.8 (4) |
N1—C2—C3 | 120.0 (2) | C9—C10—H10A | 109.3 |
N1—C2—C1 | 113.3 (2) | C11—C10—H10A | 109.3 |
C3—C2—C1 | 126.7 (3) | C9—C10—H10B | 109.3 |
C4—C3—C2 | 132.3 (3) | C11—C10—H10B | 109.3 |
C4—C3—H3 | 113.9 | H10A—C10—H10B | 107.9 |
C2—C3—H3 | 113.9 | C12—C11—C10 | 118.7 (4) |
C5—C4—C3 | 129.8 (3) | C12—C11—H11A | 107.6 |
C5—C4—H4 | 115.1 | C10—C11—H11A | 107.6 |
C3—C4—H4 | 115.1 | C12—C11—H11B | 107.6 |
O2—C5—C4 | 123.3 (3) | C10—C11—H11B | 107.6 |
O2—C5—C6 | 111.7 (2) | H11A—C11—H11B | 107.1 |
C4—C5—C6 | 125.0 (3) | C11—C12—C13 | 116.5 (5) |
C7—C6—C5 | 130.4 (3) | C11—C12—H12A | 108.2 |
C7—C6—H6 | 114.8 | C13—C12—H12A | 108.2 |
C5—C6—H6 | 114.8 | C11—C12—H12B | 108.2 |
C6—C7—C1 | 133.1 (3) | C13—C12—H12B | 108.2 |
C6—C7—H7 | 113.4 | H12A—C12—H12B | 107.3 |
C1—C7—H7 | 113.4 | C12—C13—H13A | 109.5 |
O2—C8—C9 | 107.7 (3) | C12—C13—H13B | 109.5 |
O2—C8—H8A | 110.2 | H13A—C13—H13B | 109.5 |
C9—C8—H8A | 110.2 | C12—C13—H13C | 109.5 |
O2—C8—H8B | 110.2 | H13A—C13—H13C | 109.5 |
C9—C8—H8B | 110.2 | H13B—C13—H13C | 109.5 |
H8A—C8—H8B | 108.5 | ||
O1—C1—C2—N1 | 1.6 (4) | O2—C5—C6—C7 | −177.5 (3) |
C7—C1—C2—N1 | −178.0 (3) | C4—C5—C6—C7 | 2.5 (6) |
O1—C1—C2—C3 | −177.7 (3) | C5—C6—C7—C1 | 1.1 (6) |
C7—C1—C2—C3 | 2.7 (4) | O1—C1—C7—C6 | 176.1 (3) |
N1—C2—C3—C4 | −178.3 (3) | C2—C1—C7—C6 | −4.3 (5) |
C1—C2—C3—C4 | 0.9 (5) | C5—O2—C8—C9 | 180.0 (3) |
C2—C3—C4—C5 | −1.5 (6) | O2—C8—C9—C10 | 178.7 (3) |
C8—O2—C5—C4 | 1.5 (4) | C8—C9—C10—C11 | −179.0 (4) |
C8—O2—C5—C6 | −178.5 (3) | C9—C10—C11—C12 | 173.7 (5) |
C3—C4—C5—O2 | 178.6 (3) | C10—C11—C12—C13 | −178.0 (5) |
C3—C4—C5—C6 | −1.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.89 (4) | 2.00 (4) | 2.877 (4) | 171.87 |
N1—H2···O2ii | 0.84 (4) | 2.54 (3) | 3.312 (4) | 154.38 |
Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) −x+3/2, y+1/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C13H19NO2 |
Mr | 221.29 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 296 |
a, b, c (Å) | 10.7540 (4), 13.9616 (5), 8.9464 (4) |
β (°) | 104.9458 (12) |
V (Å3) | 1297.80 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.40 × 0.37 × 0.17 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.987, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3274, 3113, 1461 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.071, 0.244, 1.03 |
No. of reflections | 3113 |
No. of parameters | 153 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.48, −0.27 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, MolEN (Fair, 1990), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), Xtal_GX (Hall & du Boulay, 1995), SHELXL97.
N1—C2 | 1.340 (4) | C1—C7 | 1.423 (4) |
N1—H1 | 0.89 (4) | C2—C3 | 1.385 (4) |
N1—H2 | 0.84 (4) | C3—C4 | 1.382 (4) |
O1—C1 | 1.250 (3) | C4—C5 | 1.376 (4) |
O2—C5 | 1.367 (3) | C5—C6 | 1.409 (4) |
C1—C2 | 1.474 (3) | C6—C7 | 1.353 (4) |
C5—O2—C8—C9 | 180.0 (3) | C9—C10—C11—C12 | 173.7 (5) |
O2—C8—C9—C10 | 178.7 (3) | C10—C11—C12—C13 | −178.0 (5) |
C8—C9—C10—C11 | −179.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.89 (4) | 2.00 (4) | 2.877 (4) | 171.87 |
N1—H2···O2ii | 0.84 (4) | 2.54 (3) | 3.312 (4) | 154.38 |
Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) −x+3/2, y+1/2, −z+2. |
Troponoids, being a remarkable class of non-benzenoid π-conjugated systems, frequently play an important role as entities determining the specific properties of molecular assemblies. Recently, we have prepared liquid crystals with a tropone core, such as 5-hydroxytropolone and 2-amino-5-hydroxytropone (Mori & Takeshita, 1995; Mori et al., 1997). The troponoid cores enhanced formation of smectic phases when compared with the corresponding benzenoids. We now report the crystal structure of 2-amino-5-hexyloxytropone, (I), which was determined in order to elucidate the substituent effect at 2- and 5-positions of tropone on the crystal packing.
The hexyl chain has an all-trans conformation thus forming an almost planar zigzag; the deviations of atoms from the least squares plane defined by atoms C8–C13 are all within 0.063 (7) Å. The planarity of the seven-membered ring is fairly good; the deviations of atoms from the least squares plane defined by atoms C1–C7 are within 0.023 (4) Å. The C—C bond lengths of the seven-membered ring, apart from the C1—C2 bond, show no apparent bond alternation in contrast to what has been observed for tropolone (Shimanouchi & Sasada, 1973). The average value of the C—C bond lengths, apart from the C1—C2 bond, is 1.388 Å, which agrees with that of tropolone (1.385 Å) and the standard aromatic C—C bond length of 1.392 Å (Lide, 1990). The C1—C2 bond [1.474 (3) Å] is significantly longer than all other bonds in the cycle; the same structural peculiarity had been noted in the tropolone structure.
The NH2 group participates in an N1—H1···O1 intermolecular hydrogen bond [N1···O1i 2.877 (4) Å; symmetry code: (i) -1/2 + x, 1/2 - y, z]. The N···O distance is close to the standard intermolecular N—H.·O distance [N···O 2.89 Å; Kuleshova & Zorkii, 1981]. These hydrogen bonds link molecules of (I) into infinite chains stretching along the a axis of the crystal. Another relatively short intermolecular contact, N1.·O2ii of 3.312 (4) Å [symmetry code: (ii) 3/2 - x, 1/2 + y, 2 - z], is much longer than the above-mentioned standard N—H.·O hydrogen-bonding distance.
The distance between the tropone planes of neighbouring molecules in crystal is greater than 4.0 Å, which is substantially longer than that in tropolone itself (3.715 Å; Shimanouchi & Sasada, 1973). This makes us believe that the π–π interaction can hardly be among those factors which determine the crystal packing of a title compound.