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The title molecule, C
12H
19NO, crystallizes with a head-to-head tail-to-tail arrangement, including very weak N—H
N and N—H
O hydrogen bonds.
Supporting information
CCDC reference: 287598
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.003 Å
- R factor = 0.050
- wR factor = 0.149
- Data-to-parameter ratio = 15.4
checkCIF/PLATON results
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Alert level B
PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............ 24.99 Deg.
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
0 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Compound (I) was prepared by reacting 4-hydroxphenylacetamide and 1-bromohexane, as described in the literature (Sudhakar et al., 2000), and was crystallized from hexane as brown dark crystals. Analysis found: C 74.6, H 9.8, O 8.3, N 7.2%; calculated for C12H19NO: C 74.6, H 9.8, O 8.2, N 7.2%. 1H NMR (400 MHz, CDCl3): δ 0.89 (d, J = 6.4 Hz, 3H, CH3), 1.32–1.42 (m, J = 6.8, 5.6 Hz, 6H, 3 × CH2), 1.73 (m, J = 6.8, 7.2 Hz, 2H, CH2), 3.21 (s, 2H, NH2), 3.87 (m, J = 6.8, 6.4 Hz, 2H, O–CH2), 6.25 (m, J = 8.8 Hz, 2H, Ph), 6.74 (m, J = 8.8 Hz, 2H, Ph).
The H atom bonded to N1 were found in a difference map and refined with free coordinates and isotropic U parameters. H atoms bonded to C atoms were placed in idealized positions and refined as riding to their parent C atom [restrained C—H distances and isotropic Uiso(H) parameters: methylene 0.97 Å and 1.2Ueq(C); methyl 0.96 Å and 1.5Ueq(C); aromatic 0.93 Å and 1.2Ueq(C)].
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 1998); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXTL-Plus.
4-(n-Hexyloxy)aniline
top
Crystal data top
C12H19NO | Dx = 1.073 Mg m−3 |
Mr = 193.28 | Melting point: 316 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 75 reflections |
a = 5.4659 (10) Å | θ = 4.8–12.5° |
b = 13.6278 (19) Å | µ = 0.07 mm−1 |
c = 32.124 (4) Å | T = 296 K |
V = 2392.8 (6) Å3 | Irregular, colorless |
Z = 8 | 0.6 × 0.3 × 0.3 mm |
F(000) = 848 | |
Data collection top
Bruker P4 diffractometer | Rint = 0.031 |
Radiation source: fine-focus sealed tube, FN4 | θmax = 25.0°, θmin = 3.0° |
Graphite monochromator | h = −6→2 |
2θ/ω scans | k = −16→1 |
3385 measured reflections | l = −38→1 |
2111 independent reflections | 2 standard reflections every 48 reflections |
1159 reflections with I > 2σ(I) | intensity decay: 2.5% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: See text |
R[F2 > 2σ(F2)] = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.149 | w = 1/[σ2(Fo2) + (0.0563P)2 + 0.637P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2111 reflections | Δρmax = 0.13 e Å−3 |
137 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXTL-Plus, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0112 (16) |
Crystal data top
C12H19NO | V = 2392.8 (6) Å3 |
Mr = 193.28 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 5.4659 (10) Å | µ = 0.07 mm−1 |
b = 13.6278 (19) Å | T = 296 K |
c = 32.124 (4) Å | 0.6 × 0.3 × 0.3 mm |
Data collection top
Bruker P4 diffractometer | Rint = 0.031 |
3385 measured reflections | 2 standard reflections every 48 reflections |
2111 independent reflections | intensity decay: 2.5% |
1159 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.149 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.13 e Å−3 |
2111 reflections | Δρmin = −0.18 e Å−3 |
137 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.0919 (3) | 0.47944 (11) | 0.15025 (5) | 0.0736 (6) | |
N1 | 0.4875 (6) | 0.14137 (17) | 0.22184 (7) | 0.0738 (7) | |
H1A | 0.637 (5) | 0.146 (2) | 0.2334 (8) | 0.095 (11)* | |
H1B | 0.467 (5) | 0.088 (2) | 0.2073 (9) | 0.094 (10)* | |
C1 | 0.3936 (4) | 0.22534 (16) | 0.20195 (6) | 0.0573 (6) | |
C2 | 0.1932 (5) | 0.21883 (17) | 0.17627 (7) | 0.0651 (7) | |
H2 | 0.1258 | 0.1574 | 0.1710 | 0.078* | |
C3 | 0.0883 (5) | 0.30087 (16) | 0.15803 (7) | 0.0637 (7) | |
H3 | −0.0448 | 0.2941 | 0.1402 | 0.076* | |
C4 | 0.1829 (5) | 0.39274 (16) | 0.16650 (7) | 0.0595 (6) | |
C5 | 0.3809 (5) | 0.40042 (17) | 0.19291 (7) | 0.0646 (7) | |
H5 | 0.4447 | 0.4620 | 0.1990 | 0.078* | |
C6 | 0.4855 (5) | 0.31844 (16) | 0.21030 (7) | 0.0645 (7) | |
H6 | 0.6195 | 0.3253 | 0.2279 | 0.077* | |
C7 | −0.1076 (5) | 0.47404 (17) | 0.12171 (8) | 0.0728 (7) | |
H7A | −0.2475 | 0.4432 | 0.1349 | 0.087* | |
H7B | −0.0619 | 0.4353 | 0.0976 | 0.087* | |
C8 | −0.1716 (5) | 0.57743 (17) | 0.10858 (8) | 0.0743 (8) | |
H8A | −0.3267 | 0.5761 | 0.0939 | 0.089* | |
H8B | −0.1932 | 0.6172 | 0.1334 | 0.089* | |
C9 | 0.0167 (5) | 0.62597 (16) | 0.08102 (7) | 0.0700 (7) | |
H9A | 0.0249 | 0.5906 | 0.0549 | 0.084* | |
H9B | 0.1756 | 0.6209 | 0.0943 | 0.084* | |
C10 | −0.0357 (5) | 0.73334 (17) | 0.07197 (8) | 0.0714 (7) | |
H10A | −0.1973 | 0.7386 | 0.0597 | 0.086* | |
H10B | −0.0380 | 0.7691 | 0.0981 | 0.086* | |
C11 | 0.1461 (6) | 0.78094 (19) | 0.04332 (8) | 0.0865 (9) | |
H11A | 0.1479 | 0.7454 | 0.0172 | 0.104* | |
H11B | 0.3078 | 0.7755 | 0.0555 | 0.104* | |
C12 | 0.0934 (7) | 0.8885 (2) | 0.03453 (11) | 0.1192 (12) | |
H12A | 0.2200 | 0.9150 | 0.0171 | 0.179* | |
H12B | 0.0882 | 0.9242 | 0.0603 | 0.179* | |
H12C | −0.0614 | 0.8944 | 0.0206 | 0.179* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0891 (13) | 0.0518 (10) | 0.0800 (11) | 0.0026 (9) | −0.0186 (11) | 0.0042 (8) |
N1 | 0.093 (2) | 0.0590 (14) | 0.0693 (14) | 0.0078 (14) | −0.0141 (14) | −0.0022 (11) |
C1 | 0.0685 (16) | 0.0555 (13) | 0.0480 (12) | 0.0031 (13) | 0.0045 (13) | −0.0023 (11) |
C2 | 0.0735 (17) | 0.0528 (14) | 0.0691 (14) | −0.0066 (13) | −0.0063 (14) | −0.0036 (12) |
C3 | 0.0708 (16) | 0.0580 (14) | 0.0622 (13) | −0.0049 (13) | −0.0083 (13) | −0.0005 (11) |
C4 | 0.0673 (16) | 0.0531 (14) | 0.0582 (14) | 0.0032 (13) | 0.0017 (13) | −0.0016 (11) |
C5 | 0.0759 (18) | 0.0503 (13) | 0.0676 (14) | −0.0082 (13) | 0.0000 (14) | −0.0004 (11) |
C6 | 0.0684 (16) | 0.0633 (15) | 0.0618 (14) | −0.0038 (13) | −0.0067 (13) | −0.0023 (12) |
C7 | 0.0718 (17) | 0.0659 (16) | 0.0805 (17) | 0.0015 (14) | −0.0019 (16) | 0.0067 (13) |
C8 | 0.0757 (18) | 0.0682 (17) | 0.0791 (16) | 0.0111 (14) | −0.0020 (15) | 0.0071 (13) |
C9 | 0.0784 (18) | 0.0654 (15) | 0.0661 (15) | 0.0118 (14) | 0.0016 (14) | 0.0024 (12) |
C10 | 0.0756 (18) | 0.0647 (15) | 0.0740 (15) | 0.0124 (14) | −0.0026 (14) | 0.0033 (13) |
C11 | 0.095 (2) | 0.0796 (19) | 0.0849 (18) | 0.0012 (17) | 0.0061 (17) | 0.0099 (15) |
C12 | 0.145 (3) | 0.076 (2) | 0.136 (3) | −0.009 (2) | 0.003 (3) | 0.0267 (19) |
Geometric parameters (Å, º) top
O1—C4 | 1.384 (3) | C7—H7B | 0.9700 |
O1—C7 | 1.427 (3) | C8—C9 | 1.510 (3) |
N1—C1 | 1.407 (3) | C8—H8A | 0.9700 |
N1—H1A | 0.90 (3) | C8—H8B | 0.9700 |
N1—H1B | 0.87 (3) | C9—C10 | 1.519 (3) |
C1—C2 | 1.374 (3) | C9—H9A | 0.9700 |
C1—C6 | 1.391 (3) | C9—H9B | 0.9700 |
C2—C3 | 1.386 (3) | C10—C11 | 1.502 (3) |
C2—H2 | 0.9300 | C10—H10A | 0.9700 |
C3—C4 | 1.382 (3) | C10—H10B | 0.9700 |
C3—H3 | 0.9300 | C11—C12 | 1.521 (4) |
C4—C5 | 1.380 (3) | C11—H11A | 0.9700 |
C5—C6 | 1.374 (3) | C11—H11B | 0.9700 |
C5—H5 | 0.9300 | C12—H12A | 0.9600 |
C6—H6 | 0.9300 | C12—H12B | 0.9600 |
C7—C8 | 1.512 (3) | C12—H12C | 0.9600 |
C7—H7A | 0.9700 | | |
| | | |
C4—O1—C7 | 118.22 (18) | C9—C8—H8A | 108.6 |
C1—N1—H1A | 117.2 (18) | C7—C8—H8A | 108.6 |
C1—N1—H1B | 112.8 (18) | C9—C8—H8B | 108.6 |
H1A—N1—H1B | 114 (3) | C7—C8—H8B | 108.6 |
C2—C1—C6 | 117.5 (2) | H8A—C8—H8B | 107.6 |
C2—C1—N1 | 120.7 (2) | C8—C9—C10 | 113.9 (2) |
C6—C1—N1 | 121.5 (2) | C8—C9—H9A | 108.8 |
C1—C2—C3 | 122.1 (2) | C10—C9—H9A | 108.8 |
C1—C2—H2 | 119.0 | C8—C9—H9B | 108.8 |
C3—C2—H2 | 119.0 | C10—C9—H9B | 108.8 |
C4—C3—C2 | 119.5 (2) | H9A—C9—H9B | 107.7 |
C4—C3—H3 | 120.2 | C11—C10—C9 | 114.1 (2) |
C2—C3—H3 | 120.2 | C11—C10—H10A | 108.7 |
C5—C4—C3 | 118.9 (2) | C9—C10—H10A | 108.7 |
C5—C4—O1 | 116.7 (2) | C11—C10—H10B | 108.7 |
C3—C4—O1 | 124.4 (2) | C9—C10—H10B | 108.7 |
C6—C5—C4 | 121.0 (2) | H10A—C10—H10B | 107.6 |
C6—C5—H5 | 119.5 | C10—C11—C12 | 113.9 (2) |
C4—C5—H5 | 119.5 | C10—C11—H11A | 108.8 |
C5—C6—C1 | 120.9 (2) | C12—C11—H11A | 108.8 |
C5—C6—H6 | 119.6 | C10—C11—H11B | 108.8 |
C1—C6—H6 | 119.6 | C12—C11—H11B | 108.8 |
O1—C7—C8 | 107.9 (2) | H11A—C11—H11B | 107.7 |
O1—C7—H7A | 110.1 | C11—C12—H12A | 109.5 |
C8—C7—H7A | 110.1 | C11—C12—H12B | 109.5 |
O1—C7—H7B | 110.1 | H12A—C12—H12B | 109.5 |
C8—C7—H7B | 110.1 | C11—C12—H12C | 109.5 |
H7A—C7—H7B | 108.4 | H12A—C12—H12C | 109.5 |
C9—C8—C7 | 114.5 (2) | H12B—C12—H12C | 109.5 |
| | | |
C6—C1—C2—C3 | 1.9 (3) | C4—C5—C6—C1 | −0.4 (4) |
N1—C1—C2—C3 | 176.4 (2) | C2—C1—C6—C5 | −0.9 (3) |
C1—C2—C3—C4 | −1.6 (4) | N1—C1—C6—C5 | −175.4 (2) |
C2—C3—C4—C5 | 0.3 (3) | C4—O1—C7—C8 | −179.8 (2) |
C2—C3—C4—O1 | −179.6 (2) | O1—C7—C8—C9 | 70.1 (3) |
C7—O1—C4—C5 | 177.9 (2) | C7—C8—C9—C10 | −173.6 (2) |
C7—O1—C4—C3 | −2.2 (3) | C8—C9—C10—C11 | −177.9 (2) |
C3—C4—C5—C6 | 0.7 (3) | C9—C10—C11—C12 | −179.7 (2) |
O1—C4—C5—C6 | −179.4 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N1i | 0.90 (3) | 2.40 (3) | 3.277 (3) | 166 (2) |
N1—H1B···O1ii | 0.87 (3) | 2.38 (3) | 3.217 (3) | 162 (2) |
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+1/2, y−1/2, z. |
Experimental details
Crystal data |
Chemical formula | C12H19NO |
Mr | 193.28 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 296 |
a, b, c (Å) | 5.4659 (10), 13.6278 (19), 32.124 (4) |
V (Å3) | 2392.8 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.6 × 0.3 × 0.3 |
|
Data collection |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3385, 2111, 1159 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.149, 1.02 |
No. of reflections | 2111 |
No. of parameters | 137 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.13, −0.18 |
Selected geometric parameters (Å, º) topO1—C4 | 1.384 (3) | C7—C8 | 1.512 (3) |
O1—C7 | 1.427 (3) | C8—C9 | 1.510 (3) |
N1—C1 | 1.407 (3) | C9—C10 | 1.519 (3) |
N1—H1A | 0.90 (3) | C10—C11 | 1.502 (3) |
N1—H1B | 0.87 (3) | C11—C12 | 1.521 (4) |
| | | |
C4—O1—C7 | 118.22 (18) | C1—N1—H1B | 112.8 (18) |
C1—N1—H1A | 117.2 (18) | H1A—N1—H1B | 114 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N1i | 0.90 (3) | 2.40 (3) | 3.277 (3) | 166 (2) |
N1—H1B···O1ii | 0.87 (3) | 2.38 (3) | 3.217 (3) | 162 (2) |
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+1/2, y−1/2, z. |
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Low molecular weight imines (Demus et al., 1998; Sudhakar et al., 2000) and polyimines (Natansohn et al., 1991) with mesomorphic behavior are continuously studied. The title compound, (I), is the starting material for the synthesis of some imines by condensation with functionalized aldehydes. A suitable functionalization of these imines with allyl groups may afford polymerizable monomers (López et al., 2005).
Compound (I) is stabilized in the solid state as a bent molecule (Fig. 1) due to the gauche conformation of the alkyl chain with respect to the aryl moiety [O1—C7—C8—C9 = 70.1 (3)°]. Geometric parameters (Table 1) are as expected. For instance, the amine group presents a pyramidal arrangement of bonds around N atom, very close to that observed for aniline. One measure of the s or p character of the N atoms in primary amines is given by the angle between the C—N bond and the bisector of the H—N—H angle (Carey, 2003). In the case of aniline, for which the structure has been determined at 252 K (Fukuyo et al., 1982), this angle is 139.1 and 141.1° for two independent molecules, while for (I), the equivalent angle is 140.6 (4)°. It is thus clear that the para substitution of the aniline by an hexyloxy group has very little influence on the amine functionality.
A common head-to-head tail-to-tail arrangement is observed for the crystal structure (Fig. 2). The angle between two forheading benzene rings is 76.62 (6)° (rings related by symmetry code 1/2 + x, y, 3/2 − z). As the O atom of alkyloxy groups is a very poor donor and acceptor for hydrogen-bonding, intermolecular interactions of very weak strength are observed in the crystal structure (Table 2); N—H···N bonds link molecules along [100] and N—H···O interactions link molecules along [010]. The weakness of these intermolecular contacts, together with the low molecular weight of (I), may be related to the low melting point for this material (m.p. 316 K).