4-(Hex­yloxy)aniline

The title mol­ecule, C₁₂H₁₉NO, crystallizes with a head-to-head tail-to-tail arrangement, including very weak N—H...N and N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](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

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S1. Comment

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).

S2. Experimental

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).

S3. Refinement

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 U_iso(H) parameters: methylene 0.97 Å and 1.2U_eq(C); methyl 0.96 Å and 1.5U_eq(C); aromatic 0.93 Å and 1.2U_eq(C)].

Computing details

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.

Figures

	Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I), viewed along the [100] axis.

4-(n-Hexyloxy)aniline

Crystal data

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) Å^3	Irregular, colorless
Z = 8	0.6 × 0.3 × 0.3 mm
F(000) = 848

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: See text
R[F^2 > 2σ(F^2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.149	w = 1/[σ^2(Fo^2) + (0.0563P)^2 + 0.637P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0112 (16)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N1^i	0.90 (3)	2.40 (3)	3.277 (3)	166 (2)
N1—H1B···O1^ii	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.