Naphthalen-1-aminium chloride

Abstract

In the crystal structure of the title compound, C₁₀H₁₀N⁺·Cl⁻, the two components are connected via N—H⋯Cl hydrogen bonds, forming a layer parallel to the bc plane.

Related literature

For applications of naphthalene, see: Griego et al. (2008 ▶). For a related structure, see: Pitchumony & Stoeckli-Evans (2005 ▶).

Experimental

Crystal data

• C₁₀H₁₀N⁺·Cl⁻

• M _r = 179.64

• Monoclinic,

• a = 13.9691 (11) Å

• b = 5.2811 (4) Å

• c = 12.164 (1) Å

• β = 93.791 (2)°

• V = 895.40 (12) ų

• Z = 4

• Mo Kα radiation

• μ = 0.37 mm⁻¹

• T = 296 K

• 0.50 × 0.11 × 0.06 mm

Data collection

• Bruker APEXII DUO CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.838, T _max = 0.978

• 7193 measured reflections

• 2612 independent reflections

• 2013 reflections with I > 2σ(I)

• R _int = 0.024

Refinement

• R[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 0.100

• S = 1.05

• 2612 reflections

• 110 parameters

• H-atom parameters constrained

• Δρ_max = 0.27 e Å⁻³

• Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811032569/is2764Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1i	0.89	2.41	3.1824 (11)	145
N1—H1B⋯Cl1ii	0.89	2.27	3.1355 (11)	164
N1—H1C⋯Cl1	0.89	2.24	3.1225 (11)	170

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Naphthalene, a bicyclic aromatic compound, can be found environmentally as a constituent of coal tar, crude oil, and cigarette smoke. It is also used in chemical manufacturing as a chemical intermediate for many commercial products ranging from pesticides to plastics. Because of its widespread human exposure (Griego et al., 2008), its toxicological properties have been the subject of numerous assessments. Of particular interest was an evaluation for the potential to induce tumors. Herein, we have present the crystal structure of napthalen-1-ammonium chloride (I).

The asymmetric unit of title compound (I), consists of a protonated napthalen-1-ammonium cation and a chloride anion as shown in Fig. 1. In the cation, the C1–C6 bonds are long [1.4260 (17) Å], while the C7–C8, C9–C10, C2—C3 and C4–C5 bonds are short, ranging from 1.357 (3) to 1.370 (2) Å . The remainder of the bonds, C8–C9, C1–C2, C1–C10, C3–C4, C5–C6, C6–C7 and C8–C9 have an intermediate length, ranging from 1.407 (2) to 1.420 (2) Å. This variation indicates that the π electrons are not fully delocalized over the whole nucleus of the naphthalene ring. This situation is similar to that observed in the crystal structure of napththalene 2,3-dicarbonitrile (Pitchumony & Stoeckli-Evans, 2005). The naphthalene ring is essentially planar, with a maximum deviation of 0.007 (2) Å for atom C2. In the crystal structure, (Fig. 2), the ion pairs are connected via N—H···Cl hydrogen bonds (Table 1) forming layers parallel to the bc-plane.

Experimental

In a round bottom flask, 25ml of toluene was mixed with 1-nitronapthalene (0.01 mol, 1.5 g) with stirring. Iron powder (0.2 g) dissolved with 5 ml of hydrochloric acid was then added. The mixture was neutralized with sodium hydroxide solution. The blue precipitate formed was washed with alkaline water and then was dissolved in methanol at room temperature. After few days, blue needle-shaped crystals was formed by slow evaporation.

Refinement

All hydrogen atoms were positioned geometrically (N—H = 0.89 Å and C—H = 0.93 Å) and were refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme. The intermolecular N—H···Cl hydrogen bond shown by a dashed line.

Fig. 2.

The crystal packing of title compound (I), dashed lines represents hydrogen bonds. H atoms not involved in the hydrogen bond interactions are omitted for clarity.

Crystal data

C10H10N+·Cl−	F(000) = 376
Mr = 179.64	Dx = 1.333 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2184 reflections
a = 13.9691 (11) Å	θ = 2.4–29.5°
b = 5.2811 (4) Å	µ = 0.37 mm−1
c = 12.164 (1) Å	T = 296 K
β = 93.791 (2)°	Needle, blue
V = 895.40 (12) Å3	0.50 × 0.11 × 0.06 mm
Z = 4

Data collection

Bruker APEXII DUO CCD area-detector diffractometer	2612 independent reflections
Radiation source: fine-focus sealed tube	2013 reflections with I > 2σ(I)
graphite	Rint = 0.024
φ and ω scans	θmax = 30.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −19→19
Tmin = 0.838, Tmax = 0.978	k = −7→7
7193 measured reflections	l = −17→17

Refinement

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0446P)2 + 0.1614P] where P = (Fo2 + 2Fc2)/3
2612 reflections	(Δ/σ)max = 0.001
110 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N1	0.09331 (7)	0.2065 (2)	0.61299 (9)	0.0337 (3)
H1A	0.0694	0.3349	0.6498	0.051*
H1B	0.0653	0.0629	0.6318	0.051*
H1C	0.0824	0.2324	0.5410	0.051*
C1	0.24993 (9)	0.0070 (3)	0.58382 (10)	0.0327 (3)
C2	0.20875 (10)	−0.1621 (3)	0.50320 (11)	0.0386 (3)
H2A	0.1430	−0.1576	0.4850	0.046*
C3	0.26516 (12)	−0.3317 (3)	0.45199 (13)	0.0481 (4)
H3A	0.2376	−0.4417	0.3993	0.058*
C4	0.36465 (12)	−0.3402 (4)	0.47879 (14)	0.0540 (4)
H4A	0.4024	−0.4558	0.4434	0.065*
C5	0.40605 (11)	−0.1815 (4)	0.55573 (14)	0.0500 (4)
H5A	0.4719	−0.1898	0.5723	0.060*
C6	0.35070 (9)	−0.0034 (3)	0.61123 (11)	0.0385 (3)
C7	0.39198 (10)	0.1629 (4)	0.69232 (13)	0.0489 (4)
H7A	0.4576	0.1557	0.7106	0.059*
C8	0.33727 (11)	0.3331 (4)	0.74393 (13)	0.0493 (4)
H8A	0.3658	0.4407	0.7971	0.059*
C9	0.23783 (10)	0.3478 (3)	0.71757 (11)	0.0390 (3)
H9A	0.2006	0.4647	0.7528	0.047*
C10	0.19664 (9)	0.1892 (3)	0.63994 (10)	0.0310 (3)
Cl1	0.02807 (2)	0.28819 (7)	0.36504 (2)	0.03865 (12)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0316 (5)	0.0390 (7)	0.0306 (5)	0.0057 (5)	0.0026 (4)	−0.0010 (5)
C1	0.0331 (6)	0.0343 (8)	0.0309 (5)	0.0033 (6)	0.0033 (4)	0.0064 (6)
C2	0.0390 (6)	0.0398 (9)	0.0370 (6)	0.0039 (6)	0.0040 (5)	−0.0009 (6)
C3	0.0569 (9)	0.0442 (10)	0.0438 (7)	0.0070 (8)	0.0080 (6)	−0.0054 (7)
C4	0.0563 (9)	0.0516 (11)	0.0557 (9)	0.0219 (9)	0.0159 (7)	0.0019 (8)
C5	0.0375 (7)	0.0562 (11)	0.0571 (9)	0.0142 (8)	0.0082 (6)	0.0076 (8)
C6	0.0329 (6)	0.0408 (9)	0.0419 (7)	0.0037 (6)	0.0032 (5)	0.0084 (6)
C7	0.0338 (6)	0.0589 (11)	0.0530 (8)	−0.0028 (7)	−0.0045 (6)	0.0052 (8)
C8	0.0438 (8)	0.0560 (11)	0.0471 (8)	−0.0101 (8)	−0.0048 (6)	−0.0070 (8)
C9	0.0411 (7)	0.0398 (8)	0.0362 (6)	0.0003 (7)	0.0034 (5)	−0.0025 (6)
C10	0.0311 (5)	0.0334 (7)	0.0286 (5)	0.0024 (6)	0.0026 (4)	0.0042 (5)
Cl1	0.04571 (19)	0.0405 (2)	0.03008 (16)	0.00534 (16)	0.00533 (12)	0.00064 (14)

Geometric parameters (Å, °)

N1—C10	1.4617 (16)	C4—C5	1.357 (3)
N1—H1A	0.8900	C4—H4A	0.9300
N1—H1B	0.8900	C5—C6	1.417 (2)
N1—H1C	0.8900	C5—H5A	0.9300
C1—C10	1.4189 (19)	C6—C7	1.415 (2)
C1—C2	1.420 (2)	C7—C8	1.360 (2)
C1—C6	1.4260 (17)	C7—H7A	0.9300
C2—C3	1.370 (2)	C8—C9	1.407 (2)
C2—H2A	0.9300	C8—H8A	0.9300
C3—C4	1.407 (2)	C9—C10	1.361 (2)
C3—H3A	0.9300	C9—H9A	0.9300
C10—N1—H1A	109.5	C4—C5—C6	121.17 (14)
C10—N1—H1B	109.5	C4—C5—H5A	119.4
H1A—N1—H1B	109.5	C6—C5—H5A	119.4
C10—N1—H1C	109.5	C7—C6—C5	122.29 (14)
H1A—N1—H1C	109.5	C7—C6—C1	119.33 (14)
H1B—N1—H1C	109.5	C5—C6—C1	118.38 (14)
C10—C1—C2	123.87 (12)	C8—C7—C6	121.10 (14)
C10—C1—C6	117.05 (13)	C8—C7—H7A	119.5
C2—C1—C6	119.08 (13)	C6—C7—H7A	119.5
C3—C2—C1	120.43 (13)	C7—C8—C9	120.51 (15)
C3—C2—H2A	119.8	C7—C8—H8A	119.7
C1—C2—H2A	119.8	C9—C8—H8A	119.7
C2—C3—C4	120.31 (16)	C10—C9—C8	119.33 (14)
C2—C3—H3A	119.8	C10—C9—H9A	120.3
C4—C3—H3A	119.8	C8—C9—H9A	120.3
C5—C4—C3	120.62 (15)	C9—C10—C1	122.68 (12)
C5—C4—H4A	119.7	C9—C10—N1	118.88 (12)
C3—C4—H4A	119.7	C1—C10—N1	118.44 (12)
C10—C1—C2—C3	179.52 (14)	C5—C6—C7—C8	179.64 (16)
C6—C1—C2—C3	−0.4 (2)	C1—C6—C7—C8	−0.4 (2)
C1—C2—C3—C4	0.0 (2)	C6—C7—C8—C9	−0.1 (3)
C2—C3—C4—C5	0.2 (3)	C7—C8—C9—C10	0.2 (2)
C3—C4—C5—C6	0.1 (3)	C8—C9—C10—C1	0.2 (2)
C4—C5—C6—C7	179.52 (17)	C8—C9—C10—N1	−179.85 (13)
C4—C5—C6—C1	−0.4 (2)	C2—C1—C10—C9	179.46 (14)
C10—C1—C6—C7	0.7 (2)	C6—C1—C10—C9	−0.6 (2)
C2—C1—C6—C7	−179.35 (14)	C2—C1—C10—N1	−0.53 (19)
C10—C1—C6—C5	−179.33 (13)	C6—C1—C10—N1	179.41 (12)
C2—C1—C6—C5	0.6 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1i	0.89	2.41	3.1824 (11)	145.
N1—H1B···Cl1ii	0.89	2.27	3.1355 (11)	164.
N1—H1C···Cl1	0.89	2.24	3.1225 (11)	170.

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z+1.