2,5-Dimethyl­anilinium chloride monohydrate

Abstract

In the title compound, C₈H₁₂N⁺·Cl⁻·H₂O, the crystal packing is influenced by O—H⋯Cl, N—H⋯Cl and N—H⋯O hydrogen bonds, resulting in a two-dimensional network propagating parallel to (001).

Related literature

For related literature, see: Aloui et al. (2006 ▶); Masse et al. (1993 ▶); Blessing (1986 ▶).

Experimental

Crystal data

• C₈H₁₂N⁺·Cl⁻·H₂O

• M _r = 175.65

• Monoclinic,

• a = 7.515 (4) Å

• b = 7.441 (3) Å

• c = 9.019 (2) Å

• β = 102.87 (3)°

• V = 491.7 (4) ų

• Z = 2

• Mo Kα radiation

• μ = 0.34 mm⁻¹

• T = 293 (2) K

• 0.50 × 0.30 × 0.20 mm

Data collection

• Enraf–Nonius TurboCAD-4 diffractometer

• Absorption correction: none

• 2058 measured reflections

• 1260 independent reflections

• 1166 reflections with I > 2σ(I)

• R _int = 0.025

• 2 standard reflections frequency: 120 min intensity decay: 5%

Refinement

• R[F ² > 2σ(F ²)] = 0.028

• wR(F ²) = 0.081

• S = 1.10

• 1260 reflections

• 111 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.20 e Å⁻³

• Δρ_min = −0.14 e Å⁻³

• Absolute structure: Flack (1983 ▶), unique data only

• Flack parameter: 0.17 (9)

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶).

Supplementary Material

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
O1—H30⋯Cl1i	0.81 (4)	2.37 (4)	3.168 (3)	171 (4)
O1—H31⋯Cl1	0.78 (4)	2.44 (4)	3.219 (3)	174 (5)
N1—H1A⋯O1ii	0.89	1.82	2.705 (4)	171
N1—H1B⋯Cl1iii	0.89	2.29	3.167 (2)	169
N1—H1C⋯Cl1iv	0.89	2.30	3.189 (3)	173

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

The preparation of inorganic anion and organic cation salts continues to be a focus area in chemistry and material science because of their abilities to combine the properties of organic and inorganic compounds within one single molecular scale, so as to exhibit some interesting crystal structure and some special properties, such as second-order nonlinear optical response, magnetism, luminescence, and even multifunctional properties (Masse et al., 1993). It is therefore vital to design and synthesize novel salts with inorganic anions and organic cations so as to explore their various properties. In this context, we report the synthesis and the crystal structure of a the title compound, (I), (Fig. 1). The crystal packing can be described as a typical layered organization. A projection of such a layer shows that the Cl^- anions are linked to the water molecules by O—H···Cl hydrogen bonds to form infinite corrugated chains along the b direction (Fig. 2). These chains are themselves connected via N—H···O and N—H···Cl hydrogen bonds originating from NH₃⁺ groups, so as to built inorganic layers spreading around the (a,b) plane. The 2,5-xylidinium cations are anchored onto the successive inorganic layers via hydrogen bonds and electrostatic interactions, to compensate their negative charges.

The examination of the organic cation shows that the values of the N—C, C—C distances and N—C—C, C—C—C angles range from 1.376 (3) to 1.503 (3) Å and 115.72 (19) to 122.80 (19)°, respectively. These values show no significant difference from those obtained in other organic materials associated with the same organic groups (Aloui et al., 2006).

In this structure, the water molecule play a very important role in the cohesion of the various groups. It participates with the organic cation and chloride anion in an H-bonding scheme of N—H···O and O—H···Cl interactions in the asymmetrical unit. Among these five H-bonds, only one could be considered to be strong according to the well known criterion of Blessing and Brown: N···O = 2.705 (4)Å (Blessing, 1986). The four remaining hydrogen bonds are relatively weak, and their donor···acceptor distances vary from 3.167 (2) to 3.219 (3) Å. Thus, these different interactions (hydrogen bonds, Van der Waals, and electrostatic) form a stable three-dimensional network.

Experimental

The title compound was prepared by slow addition, at room temperature, of an aqueous hydrochloric acid solution to an alcoholic solution of 2,5-xylidine in a 1:1 molar ratio. A crystalline precipitate was formed. After dissolution by adding H₂O, the solution was slowly evaporated at room temperature over several days resulting in the formation of transparent plates of (I).

Refinement

The water H atoms were located in a difference map and freely refined. The other H atoms were positioned geometrically (N—H = 0.89, C—H = 0.93–0.96 Å) and refined as riding with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(methyl C).

Figures

Fig. 1.

View of (I) with displacement ellipsoids for non-H atoms drawn at the 30% probability level.

Fig. 2.

A view of the atomic arrangement of the title compound along the b axis with H bonds shown as dashed lines.

Crystal data

C8H12N+·Cl−·H2O	F(000) = 188
Mr = 175.65	Dx = 1.187 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 7.515 (4) Å	θ = 9.0–10.8°
b = 7.441 (3) Å	µ = 0.34 mm−1
c = 9.019 (2) Å	T = 293 K
β = 102.87 (3)°	Plate, colourless
V = 491.7 (4) Å3	0.50 × 0.30 × 0.20 mm
Z = 2

Data collection

Enraf–Nonius TurboCAD-4 diffractometer	Rint = 0.025
Radiation source: Enraf Nonius FR590	θmax = 28.0°, θmin = 2.3°
graphite	h = −9→9
non–profiled ω scans	k = 0→9
2058 measured reflections	l = −5→11
1260 independent reflections	2 standard reflections every 120 min
1166 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap and geom
R[F2 > 2σ(F2)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.081	w = 1/[σ2(Fo2) + (0.0515P)2 + 0.0061P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
1260 reflections	Δρmax = 0.20 e Å−3
111 parameters	Δρmin = −0.13 e Å−3
1 restraint	Absolute structure: Flack (1983), unique data only
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.17 (9)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
H30	0.343 (5)	0.410 (6)	0.541 (3)	0.068 (9)*
H31	0.467 (5)	0.287 (7)	0.548 (4)	0.101 (13)*
Cl1	0.77059 (6)	0.20498 (11)	0.51544 (5)	0.05039 (16)
C1	0.7901 (2)	0.5395 (3)	1.1684 (2)	0.0384 (4)
N1	0.8345 (2)	0.5589 (3)	1.33479 (17)	0.0417 (4)
H1A	0.7624	0.6418	1.3617	0.062*
H1B	0.9505	0.5923	1.3660	0.062*
H1C	0.8174	0.4543	1.3774	0.062*
C6	0.9259 (3)	0.5724 (3)	1.0904 (2)	0.0431 (4)
H6	1.0405	0.6101	1.1431	0.052*
C2	0.6147 (2)	0.4859 (3)	1.0962 (2)	0.0427 (4)
C5	0.8914 (3)	0.5491 (3)	0.9335 (3)	0.0487 (5)
C3	0.5844 (3)	0.4628 (4)	0.9399 (2)	0.0541 (5)
H3	0.4698	0.4248	0.8873	0.065*
C7	0.4674 (3)	0.4531 (4)	1.1817 (3)	0.0560 (6)
H7A	0.5086	0.3654	1.2599	0.084*
H7B	0.3597	0.4097	1.1128	0.084*
H7C	0.4399	0.5634	1.2271	0.084*
C4	0.7171 (3)	0.4937 (4)	0.8597 (3)	0.0551 (6)
H4	0.6902	0.4773	0.7548	0.066*
O1	0.3659 (3)	0.3043 (4)	0.5526 (3)	0.0783 (6)
C8	1.0363 (4)	0.5817 (4)	0.8458 (3)	0.0682 (7)
H8A	1.1339	0.6502	0.9071	0.102*
H8B	0.9850	0.6472	0.7546	0.102*
H8C	1.0828	0.4687	0.8197	0.102*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0441 (2)	0.0462 (2)	0.0622 (3)	0.0054 (3)	0.01468 (18)	0.0086 (3)
C1	0.0394 (9)	0.0301 (8)	0.0461 (9)	−0.0005 (7)	0.0105 (7)	−0.0040 (7)
N1	0.0388 (7)	0.0414 (8)	0.0458 (8)	−0.0036 (7)	0.0115 (6)	−0.0009 (7)
C6	0.0421 (9)	0.0341 (9)	0.0555 (11)	−0.0039 (8)	0.0157 (8)	−0.0023 (9)
C2	0.0378 (8)	0.0371 (9)	0.0541 (11)	−0.0006 (8)	0.0120 (8)	−0.0042 (9)
C5	0.0574 (11)	0.0372 (9)	0.0567 (11)	−0.0024 (9)	0.0237 (9)	−0.0033 (10)
C3	0.0486 (11)	0.0568 (14)	0.0545 (12)	−0.0063 (11)	0.0064 (9)	−0.0123 (11)
C7	0.0400 (10)	0.0655 (16)	0.0649 (14)	−0.0104 (11)	0.0169 (9)	−0.0068 (12)
C4	0.0658 (13)	0.0554 (13)	0.0450 (11)	−0.0011 (12)	0.0143 (9)	−0.0082 (10)
O1	0.0586 (11)	0.0618 (13)	0.1229 (18)	0.0097 (10)	0.0381 (11)	0.0362 (12)
C8	0.0852 (18)	0.0626 (17)	0.0694 (15)	−0.0123 (15)	0.0439 (14)	−0.0039 (14)

Geometric parameters (Å, °)

C1—C6	1.383 (3)	C3—C4	1.376 (3)
C1—C2	1.393 (3)	C3—H3	0.9300
C1—N1	1.470 (2)	C7—H7A	0.9600
N1—H1A	0.8900	C7—H7B	0.9600
N1—H1B	0.8900	C7—H7C	0.9600
N1—H1C	0.8900	C4—H4	0.9300
C6—C5	1.391 (3)	O1—H30	0.80 (4)
C6—H6	0.9300	O1—H31	0.78 (4)
C2—C3	1.388 (3)	C8—H8A	0.9600
C2—C7	1.503 (3)	C8—H8B	0.9600
C5—C4	1.393 (3)	C8—H8C	0.9600
C5—C8	1.501 (3)
C6—C1—C2	122.80 (19)	C4—C3—H3	118.7
C6—C1—N1	118.46 (17)	C2—C3—H3	118.7
C2—C1—N1	118.73 (18)	C2—C7—H7A	109.5
C1—N1—H1A	109.5	C2—C7—H7B	109.5
C1—N1—H1B	109.5	H7A—C7—H7B	109.5
H1A—N1—H1B	109.5	C2—C7—H7C	109.5
C1—N1—H1C	109.5	H7A—C7—H7C	109.5
H1A—N1—H1C	109.5	H7B—C7—H7C	109.5
H1B—N1—H1C	109.5	C3—C4—C5	120.8 (2)
C1—C6—C5	120.3 (2)	C3—C4—H4	119.6
C1—C6—H6	119.9	C5—C4—H4	119.6
C5—C6—H6	119.9	H30—O1—H31	110 (4)
C3—C2—C1	115.72 (19)	C5—C8—H8A	109.5
C3—C2—C7	121.90 (19)	C5—C8—H8B	109.5
C1—C2—C7	122.38 (19)	H8A—C8—H8B	109.5
C6—C5—C4	117.7 (2)	C5—C8—H8C	109.5
C6—C5—C8	121.6 (2)	H8A—C8—H8C	109.5
C4—C5—C8	120.7 (2)	H8B—C8—H8C	109.5
C4—C3—C2	122.7 (2)
C2—C1—C6—C5	−1.2 (3)	C1—C6—C5—C8	−179.4 (2)
N1—C1—C6—C5	177.61 (19)	C1—C2—C3—C4	−1.2 (4)
C6—C1—C2—C3	1.5 (3)	C7—C2—C3—C4	179.4 (3)
N1—C1—C2—C3	−177.3 (2)	C2—C3—C4—C5	0.6 (4)
C6—C1—C2—C7	−179.1 (2)	C6—C5—C4—C3	−0.2 (4)
N1—C1—C2—C7	2.1 (3)	C8—C5—C4—C3	179.7 (3)
C1—C6—C5—C4	0.5 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H30···Cl1i	0.81 (4)	2.37 (4)	3.168 (3)	171 (4)
O1—H31···Cl1	0.78 (4)	2.44 (4)	3.219 (3)	174 (5)
N1—H1A···O1ii	0.89	1.82	2.705 (4)	171
N1—H1B···Cl1iii	0.89	2.29	3.167 (2)	169
N1—H1C···Cl1iv	0.89	2.30	3.189 (3)	173

Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y+1/2, −z+2; (iii) −x+2, y+1/2, −z+2; (iv) x, y, z+1.