2,3-Dimethyl­anilinium chloride monohydrate

Abstract

The crystal structure of the title salt, C₈H₁₂N⁺·Cl⁻·H₂O, consists of discrete organic cations, chloride anions and water mol­ecules which are connected by N—H⋯Cl, N—H⋯O and O—H⋯Cl hydrogen bonds. These inter­actions lead to the formation of layers lying parallel to the ab plane.

Related literature

For related structures, see: Dai & Chen (2010 ▶); Abid et al. (2007 ▶). For hydrogen bonds, see: Steiner (2002 ▶); Jayaraman et al. (2002 ▶).

Experimental

Crystal data

• C₈H₁₂N⁺·Cl⁻·H₂O

• M _r = 175.65

• Orthorhombic,

• a = 7.4910 (15) Å

• b = 7.5031 (15) Å

• c = 17.430 (4) Å

• V = 979.7 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.34 mm⁻¹

• T = 298 K

• 0.45 × 0.4 × 0.2 mm

Data collection

• Stoe IPDS 2T diffractometer

• 4645 measured reflections

• 2616 independent reflections

• 2095 reflections with I > 2σ(I)

• R _int = 0.031

Refinement

• R[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 0.104

• S = 1.03

• 2616 reflections

• 122 parameters

• 2 restraints

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

• Δρ_max = 0.20 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

• Absolute structure: Flack (1983 ▶), with 1088 Friedel pairs

• Flack parameter: 0.13 (9)

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2005 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811043765/bt5667Isup3.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	0.95 (2)	2.21 (2)	3.1581 (17)	172.6 (17)
N1—H1B⋯O1	0.89 (3)	1.83 (3)	2.711 (2)	170 (2)
N1—H1C⋯Cl1ii	0.80 (2)	2.41 (2)	3.1964 (17)	171 (2)
O1—H1W⋯Cl1iii	0.82 (2)	2.35 (2)	3.1578 (19)	169 (3)
O1—H2W⋯Cl1	0.82 (2)	2.39 (2)	3.1920 (18)	168 (4)

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

supplementary crystallographic information

Comment

Hydrogen bonding is of interest because of their prevalent occurrence in biological systems. Therefore, it is extremely useful to search simple molecules allowing to understanding the configuration and the function of some complex macromolecules. Furthermore, the hybrid materials are wealthy in H-bonds and they could be used to this outcome because of their capability emphasis in constructing sophisticated assemblies from isolated molecular or ionic building blocks due to its strength and directionality (Steiner, 2002; Jayaraman et al., 2002).

As shown in Fig. 1, the asymmetric unit of (I) contains a 2,3-dimethylanilinium cation, a chloride anion and a water molecule. Packing diagram of the structure across the a-axis is shown in Fig. 2. It shows that each chloride anion connected to two 2,3-dimethylanilinium cations via N—H···Cl hydrogen bonds and two water molecules. The title complex is a crystalline hydrate containing one water of crystallization, where form layers through N—H···O and O—H···Cl hydrogen bonds (Table 1).

The C—NH₃, 1.465 (2) Å distance in the organic cations are close to respect to the C—NH₃, 1.459 (2) Å observed in the crystal structure of 2,3-dimethylaniliniumchloride (Dai & Chen, 2010). Moreover the organic group moiety geometrical features shows the C—C—C and C—C—N angles are in the range usually found for this compound (Abid et al., 2007). The N—H···Cl and O—H···Cl hydrogen bond lengths are in the ranges of 2.21 (2)–2.41 (2) Å and 2.348 (18)–2.39 (2) Å, respectively. The organic species interact also with a strong N—H···O hydrogen bond with H···O separation of 1.83 (3) Å. Hydrogen bonds, electrostatic and van der Waals interactions participate to the cohesion of the three-dimensional network and add stability to this compound.

Experimental

An initial solution of 2,3-dimetylaniline was made in 10 ml methanol. To a crystallizer vessel initial solution was added in a 1:1 molar ratio of concentrated hydrochloric acid dropwise. For salt formation partnership, the obtained solution was stirrer for 1 h and then gradually evaporated in room temperature. Crystals of the title salt were removed from the crystallizer vessel to yield colorless crystals of the title salt, suitable for X-ray analysis.

Refinement

The H atoms of the protonated nitrogen and water molecule were found in difference Fourier map and refined isotropically. The water H atoms H1W, H2W were refined with distance restraints of O—H 0.844 (2), 0.860 (2) Å, respectively. The C—H protons were positioned geometrically and refined as riding atoms with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic C—H groups and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl group.

Figures

Fig. 1.

The asymmetric unit of title compound with displacement ellipsoids drawn at 50% probability level.

Fig. 2.

The packing diagram of the title compound showing the intermolecular N—H···O, N—H···Cl and O—H···Cl hydrogen bonds as dashed lines.

Crystal data

C8H12N+·Cl−·H2O	F(000) = 376.0
Mr = 175.65	Dx = 1.191 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2616 reflections
a = 7.4910 (15) Å	θ = 2.3–29.2°
b = 7.5031 (15) Å	µ = 0.34 mm−1
c = 17.430 (4) Å	T = 298 K
V = 979.7 (4) Å3	Block, colourless
Z = 4	0.45 × 0.4 × 0.2 mm

Data collection

Stoe IPDS 2T diffractometer	2095 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
graphite	θmax = 29.2°, θmin = 2.3°
Detector resolution: 0.15 pixels mm-1	h = −10→8
rotation method scans	k = −10→8
4645 measured reflections	l = −23→20
2616 independent reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104	w = 1/[σ2(Fo2) + (0.0572P)2 + 0.048P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2616 reflections	Δρmax = 0.20 e Å−3
122 parameters	Δρmin = −0.16 e Å−3
2 restraints	Absolute structure: Flack (1983), with 1088 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.13 (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
O1	0.3476 (2)	0.2420 (2)	0.73382 (12)	0.0800 (5)
Cl1	0.76090 (5)	0.33674 (6)	0.75167 (3)	0.06069 (15)
N1	0.1163 (2)	0.4774 (2)	0.67017 (9)	0.0491 (3)
C2	0.2579 (2)	0.5132 (2)	0.54351 (9)	0.0463 (3)
C1	0.1057 (2)	0.4777 (2)	0.58624 (11)	0.0446 (4)
C6	−0.0577 (3)	0.4395 (3)	0.55285 (12)	0.0621 (5)
H6	−0.1572	0.4147	0.5829	0.075*
C3	0.2418 (3)	0.5139 (2)	0.46329 (11)	0.0571 (4)
C7	0.4338 (3)	0.5486 (4)	0.58231 (14)	0.0649 (5)
H7A	0.4885	0.4375	0.5962	0.097*
H7B	0.4144	0.6187	0.6276	0.097*
H7C	0.5109	0.6123	0.5479	0.097*
C5	−0.0691 (3)	0.4392 (4)	0.47360 (14)	0.0780 (7)
H5	−0.1771	0.4134	0.4497	0.094*
C8	0.4007 (4)	0.5513 (4)	0.41222 (15)	0.0825 (8)
H8A	0.3627	0.5547	0.3596	0.124*
H8B	0.4880	0.4588	0.4187	0.124*
H8C	0.4522	0.6640	0.4259	0.124*
C4	0.0778 (4)	0.4766 (3)	0.43060 (13)	0.0709 (6)
H4	0.0676	0.4771	0.3774	0.085*
H1C	0.021 (3)	0.451 (3)	0.6876 (13)	0.060 (6)*
H1A	0.147 (3)	0.591 (3)	0.6905 (11)	0.052 (5)*
H1B	0.198 (3)	0.400 (4)	0.6859 (13)	0.079 (8)*
H1W	0.331 (4)	0.134 (2)	0.7337 (15)	0.088 (9)*
H2W	0.456 (3)	0.257 (6)	0.7323 (19)	0.131 (13)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0518 (8)	0.0643 (9)	0.1239 (15)	0.0014 (7)	−0.0103 (9)	0.0200 (10)
Cl1	0.0443 (2)	0.0566 (2)	0.0812 (3)	−0.00063 (17)	0.0040 (3)	0.0132 (2)
N1	0.0374 (7)	0.0507 (8)	0.0594 (9)	−0.0041 (6)	0.0022 (6)	−0.0012 (7)
C2	0.0419 (8)	0.0394 (7)	0.0576 (9)	−0.0017 (8)	−0.0004 (8)	0.0003 (6)
C1	0.0398 (7)	0.0380 (8)	0.0561 (9)	−0.0005 (7)	−0.0032 (7)	−0.0018 (7)
C6	0.0409 (8)	0.0708 (12)	0.0747 (12)	−0.0062 (8)	−0.0069 (8)	−0.0036 (10)
C3	0.0653 (11)	0.0487 (9)	0.0572 (10)	−0.0009 (11)	−0.0005 (10)	−0.0004 (7)
C7	0.0406 (9)	0.0825 (14)	0.0716 (12)	−0.0129 (9)	0.0035 (9)	−0.0003 (11)
C5	0.0602 (12)	0.0918 (17)	0.0822 (15)	−0.0073 (12)	−0.0260 (11)	−0.0093 (13)
C8	0.0918 (18)	0.0905 (18)	0.0652 (13)	−0.0146 (15)	0.0186 (13)	0.0035 (14)
C4	0.0820 (15)	0.0731 (14)	0.0576 (12)	−0.0029 (12)	−0.0156 (10)	−0.0011 (10)

Geometric parameters (Å, °)

O1—H1W	0.820 (17)	C3—C4	1.383 (3)
O1—H2W	0.820 (18)	C3—C8	1.512 (3)
N1—C1	1.465 (2)	C7—H7A	0.9600
N1—H1C	0.80 (2)	C7—H7B	0.9600
N1—H1A	0.95 (2)	C7—H7C	0.9600
N1—H1B	0.89 (3)	C5—C4	1.361 (3)
C2—C1	1.388 (2)	C5—H5	0.9300
C2—C3	1.404 (2)	C8—H8A	0.9600
C2—C7	1.505 (3)	C8—H8B	0.9600
C1—C6	1.385 (2)	C8—H8C	0.9600
C6—C5	1.384 (3)	C4—H4	0.9300
C6—H6	0.9300
H1W—O1—H2W	107 (4)	C2—C7—H7A	109.5
C1—N1—H1C	109.4 (16)	C2—C7—H7B	109.5
C1—N1—H1A	112.5 (11)	H7A—C7—H7B	109.5
H1C—N1—H1A	107 (2)	C2—C7—H7C	109.5
C1—N1—H1B	110.2 (15)	H7A—C7—H7C	109.5
H1C—N1—H1B	110 (2)	H7B—C7—H7C	109.5
H1A—N1—H1B	108 (2)	C4—C5—C6	120.0 (2)
C1—C2—C3	117.70 (16)	C4—C5—H5	120.0
C1—C2—C7	120.81 (15)	C6—C5—H5	120.0
C3—C2—C7	121.49 (16)	C3—C8—H8A	109.5
C6—C1—C2	122.69 (18)	C3—C8—H8B	109.5
C6—C1—N1	117.83 (17)	H8A—C8—H8B	109.5
C2—C1—N1	119.47 (15)	C3—C8—H8C	109.5
C5—C6—C1	118.3 (2)	H8A—C8—H8C	109.5
C5—C6—H6	120.8	H8B—C8—H8C	109.5
C1—C6—H6	120.8	C5—C4—C3	122.2 (2)
C4—C3—C2	119.08 (19)	C5—C4—H4	118.9
C4—C3—C8	119.6 (2)	C3—C4—H4	118.9
C2—C3—C8	121.29 (19)
C3—C2—C1—C6	1.5 (3)	C7—C2—C3—C4	178.6 (2)
C7—C2—C1—C6	−178.15 (18)	C1—C2—C3—C8	−180.0 (2)
C3—C2—C1—N1	−179.41 (16)	C7—C2—C3—C8	−0.3 (3)
C7—C2—C1—N1	0.9 (3)	C1—C6—C5—C4	−0.3 (4)
C2—C1—C6—C5	−0.8 (3)	C6—C5—C4—C3	0.7 (4)
N1—C1—C6—C5	−179.9 (2)	C2—C3—C4—C5	0.0 (4)
C1—C2—C3—C4	−1.1 (3)	C8—C3—C4—C5	178.9 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1i	0.95 (2)	2.21 (2)	3.1581 (17)	172.6 (17)
N1—H1B···O1	0.89 (3)	1.83 (3)	2.711 (2)	170 (2)
N1—H1C···Cl1ii	0.80 (2)	2.41 (2)	3.1964 (17)	171 (2)
O1—H1W···Cl1iii	0.82 (2)	2.35 (2)	3.1578 (19)	169 (3)
O1—H2W···Cl1	0.82 (2)	2.39 (2)	3.1920 (18)	168 (4)

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z+3/2.