Crystal structure of 3,4-di­chloro­anilinium hydrogen phthalate

Abstract

In the title salt, C₆H₆Cl₂N⁺·C₈H₅O₄ ⁻, the carb­oxy­lic acid and carboxyl­ate groups of the anion form dihedral angles of 20.79 (19) and 74.76 (14)°, respectively, with the plane of the benzene ring. In the crystal, mol­ecules are assembled into a two-dimensional polymeric network parallel to (100) via N—H⋯O and O—H⋯O hydrogen bonds. In addition, within the layer, there are π–π stacking inter­actions between the benzene rings of the cation and the anion [centroid–centroid distance = 3.6794 (17) Å]. A weak C—H⋯O interaction is also observed.

Related literature  

For related structures, see: Jagan & Sivakumar (2009 ▸, 2011 ▸); Kozma et al. (1994 ▸); Liang et al. (2011 ▸); Liu (2012 ▸).

Experimental  

Crystal data  

• C₆H₆Cl₂N⁺·C₈H₅O₄ ⁻

• M _r = 328.14

• Monoclinic,

• a = 29.694 (5) Å

• b = 7.7536 (13) Å

• c = 13.125 (2) Å

• β = 98.673 (12)°

• V = 2987.3 (9) ų

• Z = 8

• Mo Kα radiation

• μ = 0.45 mm⁻¹

• T = 296 K

• 0.34 × 0.28 × 0.16 mm

Data collection  

• Bruker Kappa APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005 ▸) T _min = 0.860, T _max = 0.935

• 11652 measured reflections

• 3248 independent reflections

• 1849 reflections with I > 2σ(I)

• R _int = 0.051

Refinement  

• R[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 0.133

• S = 1.02

• 3248 reflections

• 192 parameters

• H-atom parameters constrained

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸) and PLATON.

Supplementary Material

CCDC reference: 1403731

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O2H2O4i	0.82	1.77	2.583(2)	171
N1H1AO4	0.89	1.98	2.848(3)	164
N1H1BO3ii	0.89	1.85	2.713(3)	163
N1H1CO3i	0.89	1.90	2.774(3)	165
C13H13O4iii	0.93	2.54	3.328(4)	143

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

supplementary crystallographic information

S1. Comment

The crystal structures of 4-bromoanilinium hydrogen phthalate (Liang, 2011), (R,S)-α-phenylethylammonium hydrogen phthalate (Kozma et al., 1994), 4-chloroanilinium hydrogen phthalate (Jagan & Sivakumar, 2009), 3-hydroxyanilinium hydrogen phthalate (Jagan & Sivakumar, 2009), 2-hydroxyanilinium hydrogen phthalate (Jagan & Sivakumar, 2009), 3-Methylanilinium 2-carboxybenzoate (Liu, 2012) and 4-ethoxyanilinium 2- carboxybenzoate (Jagan & Sivakumar, 2011) have been published which are related to the title compound (I, Fig. 1). (I) is synthesized for the study of co-crystallization.

In (I) the benzene ring A (C2—C7) of the phathalate anion is planar with r.m.s. deviation of 0.0024 Å. The carboxylic B (C1/O1/O2) and carboxylate C (C8/O3/O4) groups are oriented at a dihedral angle of 20.79 (19)° and 74.76 (14)°, respectively, with the parent benzene ring A. The molecules form a two dimensional polymeric network parallel to (100) due to N—H···O and O—H···O hydrogen bonds (Table 1, Fig.2). There exist π···π interaction between Cg11···Cg21ⁱ [i = x, y, z] with centroid-centroid distance of 3.6794 (17) Å, where Cg1 and Cg2 are the centroids of the benzene rings A and E (C9—C14). The topology of two-dimensional hydrogen-bond network in the title compound is the same as in 4-chloroanilinium salt (Jagan & Sivakumar, 2009).

S2. Experimental

Equimolar quantities of phathalic acid (0.831 g, 5 mmol) and 3,4-dichloroaniline (0.810 g, 5 mmol) were refluxed in 20 ml of methanol for 2 h. The solution was kept at room temperature and colorless plates appeared after two days (m.p. 422–423 K).

S3. Refinement

The H atoms were positioned geometrically (C–H = 0.93 Å, N–H = 0.89 Å, O—H = 0.82 Å) and refined as riding with U_iso(H) = xU_eq (C, N, O), where x = 1.5 for NH₃ and hydroxy and x =1.2 for aromatic H-atoms.

Figures

Fig. 1.

View of the title compound with the atom numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. H-atoms are shown as small circles of arbitrary radii.

Fig. 2.

The packing (PLATON; Spek, 2009) of two-dimensional (100) polymeric networks.

Fig. 3.

Hydrogen bonds within (100) layer.

Crystal data

C6H6Cl2N+·C8H5O4−	F(000) = 1344
Mr = 328.14	Dx = 1.459 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 29.694 (5) Å	Cell parameters from 1849 reflections
b = 7.7536 (13) Å	θ = 2.8–27.0°
c = 13.125 (2) Å	µ = 0.45 mm−1
β = 98.673 (12)°	T = 296 K
V = 2987.3 (9) Å3	Plate, colorless
Z = 8	0.34 × 0.28 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	3248 independent reflections
Radiation source: fine-focus sealed tube	1849 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 7.80 pixels mm-1	θmax = 27.0°, θmin = 2.8°
ω scans	h = −37→37
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→9
Tmin = 0.860, Tmax = 0.935	l = −15→16
11652 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0503P)2 + 2.3478P] where P = (Fo2 + 2Fc2)/3
3248 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

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	0.21968 (8)	0.5928 (3)	0.41451 (18)	0.0727 (7)
O2	0.23502 (6)	0.8002 (2)	0.30759 (13)	0.0427 (5)
H2	0.2590	0.7471	0.3096	0.064*
O3	0.21509 (6)	1.1573 (2)	0.37561 (12)	0.0417 (5)
O4	0.19151 (5)	1.1301 (2)	0.20757 (12)	0.0377 (4)
C1	0.20865 (9)	0.7204 (4)	0.3646 (2)	0.0416 (7)
C2	0.16278 (8)	0.8021 (4)	0.35827 (18)	0.0379 (6)
C3	0.15350 (8)	0.9708 (4)	0.32373 (16)	0.0340 (6)
C4	0.10931 (9)	1.0324 (4)	0.3140 (2)	0.0476 (7)
H4	0.1029	1.1443	0.2907	0.057*
C5	0.07466 (10)	0.9285 (5)	0.3386 (2)	0.0575 (9)
H5	0.0451	0.9709	0.3316	0.069*
C6	0.08358 (10)	0.7643 (5)	0.3731 (2)	0.0654 (10)
H6	0.0601	0.6957	0.3900	0.078*
C7	0.12732 (10)	0.6995 (4)	0.3830 (2)	0.0533 (8)
H7	0.1332	0.5872	0.4063	0.064*
C8	0.18979 (8)	1.0937 (3)	0.30026 (18)	0.0324 (6)
Cl1	0.03331 (3)	0.83295 (14)	0.06616 (8)	0.0831 (4)
Cl2	0.04230 (3)	0.44073 (16)	0.13559 (9)	0.0970 (4)
N1	0.20521 (7)	0.8466 (3)	0.07778 (14)	0.0374 (5)
H1A	0.2041	0.9466	0.1106	0.056*
H1B	0.2057	0.8662	0.0111	0.056*
H1C	0.2303	0.7895	0.1043	0.056*
C9	0.16540 (8)	0.7446 (4)	0.08969 (16)	0.0334 (6)
C10	0.12353 (8)	0.8247 (4)	0.07404 (18)	0.0396 (6)
H10	0.1211	0.9403	0.0551	0.047*
C11	0.08537 (9)	0.7318 (4)	0.0867 (2)	0.0496 (8)
C12	0.08933 (9)	0.5597 (5)	0.1155 (2)	0.0530 (8)
C13	0.13137 (10)	0.4807 (4)	0.1296 (2)	0.0526 (8)
H13	0.1339	0.3649	0.1480	0.063*
C14	0.16975 (9)	0.5740 (4)	0.1163 (2)	0.0440 (7)
H14	0.1982	0.5214	0.1253	0.053*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0725 (15)	0.0638 (16)	0.0883 (17)	0.0207 (12)	0.0337 (12)	0.0404 (14)
O2	0.0415 (10)	0.0463 (12)	0.0432 (10)	0.0097 (9)	0.0159 (9)	0.0077 (9)
O3	0.0421 (10)	0.0544 (13)	0.0293 (9)	−0.0072 (9)	0.0077 (8)	−0.0073 (9)
O4	0.0425 (10)	0.0423 (12)	0.0297 (9)	−0.0029 (8)	0.0099 (7)	0.0012 (8)
C1	0.0494 (16)	0.0422 (18)	0.0352 (14)	0.0016 (14)	0.0130 (12)	0.0024 (13)
C2	0.0431 (15)	0.0443 (17)	0.0289 (13)	−0.0027 (13)	0.0134 (11)	0.0022 (12)
C3	0.0350 (13)	0.0466 (18)	0.0215 (12)	−0.0019 (12)	0.0081 (10)	−0.0032 (11)
C4	0.0389 (15)	0.060 (2)	0.0461 (16)	0.0032 (14)	0.0129 (12)	0.0022 (14)
C5	0.0377 (16)	0.079 (3)	0.0589 (19)	−0.0002 (16)	0.0161 (14)	0.0029 (18)
C6	0.0465 (18)	0.087 (3)	0.067 (2)	−0.0160 (19)	0.0239 (15)	0.001 (2)
C7	0.0604 (19)	0.054 (2)	0.0493 (17)	−0.0114 (16)	0.0211 (14)	0.0061 (15)
C8	0.0333 (13)	0.0358 (15)	0.0297 (13)	0.0046 (11)	0.0103 (10)	−0.0041 (11)
Cl1	0.0388 (4)	0.1064 (9)	0.1041 (7)	0.0154 (5)	0.0106 (4)	0.0168 (6)
Cl2	0.0625 (6)	0.1052 (9)	0.1236 (9)	−0.0304 (6)	0.0149 (5)	0.0246 (7)
N1	0.0389 (12)	0.0462 (15)	0.0275 (10)	0.0019 (10)	0.0061 (9)	−0.0017 (10)
C9	0.0376 (14)	0.0429 (17)	0.0205 (11)	−0.0011 (12)	0.0069 (10)	−0.0035 (11)
C10	0.0409 (15)	0.0439 (18)	0.0344 (13)	0.0058 (13)	0.0074 (11)	0.0020 (12)
C11	0.0374 (15)	0.067 (2)	0.0450 (16)	0.0050 (15)	0.0073 (12)	0.0014 (15)
C12	0.0451 (17)	0.065 (2)	0.0493 (17)	−0.0126 (16)	0.0076 (13)	0.0005 (16)
C13	0.060 (2)	0.0458 (19)	0.0521 (17)	−0.0053 (16)	0.0104 (14)	0.0020 (15)
C14	0.0440 (16)	0.0467 (19)	0.0412 (15)	0.0064 (14)	0.0057 (12)	−0.0002 (13)

Geometric parameters (Å, º)

O1—C1	1.204 (3)	C7—H7	0.9300
O2—C1	1.316 (3)	Cl1—C11	1.718 (3)
O2—H2	0.8200	Cl2—C12	1.726 (3)
O3—C8	1.250 (3)	N1—C9	1.450 (3)
O4—C8	1.257 (3)	N1—H1A	0.8900
C1—C2	1.493 (4)	N1—H1B	0.8900
C2—C7	1.396 (4)	N1—H1C	0.8900
C2—C3	1.398 (4)	C9—C14	1.369 (4)
C3—C4	1.384 (3)	C9—C10	1.377 (3)
C3—C8	1.505 (3)	C10—C11	1.374 (4)
C4—C5	1.383 (4)	C10—H10	0.9300
C4—H4	0.9300	C11—C12	1.388 (5)
C5—C6	1.364 (5)	C12—C13	1.378 (4)
C5—H5	0.9300	C13—C14	1.383 (4)
C6—C7	1.380 (4)	C13—H13	0.9300
C6—H6	0.9300	C14—H14	0.9300
C1—O2—H2	109.5	C9—N1—H1A	109.5
O1—C1—O2	124.0 (3)	C9—N1—H1B	109.5
O1—C1—C2	123.3 (2)	H1A—N1—H1B	109.5
O2—C1—C2	112.6 (2)	C9—N1—H1C	109.5
C7—C2—C3	119.3 (3)	H1A—N1—H1C	109.5
C7—C2—C1	117.3 (3)	H1B—N1—H1C	109.5
C3—C2—C1	123.2 (2)	C14—C9—C10	121.5 (2)
C4—C3—C2	119.4 (2)	C14—C9—N1	120.5 (2)
C4—C3—C8	117.4 (3)	C10—C9—N1	118.1 (2)
C2—C3—C8	123.1 (2)	C11—C10—C9	119.2 (3)
C5—C4—C3	120.4 (3)	C11—C10—H10	120.4
C5—C4—H4	119.8	C9—C10—H10	120.4
C3—C4—H4	119.8	C10—C11—C12	120.0 (3)
C6—C5—C4	120.5 (3)	C10—C11—Cl1	118.7 (3)
C6—C5—H5	119.8	C12—C11—Cl1	121.3 (2)
C4—C5—H5	119.8	C13—C12—C11	120.1 (3)
C5—C6—C7	120.3 (3)	C13—C12—Cl2	118.7 (3)
C5—C6—H6	119.9	C11—C12—Cl2	121.2 (2)
C7—C6—H6	119.9	C12—C13—C14	119.9 (3)
C6—C7—C2	120.2 (3)	C12—C13—H13	120.1
C6—C7—H7	119.9	C14—C13—H13	120.1
C2—C7—H7	119.9	C9—C14—C13	119.3 (3)
O3—C8—O4	124.7 (2)	C9—C14—H14	120.3
O3—C8—C3	116.8 (2)	C13—C14—H14	120.3
O4—C8—C3	118.4 (2)
O1—C1—C2—C7	−20.8 (4)	C2—C3—C8—O3	−74.5 (3)
O2—C1—C2—C7	157.5 (2)	C4—C3—C8—O4	−74.4 (3)
O1—C1—C2—C3	162.9 (3)	C2—C3—C8—O4	108.1 (3)
O2—C1—C2—C3	−18.9 (4)	C14—C9—C10—C11	0.8 (4)
C7—C2—C3—C4	−0.5 (4)	N1—C9—C10—C11	−178.8 (2)
C1—C2—C3—C4	175.8 (2)	C9—C10—C11—C12	0.4 (4)
C7—C2—C3—C8	176.9 (2)	C9—C10—C11—Cl1	−179.63 (18)
C1—C2—C3—C8	−6.8 (4)	C10—C11—C12—C13	−1.3 (4)
C2—C3—C4—C5	0.3 (4)	Cl1—C11—C12—C13	178.8 (2)
C8—C3—C4—C5	−177.2 (2)	C10—C11—C12—Cl2	178.2 (2)
C3—C4—C5—C6	0.2 (4)	Cl1—C11—C12—Cl2	−1.8 (4)
C4—C5—C6—C7	−0.5 (5)	C11—C12—C13—C14	0.9 (4)
C5—C6—C7—C2	0.3 (5)	Cl2—C12—C13—C14	−178.6 (2)
C3—C2—C7—C6	0.2 (4)	C10—C9—C14—C13	−1.2 (4)
C1—C2—C7—C6	−176.3 (3)	N1—C9—C14—C13	178.5 (2)
C4—C3—C8—O3	102.9 (3)	C12—C13—C14—C9	0.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4i	0.82	1.77	2.583 (2)	171
N1—H1A···O4	0.89	1.98	2.848 (3)	164
N1—H1B···O3ii	0.89	1.85	2.713 (3)	163
N1—H1C···O3i	0.89	1.90	2.774 (3)	165
C13—H13···O4iii	0.93	2.54	3.328 (4)	143

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