2-Amino­anilinium 2-chloro­acetate

Abstract

In the crystal structure of the title compound, C₆H₉N₂ ⁺·ClCH₂COO⁻, prepared by the reaction of OPDA (orthophenelynediamine) with chloro­acetic ­acid, N—H⋯O hydrogen bonds generate ladder-like chains and very weak inter­molecular C—H⋯Cl hydrogen-bonding inter­actions between the anions and cations lead to a supra­molecular network. C—H⋯O inter­actions also occur.

Related literature

For hydrogen bonding with chlorine, see: Brammer et al. (2008 ▶); Metrangolo et al. (2006 ▶, 2009 ▶). For ladder-like networks, see: Kinbara, Hashimoto et al. (1996 ▶); Kinbara, Kai et al. (1996 ▶).

Experimental

Crystal data

• C₆H₉N₂ ⁺·C₂H₂ClO₂ ⁻

• M _r = 202.64

• Monoclinic,

• a = 11.371 (3) Å

• b = 4.4852 (11) Å

• c = 20.115 (4) Å

• β = 110.439 (12)°

• V = 961.3 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.37 mm⁻¹

• T = 298 K

• 0.36 × 0.20 × 0.16 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.879, T _max = 0.944

• 9366 measured reflections

• 1922 independent reflections

• 1651 reflections with I > 2σ(I)

• R _int = 0.025

Refinement

• R[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 0.137

• S = 1.09

• 1922 reflections

• 126 parameters

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

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

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
N1—H1C⋯O2i	0.90	1.88	2.777 (2)	173
N1—H1B⋯O2ii	0.94	1.82	2.763 (2)	173
N2—H2B⋯O1	0.87	2.16	3.004 (3)	163
C4—H4⋯O1iii	0.93	2.66	3.527 (3)	156
C3—H3⋯Cl1iv	0.93	3.24	3.985 (3)	138
N2—H2A⋯N2iii	0.81	2.77	3.587 (4)	179
C8—H8A⋯Cl1v	0.90 (3)	3.10 (3)	3.878 (3)	146 (3)
C8—H8B⋯O1vi	0.99 (4)	2.71 (4)	3.491 (4)	136 (3)

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

supplementary crystallographic information

Comment

We have reported here the synthesis and structural characterization of a hitherto unknown organic ion pair compound 1, consisting of orthophenylenediammonium cation and chloroacetate anion, that provides a good supramolecular information. The ladder-type one-dimensional chainlike arrangement has been generated because of N—H···O hydrogen bonding interaction in the crystal of compound 1, as shown in Fig. 3.

Experimental

OPDA (Orthophenelynediamine)(0.108 g, 1 mmol) was dissolved in 20 ml of acetonitrile solution and which was added the solution of 25 ml of methanol containing chloroaceticacid (0.23 g, 1 mmol); this reaction mixture was stirred for 5 min and kept for crystalization at room temperature. Colorless needle-like crystals were formed after 3 days (yield: 0.145 g, 72% based on OPDA).

Refinement

All H atoms were found on difference maps, with C—H=0.93 Å and included in the final cycles of refinement using a riding model, with U_iso(H)=1.2Ueq(C)

Figures

Fig. 1.

ORTEP diagram of the compound 1 (Thermal ellipsoids are at 50% probability level).

Fig. 2.

Interactions of C—H···cl in the compound 1 give rise to diverse supramolecular network and all the inetractions arround the cation and anion respectively with symetry codes All the symetry codes for hyderogen bonding were written in the Table 1

Fig. 3.

The ladder-type one-dimensional chainlike arrangement generated by N—H···O hydrogen bonding interactions.

Fig. 4.

Hydrogen bonding situation around the cation.

Fig. 5.

Hydrogen bonding situation around the anion.

Fig. 6.

The formation of the title compound.

Crystal data

C6H9N2+·C2H2ClO2−	F(000) = 424
Mr = 202.64	Dx = 1.400 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5050 reflections
a = 11.371 (3) Å	θ = 2.3–26.1°
b = 4.4852 (11) Å	µ = 0.37 mm−1
c = 20.115 (4) Å	T = 298 K
β = 110.439 (12)°	Needle, colorless
V = 961.3 (4) Å3	0.36 × 0.20 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	1922 independent reflections
Radiation source: fine-focus sealed tube	1651 reflections with I > 2σ(I)
graphite	Rint = 0.025
phi and ω scans	θmax = 26.2°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −14→14
Tmin = 0.879, Tmax = 0.944	k = −5→5
9366 measured reflections	l = −24→24

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0676P)2 + 0.3616P] where P = (Fo2 + 2Fc2)/3
1922 reflections	(Δ/σ)max = 0.001
126 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.29 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
N1	0.38338 (15)	0.3513 (3)	0.89834 (8)	0.0425 (4)
H1A	0.4696	0.3585	0.9056	0.051*
H1B	0.3687	0.1914	0.9249	0.051*
H1C	0.3625	0.5114	0.9189	0.051*
N2	0.4570 (2)	−0.0303 (6)	0.80725 (13)	0.0819 (7)
H2A	0.4758	−0.1428	0.7809	0.098*
H2B	0.5201	0.0394	0.8428	0.098*
C1	0.1923 (2)	0.4640 (5)	0.79778 (11)	0.0539 (5)
H1	0.1695	0.5954	0.8269	0.065*
C2	0.1128 (2)	0.4187 (6)	0.72902 (12)	0.0641 (6)
H2	0.0360	0.5167	0.7117	0.077*
C3	0.1485 (3)	0.2267 (6)	0.68631 (12)	0.0655 (7)
H3	0.0950	0.1932	0.6400	0.079*
C4	0.2628 (2)	0.0833 (6)	0.71141 (12)	0.0630 (6)
H4	0.2861	−0.0422	0.6813	0.076*
C5	0.3443 (2)	0.1229 (5)	0.78112 (11)	0.0499 (5)
C6	0.30556 (18)	0.3157 (4)	0.82373 (10)	0.0422 (4)
Cl1	0.88856 (6)	−0.20415 (18)	1.05309 (4)	0.0787 (3)
O1	0.63853 (15)	0.3221 (4)	0.92605 (9)	0.0630 (5)
O2	0.65904 (16)	0.1467 (3)	1.03239 (8)	0.0563 (4)
C7	0.69161 (19)	0.1690 (4)	0.97966 (10)	0.0453 (5)
C8	0.8017 (2)	−0.0074 (7)	0.97533 (13)	0.0612 (6)
H8A	0.855 (3)	0.122 (8)	0.9661 (16)	0.090 (10)*
H8B	0.767 (3)	−0.161 (9)	0.938 (2)	0.118 (13)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0520 (9)	0.0381 (8)	0.0424 (8)	−0.0007 (7)	0.0229 (7)	−0.0024 (6)
N2	0.0660 (13)	0.0873 (16)	0.0926 (16)	0.0075 (12)	0.0278 (12)	−0.0425 (13)
C1	0.0615 (13)	0.0508 (12)	0.0534 (12)	0.0014 (10)	0.0250 (10)	0.0040 (9)
C2	0.0615 (13)	0.0702 (15)	0.0563 (13)	0.0000 (12)	0.0150 (11)	0.0151 (12)
C3	0.0715 (15)	0.0782 (16)	0.0434 (12)	−0.0223 (13)	0.0160 (11)	0.0026 (11)
C4	0.0819 (17)	0.0650 (14)	0.0515 (12)	−0.0217 (13)	0.0351 (12)	−0.0159 (11)
C5	0.0571 (12)	0.0476 (11)	0.0528 (11)	−0.0117 (9)	0.0290 (10)	−0.0088 (9)
C6	0.0515 (11)	0.0379 (9)	0.0421 (10)	−0.0073 (8)	0.0228 (8)	0.0004 (7)
Cl1	0.0550 (4)	0.0965 (6)	0.0777 (5)	0.0095 (3)	0.0146 (3)	0.0200 (4)
O1	0.0545 (9)	0.0749 (11)	0.0602 (10)	0.0028 (8)	0.0207 (8)	0.0171 (8)
O2	0.0803 (10)	0.0421 (8)	0.0640 (9)	−0.0001 (7)	0.0472 (8)	−0.0018 (6)
C7	0.0480 (11)	0.0445 (10)	0.0471 (11)	−0.0094 (8)	0.0214 (9)	−0.0046 (8)
C8	0.0584 (13)	0.0771 (17)	0.0549 (13)	0.0100 (12)	0.0285 (11)	0.0064 (12)

Geometric parameters (Å, °)

N1—C6	1.461 (2)	C3—C4	1.378 (4)
N1—H1A	0.9402	C3—H3	0.9300
N1—H1B	0.9425	C4—C5	1.396 (3)
N1—H1C	0.9015	C4—H4	0.9300
N2—C5	1.385 (3)	C5—C6	1.393 (3)
N2—H2A	0.8138	Cl1—C8	1.767 (3)
N2—H2B	0.8747	O1—C7	1.243 (3)
C1—C2	1.378 (3)	O2—C7	1.244 (2)
C1—C6	1.380 (3)	C7—C8	1.509 (3)
C1—H1	0.9300	C8—H8A	0.90 (3)
C2—C3	1.374 (4)	C8—H8B	0.99 (4)
C2—H2	0.9300
C6—N1—H1A	112.9	C3—C4—C5	121.3 (2)
C6—N1—H1B	109.6	C3—C4—H4	119.4
H1A—N1—H1B	108.6	C5—C4—H4	119.4
C6—N1—H1C	113.4	N2—C5—C6	121.6 (2)
H1A—N1—H1C	109.2	N2—C5—C4	121.3 (2)
H1B—N1—H1C	102.6	C6—C5—C4	117.1 (2)
C5—N2—H2A	118.7	C1—C6—C5	121.37 (19)
C5—N2—H2B	121.3	C1—C6—N1	119.11 (17)
H2A—N2—H2B	115.2	C5—C6—N1	119.45 (18)
C2—C1—C6	120.5 (2)	O1—C7—O2	125.8 (2)
C2—C1—H1	119.8	O1—C7—C8	113.63 (18)
C6—C1—H1	119.8	O2—C7—C8	120.5 (2)
C3—C2—C1	119.1 (2)	C7—C8—Cl1	115.41 (16)
C3—C2—H2	120.4	C7—C8—H8A	107 (2)
C1—C2—H2	120.4	Cl1—C8—H8A	107 (2)
C2—C3—C4	120.7 (2)	C7—C8—H8B	107 (2)
C2—C3—H3	119.7	Cl1—C8—H8B	106 (2)
C4—C3—H3	119.7	H8A—C8—H8B	114 (3)
C6—C1—C2—C3	−0.8 (3)	N2—C5—C6—C1	−178.9 (2)
C1—C2—C3—C4	−0.7 (4)	C4—C5—C6—C1	−0.9 (3)
C2—C3—C4—C5	1.5 (4)	N2—C5—C6—N1	−1.8 (3)
C3—C4—C5—N2	177.4 (2)	C4—C5—C6—N1	176.18 (18)
C3—C4—C5—C6	−0.7 (3)	O1—C7—C8—Cl1	174.88 (19)
C2—C1—C6—C5	1.6 (3)	O2—C7—C8—Cl1	−7.3 (3)
C2—C1—C6—N1	−175.42 (18)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2i	0.90	1.88	2.777 (2)	173
N1—H1B···O2ii	0.94	1.82	2.763 (2)	173
N2—H2B···O1	0.87	2.16	3.004 (3)	163
C4—H4···O1iii	0.93	2.66	3.527 (3)	156
C3—H3···Cl1iv	0.93	3.24	3.985 (3)	138
N2—H2A···N2iii	0.81	2.77	3.587 (4)	179
C8—H8A···Cl1v	0.90 (3)	3.10 (3)	3.878 (3)	146 (3)
C8—H8B···O1vi	0.99 (4)	2.71 (4)	3.491 (4)	136 (3)

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