2-Amino­anilinium 2-chloro­acetate

Rao, A.S.; Tripuramallu, B.K.; Ravada, K.; Das, S.K.

doi:10.1107/S1600536810024554

organic compounds

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Volume 66| Part 8| August 2010| Page o1945

https://doi.org/10.1107/S1600536810024554

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2-Aminoanilinium 2-chloroacetate

A. Srinivasa Rao,^a Bharat Kumar Tripuramallu,^a Kishore Ravada ^a and Samar K. Das ^a ^*

^aSchool of Chemistry, University of Hyderabad, Hyderabad 500 046, India
^*Correspondence e-mail: skdsc@uohyd.ernet.in

(Received 28 May 2010; accepted 23 June 2010; online 7 July 2010)

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, P 2₁ /c
a = 11.371 (3) Å
b = 4.4852 (11) Å
c = 20.115 (4) Å
β = 110.439 (12)°
V = 961.3 (4) Å³
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[F² > 2σ(F²)] = 0.047
wR(F²) = 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

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⋯Cl1^iv	0.93	3.24	3.985 (3)	138
N2—H2A⋯N2ⁱⁱⁱ	0.81	2.77	3.587 (4)	179
C8—H8A⋯Cl1^v	0.90 (3)	3.10 (3)	3.878 (3)	146 (3)
C8—H8B⋯O1^vi	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) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x-1, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) -x+2, -y, -z+2; (vi) x, y-1, z.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810024554/ds2035sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810024554/ds2035Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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).

Structure description top

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).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SMAIT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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 (Sheldrick, 2008).

Figures top

	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.

2-Aminoanilinium 2-chloroacetate top

Crystal data top

C₆H₉N₂⁺·C₂H₂ClO₂⁻	F(000) = 424
M_r = 202.64	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0676P)² + 0.3616P] where P = (F_o² + 2F_c²)/3
1922 reflections	(Δ/σ)_max = 0.001
126 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₆H₉N₂⁺·C₂H₂ClO₂⁻	V = 961.3 (4) Å³
M_r = 202.64	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.371 (3) Å	µ = 0.37 mm⁻¹
b = 4.4852 (11) Å	T = 298 K
c = 20.115 (4) Å	0.36 × 0.20 × 0.16 mm
β = 110.439 (12)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1922 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	1651 reflections with I > 2σ(I)
T_min = 0.879, T_max = 0.944	R_int = 0.025
9366 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.33 e Å⁻³
1922 reflections	Δρ_min = −0.29 e Å⁻³
126 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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···Cl1^iv	0.93	3.24	3.985 (3)	138
N2—H2A···N2ⁱⁱⁱ	0.81	2.77	3.587 (4)	179
C8—H8A···Cl1^v	0.90 (3)	3.10 (3)	3.878 (3)	146 (3)
C8—H8B···O1^vi	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.

Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₂H₂ClO₂⁻
M_r	202.64
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.371 (3), 4.4852 (11), 20.115 (4)
β (°)	110.439 (12)
V (Å³)	961.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.36 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.879, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	9366, 1922, 1651
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.621

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.137, 1.09
No. of reflections	1922
No. of parameters	126
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.29

Computer programs: SMART (Bruker, 2003), SMAIT (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2ⁱ	0.90	1.88	2.777 (2)	172.7
N1—H1B···O2ⁱⁱ	0.94	1.82	2.763 (2)	173.2
N2—H2B···O1	0.87	2.16	3.004 (3)	163.0
C4—H4···O1ⁱⁱⁱ	0.93	2.66	3.527 (3)	155.9
C3—H3···Cl1^iv	0.93	3.24	3.985 (3)	138.3
N2—H2A···N2ⁱⁱⁱ	0.81	2.77	3.587 (4)	179.1
C8—H8A···Cl1^v	0.90 (3)	3.10 (3)	3.878 (3)	146 (3)
C8—H8B···O1^vi	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.

Acknowledgements

We thank the Department of Science and Technology, Government of India, for the National X-ray Diffractometer facility at the University of Hyderabad. We acknowledge the Department of Science and Technology, Government of India, for financial support (project No. SR/S1/IC-23/2007). ASR and RK are grateful to the CSIR, Government of India, and BKT thanks the UGC, Government of India, for their fellowships. We also thank Dr A. R. Bijju, School of Chemistry, University of Hyderabad, for helpful discussions.

References

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