Crystal structure of 4-amino­benzoic acid–4-methyl­pyridine (1/1)

Kumar, M.K.; Pandi, P.; Sudhahar, S.; Chakkaravarthi, G.; Kumar, R.M.

doi:10.1107/S2056989015000791

organic compounds

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Volume 71| Part 2| February 2015| Pages o125-o126

doi:10.1107/S2056989015000791

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Crystal structure of 4-aminobenzoic acid–4-methylpyridine (1/1)

M. Krishna Kumar,^a P. Pandi,^b S. Sudhahar,^a G. Chakkaravarthi ^c ^* and R. Mohan Kumar ^a ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, ^bDepartment of Physics, Panimalar Engineering College, Chennai 600 123, India, and ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: chakkaravarthi_2005@yahoo.com, mohan66@hotmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 2 January 2015; accepted 14 January 2015; online 21 January 2015)

In the title 1:1 adduct, C₆H₇N·C₇H₇NO₂, the carboxylic acid group is twisted at an angle of 4.32 (18)° with respect to the attached benzene ring. In the crystal, the carboxylic acid group is linked to the pyridine ring by an O—H⋯N hydrogen bond, forming a dimer. The dimers are linked by N—H⋯O hydrogen bonds, generating (010) sheets.

Keywords: crystal structure; adduct; O—H⋯N and N—H⋯O hydrogen bonds; layered structure.

CCDC reference: 1043592

1. Related literature

For background to pyridine derivatives, see: Tomaru et al. (1991 ). Katritzky et al. (1996 ); Akkurt et al. (2005 ). For related structures, see: Smith & Wermuth (2010 ); Hemamalini & Fun (2010 ); Kannan et al. (2012 ); Thanigaimani et al. (2012 ); Muralidharan et al. (2013 ).

2. Experimental

2.1. Crystal data

C₆H₇N·C₇H₇NO₂
M_r = 230.26
Monoclinic, P c
a = 7.5970 (7) Å
b = 11.6665 (12) Å
c = 7.6754 (8) Å
β = 114.200 (3)°
V = 620.49 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.28 × 0.24 × 0.20 mm

2.2. Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.977, T_max = 0.983
10064 measured reflections
2144 independent reflections
1458 reflections with I > 2σ(I)
R_int = 0.030

2.3. Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.108
S = 1.03
2144 reflections
159 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2ⁱ	0.84 (1)	1.81 (1)	2.644 (3)	177 (4)
N1—H1A⋯O2ⁱⁱ	0.86	2.32	3.049 (3)	142
N1—H1B⋯O2ⁱⁱⁱ	0.86	2.17	3.031 (3)	174
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z-1; (iii) $[x-1, -y, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 1043592

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015000791/hb7348sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015000791/hb7348Isup2.hkl

checkCIF report

Chemical context top

Aminopyridine and its derivatives play an important role in heterocyclic chemistry (Katritzky et al., 1996). Some pyridine derivatives possess nonlinear optical (NLO) properties (Tomaru et al., 1991) and possess antibacterial and antifungal activities (Akkurt et al., 2005). we herewith, report the synthesis and the crystal structure of (I) (Fig. 1).

Structural commentary top

The molecular structure of the title compound (I) is shown in (Fig. 1). It consists of two independent molecules in the assymetric unit. In the 4-aminobenzoic acid molecule, the carboxyl group is twisted at an angle of 4.32 (18)° with respect to the aromatic ring. In the 4-methylpyridine molecule, the pyridine ring (C8—C12/N2) is almost planar [maximum deviation 0.002 (3) Å]. The dihedral angle between the benzene ring (C1—C6) and pyridine ring (C8—C12/N2) is 57.11 (14)°.

Supramolecular features top

In the crystal structure, 4-aminobenzoate and 4-methylpyridine molecules are linked by weak intermolecular O—H···N hydrogen bonds and forms infinite one-dimensional chain along [0 0 1]. The adjacent 4-aminobenzoate molecules are connected by weak intermolecular N—H···O hydrogen bonds, forming R²₂(12) ring motif in a two-dimensional network in the (010) plane (Table 2 & Fig. 2).

Database survey top

Several similar structures containing methylpyridinium and nitrobenzoate molecules have been reported earlier: i.e., 2-Amino-5-methylpyridinium 2-aminobenzoate (Thanigaimani et al., 2012); 2-Amino-5-chloropyridinium 4-aminobenzoate (Kannan et al., 2012); 2-Amino-4-methylpyridinium 2-nitrobenzoate (Muralidharan et al., 2013); 4-Methylpyridinium 2-carboxy-4,5-dichlorobenzoate monohydrate [Smith & Wermuth, (2010)]; 2-Amino-4-methylpyridinium 2-hydroxybenzoate [Hemamalini & Fun (2010)].

Synthesis and crystallization top

Equimolar quantity of 4-methylpyridine and 4-aminobenzoic acid were dissolved in methanol-water mixed solvent and colourless blocks of the title adduct were grown by slow evaporation of the solvents.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The hydrogen atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl) and N—H = 0.86 Å with Uiso(H) = 1.2 Ueq(C or N) or 1.5 Ueq(C) The hydroxyl H atom was located in a difference Fourier map, and refined with Uiso(H) = 1.2 Ueq(O) and distance restraint O—H = 0.82 Å.

Related literature top

For background to pyridine derivatives, see: Tomaru et al. (1991). Katritzky et al. (1996); Akkurt et al. (2005). For related structures, see: Smith & Wermuth (2010); Hemamalini & Fun (2010); Kannan et al. (2012); Thanigaimani et al. (2012); Muralidharan et al. (2013).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2015).

Figures top

Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids for non-H atoms.

4-Aminobenzoic acid–4-methylpyridine (1/1) top

Crystal data top

C₆H₇N·C₇H₇NO₂	F(000) = 244
M_r = 230.26	D_x = 1.232 Mg m⁻³
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 2749 reflections
a = 7.5970 (7) Å	θ = 3.4–21.8°
b = 11.6665 (12) Å	µ = 0.09 mm⁻¹
c = 7.6754 (8) Å	T = 295 K
β = 114.200 (3)°	Block, colourless
V = 620.49 (11) Å³	0.28 × 0.24 × 0.20 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD diffractometer	2144 independent reflections
Radiation source: fine-focus sealed tube	1458 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω and ϕ scan	θ_max = 26.7°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
T_min = 0.977, T_max = 0.983	k = −14→14
10064 measured reflections	l = −9→9

Refinement top

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) = 0.108	w = 1/[σ²(F_o²) + (0.0554P)² + 0.0229P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2144 reflections	Δρ_max = 0.12 e Å⁻³
159 parameters	Δρ_min = −0.13 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (4)

Crystal data top

C₆H₇N·C₇H₇NO₂	V = 620.49 (11) Å³
M_r = 230.26	Z = 2
Monoclinic, Pc	Mo Kα radiation
a = 7.5970 (7) Å	µ = 0.09 mm⁻¹
b = 11.6665 (12) Å	T = 295 K
c = 7.6754 (8) Å	0.28 × 0.24 × 0.20 mm
β = 114.200 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2144 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1458 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.983	R_int = 0.030
10064 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	3 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.12 e Å⁻³
2144 reflections	Δρ_min = −0.13 e Å⁻³
159 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.3693 (4)	0.1034 (2)	0.7149 (4)	0.0567 (6)
C2	0.4434 (4)	0.2029 (2)	0.6722 (4)	0.0591 (7)
H2	0.3671	0.2471	0.5675	0.071*
C3	0.6273 (4)	0.2362 (2)	0.7829 (3)	0.0558 (6)
H3	0.6737	0.3037	0.7529	0.067*
C4	0.7475 (4)	0.1730 (2)	0.9383 (4)	0.0508 (6)
C5	0.6737 (4)	0.0738 (2)	0.9798 (4)	0.0594 (7)
H5	0.7516	0.0294	1.0835	0.071*
C6	0.4892 (4)	0.0392 (2)	0.8724 (4)	0.0629 (7)
H6	0.4429	−0.0278	0.9043	0.076*
C7	0.9416 (4)	0.2104 (2)	1.0596 (4)	0.0587 (7)
C8	0.4371 (5)	0.4546 (2)	1.3188 (5)	0.0729 (8)
H8	0.3567	0.5148	1.3183	0.087*
C9	0.6306 (4)	0.4655 (2)	1.4263 (4)	0.0693 (8)
H9	0.6791	0.5319	1.4967	0.083*
C10	0.7534 (4)	0.3784 (2)	1.4304 (4)	0.0639 (7)
C11	0.6716 (4)	0.2836 (2)	1.3242 (4)	0.0718 (8)
H11	0.7487	0.2220	1.3229	0.086*
C12	0.4767 (5)	0.2790 (3)	1.2196 (4)	0.0766 (9)
H12	0.4249	0.2135	1.1479	0.092*
C13	0.9658 (5)	0.3866 (3)	1.5468 (6)	0.0954 (11)
H13A	1.0310	0.3941	1.4635	0.143*
H13B	1.0099	0.3186	1.6229	0.143*
H13C	0.9930	0.4524	1.6289	0.143*
N1	0.1840 (4)	0.0710 (2)	0.6087 (4)	0.0827 (8)
H1A	0.1113	0.1124	0.5137	0.099*
H1B	0.1395	0.0092	0.6364	0.099*
N2	0.3582 (3)	0.3627 (2)	1.2152 (4)	0.0722 (6)
O1	0.9921 (3)	0.30989 (17)	1.0123 (3)	0.0808 (6)
H1	1.109 (2)	0.324 (3)	1.076 (5)	0.121*
O2	1.0516 (3)	0.15755 (17)	1.1996 (3)	0.0778 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0545 (16)	0.0584 (15)	0.0526 (15)	−0.0071 (14)	0.0173 (13)	−0.0070 (14)
C2	0.0599 (17)	0.0581 (15)	0.0489 (15)	0.0009 (12)	0.0118 (13)	0.0088 (12)
C3	0.0582 (16)	0.0536 (13)	0.0509 (15)	−0.0050 (13)	0.0175 (13)	0.0058 (12)
C4	0.0529 (14)	0.0490 (12)	0.0442 (13)	0.0040 (12)	0.0135 (12)	0.0026 (12)
C5	0.0671 (18)	0.0516 (14)	0.0484 (16)	0.0021 (13)	0.0124 (14)	0.0046 (12)
C6	0.077 (2)	0.0518 (14)	0.0590 (17)	−0.0076 (14)	0.0273 (15)	0.0048 (13)
C7	0.0563 (17)	0.0532 (13)	0.0583 (17)	0.0045 (13)	0.0150 (14)	0.0003 (14)
C8	0.0630 (18)	0.0626 (16)	0.081 (2)	0.0031 (15)	0.0172 (16)	0.0007 (16)
C9	0.068 (2)	0.0617 (17)	0.0665 (19)	−0.0085 (14)	0.0150 (16)	−0.0042 (13)
C10	0.0579 (18)	0.0740 (17)	0.0585 (17)	−0.0045 (16)	0.0225 (14)	0.0063 (15)
C11	0.0680 (19)	0.0723 (18)	0.078 (2)	0.0015 (15)	0.0325 (18)	−0.0048 (16)
C12	0.077 (2)	0.0747 (19)	0.074 (2)	−0.0158 (17)	0.0260 (17)	−0.0171 (16)
C13	0.0604 (19)	0.105 (2)	0.104 (3)	−0.0070 (17)	0.0163 (18)	0.002 (2)
N1	0.0655 (16)	0.0852 (18)	0.0809 (18)	−0.0163 (13)	0.0132 (14)	0.0063 (15)
N2	0.0567 (14)	0.0719 (15)	0.0766 (16)	−0.0059 (13)	0.0157 (12)	−0.0023 (13)
O1	0.0588 (11)	0.0691 (12)	0.0883 (16)	−0.0105 (10)	0.0035 (11)	0.0130 (11)
O2	0.0678 (13)	0.0726 (12)	0.0665 (12)	0.0068 (10)	0.0006 (10)	0.0090 (10)

Geometric parameters (Å, º) top

C1—N1	1.359 (4)	C8—H8	0.9300
C1—C2	1.387 (3)	C9—C10	1.371 (4)
C1—C6	1.397 (4)	C9—H9	0.9300
C2—C3	1.361 (4)	C10—C11	1.363 (4)
C2—H2	0.9300	C10—C13	1.493 (5)
C3—C4	1.380 (3)	C11—C12	1.366 (4)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.379 (3)	C12—N2	1.319 (4)
C4—C7	1.452 (3)	C12—H12	0.9300
C5—C6	1.364 (4)	C13—H13A	0.9600
C5—H5	0.9300	C13—H13B	0.9600
C6—H6	0.9300	C13—H13C	0.9600
C7—O2	1.224 (3)	N1—H1A	0.8600
C7—O1	1.319 (3)	N1—H1B	0.8600
C8—N2	1.323 (3)	O1—H1	0.836 (10)
C8—C9	1.365 (4)

N1—C1—C2	120.8 (2)	C8—C9—C10	119.9 (3)
N1—C1—C6	121.2 (2)	C8—C9—H9	120.0
C2—C1—C6	118.0 (2)	C10—C9—H9	120.0
C3—C2—C1	120.2 (2)	C11—C10—C9	116.6 (3)
C3—C2—H2	119.9	C11—C10—C13	121.7 (3)
C1—C2—H2	119.9	C9—C10—C13	121.7 (3)
C2—C3—C4	122.2 (2)	C10—C11—C12	120.2 (3)
C2—C3—H3	118.9	C10—C11—H11	119.9
C4—C3—H3	118.9	C12—C11—H11	119.9
C5—C4—C3	117.4 (2)	N2—C12—C11	123.4 (3)
C5—C4—C7	120.4 (2)	N2—C12—H12	118.3
C3—C4—C7	122.1 (2)	C11—C12—H12	118.3
C6—C5—C4	121.5 (2)	C10—C13—H13A	109.5
C6—C5—H5	119.2	C10—C13—H13B	109.5
C4—C5—H5	119.2	H13A—C13—H13B	109.5
C5—C6—C1	120.6 (2)	C10—C13—H13C	109.5
C5—C6—H6	119.7	H13A—C13—H13C	109.5
C1—C6—H6	119.7	H13B—C13—H13C	109.5
O2—C7—O1	120.9 (3)	C1—N1—H1A	120.0
O2—C7—C4	124.1 (2)	C1—N1—H1B	120.0
O1—C7—C4	115.0 (2)	H1A—N1—H1B	120.0
N2—C8—C9	123.3 (3)	C12—N2—C8	116.6 (3)
N2—C8—H8	118.4	C7—O1—H1	112 (3)
C9—C8—H8	118.4

N1—C1—C2—C3	178.1 (3)	C3—C4—C7—O2	179.2 (3)
C6—C1—C2—C3	−0.5 (4)	C5—C4—C7—O1	−176.1 (2)
C1—C2—C3—C4	0.9 (4)	C3—C4—C7—O1	1.3 (3)
C2—C3—C4—C5	−0.5 (4)	N2—C8—C9—C10	0.0 (5)
C2—C3—C4—C7	−178.1 (2)	C8—C9—C10—C11	−0.2 (4)
C3—C4—C5—C6	−0.2 (4)	C8—C9—C10—C13	−179.7 (3)
C7—C4—C5—C6	177.4 (2)	C9—C10—C11—C12	0.4 (4)
C4—C5—C6—C1	0.5 (4)	C13—C10—C11—C12	179.9 (3)
N1—C1—C6—C5	−178.8 (3)	C10—C11—C12—N2	−0.4 (5)
C2—C1—C6—C5	−0.2 (4)	C11—C12—N2—C8	0.1 (5)
C5—C4—C7—O2	1.7 (4)	C9—C8—N2—C12	0.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.84 (1)	1.81 (1)	2.644 (3)	177 (4)
N1—H1A···O2ⁱⁱ	0.86	2.32	3.049 (3)	142
N1—H1B···O2ⁱⁱⁱ	0.86	2.17	3.031 (3)	174

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.836 (10)	1.809 (11)	2.644 (3)	177 (4)
N1—H1A···O2ⁱⁱ	0.86	2.32	3.049 (3)	142
N1—H1B···O2ⁱⁱⁱ	0.86	2.17	3.031 (3)	174

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

Acknowledgements

The authors wish to acknowledge the SAIF, IIT, Madras, for the data collection.

References

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