2-Amino-4-methyl­pyridinium 2-(4-nitro­phen­yl)acetate

Sivakumar, P.; Sudhahar, S.; Israel, S.; Chakkaravarthi, G.

doi:10.1107/S2414314616012037

organic compounds

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ISSN: 2414-3146

Volume 1| Part 8| August 2016| x161203

doi:10.1107/S2414314616012037

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2-Amino-4-methylpyridinium 2-(4-nitrophenyl)acetate

P. Sivakumar,^a,^b S. Sudhahar,^c S. Israel ^d ^* and G. Chakkaravarthi ^b ^*

^aResearch and Development Centre, Bharathiar University, Coimbatore 641 046, India, ^bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, ^cDepartment of Physics, Alagappa University, Karaikkudi 630 003, India, and ^dPost graduate and research department of physics, The American college, Madurai 625 002, India
^*Correspondence e-mail: israel.samuel@gmail.com, chakkaravarthi_2005@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 19 June 2016; accepted 24 July 2016; online 12 August 2016)

In the title molecular salt, C₆H₉N₂⁺·C₈H₆NO₄⁻, the cation is protonated at its pyridine N atom. In the crystal, the anions are connected by a pair of C—H⋯O contacts into [100] chains, which generate R₂²(11) loops and these chains are linked via another C—H⋯O contact which encloses an R₂⁴(10) loop. Adjacent anions and cations are connected through N—H⋯ O hydrogen bonds, generating an R₂²(8) loop. Two pairs of anions and cations are linked by N—H⋯O hydrogen bonds, forming a tetramer with an R₂²(8) loop motif. The packing also features weak C—H⋯π and π–π [centroid-to-centroid distances = 3.8972 (11) and 3.9549 (10) Å] interactions, which result in a three-dimensional network.

Keywords: crystal structure; molecular salt; hydrogen bonding.

CCDC reference: 1495632

Structure description

The asymmetric unit of of the title salt consists of a 2-amino-4-methylpyridinium cation (protonated at the pyridine N atom) and a 2-(4-nitrophenyl)acetate anion (Fig. 1). The bond lengths are comparable with reported similar structures (Babu et al., 2014 ; Rajkumar et al., 2014 ).

Figure 1
The molecular structure of the title molecular salt, shown with 30% probability displacement ellipsoids.

The anions are connected by C—H⋯O [C3—H3⋯O2ⁱⁱⁱ and C6—H6⋯O3^vi] contacts into [100] chains, generating an R₂²(11) loop; these chains are further linked via C5—H5⋯O3^iv [symmetry codes: (iii) 1 + x, y, z; (iv) −x, 1 − y, −z; (vi) x − 1, y, z] contacts, enclosing R₂⁴(10) loops (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the N2/C9–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3ⁱ	0.86	1.77	2.6263 (19)	173
N3—H3A⋯O4ⁱ	0.86	2.04	2.900 (2)	174
N3—H3B⋯O4ⁱⁱ	0.86	2.02	2.847 (2)	160
C3—H3⋯O2ⁱⁱⁱ	0.93	2.57	3.419 (2)	152
C5—H5⋯O3^iv	0.93	2.56	3.478 (2)	170
C13—H13⋯O3^v	0.93	2.48	3.396 (2)	168
C6—H6⋯O3^vi	0.93	2.70	3.475 (2)	142
C2—H2A⋯Cg2^vi	0.93	2.79	3.668 (2)	158
Symmetry codes: (i) x, y, z+1; (ii) -x, -y+2, -z+1; (iii) x+1, y, z; (iv) -x, -y+1, -z; (v) -x+1, -y+1, -z+1; (vi) x-1, y, z.

Figure 2
A partial view of the crystal packing of the title salt, showing the the anions which are connected via C—H⋯O contacts.

In the extended structure, the anions and cations are connected by N—H⋯ O [N2—H2⋯O3ⁱ and N3—H3A⋯O4ⁱ] hydrogen bonds, generating an R₂²(8) loop, and two pairs of anions and cations are linked by N—H⋯O [N3—H3A⋯O4ⁱ and N3—H3B⋯O4ⁱⁱ; symmetry codes: (i) x, y, 1 + z; (ii) −x, 2 − y, 1 − z] hydrogen bonds to form a tetramer with an R₂²(8) ring-motif (Table 1 and Fig. 3). The packing is consolidated by weak C—H⋯π (Table 1) and π–π [Cg1⋯Cg1^vii = 3.8972 (11) Å; Cg2⋯Cg2^viii = 3.9549 (10) Å; symmetry codes: (vii) −1 − x, 1 − y, 1 − z; (viii) 1 − x, 2 − y, 2 − z; Cg1 and Cg2 are the centroids of the C1–C6 and N2/C9–C13 rings, respectively] interactions, forming a three-dimensional network (Fig. 4).

Figure 3
A partial view of the crystal packing of the title salt, showing the hydrogen-bonded tetramer connected by hydrogen bonds.

Figure 4
The crystal packing of the title compound viewed along a axis. The hydrogen bonds are shown as dashed lines (see Table 1

) and C-bound H atoms have been omitted for clarity.

Synthesis and crystallization

4-Nitrophenylacetic acid (1.811 g) and 2-amino-4-methylpyridine (1.081 g) in an equimolar ratio were dissolved in 15 ml methanol, and a white solid precipitate formed from the mixture. The precipitate was dissolved in water and kept at room temperature for crystallization. After a span of 12 days, colourless blocks of the title salt were formed.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₈H₆NO₄⁻
M_r	289.29
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	295
a, b, c (Å)	7.9359 (3), 9.6283 (4), 9.6807 (5)
α, β, γ (°)	88.010 (3), 74.936 (2), 81.561 (2)
V (Å³)	706.54 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.24 × 0.22 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.976, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	17186, 3659, 2306
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.144, 1.03
No. of reflections	3659
No. of parameters	191
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.30
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1495632

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616012037/hb4061sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616012037/hb4061Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616012037/hb4061Isup3.cml

checkCIF report

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, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

2-Amino-4-methylpyridinium 2-(4-nitrophenyl)acetate top

Crystal data top

C₆H₉N₂⁺·C₈H₆NO₄⁻	Z = 2
M_r = 289.29	F(000) = 304
Triclinic, P1	D_x = 1.360 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9359 (3) Å	Cell parameters from 5711 reflections
b = 9.6283 (4) Å	θ = 2.2–28.8°
c = 9.6807 (5) Å	µ = 0.10 mm⁻¹
α = 88.010 (3)°	T = 295 K
β = 74.936 (2)°	Block, colourless
γ = 81.561 (2)°	0.24 × 0.22 × 0.18 mm
V = 706.54 (5) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	3659 independent reflections
Radiation source: fine-focus sealed tube	2306 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and φ scan	θ_max = 29.2°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→10
T_min = 0.976, T_max = 0.982	k = −13→13
17186 measured reflections	l = −12→13

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0524P)² + 0.3009P] where P = (F_o² + 2F_c²)/3
3659 reflections	(Δ/σ)_max < 0.001
191 parameters	Δρ_max = 0.30 e Å⁻³
1 restraint	Δρ_min = −0.30 e Å⁻³

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	−0.5718 (2)	0.6802 (2)	0.45065 (19)	0.0412 (4)
C2	−0.4397 (2)	0.7227 (2)	0.4973 (2)	0.0550 (5)
H2A	−0.4650	0.7753	0.5808	0.066*
C3	−0.2682 (2)	0.6864 (2)	0.4186 (2)	0.0551 (5)
H3	−0.1770	0.7151	0.4494	0.066*
C4	−0.2294 (2)	0.60809 (18)	0.2948 (2)	0.0404 (4)
C5	−0.3670 (2)	0.5717 (2)	0.2490 (2)	0.0471 (5)
H5	−0.3431	0.5217	0.1640	0.057*
C6	−0.5397 (2)	0.6075 (2)	0.3262 (2)	0.0472 (5)
H6	−0.6319	0.5826	0.2940	0.057*
C7	−0.0415 (2)	0.55678 (19)	0.2171 (2)	0.0484 (5)
H7A	−0.0412	0.4757	0.1603	0.058*
H7B	0.0221	0.5248	0.2881	0.058*
C8	0.0605 (2)	0.65936 (17)	0.11973 (19)	0.0379 (4)
C9	0.3858 (2)	0.91090 (17)	0.88276 (18)	0.0372 (4)
C10	0.5138 (2)	0.99143 (18)	0.80895 (19)	0.0417 (4)
H10	0.4794	1.0832	0.7835	0.050*
C11	0.6879 (2)	0.93718 (19)	0.7739 (2)	0.0429 (4)
C12	0.7369 (2)	0.7985 (2)	0.8130 (2)	0.0467 (5)
H12	0.8549	0.7591	0.7901	0.056*
C13	0.6117 (2)	0.72288 (18)	0.8841 (2)	0.0436 (4)
H13	0.6442	0.6309	0.9100	0.052*
C14	0.8268 (3)	1.0217 (2)	0.6948 (3)	0.0682 (7)
H14A	0.8447	1.0099	0.5937	0.102*
H14B	0.9351	0.9902	0.7205	0.102*
H14C	0.7895	1.1190	0.7196	0.102*
N1	−0.7538 (2)	0.7107 (2)	0.5390 (2)	0.0562 (5)
N2	0.43950 (18)	0.77853 (14)	0.91833 (16)	0.0391 (3)
H2	0.3622	0.7281	0.9640	0.047*
N3	0.21474 (19)	0.95774 (17)	0.92141 (19)	0.0522 (4)
H3A	0.1419	0.9040	0.9677	0.063*
H3B	0.1765	1.0419	0.9002	0.063*
O1	−0.7802 (2)	0.7713 (2)	0.6516 (2)	0.0950 (7)
O2	−0.87043 (18)	0.6723 (2)	0.4977 (2)	0.0765 (5)
O3	0.22208 (15)	0.61628 (13)	0.07048 (15)	0.0491 (4)
O4	−0.01532 (18)	0.77352 (15)	0.09299 (19)	0.0689 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0272 (8)	0.0506 (10)	0.0424 (10)	−0.0018 (7)	−0.0058 (7)	0.0070 (8)
C2	0.0401 (10)	0.0739 (14)	0.0494 (12)	−0.0005 (9)	−0.0104 (9)	−0.0172 (10)
C3	0.0323 (9)	0.0708 (14)	0.0643 (13)	−0.0084 (9)	−0.0140 (9)	−0.0137 (11)
C4	0.0304 (8)	0.0388 (9)	0.0466 (10)	−0.0031 (7)	−0.0023 (7)	0.0079 (8)
C5	0.0443 (10)	0.0527 (11)	0.0427 (10)	−0.0067 (8)	−0.0082 (8)	−0.0023 (8)
C6	0.0350 (9)	0.0546 (11)	0.0559 (12)	−0.0095 (8)	−0.0170 (8)	0.0018 (9)
C7	0.0354 (9)	0.0402 (9)	0.0595 (12)	−0.0009 (7)	0.0023 (8)	0.0085 (8)
C8	0.0309 (8)	0.0349 (8)	0.0446 (10)	−0.0029 (7)	−0.0054 (7)	0.0017 (7)
C9	0.0340 (8)	0.0333 (8)	0.0407 (9)	−0.0001 (7)	−0.0060 (7)	0.0016 (7)
C10	0.0391 (9)	0.0338 (9)	0.0475 (10)	−0.0011 (7)	−0.0063 (8)	0.0066 (7)
C11	0.0366 (9)	0.0431 (10)	0.0454 (10)	−0.0058 (7)	−0.0048 (8)	0.0058 (8)
C12	0.0307 (8)	0.0465 (10)	0.0563 (12)	0.0029 (7)	−0.0050 (8)	0.0063 (9)
C13	0.0392 (9)	0.0349 (9)	0.0519 (11)	0.0035 (7)	−0.0089 (8)	0.0058 (8)
C14	0.0468 (12)	0.0644 (14)	0.0838 (17)	−0.0124 (10)	−0.0001 (11)	0.0242 (12)
N1	0.0339 (8)	0.0682 (12)	0.0592 (11)	0.0022 (8)	−0.0060 (8)	0.0128 (9)
N2	0.0336 (7)	0.0326 (7)	0.0456 (8)	−0.0032 (6)	−0.0020 (6)	0.0056 (6)
N3	0.0333 (8)	0.0400 (8)	0.0729 (12)	0.0029 (6)	−0.0007 (7)	0.0078 (8)
O1	0.0544 (10)	0.1393 (18)	0.0742 (12)	0.0096 (10)	0.0054 (9)	−0.0338 (12)
O2	0.0312 (7)	0.1038 (13)	0.0919 (13)	−0.0129 (8)	−0.0119 (8)	0.0181 (10)
O3	0.0323 (6)	0.0398 (7)	0.0637 (9)	−0.0007 (5)	0.0045 (6)	0.0091 (6)
O4	0.0401 (7)	0.0479 (8)	0.1027 (13)	0.0041 (6)	0.0005 (8)	0.0292 (8)

Geometric parameters (Å, º) top

C1—C2	1.362 (3)	C9—N2	1.346 (2)
C1—C6	1.362 (3)	C9—C10	1.399 (2)
C1—N1	1.468 (2)	C10—C11	1.362 (2)
C2—C3	1.377 (3)	C10—H10	0.9300
C2—H2A	0.9300	C11—C12	1.402 (2)
C3—C4	1.379 (3)	C11—C14	1.498 (3)
C3—H3	0.9300	C12—C13	1.346 (3)
C4—C5	1.373 (3)	C12—H12	0.9300
C4—C7	1.503 (2)	C13—N2	1.351 (2)
C5—C6	1.380 (3)	C13—H13	0.9300
C5—H5	0.9300	C14—H14A	0.9600
C6—H6	0.9300	C14—H14B	0.9600
C7—C8	1.514 (2)	C14—H14C	0.9600
C7—H7A	0.9700	N1—O2	1.207 (2)
C7—H7B	0.9700	N1—O1	1.210 (2)
C8—O4	1.227 (2)	N2—H2	0.8600
C8—O3	1.2583 (19)	N3—H3A	0.8600
C9—N3	1.325 (2)	N3—H3B	0.8600

C2—C1—C6	122.03 (16)	N2—C9—C10	118.22 (14)
C2—C1—N1	119.00 (18)	C11—C10—C9	120.88 (16)
C6—C1—N1	118.95 (17)	C11—C10—H10	119.6
C1—C2—C3	118.81 (19)	C9—C10—H10	119.6
C1—C2—H2A	120.6	C10—C11—C12	118.63 (16)
C3—C2—H2A	120.6	C10—C11—C14	121.66 (17)
C2—C3—C4	121.02 (18)	C12—C11—C14	119.70 (17)
C2—C3—H3	119.5	C13—C12—C11	119.53 (16)
C4—C3—H3	119.5	C13—C12—H12	120.2
C5—C4—C3	118.20 (16)	C11—C12—H12	120.2
C5—C4—C7	120.93 (18)	C12—C13—N2	121.03 (16)
C3—C4—C7	120.76 (17)	C12—C13—H13	119.5
C4—C5—C6	121.57 (18)	N2—C13—H13	119.5
C4—C5—H5	119.2	C11—C14—H14A	109.5
C6—C5—H5	119.2	C11—C14—H14B	109.5
C1—C6—C5	118.28 (17)	H14A—C14—H14B	109.5
C1—C6—H6	120.9	C11—C14—H14C	109.5
C5—C6—H6	120.9	H14A—C14—H14C	109.5
C4—C7—C8	117.54 (14)	H14B—C14—H14C	109.5
C4—C7—H7A	107.9	O2—N1—O1	122.69 (19)
C8—C7—H7A	107.9	O2—N1—C1	118.86 (19)
C4—C7—H7B	107.9	O1—N1—C1	118.44 (19)
C8—C7—H7B	107.9	C9—N2—C13	121.70 (15)
H7A—C7—H7B	107.2	C9—N2—H2	119.2
O4—C8—O3	125.07 (16)	C13—N2—H2	119.2
O4—C8—C7	120.19 (15)	C9—N3—H3A	120.0
O3—C8—C7	114.73 (14)	C9—N3—H3B	120.0
N3—C9—N2	117.87 (15)	H3A—N3—H3B	120.0
N3—C9—C10	123.90 (15)

C6—C1—C2—C3	−2.4 (3)	N3—C9—C10—C11	179.25 (18)
N1—C1—C2—C3	176.04 (19)	N2—C9—C10—C11	0.1 (3)
C1—C2—C3—C4	−0.2 (3)	C9—C10—C11—C12	0.1 (3)
C2—C3—C4—C5	2.4 (3)	C9—C10—C11—C14	180.0 (2)
C2—C3—C4—C7	−173.96 (19)	C10—C11—C12—C13	−0.1 (3)
C3—C4—C5—C6	−2.2 (3)	C14—C11—C12—C13	−180.0 (2)
C7—C4—C5—C6	174.15 (17)	C11—C12—C13—N2	−0.1 (3)
C2—C1—C6—C5	2.6 (3)	C2—C1—N1—O2	−179.68 (19)
N1—C1—C6—C5	−175.85 (17)	C6—C1—N1—O2	−1.2 (3)
C4—C5—C6—C1	−0.2 (3)	C2—C1—N1—O1	−0.9 (3)
C5—C4—C7—C8	102.7 (2)	C6—C1—N1—O1	177.6 (2)
C3—C4—C7—C8	−81.0 (2)	N3—C9—N2—C13	−179.47 (17)
C4—C7—C8—O4	−8.6 (3)	C10—C9—N2—C13	−0.3 (3)
C4—C7—C8—O3	172.25 (17)	C12—C13—N2—C9	0.3 (3)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the N2/C9–C13 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3ⁱ	0.86	1.77	2.6263 (19)	173
N3—H3A···O4ⁱ	0.86	2.04	2.900 (2)	174
N3—H3B···O4ⁱⁱ	0.86	2.02	2.847 (2)	160
C3—H3···O2ⁱⁱⁱ	0.93	2.57	3.419 (2)	152
C5—H5···O3^iv	0.93	2.56	3.478 (2)	170
C13—H13···O3^v	0.93	2.48	3.396 (2)	168
C6—H6···O3^vi	0.93	2.70	3.475 (2)	142
C2—H2A···Cg2^vi	0.93	2.79	3.668 (2)	158

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

Acknowledgements

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

References

Babu, K. S. S., Peramaiyan, G., NizamMohideen, M. & Mohan, R. (2014). Acta Cryst. E70, o391–o392. CSD CrossRef CAS IUCr Journals Google Scholar
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Rajkumar, M. A., Xavier, S. S. J., Anbarasu, S., Devarajan, P. A. & NizamMohideen, M. (2014). Acta Cryst. E70, o473–o474. CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2414-3146

Volume 1| Part 8| August 2016| x161203

doi:10.1107/S2414314616012037

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-Amino-4-methyl­pyridinium 2-(4-nitro­phen­yl)acetate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

2-Amino-4-methylpyridinium 2-(4-nitrophenyl)acetate