2-Amino­pyridinium 4-methyl­benzoate dihydrate

Liu, Y.; Li, J.

doi:10.1107/S160053680803153X

organic compounds

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Volume 64| Part 11| November 2008| Page o2057

doi:10.1107/S160053680803153X

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2-Aminopyridinium 4-methylbenzoate dihydrate

Yun Liu ^a and Jie Li ^a ^*

^aBasic Experiment Teaching Center, Henan University, Kaifeng 475004, People's Republic of China
^*Correspondence e-mail: lijie_78@126.com

(Received 28 September 2008; accepted 30 September 2008; online 4 October 2008)

The crystal structure of the title salt, C₅H₇N₂⁺·C₈H₇O₂⁻·2H₂O, contains a three-dimensional supramolecular framework constructed through N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For a related structure, see: Wang & Wei (2005 ).

Experimental

Crystal data

C₅H₇N₂⁺·C₈H₇O₂⁻·2H₂O
M_r = 266.29
Monoclinic, C c
a = 12.2059 (14) Å
b = 13.1531 (16) Å
c = 8.9937 (11) Å
β = 96.617 (2)°
V = 1434.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 (2) K
0.23 × 0.18 × 0.16 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.979, T_max = 0.985
4203 measured reflections
1567 independent reflections
1406 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.089
S = 1.04
1567 reflections
175 parameters
8 restraints
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯O1Wⁱ	0.86	2.06	2.906 (2)	169
N1—H1A⋯O1	0.86	1.82	2.676 (2)	173
N2—H2B⋯O2	0.86	1.98	2.826 (3)	168
O1W—H1AW⋯O2W	0.84	1.88	2.705 (2)	168
O1W—H1BW⋯O2	0.83	1.92	2.739 (2)	169
O2W—H2AW⋯O1Wⁱⁱ	0.83	1.93	2.758 (2)	172
O2W—H2BW⋯O1ⁱⁱⁱ	0.83	1.93	2.732 (2)	160
Symmetry codes: (i) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680803153X/hb2811sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803153X/hb2811Isup2.hkl

checkCIF report

Comment top

Currently, many groups are investigating supramolecular structures of cocrystals containing organic acids and organic bases resulting from hydrogen bonding (Wang & Wei, 2005). The asymmetric unit of the title compound, (I), is composed of 4-methylbenzoate anion, one 2-amino pyridinium cation and two water molecules in general positions (Fig. 1). The carboxyl group of 4-methylbenzoic acid is deprotonated. In the crystal, 2-amino pyridinium and 4-methylbenzoic acid anion together with water molecules are linked into a three-dimensional supramolecular framework by multiple N—H···O and O—H···O hydrogen bonds (Fig. 2 and Table 1).

Related literature top

For a related structure, see: Wang & Wei (2005).

Experimental top

4-Methylbenzoic acid (1 mmol, 0.135 g) and 2-aminopyridine (1 mmol, 0.094 g) were dissolved in 20 ml of distilled water. The solution was stirred for about 20 min at 353 K, avoiding evaporation of 2-aminopyridine. Colourless blocks of (I) were obtained from the filtrate after seven days.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level.
	Fig. 2. Three-dimensional structure of (I), with H bonds indicated by dashed lines. For clarity, H atoms not involved in hydrogen bonds are omitted.

2-Aminopyridinium 4-methylbenzoate dihydrate top

Crystal data top

C₅H₇N₂⁺·C₈H₇O₂⁻·2H₂O	F(000) = 568
M_r = 266.29	D_x = 1.233 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1977 reflections
a = 12.2059 (14) Å	θ = 2.3–26.6°
b = 13.1531 (16) Å	µ = 0.09 mm⁻¹
c = 8.9937 (11) Å	T = 296 K
β = 96.617 (2)°	Block, colorless
V = 1434.3 (3) Å³	0.23 × 0.18 × 0.16 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1567 independent reflections
Radiation source: fine-focus sealed tube	1406 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ω scans	θ_max = 27.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −6→15
T_min = 0.979, T_max = 0.985	k = −16→16
4203 measured reflections	l = −11→11

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)] = 0.032	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0525P)² + 0.1161P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1567 reflections	Δρ_max = 0.12 e Å⁻³
175 parameters	Δρ_min = −0.12 e Å⁻³
8 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: 0.019 (2)

Crystal data top

C₅H₇N₂⁺·C₈H₇O₂⁻·2H₂O	V = 1434.3 (3) Å³
M_r = 266.29	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 12.2059 (14) Å	µ = 0.09 mm⁻¹
b = 13.1531 (16) Å	T = 296 K
c = 8.9937 (11) Å	0.23 × 0.18 × 0.16 mm
β = 96.617 (2)°

Data collection top

Bruker SMART CCD diffractometer	1567 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	1406 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.985	R_int = 0.019
4203 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	8 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.04	Δρ_max = 0.12 e Å⁻³
1567 reflections	Δρ_min = −0.12 e Å⁻³
175 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
C1	0.48260 (16)	0.20609 (14)	0.6527 (2)	0.0505 (4)
C2	0.43746 (18)	0.28865 (16)	0.7214 (2)	0.0563 (5)
H2A	0.4359	0.3522	0.6758	0.068*
C3	0.39515 (17)	0.27745 (17)	0.8558 (2)	0.0606 (5)
H3A	0.3662	0.3338	0.9000	0.073*
C4	0.39467 (17)	0.18356 (19)	0.9270 (2)	0.0607 (5)
C5	0.4400 (2)	0.10125 (18)	0.8588 (3)	0.0682 (6)
H5A	0.4413	0.0377	0.9044	0.082*
C6	0.4834 (2)	0.11256 (16)	0.7238 (2)	0.0625 (6)
H6A	0.5135	0.0565	0.6803	0.075*
C7	0.3478 (3)	0.1719 (2)	1.0746 (4)	0.0832 (7)
H7A	0.3541	0.1023	1.1065	0.125*
H7B	0.2715	0.1916	1.0626	0.125*
H7C	0.3881	0.2145	1.1485	0.125*
C8	0.52854 (18)	0.21761 (16)	0.5061 (2)	0.0559 (5)
C9	0.64742 (16)	0.25294 (16)	0.1096 (2)	0.0540 (5)
C10	0.6947 (2)	0.2780 (2)	−0.0219 (3)	0.0662 (6)
H10A	0.7279	0.2279	−0.0741	0.079*
C11	0.6915 (2)	0.3748 (2)	−0.0715 (3)	0.0766 (7)
H11A	0.7248	0.3912	−0.1563	0.092*
C12	0.6383 (3)	0.4515 (2)	0.0034 (3)	0.0775 (7)
H12A	0.6346	0.5180	−0.0321	0.093*
C13	0.5934 (2)	0.42557 (17)	0.1272 (3)	0.0679 (6)
H13A	0.5575	0.4747	0.1780	0.082*
N1	0.59936 (16)	0.32882 (13)	0.17948 (19)	0.0572 (4)
H1A	0.5713	0.3152	0.2607	0.069*
N2	0.64687 (16)	0.16065 (14)	0.1677 (2)	0.0616 (4)
H2B	0.6164	0.1502	0.2479	0.074*
H2C	0.6770	0.1110	0.1252	0.074*
O1	0.51630 (17)	0.30246 (12)	0.4395 (2)	0.0748 (5)
O2	0.57598 (17)	0.14398 (13)	0.4549 (2)	0.0774 (5)
O1W	0.74860 (13)	0.02177 (11)	0.56348 (16)	0.0631 (4)
H1AW	0.7767	0.0431	0.6471	0.076*
H1BW	0.7022	0.0649	0.5296	0.076*
O2W	0.85359 (18)	0.06355 (15)	0.8382 (2)	0.0886 (6)
H2AW	0.8275	0.0340	0.9081	0.133*
H2BW	0.8906	0.1114	0.8791	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0524 (10)	0.0485 (10)	0.0491 (10)	0.0065 (8)	−0.0009 (8)	−0.0026 (8)
C2	0.0571 (11)	0.0491 (10)	0.0612 (12)	0.0059 (8)	0.0005 (9)	−0.0031 (9)
C3	0.0565 (11)	0.0624 (12)	0.0624 (13)	0.0081 (9)	0.0050 (10)	−0.0100 (10)
C4	0.0511 (11)	0.0738 (14)	0.0569 (13)	−0.0057 (10)	0.0045 (9)	−0.0047 (10)
C5	0.0847 (16)	0.0545 (11)	0.0661 (13)	−0.0024 (11)	0.0115 (11)	0.0063 (10)
C6	0.0797 (15)	0.0484 (10)	0.0595 (12)	0.0090 (10)	0.0086 (11)	−0.0039 (9)
C7	0.0784 (16)	0.104 (2)	0.0709 (15)	−0.0051 (15)	0.0234 (13)	0.0001 (14)
C8	0.0607 (11)	0.0550 (11)	0.0516 (10)	0.0136 (9)	0.0042 (9)	0.0013 (8)
C9	0.0496 (10)	0.0573 (11)	0.0529 (11)	0.0052 (9)	−0.0032 (9)	−0.0067 (9)
C10	0.0607 (13)	0.0826 (16)	0.0561 (12)	0.0112 (11)	0.0105 (10)	−0.0046 (11)
C11	0.0808 (17)	0.0914 (18)	0.0589 (13)	−0.0001 (13)	0.0133 (12)	0.0119 (13)
C12	0.101 (2)	0.0654 (14)	0.0632 (14)	−0.0019 (13)	−0.0014 (12)	0.0081 (11)
C13	0.0905 (16)	0.0550 (12)	0.0565 (12)	0.0086 (11)	0.0007 (11)	−0.0039 (10)
N1	0.0655 (10)	0.0568 (9)	0.0492 (9)	0.0060 (8)	0.0060 (7)	−0.0021 (7)
N2	0.0652 (10)	0.0570 (10)	0.0627 (10)	0.0110 (8)	0.0080 (8)	−0.0044 (8)
O1	0.0988 (12)	0.0615 (9)	0.0686 (10)	0.0280 (9)	0.0295 (9)	0.0155 (8)
O2	0.1095 (13)	0.0620 (9)	0.0638 (9)	0.0332 (9)	0.0228 (8)	0.0046 (7)
O1W	0.0750 (9)	0.0564 (8)	0.0593 (8)	0.0100 (7)	0.0137 (7)	−0.0006 (7)
O2W	0.1081 (15)	0.0954 (13)	0.0626 (9)	−0.0426 (12)	0.0114 (10)	−0.0026 (9)

Geometric parameters (Å, º) top

C1—C6	1.386 (3)	C9—N1	1.349 (3)
C1—C2	1.394 (3)	C9—C10	1.414 (3)
C1—C8	1.499 (3)	C10—C11	1.347 (4)
C2—C3	1.375 (3)	C10—H10A	0.9300
C2—H2A	0.9300	C11—C12	1.412 (4)
C3—C4	1.391 (3)	C11—H11A	0.9300
C3—H3A	0.9300	C12—C13	1.341 (4)
C4—C5	1.390 (4)	C12—H12A	0.9300
C4—C7	1.513 (4)	C13—N1	1.356 (3)
C5—C6	1.388 (4)	C13—H13A	0.9300
C5—H5A	0.9300	N1—H1A	0.8600
C6—H6A	0.9300	N2—H2B	0.8600
C7—H7A	0.9600	N2—H2C	0.8600
C7—H7B	0.9600	O1W—H1AW	0.8386
C7—H7C	0.9600	O1W—H1BW	0.8339
C8—O2	1.244 (3)	O2W—H2AW	0.8328
C8—O1	1.267 (3)	O2W—H2BW	0.8345
C9—N2	1.322 (3)

C6—C1—C2	118.00 (19)	O2—C8—C1	118.96 (18)
C6—C1—C8	120.78 (17)	O1—C8—C1	117.98 (18)
C2—C1—C8	121.22 (17)	N2—C9—N1	118.26 (19)
C3—C2—C1	120.9 (2)	N2—C9—C10	124.5 (2)
C3—C2—H2A	119.5	N1—C9—C10	117.3 (2)
C1—C2—H2A	119.5	C11—C10—C9	119.9 (2)
C2—C3—C4	121.4 (2)	C11—C10—H10A	120.0
C2—C3—H3A	119.3	C9—C10—H10A	120.0
C4—C3—H3A	119.3	C10—C11—C12	121.0 (2)
C5—C4—C3	117.7 (2)	C10—C11—H11A	119.5
C5—C4—C7	121.2 (2)	C12—C11—H11A	119.5
C3—C4—C7	121.0 (2)	C13—C12—C11	117.9 (2)
C6—C5—C4	120.9 (2)	C13—C12—H12A	121.0
C6—C5—H5A	119.5	C11—C12—H12A	121.0
C4—C5—H5A	119.5	C12—C13—N1	121.1 (2)
C1—C6—C5	121.0 (2)	C12—C13—H13A	119.4
C1—C6—H6A	119.5	N1—C13—H13A	119.4
C5—C6—H6A	119.5	C9—N1—C13	122.8 (2)
C4—C7—H7A	109.5	C9—N1—H1A	118.6
C4—C7—H7B	109.5	C13—N1—H1A	118.6
H7A—C7—H7B	109.5	C9—N2—H2B	120.0
C4—C7—H7C	109.5	C9—N2—H2C	120.0
H7A—C7—H7C	109.5	H2B—N2—H2C	120.0
H7B—C7—H7C	109.5	H1AW—O1W—H1BW	106.9
O2—C8—O1	123.1 (2)	H2AW—O2W—H2BW	104.7

C6—C1—C2—C3	0.1 (3)	C2—C1—C8—O2	174.2 (2)
C8—C1—C2—C3	179.8 (2)	C6—C1—C8—O1	173.5 (2)
C1—C2—C3—C4	−0.7 (3)	C2—C1—C8—O1	−6.2 (3)
C2—C3—C4—C5	0.9 (3)	N2—C9—C10—C11	−179.6 (2)
C2—C3—C4—C7	−179.9 (2)	N1—C9—C10—C11	0.7 (3)
C3—C4—C5—C6	−0.5 (3)	C9—C10—C11—C12	−2.1 (4)
C7—C4—C5—C6	−179.6 (2)	C10—C11—C12—C13	1.5 (4)
C2—C1—C6—C5	0.4 (3)	C11—C12—C13—N1	0.4 (4)
C8—C1—C6—C5	−179.3 (2)	N2—C9—N1—C13	−178.5 (2)
C4—C5—C6—C1	−0.2 (4)	C10—C9—N1—C13	1.2 (3)
C6—C1—C8—O2	−6.0 (3)	C12—C13—N1—C9	−1.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O1Wⁱ	0.86	2.06	2.906 (2)	169
N1—H1A···O1	0.86	1.82	2.676 (2)	173
N2—H2B···O2	0.86	1.98	2.826 (3)	168
O1W—H1AW···O2W	0.84	1.88	2.705 (2)	168
O1W—H1BW···O2	0.83	1.92	2.739 (2)	169
O2W—H2AW···O1Wⁱⁱ	0.83	1.93	2.758 (2)	172
O2W—H2BW···O1ⁱⁱⁱ	0.83	1.93	2.732 (2)	160

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

Experimental details

Crystal data
Chemical formula	C₅H₇N₂⁺·C₈H₇O₂⁻·2H₂O
M_r	266.29
Crystal system, space group	Monoclinic, Cc
Temperature (K)	296
a, b, c (Å)	12.2059 (14), 13.1531 (16), 8.9937 (11)
β (°)	96.617 (2)
V (Å³)	1434.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.23 × 0.18 × 0.16

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.979, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	4203, 1567, 1406
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.04
No. of reflections	1567
No. of parameters	175
No. of restraints	8
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.12

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O1Wⁱ	0.86	2.06	2.906 (2)	169
N1—H1A···O1	0.86	1.82	2.676 (2)	173
N2—H2B···O2	0.86	1.98	2.826 (3)	168
O1W—H1AW···O2W	0.84	1.88	2.705 (2)	168
O1W—H1BW···O2	0.83	1.92	2.739 (2)	169
O2W—H2AW···O1Wⁱⁱ	0.83	1.93	2.758 (2)	172
O2W—H2BW···O1ⁱⁱⁱ	0.83	1.93	2.732 (2)	160

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

Acknowledgements

This work was supported by the Basic Research Foundation for Natural Science of Henan University.

References

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