Pyridinium-2-carboxyl­ate–benzene-1,2-diol (1/1)

Ton, C.Q.; Bolte, M.

doi:10.1107/S1600536809043207

organic compounds

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Volume 65| Part 11| November 2009| Page o2834

https://doi.org/10.1107/S1600536809043207

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Pyridinium-2-carboxylate–benzene-1,2-diol (1/1)

Cuong Quoc Ton ^a and Michael Bolte ^b ^*

^aInstitut für Organische Chemie der Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany, and ^bInstitut für Anorganische Chemie der Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany
^*Correspondence e-mail: bolte@chemie.uni-frankfurt.de

(Received 20 October 2009; accepted 20 October 2009; online 23 October 2009)

The title compound, C₆H₅NO₂·C₆H₆O₂, crystallizes with one pyridinium-2-carboxylate zwitterion and one molecule of benzene-1,2-diol in the asymmetric unit. The crystal structure is characterized by alternating molecules forming zigzag chains running along the a axis: the molecules are connected by O—H⋯O and N—H⋯(O,O) hydrogen bonds.

Related literature

For co-crystallization experiments, see: Ton & Bolte (2005 ); Tutughamiarso et al. (2009 ).

Experimental

Crystal data

C₆H₅NO₂·C₆H₆O₂
M_r = 233.22
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.9710 (14) Å
b = 6.9855 (14) Å
c = 21.806 (4) Å
V = 1061.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 173 K
0.21 × 0.18 × 0.16 mm

Data collection

Stoe IPDSII two-circle diffractometer
Absorption correction: none
11928 measured reflections
1196 independent reflections
1105 reflections with I > 2σ(I)
R_int = 0.081

Refinement

R[F² > 2σ(F²)] = 0.096
wR(F²) = 0.197
S = 1.23
1196 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O11ⁱ	0.84	1.84	2.655 (6)	163
O2—H2⋯O12	0.84	1.89	2.662 (7)	153
N1—H31⋯O12	0.91	2.16	2.617 (7)	110
N1—H31⋯O1	0.91	2.18	2.984 (7)	147
Symmetry code: (i) x+1, y, z.

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009 ) and SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809043207/ng2670sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809043207/ng2670Isup2.hkl

checkCIF report

Comment top

The aim of our research is the cocrystallization of two small organic compounds in order to examine the hydrogen bonds formed between hydrogen-bond acceptors and hydrogen-bond donors (Ton & Bolte, 2005; Tutughamiarso et al., 2009). When pyridinecarboxaldehyde and 1,2-dihydroxybenzene were mixed in order to obtain a hydrogen bonded supermolecular complex, it turned out that the aldehyd had been oxidized to the carboxylic acid. The title compound crystallizes with one pyridinium-2-carboxylate zwitterion and one molecule of benzene-1,2-diol in the asymmetric unit. The crystal structure is characterized by alternating molecules forming zigzag chains running along the a axis. The molecules are connected by O—H···N and O—H···O hydrogen bonds.

Related literature top

For co-crystallization experiments, see: Ton & Bolte (2005); Tutughamiarso et al. (2009).

Experimental top

40 mg pyridinecarboxaldehyde and 40 mg 1,2-dihydroxybenzene were diluted in 2 ml diethyl ether in a nitrogen atmosphere. After five weeks a brown precipitate emerged from the mixture. On the surface white crystals has been sedimented, one of which was used for structure determination. It turned out that the pyridinecarboxaldehyde had been oxidized to the carboxylic acid.

Structure description top

For co-crystallization experiments, see: Ton & Bolte (2005); Tutughamiarso et al. (2009).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009) and SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

Pyridinium-2-carboxylate–benzene-1,2-diol (1/1) top

Crystal data top

C₆H₅NO₂·C₆H₆O₂	F(000) = 488
M_r = 233.22	D_x = 1.459 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6345 reflections
a = 6.9710 (14) Å	θ = 3.5–24.3°
b = 6.9855 (14) Å	µ = 0.11 mm⁻¹
c = 21.806 (4) Å	T = 173 K
V = 1061.9 (4) Å³	Block, colourless
Z = 4	0.21 × 0.18 × 0.16 mm

Data collection top

Stoe IPDSII two-circle diffractometer	1105 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.081
Graphite monochromator	θ_max = 25.8°, θ_min = 3.1°
ω scans	h = −8→8
11928 measured reflections	k = −8→8
1196 independent reflections	l = −26→25

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)] = 0.096	H-atom parameters constrained
wR(F²) = 0.197	w = 1/[σ²(F_o²) + (0.0513P)² + 3.5668P] where P = (F_o² + 2F_c²)/3
S = 1.23	(Δ/σ)_max = 0.001
1196 reflections	Δρ_max = 0.44 e Å⁻³
155 parameters	Δρ_min = −0.34 e Å⁻³
0 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: 0.036 (6)

Crystal data top

C₆H₅NO₂·C₆H₆O₂	V = 1061.9 (4) Å³
M_r = 233.22	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.9710 (14) Å	µ = 0.11 mm⁻¹
b = 6.9855 (14) Å	T = 173 K
c = 21.806 (4) Å	0.21 × 0.18 × 0.16 mm

Data collection top

Stoe IPDSII two-circle diffractometer	1105 reflections with I > 2σ(I)
11928 measured reflections	R_int = 0.081
1196 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.096	0 restraints
wR(F²) = 0.197	H-atom parameters constrained
S = 1.23	Δρ_max = 0.44 e Å⁻³
1196 reflections	Δρ_min = −0.34 e Å⁻³
155 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
O1	1.1064 (7)	0.3802 (7)	0.0845 (2)	0.0257 (11)
H1	1.2093	0.4153	0.0679	0.039*
O2	0.8174 (6)	0.1866 (8)	0.1466 (2)	0.0295 (12)
H2	0.7994	0.2756	0.1214	0.044*
C1	1.1455 (9)	0.3029 (9)	0.1410 (3)	0.0200 (13)
C2	0.9985 (9)	0.2048 (10)	0.1716 (3)	0.0220 (13)
C3	1.0330 (10)	0.1145 (11)	0.2274 (3)	0.0259 (14)
H3	0.9332	0.0460	0.2473	0.031*
C4	1.2160 (10)	0.1249 (11)	0.2542 (3)	0.0303 (16)
H4	1.2399	0.0649	0.2925	0.036*
C5	1.3612 (9)	0.2231 (10)	0.2244 (3)	0.0280 (15)
H5	1.4850	0.2302	0.2424	0.034*
C6	1.3273 (9)	0.3110 (10)	0.1686 (3)	0.0254 (14)
H6	1.4284	0.3777	0.1487	0.031*
O11	0.3875 (7)	0.5038 (7)	0.0125 (2)	0.0307 (12)
O12	0.6497 (8)	0.4131 (10)	0.0643 (3)	0.0516 (18)
N1	0.8827 (8)	0.5092 (8)	−0.0246 (2)	0.0222 (12)
H31	0.9086	0.4912	0.0160	0.027*
C11	1.0169 (10)	0.5516 (10)	−0.0666 (3)	0.0260 (15)
H11	1.1479	0.5226	−0.0591	0.031*
C13	0.6922 (9)	0.5494 (9)	−0.0326 (3)	0.0208 (13)
C14	0.6360 (10)	0.6404 (9)	−0.0853 (3)	0.0237 (14)
H14	0.5049	0.6725	−0.0914	0.028*
C15	0.7722 (10)	0.6856 (10)	−0.1299 (3)	0.0275 (15)
H15	0.7347	0.7491	−0.1665	0.033*
C16	0.9629 (10)	0.6368 (11)	−0.1202 (3)	0.0301 (17)
H16	1.0559	0.6628	−0.1510	0.036*
C131	0.5649 (10)	0.4815 (11)	0.0200 (3)	0.0283 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.015 (2)	0.032 (2)	0.030 (2)	−0.002 (2)	0.0002 (18)	0.006 (2)
O2	0.015 (2)	0.033 (3)	0.041 (3)	−0.005 (2)	−0.003 (2)	0.007 (2)
C1	0.017 (3)	0.015 (3)	0.028 (3)	−0.007 (3)	0.002 (3)	−0.001 (3)
C2	0.017 (3)	0.020 (3)	0.029 (3)	−0.004 (3)	0.000 (3)	−0.003 (3)
C3	0.025 (3)	0.026 (3)	0.027 (3)	−0.002 (3)	0.006 (3)	−0.002 (3)
C4	0.032 (4)	0.034 (4)	0.026 (3)	0.001 (3)	−0.004 (3)	0.006 (3)
C5	0.019 (3)	0.035 (4)	0.030 (3)	0.000 (3)	−0.004 (3)	−0.003 (3)
C6	0.019 (3)	0.029 (3)	0.028 (3)	−0.005 (3)	0.003 (3)	−0.003 (3)
O11	0.016 (2)	0.043 (3)	0.033 (2)	−0.002 (2)	0.002 (2)	0.002 (3)
O12	0.024 (3)	0.086 (5)	0.044 (3)	0.015 (3)	0.007 (2)	0.033 (3)
N1	0.019 (3)	0.025 (3)	0.023 (2)	0.004 (3)	0.001 (2)	0.000 (2)
C11	0.022 (3)	0.022 (3)	0.034 (3)	0.000 (3)	0.005 (3)	−0.002 (3)
C13	0.015 (3)	0.015 (3)	0.033 (3)	−0.001 (2)	0.002 (3)	0.000 (3)
C14	0.019 (3)	0.025 (3)	0.027 (3)	0.000 (3)	−0.002 (3)	0.002 (3)
C15	0.038 (4)	0.021 (3)	0.024 (3)	−0.001 (3)	−0.002 (3)	−0.002 (3)
C16	0.028 (4)	0.034 (4)	0.028 (3)	−0.001 (3)	0.004 (3)	0.002 (3)
C131	0.028 (4)	0.028 (3)	0.029 (3)	0.004 (3)	0.003 (3)	0.005 (3)

Geometric parameters (Å, º) top

O1—C1	1.374 (8)	O11—C131	1.257 (8)
O1—H1	0.8397	O12—C131	1.229 (9)
O2—C2	1.381 (7)	N1—C11	1.342 (9)
O2—H2	0.8392	N1—C13	1.368 (8)
C1—C2	1.401 (9)	N1—H31	0.9123
C1—C6	1.404 (9)	C11—C16	1.365 (10)
C2—C3	1.391 (9)	C11—H11	0.9500
C3—C4	1.405 (9)	C13—C14	1.370 (9)
C3—H3	0.9500	C13—C131	1.526 (9)
C4—C5	1.384 (10)	C14—C15	1.396 (10)
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.383 (9)	C15—C16	1.389 (10)
C5—H5	0.9500	C15—H15	0.9500
C6—H6	0.9500	C16—H16	0.9500

C1—O1—H1	109.4	C11—N1—H31	123.7
C2—O2—H2	109.1	C13—N1—H31	110.1
O1—C1—C2	118.3 (5)	N1—C11—C16	119.3 (7)
O1—C1—C6	123.2 (5)	N1—C11—H11	120.4
C2—C1—C6	118.5 (6)	C16—C11—H11	120.4
O2—C2—C3	117.5 (6)	N1—C13—C14	118.6 (6)
O2—C2—C1	121.7 (6)	N1—C13—C131	113.9 (6)
C3—C2—C1	120.7 (6)	C14—C13—C131	127.4 (6)
C2—C3—C4	119.8 (6)	C13—C14—C15	119.7 (6)
C2—C3—H3	120.1	C13—C14—H14	120.2
C4—C3—H3	120.1	C15—C14—H14	120.2
C5—C4—C3	119.6 (6)	C16—C15—C14	119.4 (6)
C5—C4—H4	120.2	C16—C15—H15	120.3
C3—C4—H4	120.2	C14—C15—H15	120.3
C6—C5—C4	120.5 (6)	C11—C16—C15	120.0 (7)
C6—C5—H5	119.8	C11—C16—H16	120.0
C4—C5—H5	119.8	C15—C16—H16	120.0
C5—C6—C1	120.9 (6)	O12—C131—O11	128.6 (7)
C5—C6—H6	119.6	O12—C131—C13	115.6 (6)
C1—C6—H6	119.6	O11—C131—C13	115.8 (6)
C11—N1—C13	123.0 (6)

O1—C1—C2—O2	−0.7 (10)	C11—N1—C13—C14	−1.3 (10)
C6—C1—C2—O2	−178.3 (6)	C11—N1—C13—C131	177.8 (6)
O1—C1—C2—C3	176.4 (6)	N1—C13—C14—C15	1.5 (9)
C6—C1—C2—C3	−1.2 (10)	C131—C13—C14—C15	−177.4 (6)
O2—C2—C3—C4	178.6 (6)	C13—C14—C15—C16	0.2 (10)
C1—C2—C3—C4	1.4 (10)	N1—C11—C16—C15	2.5 (11)
C2—C3—C4—C5	−0.8 (11)	C14—C15—C16—C11	−2.3 (11)
C3—C4—C5—C6	0.1 (11)	N1—C13—C131—O12	5.1 (9)
C4—C5—C6—C1	0.1 (11)	C14—C13—C131—O12	−176.0 (7)
O1—C1—C6—C5	−177.0 (6)	N1—C13—C131—O11	−175.2 (6)
C2—C1—C6—C5	0.5 (10)	C14—C13—C131—O11	3.7 (10)
C13—N1—C11—C16	−0.8 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O11ⁱ	0.84	1.84	2.655 (6)	163
O2—H2···O12	0.84	1.89	2.662 (7)	153
N1—H31···O12	0.91	2.16	2.617 (7)	110
N1—H31···O1	0.91	2.18	2.984 (7)	147

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₆H₅NO₂·C₆H₆O₂
M_r	233.22
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	6.9710 (14), 6.9855 (14), 21.806 (4)
V (Å³)	1061.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.21 × 0.18 × 0.16

Data collection
Diffractometer	Stoe IPDSII two-circle
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11928, 1196, 1105
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.612

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.096, 0.197, 1.23
No. of reflections	1196
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.34

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), XP in SHELXTL-Plus (Sheldrick, 2008), PLATON (Spek, 2009) and SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O11ⁱ	0.84	1.84	2.655 (6)	163.2
O2—H2···O12	0.84	1.89	2.662 (7)	153.1
N1—H31···O12	0.91	2.16	2.617 (7)	110.0
N1—H31···O1	0.91	2.18	2.984 (7)	147.2

Symmetry code: (i) x+1, y, z.

References

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
Stoe & Cie (2001). X-AREA and X-RED. Stoe & Cie, Darmstadt, Germany. Google Scholar
Ton, Q. C. & Bolte, M. (2005). Acta Cryst. E61, o1406–o1407. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Tutughamiarso, M., Bolte, M. & Egert, E. (2009). Acta Cryst. C65, o574–o578. Web of Science CSD CrossRef IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2834

https://doi.org/10.1107/S1600536809043207

Open

access