3,4-Dihy­droxy­benzoic acid pyridine monosolvate

Zhu, L.-C.

doi:10.1107/S1600536810047082

organic compounds

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Volume 66| Part 12| December 2010| Page o3225

https://doi.org/10.1107/S1600536810047082

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3,4-Dihydroxybenzoic acid pyridine monosolvate

Li-Cai Zhu ^a ^*

^aSchool of Chemistry and the Environment, South China Normal University, Guangzhou 510631, People's Republic of China
^*Correspondence e-mail: licaizhu1977@yahoo.com.cn

(Received 14 October 2010; accepted 13 November 2010; online 20 November 2010)

The asymmetric unit of the title compound, C₇H₆O₄·C₅H₅N, consists of one 3,4-dihydroxybenzoic acid and one pyridine molecule, both located on general positions. The 3,4-dihydroxybenzoic acid molecules are arranged in layers and are connected by intermolecular O—H⋯O hydrogen bonding, forming channels along the a axis in which the pyridine molecules are located. The pyridine and the acid molecules are additionally linked by strong O—H⋯N hydrogen bonding and by weak π–π stacking interactions with centroid–centroid distances between the pyridine rings of 3.727 (2) Å.

Related literature

For related structures see: Aitipamula & Nangia (2005 ); Mazurek et al. (2007 ).

Experimental

Crystal data

C₇H₆O₄·C₅H₅N
M_r = 233.22
Monoclinic, P 2₁ /c
a = 11.9907 (11) Å
b = 9.1400 (8) Å
c = 10.3541 (9) Å
β = 108.042 (1)°
V = 1078.96 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.30 × 0.28 × 0.26 mm

Data collection

Bruker APEXII area-detector diffractometer
5415 measured reflections
1939 independent reflections
1484 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.107
S = 1.05
1939 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O4ⁱ	0.82	1.95	2.6631 (17)	145
O2—H2⋯O1ⁱⁱ	0.82	1.95	2.7654 (16)	173
O3—H3⋯N1ⁱⁱⁱ	0.82	1.77	2.5869 (19)	177
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x, y-1, z.

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, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810047082/nc2201sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047082/nc2201Isup2.hkl

checkCIF report

Comment top

The title compound was obtained unexpectedly in an unsuccessful attempt to prepare a 3,4-dihydroxybenzoate zinc complex. To identify the product a single crystal structure determination was performed. In the crystal structure of the title compound (Fig. 1), the 3,4-dihydroxybenzoic acid molecules are connected via intermolecular O—H···O hydrogen bonding into layers, that are located in the b-c-plane (Table 1 and Fig. 2). These layers are stacked in order that channels are formed, that elongate in the direction of the b axis. The channels are occupied by solvate molecules in a manner similar to that observed previously in related structure (Aitipamula & Nangia, 2005; Mazurek et al., 2007). The pyridine solvate molecules within the channels are connected to the acid molecules by O—H···N hydrogen bonding and by weak π-π stacking interactions with centroid-to-centroid distances between related pyridine rings of 3.727 (2)Å (Fig. 2).

Related literature top

For related structures see: Aitipamula & Nangia (2005); Mazurek et al. (2007).

Experimental top

The compound was obtained unexpectedly in an unsuccessful attempt to prepare a 3,4-dihydroxybenzoate zinc complex. A mixture of 3,4-dihydroxybenzoic acid (0.31 g, 2 mmol), zinc chloride (0.136 g, 1 mmol) and pyridine (0.16 ml, 2 mmol) was stirred with methanol (15 ml) for 0.5 h at room temperature. Several days later, colorless block crystals suitable for X-ray analysis were obtained by slow evaporation of the mixed solution.

Structure description top

For related structures see: Aitipamula & Nangia (2005); Mazurek et al. (2007).

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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure showing the atomic-numbering scheme and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The molecular packing showing the intermolecular hydrogen bonding interactions as broken lines.

3,4-Dihydroxybenzoic acid pyridine monosolvate top

Crystal data top

C₇H₆O₄·C₅H₅N	F(000) = 488
M_r = 233.22	D_x = 1.436 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1420 reflections
a = 11.9907 (11) Å	θ = 2.9–25.4°
b = 9.1400 (8) Å	µ = 0.11 mm⁻¹
c = 10.3541 (9) Å	T = 296 K
β = 108.042 (1)°	Block, colorless
V = 1078.96 (17) Å³	0.30 × 0.28 × 0.26 mm
Z = 4

Data collection top

Bruker APEXII area-detector diffractometer	1484 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 25.2°, θ_min = 1.8°
f and ω scan	h = −6→14
5415 measured reflections	k = −10→10
1939 independent reflections	l = −12→12

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0507P)² + 0.1871P] where P = (F_o² + 2F_c²)/3
1939 reflections	(Δ/σ)_max < 0.001
157 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₇H₆O₄·C₅H₅N	V = 1078.96 (17) Å³
M_r = 233.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.9907 (11) Å	µ = 0.11 mm⁻¹
b = 9.1400 (8) Å	T = 296 K
c = 10.3541 (9) Å	0.30 × 0.28 × 0.26 mm
β = 108.042 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	1484 reflections with I > 2σ(I)
5415 measured reflections	R_int = 0.028
1939 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.05	Δρ_max = 0.19 e Å⁻³
1939 reflections	Δρ_min = −0.20 e Å⁻³
157 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	0.10603 (14)	0.03303 (18)	0.32574 (17)	0.0312 (4)
H1	0.0994	−0.0100	0.2423	0.037*
C2	0.02226 (14)	0.13119 (18)	0.33621 (16)	0.0298 (4)
C3	0.03141 (15)	0.19523 (18)	0.46141 (17)	0.0325 (4)
C4	0.12446 (16)	0.1597 (2)	0.57352 (17)	0.0386 (4)
H4	0.1305	0.2020	0.6571	0.046*
C5	0.20928 (15)	0.0613 (2)	0.56300 (17)	0.0377 (4)
H5	0.2719	0.0382	0.6392	0.045*
C6	0.20063 (14)	−0.00256 (18)	0.43869 (16)	0.0307 (4)
C7	0.28879 (14)	−0.11003 (19)	0.42301 (17)	0.0329 (4)
C8	0.50997 (17)	0.6408 (2)	0.35399 (19)	0.0449 (5)
H8	0.4397	0.6633	0.2877	0.054*
C9	0.58295 (18)	0.5384 (2)	0.3254 (2)	0.0503 (5)
H9	0.5626	0.4930	0.2408	0.060*
C10	0.68609 (18)	0.5041 (2)	0.4233 (2)	0.0500 (5)
H10	0.7361	0.4339	0.4067	0.060*
C11	0.71475 (17)	0.5750 (2)	0.5466 (2)	0.0496 (5)
H11	0.7847	0.5545	0.6142	0.060*
C12	0.63792 (17)	0.6765 (2)	0.56739 (19)	0.0455 (5)
H12	0.6573	0.7247	0.6505	0.055*
O1	−0.06869 (10)	0.16177 (13)	0.22200 (11)	0.0382 (3)
H1A	−0.1153	0.2163	0.2415	0.057*
O2	−0.05466 (11)	0.29250 (14)	0.46347 (12)	0.0425 (3)
H2	−0.0526	0.3074	0.5423	0.064*
O3	0.38824 (10)	−0.10876 (15)	0.51991 (13)	0.0486 (4)
H3	0.4329	−0.1683	0.5030	0.073*
O4	0.26885 (10)	−0.19100 (13)	0.32362 (12)	0.0384 (3)
N1	0.53651 (13)	0.70907 (16)	0.47356 (15)	0.0406 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0317 (9)	0.0346 (9)	0.0286 (9)	−0.0025 (8)	0.0110 (7)	−0.0007 (7)
C2	0.0274 (9)	0.0338 (9)	0.0265 (8)	−0.0004 (7)	0.0060 (7)	0.0050 (7)
C3	0.0339 (9)	0.0334 (9)	0.0329 (9)	0.0022 (8)	0.0140 (8)	0.0023 (7)
C4	0.0411 (10)	0.0464 (10)	0.0272 (9)	0.0039 (9)	0.0089 (8)	−0.0040 (8)
C5	0.0326 (10)	0.0453 (10)	0.0309 (9)	0.0041 (8)	0.0039 (8)	0.0002 (8)
C6	0.0278 (9)	0.0340 (9)	0.0299 (9)	−0.0015 (7)	0.0086 (7)	0.0016 (7)
C7	0.0287 (9)	0.0366 (9)	0.0323 (9)	−0.0012 (8)	0.0081 (8)	0.0032 (7)
C8	0.0391 (11)	0.0522 (12)	0.0403 (11)	0.0056 (9)	0.0075 (9)	−0.0002 (9)
C9	0.0507 (12)	0.0546 (12)	0.0460 (11)	0.0056 (10)	0.0158 (10)	−0.0064 (10)
C10	0.0480 (12)	0.0494 (12)	0.0568 (13)	0.0128 (10)	0.0225 (11)	0.0041 (10)
C11	0.0397 (11)	0.0587 (13)	0.0477 (12)	0.0116 (10)	0.0093 (9)	0.0084 (10)
C12	0.0424 (11)	0.0538 (12)	0.0376 (10)	0.0046 (10)	0.0087 (9)	−0.0006 (9)
O1	0.0351 (7)	0.0481 (8)	0.0290 (6)	0.0102 (6)	0.0065 (6)	0.0007 (5)
O2	0.0464 (8)	0.0500 (8)	0.0311 (7)	0.0165 (6)	0.0122 (6)	0.0008 (6)
O3	0.0322 (7)	0.0618 (9)	0.0437 (8)	0.0133 (7)	0.0001 (6)	−0.0137 (6)
O4	0.0309 (7)	0.0457 (7)	0.0363 (7)	0.0017 (6)	0.0072 (5)	−0.0079 (6)
N1	0.0361 (9)	0.0441 (9)	0.0409 (9)	0.0054 (7)	0.0109 (7)	0.0005 (7)

Geometric parameters (Å, º) top

C1—C2	1.376 (2)	C8—N1	1.334 (2)
C1—C6	1.392 (2)	C8—C9	1.375 (3)
C1—H1	0.9300	C8—H8	0.9300
C2—O1	1.3664 (18)	C9—C10	1.371 (3)
C2—C3	1.395 (2)	C9—H9	0.9300
C3—O2	1.367 (2)	C10—C11	1.377 (3)
C3—C4	1.377 (2)	C10—H10	0.9300
C4—C5	1.387 (2)	C11—C12	1.371 (3)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.388 (2)	C12—N1	1.334 (2)
C5—H5	0.9300	C12—H12	0.9300
C6—C7	1.488 (2)	O1—H1A	0.8200
C7—O4	1.2294 (19)	O2—H2	0.8200
C7—O3	1.299 (2)	O3—H3	0.8200

C2—C1—C6	120.72 (15)	O3—C7—C6	115.02 (15)
C2—C1—H1	119.6	N1—C8—C9	122.25 (18)
C6—C1—H1	119.6	N1—C8—H8	118.9
O1—C2—C1	118.14 (14)	C9—C8—H8	118.9
O1—C2—C3	122.02 (15)	C10—C9—C8	118.97 (19)
C1—C2—C3	119.83 (15)	C10—C9—H9	120.5
O2—C3—C4	123.97 (15)	C8—C9—H9	120.5
O2—C3—C2	116.41 (15)	C9—C10—C11	119.18 (19)
C4—C3—C2	119.62 (15)	C9—C10—H10	120.4
C3—C4—C5	120.62 (16)	C11—C10—H10	120.4
C3—C4—H4	119.7	C12—C11—C10	118.50 (19)
C5—C4—H4	119.7	C12—C11—H11	120.7
C4—C5—C6	119.97 (16)	C10—C11—H11	120.7
C4—C5—H5	120.0	N1—C12—C11	122.82 (18)
C6—C5—H5	120.0	N1—C12—H12	118.6
C5—C6—C1	119.23 (15)	C11—C12—H12	118.6
C5—C6—C7	121.82 (15)	C2—O1—H1A	109.5
C1—C6—C7	118.94 (15)	C3—O2—H2	109.5
O4—C7—O3	123.08 (16)	C7—O3—H3	109.5
O4—C7—C6	121.87 (15)	C8—N1—C12	118.25 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4ⁱ	0.82	1.95	2.6631 (17)	145
O2—H2···O1ⁱⁱ	0.82	1.95	2.7654 (16)	173
O3—H3···N1ⁱⁱⁱ	0.82	1.77	2.5869 (19)	177

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

Experimental details

Crystal data
Chemical formula	C₇H₆O₄·C₅H₅N
M_r	233.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	11.9907 (11), 9.1400 (8), 10.3541 (9)
β (°)	108.042 (1)
V (Å³)	1078.96 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.28 × 0.26

Data collection
Diffractometer	Bruker APEXII area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5415, 1939, 1484
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.107, 1.05
No. of reflections	1939
No. of parameters	157
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.20

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4ⁱ	0.82	1.95	2.6631 (17)	145.4
O2—H2···O1ⁱⁱ	0.82	1.95	2.7654 (16)	172.9
O3—H3···N1ⁱⁱⁱ	0.82	1.77	2.5869 (19)	176.5

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

Acknowledgements

The author acknowledges South China Normal University for supporting this work.

References

Aitipamula, S. & Nangia, A. (2005). Supramol. Chem. 17, 17–25. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Mazurek, J., Dova, E. & Helmond, R. (2007). Acta Cryst. E63, o3289. Web of Science CSD CrossRef IUCr Journals Google Scholar
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