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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3225.
Published online 2010 November 20. doi:  10.1107/S1600536810047082
PMCID: PMC3011498

3,4-Dihy­droxy­benzoic acid pyridine monosolvate

Abstract

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 [triangle]); Mazurek et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3225-scheme1.jpg

Experimental

Crystal data

  • C7H6O4·C5H5N
  • M r = 233.22
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3225-efi1.jpg
  • 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[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.107
  • S = 1.05
  • 1939 reflections
  • 157 parameters
  • H-atom parameters constrained
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047082/nc2201Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H atoms were placed at calculated positions (O-H H atoms allowed to rotate but not to tip and were treated as riding, with C—H = 0.93 and O—H = 0.82 Å, and with Uiso(H) = 1.2 or 1.5 Ueq(C, O).

Figures

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.

Crystal data

C7H6O4·C5H5NF(000) = 488
Mr = 233.22Dx = 1.436 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1420 reflections
a = 11.9907 (11) Åθ = 2.9–25.4°
b = 9.1400 (8) ŵ = 0.11 mm1
c = 10.3541 (9) ÅT = 296 K
β = 108.042 (1)°Block, colorless
V = 1078.96 (17) Å30.30 × 0.28 × 0.26 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer1484 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.028
graphiteθmax = 25.2°, θmin = 1.8°
f and ω scanh = −6→14
5415 measured reflectionsk = −10→10
1939 independent reflectionsl = −12→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0507P)2 + 0.1871P] where P = (Fo2 + 2Fc2)/3
1939 reflections(Δ/σ)max < 0.001
157 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = −0.20 e Å3

Special details

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)

xyzUiso*/Ueq
C10.10603 (14)0.03303 (18)0.32574 (17)0.0312 (4)
H10.0994−0.01000.24230.037*
C20.02226 (14)0.13119 (18)0.33621 (16)0.0298 (4)
C30.03141 (15)0.19523 (18)0.46141 (17)0.0325 (4)
C40.12446 (16)0.1597 (2)0.57352 (17)0.0386 (4)
H40.13050.20200.65710.046*
C50.20928 (15)0.0613 (2)0.56300 (17)0.0377 (4)
H50.27190.03820.63920.045*
C60.20063 (14)−0.00256 (18)0.43869 (16)0.0307 (4)
C70.28879 (14)−0.11003 (19)0.42301 (17)0.0329 (4)
C80.50997 (17)0.6408 (2)0.35399 (19)0.0449 (5)
H80.43970.66330.28770.054*
C90.58295 (18)0.5384 (2)0.3254 (2)0.0503 (5)
H90.56260.49300.24080.060*
C100.68609 (18)0.5041 (2)0.4233 (2)0.0500 (5)
H100.73610.43390.40670.060*
C110.71475 (17)0.5750 (2)0.5466 (2)0.0496 (5)
H110.78470.55450.61420.060*
C120.63792 (17)0.6765 (2)0.56739 (19)0.0455 (5)
H120.65730.72470.65050.055*
O1−0.06869 (10)0.16177 (13)0.22200 (11)0.0382 (3)
H1A−0.11530.21630.24150.057*
O2−0.05466 (11)0.29250 (14)0.46347 (12)0.0425 (3)
H2−0.05260.30740.54230.064*
O30.38824 (10)−0.10876 (15)0.51991 (13)0.0486 (4)
H30.4329−0.16830.50300.073*
O40.26885 (10)−0.19100 (13)0.32362 (12)0.0384 (3)
N10.53651 (13)0.70907 (16)0.47356 (15)0.0406 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0317 (9)0.0346 (9)0.0286 (9)−0.0025 (8)0.0110 (7)−0.0007 (7)
C20.0274 (9)0.0338 (9)0.0265 (8)−0.0004 (7)0.0060 (7)0.0050 (7)
C30.0339 (9)0.0334 (9)0.0329 (9)0.0022 (8)0.0140 (8)0.0023 (7)
C40.0411 (10)0.0464 (10)0.0272 (9)0.0039 (9)0.0089 (8)−0.0040 (8)
C50.0326 (10)0.0453 (10)0.0309 (9)0.0041 (8)0.0039 (8)0.0002 (8)
C60.0278 (9)0.0340 (9)0.0299 (9)−0.0015 (7)0.0086 (7)0.0016 (7)
C70.0287 (9)0.0366 (9)0.0323 (9)−0.0012 (8)0.0081 (8)0.0032 (7)
C80.0391 (11)0.0522 (12)0.0403 (11)0.0056 (9)0.0075 (9)−0.0002 (9)
C90.0507 (12)0.0546 (12)0.0460 (11)0.0056 (10)0.0158 (10)−0.0064 (10)
C100.0480 (12)0.0494 (12)0.0568 (13)0.0128 (10)0.0225 (11)0.0041 (10)
C110.0397 (11)0.0587 (13)0.0477 (12)0.0116 (10)0.0093 (9)0.0084 (10)
C120.0424 (11)0.0538 (12)0.0376 (10)0.0046 (10)0.0087 (9)−0.0006 (9)
O10.0351 (7)0.0481 (8)0.0290 (6)0.0102 (6)0.0065 (6)0.0007 (5)
O20.0464 (8)0.0500 (8)0.0311 (7)0.0165 (6)0.0122 (6)0.0008 (6)
O30.0322 (7)0.0618 (9)0.0437 (8)0.0133 (7)0.0001 (6)−0.0137 (6)
O40.0309 (7)0.0457 (7)0.0363 (7)0.0017 (6)0.0072 (5)−0.0079 (6)
N10.0361 (9)0.0441 (9)0.0409 (9)0.0054 (7)0.0109 (7)0.0005 (7)

Geometric parameters (Å, °)

C1—C21.376 (2)C8—N11.334 (2)
C1—C61.392 (2)C8—C91.375 (3)
C1—H10.9300C8—H80.9300
C2—O11.3664 (18)C9—C101.371 (3)
C2—C31.395 (2)C9—H90.9300
C3—O21.367 (2)C10—C111.377 (3)
C3—C41.377 (2)C10—H100.9300
C4—C51.387 (2)C11—C121.371 (3)
C4—H40.9300C11—H110.9300
C5—C61.388 (2)C12—N11.334 (2)
C5—H50.9300C12—H120.9300
C6—C71.488 (2)O1—H1A0.8200
C7—O41.2294 (19)O2—H20.8200
C7—O31.299 (2)O3—H30.8200
C2—C1—C6120.72 (15)O3—C7—C6115.02 (15)
C2—C1—H1119.6N1—C8—C9122.25 (18)
C6—C1—H1119.6N1—C8—H8118.9
O1—C2—C1118.14 (14)C9—C8—H8118.9
O1—C2—C3122.02 (15)C10—C9—C8118.97 (19)
C1—C2—C3119.83 (15)C10—C9—H9120.5
O2—C3—C4123.97 (15)C8—C9—H9120.5
O2—C3—C2116.41 (15)C9—C10—C11119.18 (19)
C4—C3—C2119.62 (15)C9—C10—H10120.4
C3—C4—C5120.62 (16)C11—C10—H10120.4
C3—C4—H4119.7C12—C11—C10118.50 (19)
C5—C4—H4119.7C12—C11—H11120.7
C4—C5—C6119.97 (16)C10—C11—H11120.7
C4—C5—H5120.0N1—C12—C11122.82 (18)
C6—C5—H5120.0N1—C12—H12118.6
C5—C6—C1119.23 (15)C11—C12—H12118.6
C5—C6—C7121.82 (15)C2—O1—H1A109.5
C1—C6—C7118.94 (15)C3—O2—H2109.5
O4—C7—O3123.08 (16)C7—O3—H3109.5
O4—C7—C6121.87 (15)C8—N1—C12118.25 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1A···O4i0.821.952.6631 (17)145
O2—H2···O1ii0.821.952.7654 (16)173
O3—H3···N1iii0.821.772.5869 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2201).

References

  • Aitipamula, S. & Nangia, A. (2005). Supramol. Chem.17, 17–25.
  • Bruker (2004). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Mazurek, J., Dova, E. & Helmond, R. (2007). Acta Cryst. E63, o3289.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography