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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1551.
Published online 2010 June 5. doi:  10.1107/S1600536810020337
PMCID: PMC3006685

4-Amino­benzoic acid–1,2-bis­(4-pyrid­yl)ethane (2/1)

Abstract

In the title compound, C12H12N2·2C7H7NO2, the 4-amino­benzoic acid mol­ecules are linked by O—H(...)N hydrogen bonds to 1,2-bis­(4-pyrid­yl)ethane, forming linear hydrogen bonded chains parallel to [2An external file that holds a picture, illustration, etc.
Object name is e-66-o1551-efi1.jpg1]. The structure exhibits a hydrogen-bonding network involving COOH(...)N(pyrid­yl) and amine and carb­oxy­lic N—H(...) O inter­actions. In addition, π–π stacking inter­actions [centroid–centroid distance = 3.8622 (14) Å] are also present.

Related literature

For linear hydrogen bonding associations involving 4-amino­benzoic acid, see: Smith et al. (1997 [triangle]). For related structures, see: Smith et al. (2000 [triangle], 2005 [triangle]); Lynch & McClenaghan (2001 [triangle]). For hydrogen-bond motifs, see: Etter et al. (1990 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1551-scheme1.jpg

Experimental

Crystal data

  • C12H12N2·2C7H7NO2
  • M r = 458.51
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1551-efi2.jpg
  • a = 7.3556 (10) Å
  • b = 23.230 (3) Å
  • c = 7.9373 (11) Å
  • β = 115.579 (2)°
  • V = 1223.3 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 297 K
  • 0.76 × 0.34 × 0.22 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SMART; Bruker, 2000 [triangle]) T min = 0.674, T max = 1.000
  • 6871 measured reflections
  • 2406 independent reflections
  • 1530 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.051
  • wR(F 2) = 0.165
  • S = 1.03
  • 2406 reflections
  • 162 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 1999 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXL97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810020337/pb2029sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810020337/pb2029Isup2.hkl

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

Acknowledgments

This work was supported financially by Yuanpei University.

supplementary crystallographic information

Comment

4-Aminobenzoic acid is a useful ligand for structure extension through both the carboxylic acid and amine functional groups, forming linear hydrogen bonding associations (Smith et al., 2005). Other related reports with 4-aminobenzoic acid and Lewis base such as 4-(4-nitrobenzyl)pyridine (Smith, 1997), 4-aminobenzonitrile (Smith et al., 2000) and 2-amino-4-(4-pyridyl)pyrimidine (Lynch & McClenaghan, 2001).

We present here the crystal structure analysis of the 2:1 4-aminobenzoic acid and 1,2-bis(4-pyridyl)ethane adduct (Fig 1). The structure of the title compound comprises two 4-aminobenzoic acid molecules and one 1,2-bis(4-pyridyl)ethane molecule, with no proton transfer. In the structure, the molecules associate 4-aminobenzoic acid and 1,2-bis(4-pyridyl)ethane via carboxylic and pyridine group O—H···N [ O···N 2.613 (2) Å ] D22 12( Etter et al., 1990), forming linear hydrogen bonding parallel to [ 2 1 1], further connect into a three dimensional network via amine and carboxylic N—H··· O [N···O 3.030 (3) and 3.081 (3) Å ], respectively.

The title compound's supramolecular structure can be readily analyzed in terms of pyridyl atom N2 acts as hydrogen-bond donor to carboxyl atom O2. Similarly, O1 acts as hydrogen-bond donor to amino group N1, respectively (Table 1 and Fig. 2). Furthermore, p -p ring stacking interaction is between neighboring heteraromatic ring in the structure. The distance between Cg1 (N2/C8—C12)···Cg1i is 3.8622 (14) Å[ symmetry code: (i) = 2-X,1-Y,1-Z].

Experimental

The 4-aminobenzoic acid (0.137 mg, 1.0 mmol) and 1,2-bis(4-pyridyl)ethane (184 mg, 1.0 mmol) were dissolved in 20 ml 50% methanol-water, the solution was refluxed for 30 min. The filtered solution was transferred to a 25 ml tube after one week at room temperature, and colorless transparent crystals formed (yield 60.48%).

Refinement

N and O-bound H atoms were located in a difference Fourier map and were refined isotropically. Other H atoms were positioned geometrically with C—H=0.93 (aromatic) and 0.97 Å(methylene), and refined using a riding model with Uiso(H)=1.2Ueq(C).

Figures

Fig. 1.
View of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
The molecular packing for the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.

Crystal data

C12H12N2·2C7H7NO2F(000) = 484
Mr = 458.51Dx = 1.239 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2347 reflections
a = 7.3556 (10) Åθ = 3.0–23.7°
b = 23.230 (3) ŵ = 0.09 mm1
c = 7.9373 (11) ÅT = 297 K
β = 115.579 (2)°Parallelepiped, colorless
V = 1223.3 (3) Å30.76 × 0.34 × 0.22 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer2406 independent reflections
Radiation source: fine-focus sealed tube1530 reflections with I > 2σ(I)
graphiteRint = 0.032
phi and ω scansθmax = 26.1°, θmin = 1.8°
Absorption correction: multi-scan (SMART; Bruker, 2000)h = −9→5
Tmin = 0.674, Tmax = 1.000k = −27→28
6871 measured reflectionsl = −9→9

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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.165H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0959P)2 + 0.0431P] where P = (Fo2 + 2Fc2)/3
2406 reflections(Δ/σ)max < 0.001
162 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = −0.23 e Å3
0 constraints

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
N21.1453 (2)0.43421 (8)0.3904 (2)0.0738 (7)
C81.0950 (3)0.48682 (10)0.3233 (3)0.0783 (8)
C90.8987 (3)0.50396 (11)0.2231 (4)0.0864 (9)
C100.7437 (3)0.46541 (11)0.1882 (3)0.0739 (8)
C110.7978 (3)0.41122 (10)0.2571 (3)0.0806 (8)
C120.9970 (3)0.39735 (10)0.3566 (3)0.0826 (9)
C130.5251 (3)0.48182 (15)0.0801 (4)0.1066 (13)
O10.4674 (2)0.33090 (7)0.4157 (2)0.0841 (5)
O20.51671 (19)0.40480 (7)0.6066 (2)0.0837 (6)
N11.3716 (3)0.28863 (10)1.0252 (3)0.0824 (8)
C10.5750 (3)0.35702 (8)0.5572 (3)0.0624 (6)
C20.7798 (3)0.33843 (8)0.6832 (2)0.0560 (6)
C30.8914 (3)0.36554 (8)0.8520 (3)0.0621 (6)
C41.0858 (3)0.34892 (8)0.9655 (3)0.0649 (6)
C51.1749 (3)0.30406 (8)0.9143 (3)0.0601 (6)
C61.0617 (3)0.27578 (9)0.7479 (3)0.0722 (7)
C70.8687 (3)0.29233 (9)0.6355 (3)0.0690 (7)
H8A1.197100.513500.345000.0940*
H9A0.870200.541500.178800.1040*
H11A0.699100.383500.236500.0970*
H12A1.029500.360100.402800.0990*
H13A0.447000.446700.039000.1280*
H13B0.481900.501000.165100.1280*
H1A1.413 (4)0.3021 (12)1.142 (4)0.108 (9)*
H1B1.409 (3)0.2543 (12)0.988 (3)0.095 (8)*
H2A0.387300.412200.527800.1600*
H3A0.833800.395600.889400.0750*
H4A1.158000.368001.077800.0780*
H6A1.118100.245000.712100.0870*
H7A0.795500.272400.525100.0830*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N20.0497 (10)0.0777 (12)0.0824 (12)0.0081 (8)0.0176 (9)0.0039 (9)
C80.0490 (11)0.0770 (14)0.0935 (16)−0.0026 (10)0.0163 (11)0.0066 (12)
C90.0549 (13)0.0798 (15)0.1084 (18)0.0100 (10)0.0201 (12)0.0279 (13)
C100.0445 (10)0.0941 (16)0.0755 (13)0.0038 (10)0.0189 (9)0.0124 (11)
C110.0565 (13)0.0847 (15)0.0937 (15)−0.0058 (10)0.0260 (12)0.0087 (12)
C120.0670 (14)0.0707 (13)0.1014 (17)0.0099 (11)0.0281 (13)0.0117 (12)
C130.0498 (13)0.146 (3)0.110 (2)0.0138 (13)0.0212 (13)0.0438 (17)
O10.0607 (8)0.0805 (10)0.0741 (9)−0.0025 (7)−0.0058 (7)−0.0085 (8)
O20.0553 (8)0.0796 (10)0.0888 (11)0.0151 (7)0.0052 (7)−0.0106 (8)
N10.0556 (11)0.0881 (14)0.0825 (14)0.0129 (10)0.0100 (10)0.0009 (11)
C10.0496 (10)0.0616 (11)0.0620 (11)−0.0040 (8)0.0110 (9)0.0041 (9)
C20.0480 (10)0.0548 (10)0.0557 (10)−0.0022 (8)0.0134 (8)0.0004 (8)
C30.0574 (11)0.0591 (11)0.0592 (11)0.0088 (8)0.0152 (9)−0.0038 (9)
C40.0570 (11)0.0638 (11)0.0546 (10)0.0021 (9)0.0060 (9)−0.0047 (9)
C50.0483 (10)0.0596 (11)0.0627 (11)0.0042 (8)0.0147 (9)0.0075 (9)
C60.0662 (12)0.0703 (12)0.0705 (12)0.0141 (10)0.0206 (10)−0.0085 (10)
C70.0628 (12)0.0690 (12)0.0593 (11)0.0029 (9)0.0114 (9)−0.0099 (9)

Geometric parameters (Å, °)

O1—C11.220 (3)C11—H11A0.9300
O2—C11.310 (3)C12—H12A0.9300
O2—H2A0.9000C13—H13B0.9700
N2—C121.320 (3)C13—H13A0.9700
N2—C81.321 (3)C1—C21.468 (3)
N1—C51.377 (3)C2—C71.390 (3)
N1—H1A0.90 (3)C2—C31.384 (3)
N1—H1B0.93 (3)C3—C41.376 (3)
C8—C91.373 (4)C4—C51.382 (3)
C9—C101.381 (4)C5—C61.386 (3)
C10—C131.509 (4)C6—C71.366 (3)
C10—C111.362 (3)C3—H3A0.9300
C11—C121.369 (3)C4—H4A0.9300
C13—C13i1.436 (4)C6—H6A0.9300
C8—H8A0.9300C7—H7A0.9300
C9—H9A0.9300
O1···N1ii3.081 (3)C12···H4Axi3.0000
O1···N1iii3.030 (3)C13···H9Ai2.7900
O2···N2iv2.613 (2)H1A···O1vii2.14 (3)
O1···H1Aiii2.14 (3)H1A···H4A2.3000
O1···H1Bii2.16 (3)H1B···H6A2.3200
O1···H7A2.5700H1B···O1viii2.16 (3)
O1···H11A2.9200H1B···C1viii2.81 (3)
O1···H4Aiii2.8000H2A···C8iv2.6900
O2···H3A2.4500H2A···C12iv2.6200
O2···H8Av2.7400H2A···N2iv1.7200
O2···H13Bvi2.8400H3A···O22.4500
N1···O1vii3.030 (3)H3A···C11xii3.0600
N1···O1viii3.081 (3)H4A···H1A2.3000
N2···O2ix2.613 (2)H4A···C12xii3.0000
N2···C1ix3.368 (3)H4A···O1vii2.8000
N1···H6Ax2.9500H6A···H1B2.3200
N2···H2Aix1.7200H6A···N1xiii2.9500
C1···N2iv3.368 (3)H6A···C4xiii2.8700
C3···C9v3.567 (3)H6A···C5xiii2.8100
C8···C9v3.587 (4)H7A···O12.5700
C9···C8v3.587 (4)H8A···O2v2.7400
C9···C3v3.567 (3)H9A···C4v2.8700
C1···H1Bii2.81 (3)H9A···C13i2.7900
C3···H9Av2.8600H9A···C3v2.8600
C4···H9Av2.8700H9A···H13Ai2.2400
C4···H6Ax2.8700H11A···O12.9200
C5···H6Ax2.8100H11A···H13A2.3500
C7···H12A3.0300H12A···C73.0300
C8···H2Aix2.6900H13A···H11A2.3500
C9···H13Ai2.7500H13A···C9i2.7500
C11···H3Axi3.0600H13A···H9Ai2.2400
C12···H2Aix2.6200H13B···O2vi2.8400
C1—O2—H2A110.00C13i—C13—H13A108.00
C8—N2—C12117.08 (19)C13i—C13—H13B108.00
C5—N1—H1A111 (2)O2—C1—C2114.69 (17)
C5—N1—H1B113.1 (14)O1—C1—O2122.1 (2)
H1A—N1—H1B128 (2)O1—C1—C2123.22 (19)
N2—C8—C9122.9 (2)C1—C2—C7120.41 (16)
C8—C9—C10119.9 (2)C3—C2—C7117.52 (19)
C9—C10—C11116.5 (2)C1—C2—C3122.07 (19)
C11—C10—C13121.1 (2)C2—C3—C4121.4 (2)
C9—C10—C13122.4 (2)C3—C4—C5120.6 (2)
C10—C11—C12120.2 (2)N1—C5—C4120.6 (2)
N2—C12—C11123.3 (2)C4—C5—C6118.1 (2)
C10—C13—C13i117.1 (2)N1—C5—C6121.3 (2)
C9—C8—H8A118.00C5—C6—C7121.1 (2)
N2—C8—H8A119.00C2—C7—C6121.17 (19)
C8—C9—H9A120.00C2—C3—H3A119.00
C10—C9—H9A120.00C4—C3—H3A119.00
C10—C11—H11A120.00C3—C4—H4A120.00
C12—C11—H11A120.00C5—C4—H4A120.00
N2—C12—H12A118.00C5—C6—H6A119.00
C11—C12—H12A118.00C7—C6—H6A119.00
C10—C13—H13B108.00C2—C7—H7A119.00
H13A—C13—H13B107.00C6—C7—H7A119.00
C10—C13—H13A108.00
C12—N2—C8—C90.3 (3)O2—C1—C2—C37.6 (3)
C8—N2—C12—C110.0 (3)O2—C1—C2—C7−172.38 (19)
N2—C8—C9—C10−0.2 (4)C1—C2—C3—C4−177.7 (2)
C8—C9—C10—C11−0.3 (4)C7—C2—C3—C42.3 (3)
C8—C9—C10—C13179.6 (2)C1—C2—C7—C6177.6 (2)
C9—C10—C11—C120.6 (3)C3—C2—C7—C6−2.3 (3)
C13—C10—C11—C12−179.3 (2)C2—C3—C4—C5−0.5 (3)
C9—C10—C13—C13i40.3 (4)C3—C4—C5—N1178.0 (2)
C11—C10—C13—C13i−139.9 (3)C3—C4—C5—C6−1.2 (3)
C10—C11—C12—N2−0.4 (3)N1—C5—C6—C7−178.0 (2)
C10—C13—C13i—C10i−180.0 (2)C4—C5—C6—C71.2 (3)
O1—C1—C2—C3−173.5 (2)C5—C6—C7—C20.6 (3)
O1—C1—C2—C76.5 (3)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, −y+1/2, z−1/2; (iii) x−1, y, z−1; (iv) x−1, y, z; (v) −x+2, −y+1, −z+1; (vi) −x+1, −y+1, −z+1; (vii) x+1, y, z+1; (viii) x+1, −y+1/2, z+1/2; (ix) x+1, y, z; (x) x, −y+1/2, z+1/2; (xi) x, y, z−1; (xii) x, y, z+1; (xiii) x, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O1vii0.90 (3)2.14 (3)3.030 (3)171 (3)
N1—H1B···O1viii0.93 (3)2.16 (3)3.081 (3)172 (2)
O2—H2A···N2iv0.901.722.613 (2)173

Symmetry codes: (vii) x+1, y, z+1; (viii) x+1, −y+1/2, z+1/2; (iv) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PB2029).

References

  • Bruker (1999). SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2000). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. [PubMed]
  • Lynch, D. E. & McClenaghan, I. (2001). Acta Cryst. C57, 830–832. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Smith, G., Baldry, K. E., Byriel, K. A. & Kennard, C. H. L. (1997). Aust. J. Chem.50, 727–736.
  • Smith, G., Wermuth, U. D. & White, J. M. (2005). Acta Cryst. E61, o313–o316.
  • Smith, G., Bott, R. C. & Lynch, D. E. (2000). Acta Cryst. C56, 1155–1156. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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