organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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4,4′-Bi­pyridine–cyano­acetic acid (1/2)

aCollege of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007, People's Republic of China
*Correspondence e-mail: guocx2008@126.com

(Received 16 September 2008; accepted 27 September 2008; online 4 October 2008)

Crystals of the title adduct, C10H8N2·2C3H3NO2, were obtained from a methanol/water solution of cyano­acetic acid and 4,4′-bipyridine at room temperature. In the crystal structure, cyano­acetic acid and centrosymmetric 4,4′-bipyridine mol­ecules are linked by O—H⋯N hydrogen bonds to form three-component supra­molecular adducts. The acidic H atom is almost midway between the O and N atoms of the cyano­acetic acid and bipyridine mol­ecules, with O—H and N—H distances of 1.19 (3) and 1.39 (3) Å, respectively, so that the H-atom transfer is best regarded as partial. The three-component adducts are further inter­connected with neighboring mol­ecules by weak inter­molecular C—H⋯O and C—H⋯N hydrogen bonds and by ππ stacking inter­actions [centroid–centroid distance = 3.7200 (11) Å] to generate a three-dimensional supra­molecular structure.

Related literature

For similar partial proton transfer from a carbonic acid towards a nitro­gen base, see: Farrell et al. (2002a[Farrell, D. M. M., Ferguson, G., Lough, A. J. & Glidewell, C. (2002a). Acta Cryst. B58, 272-288.],b[Farrell, D. M. M., Ferguson, G., Lough, A. J. & Glidewell, C. (2002b). Acta Cryst. B58, 530-544.]); For C—H⋯O and C—H⋯N hydrogen bonds, see: Balakrishna et al. (2005[Balakrishna, R. B., Srinivas, B. & Ashwini, N. (2005). Cryst. Growth Des. 5, 1683-1686.]); Wang et al. (2008[Wang, Y.-T., Tang, G.-M., Zhang, Y.-C. & Wan, W.-Z. (2008). Acta Cryst. E64, o1753.]).

[Scheme 1]

Experimental

Crystal data
  • C10H8N2·2C3H3NO2

  • Mr = 326.31

  • Monoclinic, P 21 /n

  • a = 4.887 (2) Å

  • b = 21.383 (10) Å

  • c = 7.921 (4) Å

  • β = 100.664 (8)°

  • V = 813.4 (7) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 291 (2) K

  • 0.34 × 0.26 × 0.19 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 1997[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.952, Tmax = 0.982

  • 3537 measured reflections

  • 1487 independent reflections

  • 1153 reflections with I > 2σ(I)

  • Rint = 0.031

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.133

  • S = 1.04

  • 1487 reflections

  • 112 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.15 e Å−3

  • Δρmin = −0.15 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C7—H7A⋯N2i 0.97 2.92 3.420 (3) 113
C2—H2⋯O2ii 0.93 2.62 3.361 (3) 137
C2—H2⋯N2iii 0.93 2.75 3.322 (3) 121
O1—H1D⋯N1 1.19 (3) 1.39 (3) 2.566 (2) 170 (2)
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]; (ii) x-1, y, z-1; (iii) [x-{\script{3\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}].

Data collection: SMART (Bruker, 1997[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

A view of the title structure is shown in Fig. 1. The asymmetric unit consists of one cyanoacetic acid molecule and half a 4,4'-bipyridine molecule. The H1D was found in a Fourier map and its position was refined freely. Within the asymmetric unit, atom H1D is almost mid-way between atoms O1 and N1, so that the H-atom transfer is best regarded as partial. The distances of O1—H1D and N1—H1D are 1.19 (3) Å and 1.39 (3) Å, respectively, which are comparable with literature data (Farrell et al., 2002a,b). Cyanoacetic acid and 4,4'-bipyridine molecules are linked by these O—H···N hydrogen bonds to form 3-component supramolecular adducts.

The 3-compenent adducts interact with neigboring molecules via by weak intermolecular C—H···O and C—H···N hydrogen bonds, and by π-π stacking interactions. Within the asymmetric unit, the atoms C2 and C7 act as hydrogen-bond donors, via atoms H2, H2, and H7A, to atoms O2ii , N2iii and N2i, respectively (symmetry operators: i = x + 1/2,-y + 1/2,z + 1/2; ii = x - 1,y,z -1; iii = x - 3/2,-y + 1/2,z - 1/2). The bond lengths and angles of the above three hydrogen bonds (Table 1) are comparable with literature data (Balakrishna et al., 2005; Wang et al., 2008). These hydrogen bonds, albeit rather weak, link the 3-component supramolecular adducts into a three-dimensional supramolecular structure, which is further stabilized by weak intermolecular π-π stacking interactions, formed by adjacent bipyridine rings (centroid–centroid distance = 3.7200 (11) Å) (Fig. 2 and Fig. 3).

Related literature top

For similar partial proton transfer from a carbonic acid towards a nitrogen base, see: Farrell et al. (2002a,b); For C—H···O and C—H···N hydrogen bonds, see: Balakrishna et al. (2005); Wang et al. (2008).

Experimental top

Cyanoacetic acid (0.2 mmol) and 4,4'-bipyridine (0.2 mmol) were dissolved in methanol (5 ml) and water (1 ml) at room temperature. The single crystals of the title compound were obtained from the solution after ten days.

Refinement top

H1D was found in a difference Fourier map and was refined with Uiso(H) = 1.5Ueq(O). All other H atoms were positioned geometrically and treated as riding, with C—H bonding lengths constrained to 0.93 (aromatic CH) or 0.97 Å (methylene CH2), and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title compound, showing 30% probability displacement ellipsoids. Symmetry code: (iv) -x, 1 - y,-z.
[Figure 2] Fig. 2. A view of the three-dimensional hydrogen-bonding pattern network.
[Figure 3] Fig. 3. View of the π-π interactions between bipyridine rings in the crystal structure of the title compound.
4,4'-Bipyridine–cyanoacetic acid (1/2) top
Crystal data top
C10H8N2·2C3H3NO2F(000) = 340
Mr = 326.31Dx = 1.332 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 4.887 (2) ÅCell parameters from 1445 reflections
b = 21.383 (10) Åθ = 2.8–27.1°
c = 7.921 (4) ŵ = 0.10 mm1
β = 100.664 (8)°T = 291 K
V = 813.4 (7) Å3Block, colorless
Z = 20.34 × 0.26 × 0.19 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
1487 independent reflections
Radiation source: fine-focus sealed tube1153 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ϕ and ω scansθmax = 25.5°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 55
Tmin = 0.952, Tmax = 0.982k = 2524
3537 measured reflectionsl = 97
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0577P)2 + 0.1963P]
where P = (Fo2 + 2Fc2)/3
1487 reflections(Δ/σ)max < 0.001
112 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.15 e Å3
Crystal data top
C10H8N2·2C3H3NO2V = 813.4 (7) Å3
Mr = 326.31Z = 2
Monoclinic, P21/nMo Kα radiation
a = 4.887 (2) ŵ = 0.10 mm1
b = 21.383 (10) ÅT = 291 K
c = 7.921 (4) Å0.34 × 0.26 × 0.19 mm
β = 100.664 (8)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1487 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
1153 reflections with I > 2σ(I)
Tmin = 0.952, Tmax = 0.982Rint = 0.031
3537 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.16 e Å3
1487 reflectionsΔρmin = 0.15 e Å3
112 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.9569 (3)0.33450 (7)0.35022 (19)0.0763 (5)
H1D0.779 (6)0.3714 (12)0.298 (3)0.114*
O21.0674 (4)0.40335 (8)0.5596 (2)0.1022 (6)
N10.5590 (3)0.40726 (7)0.21445 (19)0.0595 (4)
N21.4242 (5)0.21975 (10)0.3693 (3)0.1017 (7)
C10.3898 (4)0.38664 (9)0.0757 (3)0.0729 (6)
H10.41960.34680.03540.087*
C20.1717 (4)0.42138 (9)0.0118 (3)0.0682 (6)
H20.06040.40520.11000.082*
C30.1174 (3)0.48036 (7)0.04596 (19)0.0464 (4)
C40.2939 (4)0.50109 (9)0.1930 (2)0.0652 (5)
H40.26620.54020.23840.078*
C50.5109 (4)0.46370 (9)0.2722 (2)0.0685 (6)
H50.62780.47870.37000.082*
C61.1058 (4)0.35458 (9)0.4903 (2)0.0598 (5)
C71.3428 (4)0.31156 (10)0.5682 (3)0.0707 (6)
H7A1.51250.33600.59550.085*
H7B1.30380.29480.67500.085*
C81.3896 (4)0.25990 (10)0.4580 (3)0.0699 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0708 (9)0.0714 (9)0.0772 (9)0.0193 (7)0.0112 (7)0.0097 (7)
O20.1424 (17)0.0813 (11)0.0760 (11)0.0340 (11)0.0021 (10)0.0164 (8)
N10.0558 (9)0.0595 (9)0.0611 (9)0.0096 (7)0.0053 (7)0.0059 (7)
N20.1006 (16)0.0809 (13)0.1175 (17)0.0300 (12)0.0043 (13)0.0100 (12)
C10.0752 (14)0.0532 (11)0.0818 (14)0.0146 (9)0.0073 (11)0.0079 (9)
C20.0700 (13)0.0540 (10)0.0708 (12)0.0087 (9)0.0122 (10)0.0092 (9)
C30.0465 (9)0.0460 (8)0.0468 (8)0.0003 (7)0.0088 (7)0.0027 (7)
C40.0685 (12)0.0620 (11)0.0592 (11)0.0143 (9)0.0038 (9)0.0121 (8)
C50.0663 (13)0.0744 (12)0.0583 (11)0.0123 (10)0.0051 (9)0.0077 (9)
C60.0676 (12)0.0595 (10)0.0536 (10)0.0058 (9)0.0143 (9)0.0026 (8)
C70.0672 (13)0.0827 (13)0.0586 (11)0.0084 (10)0.0025 (9)0.0020 (9)
C80.0613 (12)0.0669 (12)0.0773 (14)0.0145 (10)0.0021 (10)0.0099 (10)
Geometric parameters (Å, º) top
O1—C61.283 (2)C3—C41.388 (2)
O1—H1D1.19 (3)C3—C3i1.498 (3)
O2—C61.209 (2)C4—C51.382 (3)
N1—C11.323 (2)C4—H40.9300
N1—C51.327 (2)C5—H50.9300
N2—C81.142 (3)C6—C71.518 (3)
C1—C21.377 (3)C7—C81.452 (3)
C1—H10.9300C7—H7A0.9700
C2—C31.384 (2)C7—H7B0.9700
C2—H20.9300
C6—O1—H1D109.8 (12)C5—C4—H4119.9
C1—N1—C5117.80 (16)C3—C4—H4119.9
C1—N1—H1D121.6 (10)N1—C5—C4122.65 (17)
C5—N1—H1D120.6 (10)N1—C5—H5118.7
C1—N1—H1D121.6 (10)C4—C5—H5118.7
C5—N1—H1D120.6 (10)O2—C6—O1124.78 (19)
N1—C1—C2123.03 (18)O2—C6—C7120.59 (19)
N1—C1—H1118.5O1—C6—C7114.63 (17)
C2—C1—H1118.5C8—C7—C6114.18 (17)
C1—C2—C3120.22 (18)C8—C7—H7A108.7
C1—C2—H2119.9C6—C7—H7A108.7
C3—C2—H2119.9C8—C7—H7B108.7
C2—C3—C4116.19 (16)C6—C7—H7B108.7
C2—C3—C3i121.79 (18)H7A—C7—H7B107.6
C4—C3—C3i122.02 (18)N2—C8—C7179.0 (2)
C5—C4—C3120.11 (17)
C5—N1—C1—C21.2 (3)C3i—C3—C4—C5178.96 (19)
H1D—N1—C1—C2179.1 (12)C1—N1—C5—C40.3 (3)
N1—C1—C2—C31.2 (3)H1D—N1—C5—C4180.0 (12)
C1—C2—C3—C40.2 (3)C3—C4—C5—N10.7 (3)
C1—C2—C3—C3i179.8 (2)O2—C6—C7—C8170.9 (2)
C2—C3—C4—C50.7 (3)O1—C6—C7—C89.4 (3)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···N2ii0.972.923.420 (3)113
C2—H2···O2iii0.932.623.361 (3)137
C2—H2···N2iv0.932.753.322 (3)121
O1—H1D···N11.19 (3)1.39 (3)2.566 (2)170 (2)
Symmetry codes: (ii) x+1/2, y+1/2, z+1/2; (iii) x1, y, z1; (iv) x3/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC10H8N2·2C3H3NO2
Mr326.31
Crystal system, space groupMonoclinic, P21/n
Temperature (K)291
a, b, c (Å)4.887 (2), 21.383 (10), 7.921 (4)
β (°) 100.664 (8)
V3)813.4 (7)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.34 × 0.26 × 0.19
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.952, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections
3537, 1487, 1153
Rint0.031
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.133, 1.04
No. of reflections1487
No. of parameters112
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.16, 0.15

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···N2i0.972.923.420 (3)112.8
C2—H2···O2ii0.932.623.361 (3)136.6
C2—H2···N2iii0.932.753.322 (3)120.7
O1—H1D···N11.19 (3)1.39 (3)2.566 (2)170 (2)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x1, y, z1; (iii) x3/2, y+1/2, z1/2.
 

References

First citationBalakrishna, R. B., Srinivas, B. & Ashwini, N. (2005). Cryst. Growth Des. 5, 1683–1686.
First citationBruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationFarrell, D. M. M., Ferguson, G., Lough, A. J. & Glidewell, C. (2002a). Acta Cryst. B58, 272–288.  Web of Science CSD CrossRef CAS IUCr Journals
First citationFarrell, D. M. M., Ferguson, G., Lough, A. J. & Glidewell, C. (2002b). Acta Cryst. B58, 530–544.  Web of Science CSD CrossRef CAS IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWang, Y.-T., Tang, G.-M., Zhang, Y.-C. & Wan, W.-Z. (2008). Acta Cryst. E64, o1753.  Web of Science CSD CrossRef IUCr Journals

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