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

Song, G.; Hao, E.-J.; Li, W.

doi:10.1107/S1600536808031322

organic compounds

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Volume 64| Part 11| November 2008| Page o2058

doi:10.1107/S1600536808031322

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

Ge Song,^a Er-Jun Hao ^a and Wei Li ^a ^*

^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 π–π 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 ,b ); For C—H⋯O and C—H⋯N hydrogen bonds, see: Balakrishna et al. (2005 ); Wang et al. (2008 ).

Experimental

Crystal data

C₁₀H₈N₂·2C₃H₃NO₂
M_r = 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 ) T_min = 0.952, T_max = 0.982
3537 measured reflections
1487 independent reflections
1153 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808031322/zl2142sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808031322/zl2142Isup2.hkl

checkCIF report

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.

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

	Fig. 1. A view of the title compound, showing 30% probability displacement ellipsoids. Symmetry code: (iv) -x, 1 - y,-z.
	Fig. 2. A view of the three-dimensional hydrogen-bonding pattern network.
	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

C₁₀H₈N₂·2C₃H₃NO₂	F(000) = 340
M_r = 326.31	D_x = 1.332 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.887 (2) Å	Cell parameters from 1445 reflections
b = 21.383 (10) Å	θ = 2.8–27.1°
c = 7.921 (4) Å	µ = 0.10 mm⁻¹
β = 100.664 (8)°	T = 291 K
V = 813.4 (7) Å³	Block, colorless
Z = 2	0.34 × 0.26 × 0.19 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1487 independent reflections
Radiation source: fine-focus sealed tube	1153 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −5→5
T_min = 0.952, T_max = 0.982	k = −25→24
3537 measured reflections	l = −9→7

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0577P)² + 0.1963P] where P = (F_o² + 2F_c²)/3
1487 reflections	(Δ/σ)_max < 0.001
112 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₀H₈N₂·2C₃H₃NO₂	V = 813.4 (7) Å³
M_r = 326.31	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.887 (2) Å	µ = 0.10 mm⁻¹
b = 21.383 (10) Å	T = 291 K
c = 7.921 (4) Å	0.34 × 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)
T_min = 0.952, T_max = 0.982	R_int = 0.031
3537 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.16 e Å⁻³
1487 reflections	Δρ_min = −0.15 e Å⁻³
112 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.9569 (3)	0.33450 (7)	0.35022 (19)	0.0763 (5)
H1D	0.779 (6)	0.3714 (12)	0.298 (3)	0.114*
O2	1.0674 (4)	0.40335 (8)	0.5596 (2)	0.1022 (6)
N1	0.5590 (3)	0.40726 (7)	0.21445 (19)	0.0595 (4)
N2	1.4242 (5)	0.21975 (10)	0.3693 (3)	0.1017 (7)
C1	0.3898 (4)	0.38664 (9)	0.0757 (3)	0.0729 (6)
H1	0.4196	0.3468	0.0354	0.087*
C2	0.1717 (4)	0.42138 (9)	−0.0118 (3)	0.0682 (6)
H2	0.0604	0.4052	−0.1100	0.082*
C3	0.1174 (3)	0.48036 (7)	0.04596 (19)	0.0464 (4)
C4	0.2939 (4)	0.50109 (9)	0.1930 (2)	0.0652 (5)
H4	0.2662	0.5402	0.2384	0.078*
C5	0.5109 (4)	0.46370 (9)	0.2722 (2)	0.0685 (6)
H5	0.6278	0.4787	0.3700	0.082*
C6	1.1058 (4)	0.35458 (9)	0.4903 (2)	0.0598 (5)
C7	1.3428 (4)	0.31156 (10)	0.5682 (3)	0.0707 (6)
H7A	1.5125	0.3360	0.5955	0.085*
H7B	1.3038	0.2948	0.6750	0.085*
C8	1.3896 (4)	0.25990 (10)	0.4580 (3)	0.0699 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0708 (9)	0.0714 (9)	0.0772 (9)	0.0193 (7)	−0.0112 (7)	−0.0097 (7)
O2	0.1424 (17)	0.0813 (11)	0.0760 (11)	0.0340 (11)	0.0021 (10)	−0.0164 (8)
N1	0.0558 (9)	0.0595 (9)	0.0611 (9)	0.0096 (7)	0.0053 (7)	0.0059 (7)
N2	0.1006 (16)	0.0809 (13)	0.1175 (17)	0.0300 (12)	0.0043 (13)	−0.0100 (12)
C1	0.0752 (14)	0.0532 (11)	0.0818 (14)	0.0146 (9)	−0.0073 (11)	−0.0079 (9)
C2	0.0700 (13)	0.0540 (10)	0.0708 (12)	0.0087 (9)	−0.0122 (10)	−0.0092 (9)
C3	0.0465 (9)	0.0460 (8)	0.0468 (8)	0.0003 (7)	0.0088 (7)	0.0027 (7)
C4	0.0685 (12)	0.0620 (11)	0.0592 (11)	0.0143 (9)	−0.0038 (9)	−0.0121 (8)
C5	0.0663 (13)	0.0744 (12)	0.0583 (11)	0.0123 (10)	−0.0051 (9)	−0.0077 (9)
C6	0.0676 (12)	0.0595 (10)	0.0536 (10)	0.0058 (9)	0.0143 (9)	0.0026 (8)
C7	0.0672 (13)	0.0827 (13)	0.0586 (11)	0.0084 (10)	0.0025 (9)	0.0020 (9)
C8	0.0613 (12)	0.0669 (12)	0.0773 (14)	0.0145 (10)	0.0021 (10)	0.0099 (10)

Geometric parameters (Å, º) top

O1—C6	1.283 (2)	C3—C4	1.388 (2)
O1—H1D	1.19 (3)	C3—C3ⁱ	1.498 (3)
O2—C6	1.209 (2)	C4—C5	1.382 (3)
N1—C1	1.323 (2)	C4—H4	0.9300
N1—C5	1.327 (2)	C5—H5	0.9300
N2—C8	1.142 (3)	C6—C7	1.518 (3)
C1—C2	1.377 (3)	C7—C8	1.452 (3)
C1—H1	0.9300	C7—H7A	0.9700
C2—C3	1.384 (2)	C7—H7B	0.9700
C2—H2	0.9300

C6—O1—H1D	109.8 (12)	C5—C4—H4	119.9
C1—N1—C5	117.80 (16)	C3—C4—H4	119.9
C1—N1—H1D	121.6 (10)	N1—C5—C4	122.65 (17)
C5—N1—H1D	120.6 (10)	N1—C5—H5	118.7
C1—N1—H1D	121.6 (10)	C4—C5—H5	118.7
C5—N1—H1D	120.6 (10)	O2—C6—O1	124.78 (19)
N1—C1—C2	123.03 (18)	O2—C6—C7	120.59 (19)
N1—C1—H1	118.5	O1—C6—C7	114.63 (17)
C2—C1—H1	118.5	C8—C7—C6	114.18 (17)
C1—C2—C3	120.22 (18)	C8—C7—H7A	108.7
C1—C2—H2	119.9	C6—C7—H7A	108.7
C3—C2—H2	119.9	C8—C7—H7B	108.7
C2—C3—C4	116.19 (16)	C6—C7—H7B	108.7
C2—C3—C3ⁱ	121.79 (18)	H7A—C7—H7B	107.6
C4—C3—C3ⁱ	122.02 (18)	N2—C8—C7	179.0 (2)
C5—C4—C3	120.11 (17)

C5—N1—C1—C2	1.2 (3)	C3ⁱ—C3—C4—C5	−178.96 (19)
H1D—N1—C1—C2	−179.1 (12)	C1—N1—C5—C4	−0.3 (3)
N1—C1—C2—C3	−1.2 (3)	H1D—N1—C5—C4	−180.0 (12)
C1—C2—C3—C4	0.2 (3)	C3—C4—C5—N1	−0.7 (3)
C1—C2—C3—C3ⁱ	179.8 (2)	O2—C6—C7—C8	−170.9 (2)
C2—C3—C4—C5	0.7 (3)	O1—C6—C7—C8	9.4 (3)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···N2ⁱⁱ	0.97	2.92	3.420 (3)	113
C2—H2···O2ⁱⁱⁱ	0.93	2.62	3.361 (3)	137
C2—H2···N2^iv	0.93	2.75	3.322 (3)	121
O1—H1D···N1	1.19 (3)	1.39 (3)	2.566 (2)	170 (2)

Symmetry codes: (ii) x+1/2, −y+1/2, z+1/2; (iii) x−1, y, z−1; (iv) x−3/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₂·2C₃H₃NO₂
M_r	326.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	4.887 (2), 21.383 (10), 7.921 (4)
β (°)	100.664 (8)
V (Å³)	813.4 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.34 × 0.26 × 0.19

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.952, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	3537, 1487, 1153
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.133, 1.04
No. of reflections	1487
No. of parameters	112
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
C7—H7A···N2ⁱ	0.97	2.92	3.420 (3)	112.8
C2—H2···O2ⁱⁱ	0.93	2.62	3.361 (3)	136.6
C2—H2···N2ⁱⁱⁱ	0.93	2.75	3.322 (3)	120.7
O1—H1D···N1	1.19 (3)	1.39 (3)	2.566 (2)	170 (2)

Symmetry codes: (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.

References

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

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2058

doi:10.1107/S1600536808031322

Open

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