4,4'-Bipyridine-cyano-acetic acid (1/2).

Crystals of the title adduct, C(10)H(8)N(2)·2C(3)H(3)NO(2), were obtained from a methanol/water solution of cyano-acetic acid and 4,4'-bipyridine at room temperature. In the crystal structure, cyano-acetic acid and centrosymmetric 4,4'-bipyridine mol-ecules are linked by O-H⋯N hydrogen bonds to form three-component supra-molecular adducts. The acidic H atom is almost midway between the O and N atoms of the cyano-acetic acid and bipyridine mol-ecules, 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 inter-connected with neighboring mol-ecules by weak inter-molecular C-H⋯O and C-H⋯N hydrogen bonds and by π-π stacking inter-actions [centroid-centroid distance = 3.7200 (11) Å] to generate a three-dimensional supra-molecular 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 = 326.31

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 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

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.

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

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

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

C10H8N2·2C3H3NO2	F(000) = 340
Mr = 326.31	Dx = 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

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

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(Fo2) + (0.0577P)2 + 0.1963P] where P = (Fo2 + 2Fc2)/3
1487 reflections	(Δ/σ)max < 0.001
112 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.15 e Å−3

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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···N2iv	0.93	2.75	3.322 (3)	121
O1—H1D···N1	1.19 (3)	1.39 (3)	2.566 (2)	170 (2)

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) ; (ii) ; (iii) .