4,4′-Bipyridine acetic acid disolvate

The crystal structure of the title compound, C₁₀H₈N₂·2C₂H₄O₂, is built up from 4,4′-bipyridine and acetic acid mol­ecules linked by strong O—H...N hydrogen bonds. The 4,4′-bipyridine and the two acetic acid mol­ecules are further connected through weak C—H...O hydrogen bonds to form a supra­molecular two-dimensional network parallel to the (001) plane. The two pyridine rings make a dihedral angle of 31.8 (1)°.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.050
• wR factor = 0.119
• Data-to-parameter ratio = 8.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT115_ALERT_5_B ADDSYM Detects Noncrystallographic Inversion ...         90 PerFi

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C14
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7     ..  O1      ..       2.62 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C2 H4 O2

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.46
           From the CIF: _reflns_number_total               1595
           Count of symmetry unique reflns         1628
           Completeness (_total/calc)             97.97%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

2,2-bipyridine is widely used to build up supramolecular network with carboxylic acid (Dai et al., 2005; Li et al., 2005; Pedireddi et al., 1998; Wang et al., 2006). Herein, we report the co-crystal structure of 2,2-bipyridine and acetic acid.

The asymmetric unit of (I) contains one 4,4-bipyridine molecule and two acetic acid molecules linked trough strong O—H···O hydogen bonds (Fig. 1). The two pyridine rings are both planar, with a RMS deviation of fitted atoms being 0.0033 Å and 0.0074 Å, respectively. The dihedral angle between them is 31.8 (1) °.

The 4,4-bipyridine and the two acetic acid molecules are further connected through C—H···O weak hydrogen bonds (PLATON, Spek, 2003) involving the carboxyl oxygen atoms (Table 1) to build up a supramolecular two dimensionnal network.parallel to the (0 0 1) plane (Fig. 2).

Related literature

For related literature, see: Dai et al. (2005); Li et al. (2005); Pedireddi et al. (1998); Wang et al. (2006). For strutural analysis, se: Spek (2003).

S2. Experimental

A mixture of 2,2-bipyridine (5 mmol, 0.78 g) and acetic acid (10 mmol, 0.60 g) in water (10 ml) was stirred for 2 h, and filtrate was allowed to evaporate at room temperature. Colorless single crystals of the title compound were formed after two weeks.

S3. Refinement

All H atoms attached to C atoms and O atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl) and O—H = 0.82 Å with U_iso(H) = 1.2U_eq(C_aromatic or O) or U_iso(H) = 1.5U_eq(Cmethyl).

In the absence of significant anomalous scattering, the absolute structure could not be reliably determined and then the Friedel pairs were merged and any references to the Flack parameter were removed.

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The asymmetric unit, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Packing view showing the Hydrogen bonding network. H atoms not involved in hydrogen bonds have been omitted for clarity.

4,4-Bipyridine acetic acid disolvate

Crystal data

C10H8N2·2C2H4O2	F(000) = 292
Mr = 276.29	Dx = 1.291 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 4188 reflections
a = 3.893 (2) Å	θ = 3.1–27.5°
b = 8.181 (5) Å	µ = 0.10 mm^−1
c = 22.563 (15) Å	T = 291 K
β = 98.46 (3)°	Block, colorless
V = 710.7 (7) Å^3	0.15 × 0.13 × 0.12 mm
Z = 2

Data collection

Rigaku RAXIS-RAPID diffractometer	1595 independent reflections
Radiation source: fine-focus sealed tube	995 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −5→5
Tmin = 0.986, Tmax = 0.988	k = −10→10
6467 measured reflections	l = −29→24

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0545P)^2 + 0.0575P] where P = (Fo^2 + 2Fc^2)/3
1595 reflections	(Δ/σ)max = 0.003
185 parameters	Δρmax = 0.15 e Å^−3
2 restraints	Δρmin = −0.12 e Å^−3

Special details

Experimental. (See detailed section in the paper)

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 (Ų)

	x	y	z	Uiso*/Ueq
C13	−0.0181 (13)	−0.0149 (6)	0.6249 (2)	0.0728 (12)
H13A	0.1830	−0.0660	0.6470	0.109*
H13B	−0.1649	−0.0968	0.6039	0.109*
H13C	−0.1437	0.0423	0.6521	0.109*
C14	0.0919 (10)	0.1019 (5)	0.5814 (2)	0.0568 (10)
C1	0.4437 (12)	0.3978 (5)	0.47047 (19)	0.0697 (11)
H1	0.4572	0.2861	0.4636	0.084*
C2	0.4896 (13)	0.5031 (5)	0.4247 (2)	0.0640 (10)
H2	0.5306	0.4622	0.3879	0.077*
C3	0.4742 (9)	0.6695 (4)	0.43371 (16)	0.0488 (9)
C4	0.4131 (11)	0.7207 (5)	0.48979 (19)	0.0613 (11)
H4	0.4020	0.8316	0.4984	0.074*
C5	0.3695 (12)	0.6071 (5)	0.5321 (2)	0.0690 (12)
H5	0.3285	0.6441	0.5694	0.083*
C6	0.5176 (9)	0.7891 (4)	0.38616 (17)	0.0483 (9)
C7	0.4150 (11)	0.7538 (5)	0.32659 (19)	0.0599 (11)
H7	0.3218	0.6520	0.3152	0.072*
C8	0.4513 (11)	0.8706 (5)	0.2839 (2)	0.0654 (11)
H8	0.3770	0.8449	0.2440	0.078*
C9	0.6937 (12)	1.0494 (5)	0.35465 (19)	0.0649 (11)
H9	0.7942	1.1507	0.3646	0.078*
C10	0.6649 (11)	0.9422 (5)	0.39995 (18)	0.0599 (10)
H10	0.7426	0.9709	0.4395	0.072*
N1	0.3818 (10)	0.4468 (4)	0.52352 (16)	0.0655 (9)
O1	0.9176 (9)	1.3967 (4)	0.29266 (15)	0.0859 (11)
O3	0.0627 (10)	0.0786 (4)	0.52832 (15)	0.0938 (11)
C11	0.8647 (13)	1.5081 (6)	0.1948 (2)	0.0764 (14)
H11A	1.0155	1.5926	0.2131	0.115*
H11B	0.6438	1.5545	0.1789	0.115*
H11C	0.9664	1.4585	0.1630	0.115*
C12	0.8156 (11)	1.3817 (4)	0.2405 (2)	0.0565 (10)
N2	0.5861 (9)	1.0176 (4)	0.29663 (16)	0.0631 (9)
O2	0.6441 (8)	1.2545 (3)	0.21698 (13)	0.0698 (8)
H2A	0.6294	1.1864	0.2432	0.105*
O4	0.2338 (8)	0.2354 (3)	0.60567 (13)	0.0711 (9)
H4A	0.2902	0.2947	0.5794	0.107*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C13	0.074 (3)	0.066 (3)	0.075 (3)	−0.009 (2)	0.001 (2)	0.010 (2)
C14	0.056 (2)	0.051 (2)	0.061 (3)	0.0012 (18)	0.0008 (19)	−0.005 (2)
C1	0.097 (3)	0.050 (2)	0.063 (3)	0.005 (2)	0.013 (2)	0.004 (2)
C2	0.082 (3)	0.053 (2)	0.057 (2)	0.002 (2)	0.0112 (19)	0.000 (2)
C3	0.049 (2)	0.0470 (19)	0.049 (2)	0.0035 (17)	0.0013 (16)	0.0002 (17)
C4	0.078 (3)	0.048 (2)	0.058 (3)	0.0023 (19)	0.012 (2)	0.0001 (19)
C5	0.083 (3)	0.070 (3)	0.054 (2)	0.003 (2)	0.013 (2)	−0.001 (2)
C6	0.0467 (19)	0.0427 (18)	0.055 (2)	−0.0021 (16)	0.0050 (16)	0.0016 (17)
C7	0.075 (3)	0.048 (2)	0.054 (2)	−0.0082 (19)	0.003 (2)	0.002 (2)
C8	0.080 (3)	0.056 (2)	0.058 (2)	−0.009 (2)	0.004 (2)	0.000 (2)
C9	0.075 (3)	0.048 (2)	0.070 (3)	−0.0104 (19)	0.003 (2)	−0.002 (2)
C10	0.069 (3)	0.051 (2)	0.056 (2)	−0.0030 (19)	−0.001 (2)	−0.0051 (19)
N1	0.077 (2)	0.058 (2)	0.062 (2)	−0.0027 (17)	0.0123 (17)	0.0040 (18)
O1	0.119 (3)	0.072 (2)	0.062 (2)	−0.0298 (19)	−0.0012 (19)	−0.0039 (17)
O3	0.143 (3)	0.076 (2)	0.059 (2)	−0.021 (2)	0.002 (2)	−0.0126 (18)
C11	0.079 (3)	0.067 (3)	0.083 (4)	−0.012 (2)	0.008 (2)	0.015 (2)
C12	0.067 (3)	0.044 (2)	0.059 (3)	−0.0042 (19)	0.010 (2)	0.000 (2)
N2	0.076 (2)	0.0469 (19)	0.065 (2)	−0.0092 (16)	0.0076 (17)	0.0014 (17)
O2	0.096 (2)	0.0558 (17)	0.0559 (18)	−0.0206 (16)	0.0061 (16)	−0.0045 (13)
O4	0.098 (2)	0.0591 (18)	0.0567 (19)	−0.0146 (16)	0.0117 (16)	−0.0058 (14)

Geometric parameters (Å, º)

C13—C14	1.478 (6)	C6—C10	1.393 (5)
C13—H13A	0.9600	C7—C8	1.378 (6)
C13—H13B	0.9600	C7—H7	0.9300
C13—H13C	0.9600	C8—N2	1.326 (5)
C14—O3	1.201 (5)	C8—H8	0.9300
C14—O4	1.307 (5)	C9—N2	1.340 (5)
C1—N1	1.317 (6)	C9—C10	1.364 (6)
C1—C2	1.377 (6)	C9—H9	0.9300
C1—H1	0.9300	C10—H10	0.9300
C2—C3	1.380 (5)	O1—C12	1.191 (5)
C2—H2	0.9300	C11—C12	1.493 (6)
C3—C4	1.386 (6)	C11—H11A	0.9600
C3—C6	1.480 (5)	C11—H11B	0.9600
C4—C5	1.361 (6)	C11—H11C	0.9600
C4—H4	0.9300	C12—O2	1.306 (4)
C5—N1	1.328 (5)	O2—H2A	0.8200
C5—H5	0.9300	O4—H4A	0.8200
C6—C7	1.375 (5)
C14—C13—H13A	109.5	C10—C6—C3	121.3 (3)
C14—C13—H13B	109.5	C6—C7—C8	119.5 (4)
H13A—C13—H13B	109.5	C6—C7—H7	120.3
C14—C13—H13C	109.5	C8—C7—H7	120.3
H13A—C13—H13C	109.5	N2—C8—C7	123.8 (4)
H13B—C13—H13C	109.5	N2—C8—H8	118.1
O3—C14—O4	121.5 (4)	C7—C8—H8	118.1
O3—C14—C13	124.4 (4)	N2—C9—C10	124.0 (4)
O4—C14—C13	114.0 (4)	N2—C9—H9	118.0
N1—C1—C2	123.6 (4)	C10—C9—H9	118.0
N1—C1—H1	118.2	C9—C10—C6	119.2 (4)
C2—C1—H1	118.2	C9—C10—H10	120.4
C1—C2—C3	119.5 (4)	C6—C10—H10	120.4
C1—C2—H2	120.2	C1—N1—C5	116.6 (4)
C3—C2—H2	120.2	C12—C11—H11A	109.5
C2—C3—C4	116.8 (4)	C12—C11—H11B	109.5
C2—C3—C6	122.2 (3)	H11A—C11—H11B	109.5
C4—C3—C6	121.0 (3)	C12—C11—H11C	109.5
C5—C4—C3	119.4 (4)	H11A—C11—H11C	109.5
C5—C4—H4	120.3	H11B—C11—H11C	109.5
C3—C4—H4	120.3	O1—C12—O2	124.1 (4)
N1—C5—C4	124.1 (4)	O1—C12—C11	123.6 (4)
N1—C5—H5	117.9	O2—C12—C11	112.3 (4)
C4—C5—H5	117.9	C8—N2—C9	116.3 (4)
C7—C6—C10	117.3 (3)	C12—O2—H2A	109.5
C7—C6—C3	121.4 (3)	C14—O4—H4A	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N2	0.82	1.86	2.675 (5)	175
O4—H4A···N1	0.82	1.84	2.659 (5)	173
C7—H7···O1^i	0.93	2.62	3.526 (5)	165
C10—H10···O3^ii	0.93	2.37	3.273 (5)	164
C4—H4···O3^iii	0.93	2.56	3.397 (6)	150

Symmetry codes: (i) x−1, y−1, z; (ii) x+1, y+1, z; (iii) x, y+1, z.