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The 4,4′-bi­pyridine mol­ecules in the title compound, C10H8N2·2H2O, are stacked in the direction of the crystallographic b axis. These stacks are connected via O—H...N and O—H...O hydrogen bonds to form sheets which lie parallel to (100). Chains of O—H...O hydrogen-bonded water mol­ecules are located between the bi­pyridine stacks. Altogether, four crystallographically independent water mol­ecules and two crystallographically independent bi­pyridine mol­ecules are involved.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100014888/ln1112sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100014888/ln1112Isup2.hkl
Contains datablock I

CCDC reference: 158276

Comment top

The title compound, (I), was obtained as a by-product in a synthesis for the preparation of new coordination polymers under hydrothermal conditions. Whereas the crystal structure of anhydrous 4,4'-bipyridine is known (Boag et al., 1999), no structure of a hydrated form has been reported so far. \sch

In the crystal structure of (I), the 4,4'-bipyridine molecules are stacked in the direction of the crystallographic b axis (Fig. 1a). There are two different stacks, each built up of one of the two crystallographically independent 4,4'-bipyridine molecules. Within the stacks, each of the two six-membered rings of neighbouring molecules are stacked perfectly onto each other and are always parallel. The distances between the centres of neighbouring rings are 3.70 (1) and 3.74 (1) Å in one stack (C1—C10), and 3.71 (1) and 3.72 (1) Å in the other stack (C11—C20). Between the stacks are channels in which the water molecules are located. The water molecules are connected via O—H···O hydrogen bonds to form two crystallographically independent chains parallel to the b axis, each built up of two crystallographically independent water molecules (Fig. 1 b). Within the chains, the O atom of each water molecule acts as an acceptor for a hydrogen bond from a neighbouring water molecule, and as a donor through one H atom to a 4,4'-bipyridine molecule and through the other H atom to the next neighbouring water molecule. The ranges of the O···H distances (1.84–1.90 Å) and the O···O distances [2.736 (7)–2.785 (7) Å] indicate strong hydrogen bonding. The O—H···O angles are between 167 and 178°. The H···N distances range from 1.99 to 2.01 Å and the O···N distances range from 2.829 (4) to 2.874 (4) Å. The O—H···N angles are between 155 and 164°. The interactions between the water and the 4,4'-bipyridine molecules lead to 4,4'-bipyridine···H2O···H2O···4,4'-bipyridine chains, which proceed in the direction of the c axis. The combination of all these hydrogen-bonding interactions results in the formation of sheets which lie parallel to (100).

The two crystallographically independent 4,4'-bipyridine molecules in the asymmetric unit have similar geometrical parameters. The six-membered rings are twisted by 41.6 (1)° in both molecules. This value is similar to that of 37.2° determined for 4,4'-bipyridine in the gas phase (Almenningen & Bastiansen, 1958) and corresponds closely with the value of 48.6° obtained from theoretical calculations (Ould-Moussa et al., 1996). In contrast, in the structure of anhydrous 4,4'-bipyridine, which also exhibits two crystallographically independent molecules in the asymmetric unit, these angles amount to 18.5 (1) and 34.9 (1)° (Boag et al., 1999). All other geometrical parameters are similar to those in the anhydrous structure of 4,4'-bipyridine (Boag et al., 1999).

Experimental top

Compound (I) was obtained as a by-product in the reaction of PbCl2, 4,4'-bipyridine (ACROS) and squaric acid (ACROS) in the ratio 1:4:1 in water under hydrothermal conditions using Teflon-lined steel autoclaves. The reaction mixture was heated at 423 K for 1 d and cooled to room temperature at 1 K min-1. The precipitate was filtered off and the residue consisted of colourless needles of (I) as the major phase and only a few colourless blocks of a second phase which it has not been possible to identify up to now. Compound (I) decomposes in air within a few hours, leading to a white powder of 4,4'-bipyridine which is amorphous under X-ray powder diffraction.

Refinement top

H atoms bound to C were positioned with idealized geometry and refined with fixed isotropic displacement parameters using a riding model with C—H 0.95 Å. The water H atoms were initially located in a difference map; however, this resulted in some excessively large O—H distances. Free refinement of the water H atoms or with restrained O—H bond lengths always yielded a poor O—H geometry. Therefore, the coordinates of the H atoms from the difference map were recalculated to give O—H distances of 0.90 Å and refined with fixed isotropic displacement parameters using a riding model. The origin was fixed by floating-origin restraints (Flack & Schwarzenbach, 1988). Because no heavy atom was present, the absolute structure could not be determined. Therefore, all Friedel equivalents measured were merged. The observed reflection conditions are in agreement with the centrosymmetric space group P21/n, but the structure cannot be solved in this space group. In addition, the structures of both independent molecules are very similar. However, a detailed analysis of the crystal structure shows that the correct space group is P21 and that the structure is pseudo-centrosymmetric.

Computing details top

Data collection: IPDS (Stoe & Cie, 1998); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Siemens, 1990); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. (a) The crystal structure of (I) with the atom-labelling scheme, viewed along the b axis. Displacement ellipsoids are drawn at the 50% probability level and hydrogen bonds are shown as dotted lines. H atoms are drawn as small spheres of arbitrary radii. (b) A view of the chains formed in (I) by the water molecules.
(I) top
Crystal data top
C10H8N2·2H2OF(000) = 408
Mr = 192.22Dx = 1.302 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 9.1333 (7) ÅCell parameters from 5270 reflections
b = 7.4310 (4) Åθ = 3–26°
c = 14.7171 (12) ŵ = 0.09 mm1
β = 101.052 (9)°T = 130 K
V = 980.32 (12) Å3Needle, colourless
Z = 40.50 × 0.06 × 0.05 mm
Data collection top
Stoe IPDS
diffractometer
1278 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.043
Graphite monochromatorθmax = 26.0°, θmin = 2.4°
ϕ scansh = 1110
7618 measured reflectionsk = 98
2044 independent reflectionsl = 1818
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0803P)2]
where P = (Fo2 + 2Fc2)/3
2044 reflections(Δ/σ)max < 0.001
253 parametersΔρmax = 0.19 e Å3
1 restraintΔρmin = 0.21 e Å3
Crystal data top
C10H8N2·2H2OV = 980.32 (12) Å3
Mr = 192.22Z = 4
Monoclinic, P21Mo Kα radiation
a = 9.1333 (7) ŵ = 0.09 mm1
b = 7.4310 (4) ÅT = 130 K
c = 14.7171 (12) Å0.50 × 0.06 × 0.05 mm
β = 101.052 (9)°
Data collection top
Stoe IPDS
diffractometer
1278 reflections with I > 2σ(I)
7618 measured reflectionsRint = 0.043
2044 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0411 restraint
wR(F2) = 0.126H-atom parameters constrained
S = 1.02Δρmax = 0.19 e Å3
2044 reflectionsΔρmin = 0.21 e Å3
253 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
N10.5589 (4)0.5588 (6)0.2292 (2)0.0208 (9)
N20.4503 (4)0.5629 (7)0.2362 (2)0.0212 (9)
N31.0492 (4)0.8127 (6)0.2680 (2)0.0204 (8)
N40.9438 (4)0.8117 (7)0.7329 (3)0.0219 (9)
C10.5186 (4)0.5674 (7)0.0443 (3)0.0164 (8)
C20.4061 (4)0.6219 (7)0.1172 (3)0.0176 (8)
H20.31290.66190.10500.021*
C30.4298 (4)0.6179 (7)0.2057 (3)0.0191 (8)
H30.35210.65860.25370.023*
C40.6675 (4)0.5084 (7)0.1594 (3)0.0201 (9)
H40.75910.46860.17400.024*
C50.6543 (4)0.5107 (7)0.0663 (3)0.0187 (9)
H50.73520.47470.01910.022*
C60.4958 (4)0.5684 (7)0.0523 (3)0.0162 (8)
C70.3608 (4)0.5105 (7)0.0736 (3)0.0196 (9)
H70.28180.47160.02590.024*
C80.3431 (4)0.5106 (8)0.1657 (3)0.0205 (9)
H80.25050.47160.17900.025*
C90.5794 (4)0.6223 (7)0.2137 (3)0.0198 (8)
H90.65560.66450.26220.024*
C100.6066 (4)0.6252 (7)0.1256 (3)0.0191 (8)
H100.70020.66560.11440.023*
C111.0061 (4)0.8170 (7)0.4517 (3)0.0169 (9)
C120.8945 (4)0.8764 (7)0.3796 (3)0.0176 (8)
H120.80190.91900.39130.021*
C130.9230 (4)0.8714 (7)0.2895 (3)0.0201 (9)
H130.84700.91270.24060.024*
C141.1555 (5)0.7566 (8)0.3388 (3)0.0216 (9)
H141.24670.71370.32490.026*
C151.1401 (4)0.7577 (7)0.4293 (3)0.0183 (9)
H151.21970.71850.47660.022*
C160.9830 (4)0.8163 (8)0.5484 (3)0.0172 (9)
C170.8488 (4)0.7628 (7)0.5719 (3)0.0192 (9)
H170.76710.72810.52490.023*
C180.8352 (5)0.7604 (8)0.6632 (3)0.0223 (9)
H180.74370.72020.67770.027*
C191.0706 (4)0.8647 (7)0.7109 (3)0.0211 (9)
H191.14860.90160.75970.025*
C201.0980 (4)0.8703 (7)0.6206 (3)0.0180 (8)
H201.19150.90950.60860.022*
O10.4437 (3)0.5899 (6)0.57807 (17)0.0294 (11)
H1O10.50310.57040.63350.044*
H2O10.47690.54340.52930.044*
O20.5446 (3)0.4639 (6)0.42664 (18)0.0288 (11)
H1O20.49840.49940.36990.043*
H2O20.54750.34300.42370.043*
O30.9399 (3)0.8450 (6)0.07543 (18)0.0287 (10)
H1O31.00120.83070.13060.043*
H2O30.97440.79620.02760.043*
O41.0446 (3)0.7191 (7)0.92429 (18)0.0293 (11)
H1O40.99300.74940.86800.044*
H2O41.03440.59860.92550.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0232 (16)0.024 (2)0.0171 (15)0.0009 (15)0.0080 (12)0.0007 (14)
N20.0219 (15)0.026 (2)0.0170 (15)0.0007 (16)0.0080 (12)0.0022 (14)
N30.0182 (14)0.022 (2)0.0204 (16)0.0010 (15)0.0025 (12)0.0006 (15)
N40.0204 (15)0.022 (2)0.0232 (17)0.0019 (16)0.0053 (13)0.0015 (15)
C10.0157 (15)0.015 (2)0.0179 (17)0.0016 (14)0.0029 (13)0.0025 (15)
C20.0135 (15)0.014 (2)0.0246 (17)0.0002 (15)0.0021 (13)0.0003 (16)
C30.0171 (15)0.020 (2)0.0198 (16)0.0005 (15)0.0035 (12)0.0003 (16)
C40.0135 (15)0.023 (3)0.0240 (19)0.0021 (16)0.0049 (13)0.0006 (17)
C50.0171 (16)0.021 (3)0.0178 (18)0.0032 (15)0.0035 (13)0.0012 (16)
C60.0156 (15)0.014 (2)0.0191 (17)0.0008 (15)0.0028 (12)0.0007 (16)
C70.0186 (16)0.021 (3)0.0200 (18)0.0032 (16)0.0049 (13)0.0011 (17)
C80.0159 (15)0.025 (3)0.0213 (18)0.0021 (16)0.0047 (13)0.0029 (17)
C90.0179 (15)0.021 (2)0.0198 (15)0.0024 (15)0.0020 (12)0.0011 (16)
C100.0164 (15)0.016 (2)0.0242 (17)0.0009 (15)0.0031 (14)0.0004 (16)
C110.0171 (16)0.015 (2)0.0199 (18)0.0030 (15)0.0061 (13)0.0020 (16)
C120.0158 (15)0.021 (2)0.0175 (16)0.0003 (15)0.0061 (13)0.0014 (15)
C130.0210 (16)0.022 (3)0.0170 (16)0.0003 (16)0.0028 (12)0.0020 (16)
C140.0193 (16)0.023 (3)0.024 (2)0.0008 (17)0.0080 (14)0.0000 (17)
C150.0126 (15)0.019 (2)0.0225 (19)0.0003 (15)0.0020 (12)0.0007 (16)
C160.0168 (16)0.014 (2)0.0210 (18)0.0016 (15)0.0046 (13)0.0019 (16)
C170.0141 (15)0.019 (3)0.0239 (19)0.0011 (15)0.0033 (13)0.0003 (17)
C180.0193 (16)0.026 (3)0.0228 (19)0.0003 (17)0.0072 (13)0.0014 (18)
C190.0202 (16)0.025 (3)0.0182 (16)0.0019 (16)0.0026 (13)0.0007 (17)
C200.0159 (16)0.022 (2)0.0171 (16)0.0003 (16)0.0051 (13)0.0008 (15)
O10.0279 (14)0.041 (3)0.0185 (13)0.0043 (12)0.0021 (11)0.0022 (13)
O20.0293 (14)0.039 (3)0.0173 (13)0.0029 (11)0.0027 (11)0.0022 (11)
O30.0269 (14)0.039 (3)0.0199 (14)0.0077 (11)0.0030 (11)0.0021 (11)
O40.0298 (15)0.038 (3)0.0196 (14)0.0044 (12)0.0035 (11)0.0000 (12)
Geometric parameters (Å, º) top
N1—C41.337 (6)C6—C101.396 (6)
N1—C31.363 (5)C6—C71.397 (6)
N2—C81.341 (6)C7—C81.395 (6)
N2—C91.359 (5)C9—C101.365 (5)
N3—C131.326 (5)C11—C121.394 (6)
N3—C141.347 (6)C11—C151.399 (6)
N4—C191.321 (5)C11—C161.478 (6)
N4—C181.339 (6)C12—C131.400 (5)
C1—C21.396 (5)C14—C151.366 (6)
C1—C51.404 (6)C16—C171.395 (6)
C1—C61.476 (6)C16—C201.401 (6)
C2—C31.361 (5)C17—C181.373 (6)
C4—C51.399 (6)C19—C201.399 (5)
C4—N1—C3116.5 (4)N2—C9—C10124.2 (4)
C8—N2—C9116.3 (4)C9—C10—C6119.5 (4)
C13—N3—C14116.6 (4)C12—C11—C15117.7 (4)
C19—N4—C18116.9 (4)C12—C11—C16121.1 (4)
C2—C1—C5117.5 (4)C15—C11—C16121.2 (4)
C2—C1—C6121.3 (4)C11—C12—C13118.1 (4)
C5—C1—C6121.1 (4)N3—C13—C12124.2 (4)
C3—C2—C1120.0 (4)N3—C14—C15124.0 (4)
C2—C3—N1123.6 (4)C14—C15—C11119.3 (4)
N1—C4—C5123.9 (4)C17—C16—C20117.4 (4)
C4—C5—C1118.3 (4)C17—C16—C11122.2 (4)
C10—C6—C7117.4 (4)C20—C16—C11120.3 (4)
C10—C6—C1122.1 (4)C18—C17—C16119.6 (4)
C7—C6—C1120.5 (4)N4—C18—C17123.7 (4)
C8—C7—C6119.3 (4)N4—C19—C20124.5 (4)
N2—C8—C7123.3 (4)C19—C20—C16117.8 (4)
C5—C1—C2—C30.4 (7)C15—C11—C12—C130.6 (7)
C6—C1—C2—C3179.4 (4)C16—C11—C12—C13179.2 (4)
C1—C2—C3—N11.5 (8)C14—N3—C13—C120.6 (7)
C4—N1—C3—C22.2 (7)C11—C12—C13—N30.4 (8)
C3—N1—C4—C51.1 (8)C13—N3—C14—C150.2 (8)
N1—C4—C5—C10.7 (9)N3—C14—C15—C111.2 (9)
C2—C1—C5—C41.4 (8)C12—C11—C15—C141.3 (8)
C6—C1—C5—C4178.3 (4)C16—C11—C15—C14178.5 (4)
C2—C1—C6—C10139.2 (6)C12—C11—C16—C1741.1 (6)
C5—C1—C6—C1041.1 (6)C15—C11—C16—C17138.6 (7)
C2—C1—C6—C741.2 (6)C12—C11—C16—C20139.0 (7)
C5—C1—C6—C7138.6 (7)C15—C11—C16—C2041.2 (6)
C10—C6—C7—C80.5 (8)C20—C16—C17—C181.6 (8)
C1—C6—C7—C8179.1 (4)C11—C16—C17—C18178.3 (4)
C9—N2—C8—C71.8 (8)C19—N4—C18—C170.9 (8)
C6—C7—C8—N20.4 (9)C16—C17—C18—N41.8 (9)
C8—N2—C9—C102.4 (7)C18—N4—C19—C200.1 (7)
N2—C9—C10—C61.6 (8)N4—C19—C20—C160.1 (8)
C7—C6—C10—C90.0 (7)C17—C16—C20—C190.7 (7)
C1—C6—C10—C9179.7 (4)C11—C16—C20—C19179.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H11O···N1i0.901.992.839 (4)157
O1—H21O···O20.901.842.735 (4)176
O2—H12O···N20.901.992.866 (4)164
O2—H22O···O1ii0.901.882.783 (6)178
O3—H13O···N30.901.992.829 (4)155
O3—H23O···O4iii0.901.852.748 (4)174
O4—H14O···N40.902.012.874 (5)162
O4—H24O···O3iv0.901.902.784 (7)167
Symmetry codes: (i) x, y, z+1; (ii) x+1, y1/2, z+1; (iii) x, y, z1; (iv) x+2, y1/2, z+1.

Experimental details

Crystal data
Chemical formulaC10H8N2·2H2O
Mr192.22
Crystal system, space groupMonoclinic, P21
Temperature (K)130
a, b, c (Å)9.1333 (7), 7.4310 (4), 14.7171 (12)
β (°) 101.052 (9)
V3)980.32 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.50 × 0.06 × 0.05
Data collection
DiffractometerStoe IPDS
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7618, 2044, 1278
Rint0.043
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.126, 1.02
No. of reflections2044
No. of parameters253
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.21

Computer programs: IPDS (Stoe & Cie, 1998), IPDS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Siemens, 1990), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H11O···N1i0.901.992.839 (4)157
O1—H21O···O20.901.842.735 (4)176
O2—H12O···N20.901.992.866 (4)164
O2—H22O···O1ii0.901.882.783 (6)178
O3—H13O···N30.901.992.829 (4)155
O3—H23O···O4iii0.901.852.748 (4)174
O4—H14O···N40.902.012.874 (5)162
O4—H24O···O3iv0.901.902.784 (7)167
Symmetry codes: (i) x, y, z+1; (ii) x+1, y1/2, z+1; (iii) x, y, z1; (iv) x+2, y1/2, z+1.
 

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