Di-4-pyridylmethane­diol

Abstract

In the title compound, C₁₁H₁₀N₂O₂, individual mol­ecules lie across crystallographic twofold rotation axes. Neighboring mol­ecules engage in O—H⋯N hydrogen bonding, forming square-grid layers parallel to the ab plane.

Related literature

For related literature, see: Chen & Mak (2005 ▶); Montney et al. (2008 ▶); Zaworotko (2007 ▶).

Experimental

Crystal data

• C₁₁H₁₀N₂O₂

• M _r = 202.21

• Tetragonal,

• a = 7.6130 (2) Å

• c = 17.5864 (11) Å

• V = 1019.27 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 173 (2) K

• 0.30 × 0.22 × 0.16 mm

Data collection

• Bruker APEXII diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.686, T _max = 0.745 (expected range = 0.907–0.985)

• 14287 measured reflections

• 605 independent reflections

• 549 reflections with I > 2σ(I)

• R _int = 0.040

Refinement

• R[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 0.076

• S = 1.13

• 605 reflections

• 72 parameters

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

• Δρ_max = 0.13 e Å⁻³

• Δρ_min = −0.13 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶) and COSMO (Bruker, 2006 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Crystal Maker (Palmer, 2007 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1i	0.87 (2)	1.87 (2)	2.7376 (19)	173.4 (19)

Symmetry code: (i) .

supplementary crystallographic information

Comment

While coordination polymers constructed from 4,4'-bipyridine are very common (Zaworotko, 2007), related phases based on its hydrogen-bonding capable analog di-4-pyridylketone (dpk) have not yet been reported (Montney et al., 2008). In an attempt to prepare a zinc nitrate coordination polymer incorporating dpk through an aqueous solution method, an in situ hydration reaction took place, resulting in the crystallization of di(4-pyridyl)methanediol (dpmd).

Crystals of (I) crystallize in an noncentrosymmetric tetragonal space group, with an asymmetric unit consisting of one half of a dpmd molecule. Its central sp³ hybridized C atom rests on a crystallographic 2-fold rotation axis. Operation of this symmetry element generates a complete dpmd molecule (Figure 1).

Each molecule of (I) is conjoined to four others, two via O—H···N hydrogen bonding donation from its alcohol functional groups and two via O—H···N hydrogen bonding acceptance at its pyridyl N atoms. As a result, a grid-like layer motif is formed, which is parallel to the ab crystal plane (Figure 2).

Adjacent layer patterns aggregate through weak C—H···O interactions to construct double layer slab motifs (Figure 3). In turn the double slabs stack along the c crystal direction by packing forces to form the pseudo three-dimensional crystal structure of (I).

Experimental

Zinc nitrate hexahydrate was obtained commercially. Di-4-pyridylketone (dpk) was prepared via a published procedure (Chen & Mak, 2005). Zinc nitrate hexahydrate (55 mg, 0.19 mmol) was dissolved in 3.0 ml water in a glass test tube. A 2 ml aliquot of a 1:1 water:methanol mixture was then added, followed by 3 ml of a methanolic solution of dpk (70 mg, 0.38 mmol). Colourless blocks of (I) were deposited after standing at 298 K for one week.

Figures

Fig. 1.

A complete molecule of the title compound. H atom positions are shown as gray sticks. Color code: C black, N blue, O red.

Fig. 2.

A view down c showing the aggregation of molecules of the title compound into a (4,4) square grid. Hydrogen bonding is indicated as dashed lines.

Fig. 3.

A view down c of the offset double layer motif in the title compound.

Crystal data

C11H10N2O2	Z = 4
Mr = 202.21	F000 = 424
Tetragonal, P43212	Dx = 1.318 Mg m−3
Hall symbol: P 4nw 2abw	Mo Kα radiation λ = 0.71073 Å
a = 7.6130 (2) Å	Cell parameters from 14287 reflections
b = 7.6130 (2) Å	θ = 2.9–25.3º
c = 17.5864 (11) Å	µ = 0.09 mm−1
α = 90º	T = 173 (2) K
β = 90º	Block, colourless
γ = 90º	0.30 × 0.22 × 0.16 mm
V = 1019.27 (7) Å3

Data collection

Bruker APEXII diffractometer	605 independent reflections
Radiation source: fine-focus sealed tube	549 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.040
T = 173(2) K	θmax = 25.3º
ω and ψ scans	θmin = 2.9º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −8→9
Tmin = 0.686, Tmax = 0.745	k = −9→9
14287 measured reflections	l = −21→20

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.076	w = 1/[σ2(Fo2) + (0.0412P)2 + 0.1593P] where P = (Fo2 + 2Fc2)/3
S = 1.13	(Δ/σ)max < 0.001
605 reflections	Δρmax = 0.13 e Å−3
72 parameters	Δρmin = −0.12 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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
O1	0.62268 (16)	0.65611 (15)	0.06536 (7)	0.0256 (3)
H1A	0.616 (3)	0.768 (3)	0.0580 (11)	0.031*
N1	0.6238 (2)	0.01378 (19)	0.04930 (8)	0.0317 (4)
C1	0.5269 (3)	0.1201 (3)	0.09305 (11)	0.0377 (5)
H1	0.4681	0.0717	0.1344	0.045*
C2	0.5099 (3)	0.2974 (2)	0.07980 (10)	0.0322 (5)
H2	0.4422	0.3665	0.1121	0.039*
C3	0.5945 (2)	0.3724 (2)	0.01785 (9)	0.0216 (4)
C4	0.6967 (2)	0.2639 (2)	−0.02701 (10)	0.0263 (4)
H4	0.7573	0.3089	−0.0686	0.032*
C5	0.7075 (2)	0.0872 (2)	−0.00905 (11)	0.0307 (5)
H5	0.7772	0.0157	−0.0395	0.037*
C6	0.5671 (2)	0.5671 (2)	0.0000	0.0207 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0303 (7)	0.0177 (6)	0.0287 (7)	−0.0006 (5)	−0.0056 (6)	−0.0012 (5)
N1	0.0390 (10)	0.0217 (8)	0.0343 (8)	0.0022 (7)	−0.0040 (8)	0.0004 (7)
C1	0.0455 (13)	0.0300 (11)	0.0377 (10)	0.0023 (10)	0.0098 (9)	0.0074 (9)
C2	0.0352 (11)	0.0266 (10)	0.0349 (10)	0.0056 (8)	0.0095 (9)	0.0023 (8)
C3	0.0196 (9)	0.0221 (9)	0.0232 (8)	−0.0007 (7)	−0.0047 (7)	−0.0016 (7)
C4	0.0267 (10)	0.0256 (10)	0.0264 (9)	0.0007 (8)	0.0018 (8)	−0.0017 (8)
C5	0.0342 (10)	0.0254 (10)	0.0325 (10)	0.0059 (8)	−0.0021 (9)	−0.0057 (9)
C6	0.0208 (8)	0.0208 (8)	0.0205 (11)	0.0008 (10)	0.0002 (7)	−0.0002 (7)

Geometric parameters (Å, °)

O1—C6	1.3998 (17)	C3—C4	1.382 (2)
O1—H1A	0.87 (2)	C3—C6	1.529 (2)
N1—C5	1.331 (2)	C4—C5	1.384 (2)
N1—C1	1.338 (2)	C4—H4	0.9300
C1—C2	1.376 (3)	C5—H5	0.9300
C1—H1	0.9300	C6—O1i	1.3998 (17)
C2—C3	1.389 (2)	C6—C3i	1.529 (2)
C2—H2	0.9300
C6—O1—H1A	109.7 (13)	C3—C4—H4	120.5
C5—N1—C1	116.94 (15)	C5—C4—H4	120.5
N1—C1—C2	123.20 (17)	N1—C5—C4	123.77 (17)
N1—C1—H1	118.4	N1—C5—H5	118.1
C2—C1—H1	118.4	C4—C5—H5	118.1
C1—C2—C3	119.53 (17)	O1—C6—O1i	112.43 (19)
C1—C2—H2	120.2	O1—C6—C3	105.03 (8)
C3—C2—H2	120.2	O1i—C6—C3	113.29 (8)
C4—C3—C2	117.59 (16)	O1—C6—C3i	113.30 (8)
C4—C3—C6	122.61 (14)	O1i—C6—C3i	105.03 (8)
C2—C3—C6	119.76 (14)	C3—C6—C3i	107.87 (19)
C3—C4—C5	118.94 (17)
C5—N1—C1—C2	0.6 (3)	C3—C4—C5—N1	0.3 (3)
N1—C1—C2—C3	0.8 (3)	C4—C3—C6—O1	−123.43 (16)
C1—C2—C3—C4	−1.6 (3)	C2—C3—C6—O1	58.9 (2)
C1—C2—C3—C6	176.25 (17)	C4—C3—C6—O1i	−0.4 (2)
C2—C3—C4—C5	1.0 (3)	C2—C3—C6—O1i	−178.06 (15)
C6—C3—C4—C5	−176.72 (15)	C4—C3—C6—C3i	115.45 (17)
C1—N1—C5—C4	−1.1 (3)	C2—C3—C6—C3i	−62.25 (14)

Symmetry codes: (i) y, x, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1ii	0.87 (2)	1.87 (2)	2.7376 (19)	173.4 (19)

Symmetry codes: (ii) x, y+1, z.