5,5′-Bis[(1H-imidazol-1-yl)meth­yl]-2,2′-bipyridine methanol disolvate

Abstract

The title compound, C₁₈H₁₆N₆·2CH₃OH, was prepared by the reaction of 5,5′-bis­(bromo­meth­yl)-2,2′-bipyridine with imidazole. The main mol­ecule lies on an inversion center located at the mid-point of the C—C bond joining the two pyridine rings. The asymmetric unit therefore contains one half-mol­ecule and one methanol solvent mol­ecule. The dihedral angle between the pyridine and imidazole rings is 72.32 (5)°. In the crystal, weak inter­molecular O—H⋯N, C—H⋯N and C—H⋯O hydrogen bonds contribute to the stabilization of the packing.

Related literature

For related syntheses, see: Sambrook et al. (2006 ▶); Zang et al. (2010 ▶). For a related structure, see: Zang et al. (2010 ▶). For reference bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₁₈H₁₆N₆·2CH₄O

• M _r = 380.45

• Monoclinic,

• a = 4.5653 (4) Å

• b = 14.7886 (12) Å

• c = 14.5378 (11) Å

• β = 93.805 (2)°

• V = 979.35 (14) ų

• Z = 2

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 173 K

• 0.35 × 0.30 × 0.10 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.970, T _max = 0.991

• 5948 measured reflections

• 2136 independent reflections

• 1619 reflections with I > 2σ(I)

• R _int = 0.053

Refinement

• R[F ² > 2σ(F ²)] = 0.041

• wR(F ²) = 0.144

• S = 1.09

• 2136 reflections

• 128 parameters

• H-atom parameters constrained

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXTL.

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⋯N3i	0.84	1.93	2.7662 (19)	171
C3—H3⋯O1	0.95	2.44	3.360 (2)	162
C8—H8⋯N1ii	0.95	2.57	3.422 (2)	149
C9—H9⋯O1iii	0.95	2.54	3.470 (2)	168

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

The title compound was prepared to use as a multi-dentate ligand in the formation of metallosupramolecules in line with similar previously reported compounds (Sambrook et al., 2006; Zang et al., 2010).

In the title compound (Scheme 1, Fig. 1), two pyridine rings are coplanar because the title compound lies on a crystallographic inversion center. The dihedral angle between the pyridine and imidazole rings is 72.32 (5)°. All the bond lengths are within normal values (Allen et al., 1987).

In the crystal structure, as shown in Fig. 2, weak intermolecular O–H···N, C–H···N and C–H···O hydrogen bonds are observed (Table 1). These intermolecular interactions may be contribute to the stabilization of the packing.

Experimental

A mixture of imidazole (0.120 g, 1.76 mmol) and potassium hydroxide (0.440 g, 7.84 mmol) in DMSO (10 ml) was stirred for 1 h. A DMSO solution (20 ml) of 5,5'-bis(bromomethyl)-2,2'-bipyridine (0.30 g, 0.88 mmol) was slowly added and the solution stirred for 6 h at room temperature. After water (100 ml) was added, the reaction mixture was extracted with chloroform (3×100 ml), washed with water and then dried over anhydrous MgSO₄. The solvent was removed to give the title compound in 63% yield. X-ray quality single crystals were obtained by slow evaporation of a solution in MeOH.

Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.95 Å, U_iso = 1.2U_eq(C) for aromatic, d(C—H) = 0.84 Å, U_iso = 1.5U_eq(C) for hydroxyl, d(C—H) = 0.98 Å, U_iso = 1.5U_eq(C) for methyl protons.

Figures

Fig. 1.

The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. (Symmetry code: i) -x + 2, -y + 1, -z + 1)

Fig. 2.

Crystal packing of the title compound with intermolecular O–H···N, C–H···N and C–H···O hydrogen bonds shown as dashed lines. H atoms not involved in intermolecular interactions have been omitted for clarity (Symmetry codes: i) -x + 1, -y + 1, -z; ii) x, -y + 1/2, z - 1/2; iii) -x + 1, y - 1/2, -z + 1/2; iv) x, -y + 1/2, z + 1/2; v) -x + 2, -y + 1, -z + 1).

Crystal data

C18H16N6·2CH4O	F(000) = 404
Mr = 380.45	Dx = 1.290 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2441 reflections
a = 4.5653 (4) Å	θ = 2.8–28.2°
b = 14.7886 (12) Å	µ = 0.09 mm−1
c = 14.5378 (11) Å	T = 173 K
β = 93.805 (2)°	Plate, colorless
V = 979.35 (14) Å3	0.35 × 0.30 × 0.10 mm
Z = 2

Data collection

Bruker APEXII CCD diffractometer	2136 independent reflections
Radiation source: fine-focus sealed tube	1619 reflections with I > 2σ(I)
graphite	Rint = 0.053
φ and ω scans	θmax = 27.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→5
Tmin = 0.970, Tmax = 0.991	k = −18→18
5948 measured reflections	l = −16→18

Refinement

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0772P)2 + 0.1442P] where P = (Fo2 + 2Fc2)/3
2136 reflections	(Δ/σ)max < 0.001
128 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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
N1	0.8022 (3)	0.40136 (8)	0.45831 (9)	0.0287 (3)
N2	0.4002 (3)	0.36956 (9)	0.17390 (9)	0.0281 (3)
N3	0.5877 (4)	0.36182 (11)	0.03818 (10)	0.0441 (4)
C1	0.5974 (4)	0.37871 (10)	0.39254 (11)	0.0301 (4)
H1	0.5329	0.3176	0.3901	0.036*
C2	0.4722 (3)	0.43832 (10)	0.32748 (10)	0.0254 (4)
C3	0.5628 (4)	0.52770 (11)	0.33297 (11)	0.0302 (4)
H3	0.4831	0.5710	0.2900	0.036*
C4	0.7704 (4)	0.55308 (10)	0.40161 (11)	0.0290 (4)
H4	0.8328	0.6143	0.4070	0.035*
C5	0.8868 (3)	0.48825 (9)	0.46263 (10)	0.0230 (3)
C6	0.2535 (4)	0.40622 (11)	0.25242 (11)	0.0309 (4)
H6B	0.1273	0.3589	0.2774	0.037*
H6A	0.1260	0.4573	0.2313	0.037*
C7	0.4342 (4)	0.41095 (12)	0.09281 (12)	0.0370 (4)
H7	0.3563	0.4689	0.0770	0.044*
C8	0.6558 (4)	0.28448 (12)	0.08778 (13)	0.0408 (5)
H8	0.7665	0.2353	0.0663	0.049*
C9	0.5437 (4)	0.28818 (11)	0.17102 (12)	0.0357 (4)
H9	0.5604	0.2436	0.2181	0.043*
O1	0.2950 (3)	0.64181 (9)	0.14603 (8)	0.0371 (3)
H1A	0.3447	0.6360	0.0917	0.056*
C10	−0.0113 (4)	0.65194 (15)	0.14519 (15)	0.0484 (5)
H10B	−0.0687	0.6604	0.2084	0.073*
H10A	−0.1069	0.5977	0.1186	0.073*
H10C	−0.0717	0.7048	0.1080	0.073*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0345 (8)	0.0239 (7)	0.0274 (7)	−0.0042 (5)	0.0002 (6)	0.0016 (5)
N2	0.0318 (8)	0.0278 (7)	0.0244 (7)	0.0002 (5)	0.0000 (6)	−0.0046 (5)
N3	0.0533 (10)	0.0507 (9)	0.0289 (8)	0.0131 (8)	0.0063 (7)	−0.0033 (7)
C1	0.0367 (9)	0.0246 (8)	0.0290 (8)	−0.0063 (6)	0.0016 (7)	−0.0023 (6)
C2	0.0250 (8)	0.0304 (8)	0.0215 (7)	0.0000 (6)	0.0065 (6)	−0.0043 (6)
C3	0.0337 (9)	0.0288 (8)	0.0279 (8)	0.0038 (7)	−0.0008 (7)	0.0034 (6)
C4	0.0351 (9)	0.0219 (8)	0.0296 (8)	−0.0011 (6)	−0.0009 (7)	0.0008 (6)
C5	0.0256 (8)	0.0240 (7)	0.0201 (7)	0.0001 (6)	0.0065 (6)	−0.0015 (5)
C6	0.0267 (9)	0.0379 (9)	0.0283 (9)	−0.0004 (6)	0.0034 (7)	−0.0065 (7)
C7	0.0471 (11)	0.0361 (9)	0.0280 (9)	0.0088 (8)	0.0030 (8)	0.0007 (7)
C8	0.0483 (11)	0.0390 (10)	0.0345 (10)	0.0132 (8)	−0.0015 (8)	−0.0112 (8)
C9	0.0456 (11)	0.0273 (8)	0.0337 (9)	0.0037 (7)	−0.0014 (8)	−0.0043 (7)
O1	0.0342 (7)	0.0493 (7)	0.0277 (6)	0.0074 (5)	0.0024 (5)	0.0017 (5)
C10	0.0350 (10)	0.0590 (13)	0.0515 (12)	0.0067 (9)	0.0053 (9)	−0.0012 (9)

Geometric parameters (Å, °)

N1—C1	1.335 (2)	C4—H4	0.9500
N1—C5	1.3420 (19)	C5—C5i	1.490 (3)
N2—C7	1.346 (2)	C6—H6B	0.9900
N2—C9	1.372 (2)	C6—H6A	0.9900
N2—C6	1.4653 (19)	C7—H7	0.9500
N3—C7	1.313 (2)	C8—C9	1.346 (3)
N3—C8	1.377 (2)	C8—H8	0.9500
C1—C2	1.388 (2)	C9—H9	0.9500
C1—H1	0.9500	O1—C10	1.406 (2)
C2—C3	1.386 (2)	O1—H1A	0.8400
C2—C6	1.506 (2)	C10—H10B	0.9800
C3—C4	1.382 (2)	C10—H10A	0.9800
C3—H3	0.9500	C10—H10C	0.9800
C4—C5	1.388 (2)
C1—N1—C5	117.36 (14)	N2—C6—H6B	109.3
C7—N2—C9	106.80 (14)	C2—C6—H6B	109.3
C7—N2—C6	126.80 (14)	N2—C6—H6A	109.3
C9—N2—C6	126.30 (14)	C2—C6—H6A	109.3
C7—N3—C8	104.71 (15)	H6B—C6—H6A	108.0
N1—C1—C2	124.46 (14)	N3—C7—N2	112.04 (16)
N1—C1—H1	117.8	N3—C7—H7	124.0
C2—C1—H1	117.8	N2—C7—H7	124.0
C3—C2—C1	117.31 (15)	C9—C8—N3	110.55 (15)
C3—C2—C6	121.56 (15)	C9—C8—H8	124.7
C1—C2—C6	121.11 (14)	N3—C8—H8	124.7
C4—C3—C2	119.24 (15)	C8—C9—N2	105.89 (15)
C4—C3—H3	120.4	C8—C9—H9	127.1
C2—C3—H3	120.4	N2—C9—H9	127.1
C3—C4—C5	119.28 (14)	C10—O1—H1A	109.5
C3—C4—H4	120.4	O1—C10—H10B	109.5
C5—C4—H4	120.4	O1—C10—H10A	109.5
N1—C5—C4	122.32 (14)	H10B—C10—H10A	109.5
N1—C5—C5i	116.18 (16)	O1—C10—H10C	109.5
C4—C5—C5i	121.50 (16)	H10B—C10—H10C	109.5
N2—C6—C2	111.44 (13)	H10A—C10—H10C	109.5
C5—N1—C1—C2	1.6 (2)	C9—N2—C6—C2	73.5 (2)
N1—C1—C2—C3	−1.5 (2)	C3—C2—C6—N2	94.07 (17)
N1—C1—C2—C6	176.79 (15)	C1—C2—C6—N2	−84.11 (18)
C1—C2—C3—C4	0.1 (2)	C8—N3—C7—N2	−0.1 (2)
C6—C2—C3—C4	−178.13 (14)	C9—N2—C7—N3	0.3 (2)
C2—C3—C4—C5	1.0 (2)	C6—N2—C7—N3	177.02 (15)
C1—N1—C5—C4	−0.3 (2)	C7—N3—C8—C9	−0.1 (2)
C1—N1—C5—C5i	179.33 (15)	N3—C8—C9—N2	0.3 (2)
C3—C4—C5—N1	−0.9 (2)	C7—N2—C9—C8	−0.3 (2)
C3—C4—C5—C5i	179.44 (16)	C6—N2—C9—C8	−177.10 (16)
C7—N2—C6—C2	−102.61 (19)

Symmetry codes: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N3ii	0.84	1.93	2.7662 (19)	171
C3—H3···O1	0.95	2.44	3.360 (2)	162
C8—H8···N1iii	0.95	2.57	3.422 (2)	149
C9—H9···O1iv	0.95	2.54	3.470 (2)	168

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