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

Moon, S.-H.; Kim, T.H.; Park, K.-M.

doi:10.1107/S1600536811003643

organic compounds

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Volume 67| Part 3| March 2011| Page o554

doi:10.1107/S1600536811003643

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

Suk-Hee Moon,^a Tae Ho Kim ^b and Ki-Min Park ^b ^*

^aDepartment of Food & Nutrition, Kyungnam College of Information and Technology, Busan 616-701, Republic of Korea, and ^bDepartment of Chemistry and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 660-701, Republic of Korea
^*Correspondence e-mail: kmpark@gnu.ac.kr

(Received 25 January 2011; accepted 28 January 2011; online 2 February 2011)

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, P 2₁ /c
a = 4.5653 (4) Å
b = 14.7886 (12) Å
c = 14.5378 (11) Å
β = 93.805 (2)°
V = 979.35 (14) Å³
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[F² > 2σ(F²)] = 0.041
wR(F²) = 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

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) -x+1, -y+1, -z; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003643/sj5094sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003643/sj5094Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

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

Figures top

	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).

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

Crystal data top

C₁₈H₁₆N₆·2CH₄O	F(000) = 404
M_r = 380.45	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0772P)² + 0.1442P] where P = (F_o² + 2F_c²)/3
2136 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₈H₁₆N₆·2CH₄O	V = 979.35 (14) Å³
M_r = 380.45	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.5653 (4) Å	µ = 0.09 mm⁻¹
b = 14.7886 (12) Å	T = 173 K
c = 14.5378 (11) Å	0.35 × 0.30 × 0.10 mm
β = 93.805 (2)°

Data collection top

Bruker APEXII CCD diffractometer	2136 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1619 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.991	R_int = 0.053
5948 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 1.09	Δρ_max = 0.21 e Å⁻³
2136 reflections	Δρ_min = −0.24 e Å⁻³
128 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

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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 code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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···O1^iv	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.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆N₆·2CH₄O
M_r	380.45
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	4.5653 (4), 14.7886 (12), 14.5378 (11)
β (°)	93.805 (2)
V (Å³)	979.35 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.35 × 0.30 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.970, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	5948, 2136, 1619
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.144, 1.09
No. of reflections	2136
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.24

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top

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) −x+1, −y+1, −z; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y−1/2, −z+1/2.

Acknowledgements

This research was supported by the National Nuclear R&D Program through the National Research Foundation (NRF) funded by the Ministry of Education, Science and Technology (2010–0018586)

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sambrook, M. R., Curiel, D., Hayes, E. J., Beer, P. D., Pope, S. J. A. & Faulkner, S. (2006). New J. Chem. 30, 1133–1136. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zang, H.-Y., Lan, Y.-Q., Yang, G.-S., Wang, X.-L., Shao, K.-Z., Xu, G.-J. & Su, Z.-M. (2010). CrystEngComm, 12, 434–445. Web of Science CSD CrossRef CAS Google Scholar