4,4′-Bipyridine–dimethyl­glyoxime (1/1)

Yang, Y.; Huang, Z.; Lv, H.; Han, A.

doi:10.1107/S1600536811054341

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o242

doi:10.1107/S1600536811054341

Open

access

4,4′-Bipyridine–dimethylglyoxime (1/1)

Yan Yang,^a Ziping Huang,^a Haitang Lv ^a and Aixia Han ^a ^*

^aCollege of Chemical Engineering,Qinghai University, Xining 810016, People's Republic of China
^*Correspondence e-mail: yyan217@163.com

(Received 14 November 2011; accepted 17 December 2011; online 23 December 2011)

In the title compound, C₁₀H₈N₂·C₄H₈N₂O₂, both the dimethylglyoxime and the 4,4′-bipyridine molecules have crystallographic C_i symmetry. The molecules stack along the a-axis direction with a dihedral angle of 20.4 (8)° between their planes. In the crystal, the components are linked by O—H⋯N hydrogen bonds into alternating chains along [120] and [1 $[\overline2]$ 0].

Related literature

For the coordination modes of dimethylglyoxime, see: Malinovskii et al. (2004 ); Coropceanu et al. (2009 ). For its use in mediate magnetic interactions, see: Cervera et al. (1997 ).

Experimental

Crystal data

C₁₀H₈N₂·C₄H₈N₂O₂
M_r = 272.31
Monoclinic, P 2₁ /c
a = 8.7247 (17) Å
b = 7.1486 (14) Å
c = 11.502 (2) Å
β = 99.44 (3)°
V = 707.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.20 × 0.18 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.982, T_max = 0.987
9684 measured reflections
1636 independent reflections
1265 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.133
S = 1.05
1636 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.82	1.94	2.7459 (17)	169
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811054341/ld2038sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811054341/ld2038Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811054341/ld2038Isup3.mol

checkCIF report

Comment top

Dimethylglyoxime (H₂dmg) with its two oximate group (═N–O–) is a suitable scaffold to construct metal-containing building blocks for extended supramolecular architectures. Several complexes of transition metals with this ligand and its derivatives have been reported (Malinovskii et al., 2004; Coropceanu et al., 2009). Moreover, the NO oxime group has a remarkable efficiency to mediate magnetic interactions when it acts as a bridging ligand (Cervera et al., 1997).

Starting from Mn(CH₃COO)₂ and H₂dmg, and using 4,4'-dpy as a bridging ligand, we have aimed to prepare a complex with superior magnetic properties. However, the reaction resulted in a stoichiometric (1:1) molecular complex of dimethylglyoxime-4,4'-bipyridine.

In this structure, the molecules of H₂dmg and 4,4'-dpy are linked through O—H···N hydrogen bonds into alternating chains (Fig. 2).

Related literature top

For the coordination modes of dimethylglyoxime, see: Malinovskii et al. (2004); Coropceanu et al. (2009). For its use in mediate magnetic interactions, see: Cervera et al. (1997).

Experimental top

Mn(CH₃COO)₂.4H₂O (0.025 g, 0.1 mmol) in 5 ml of water and CH₃COONa(0.016 g, 0.2 mmol) were added to a mixture of H₂dmg (0.024 g, 0.2 mmol) and 4,4'-dpy in 10 ml of methanol. The reaction mixture was boiled in a crucible for ~10 min. The solvent was then evaporated and colorless crystals of the title compound were obtained.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure showing 50% probability displacement ellipsoids.
	Fig. 2. Heterosoric stacks of the molecules.

4,4'-Bipyridine–dimethylglyoxime (1/1) top

Crystal data top

C₁₀H₈N₂·C₄H₈N₂O₂	F(000) = 288
M_r = 272.31	707.6(2)
Monoclinic, P2₁/c	D_x = 1.278 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.7247 (17) Å	Cell parameters from 1636 reflections
b = 7.1486 (14) Å	θ = 2.4–27.5°
c = 11.502 (2) Å	µ = 0.09 mm⁻¹
β = 99.44 (3)°	T = 298 K
V = 707.6 (2) Å³	Block, colourless
Z = 2	0.20 × 0.18 × 0.15 mm

Data collection top

Bruker SMART APEX CCD diffractometer	1636 independent reflections
Radiation source: fine-focus sealed tube	1265 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
T_min = 0.982, T_max = 0.987	k = −9→9
9684 measured reflections	l = −14→14

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.062P)² + 0.1229P] where P = (F_o² + 2F_c²)/3
1636 reflections	(Δ/σ)_max = 0.021
93 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₀H₈N₂·C₄H₈N₂O₂	V = 707.6 (2) Å³
M_r = 272.31	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.7247 (17) Å	µ = 0.09 mm⁻¹
b = 7.1486 (14) Å	T = 298 K
c = 11.502 (2) Å	0.20 × 0.18 × 0.15 mm
β = 99.44 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	1636 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1265 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.987	R_int = 0.040
9684 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.05	Δρ_max = 0.19 e Å⁻³
1636 reflections	Δρ_min = −0.13 e Å⁻³
93 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
C1	0.02851 (14)	0.09220 (19)	0.48302 (12)	0.0464 (3)
O1	0.72158 (14)	0.26180 (17)	0.14282 (10)	0.0699 (4)
H1	0.7740	0.1714	0.1296	0.105*
N1	0.14118 (15)	0.43625 (18)	0.41432 (12)	0.0600 (4)
N2	0.62500 (14)	0.31488 (17)	0.03926 (12)	0.0556 (4)
C5	−0.04603 (17)	0.1905 (2)	0.38632 (14)	0.0557 (4)
H5	−0.1364	0.1429	0.3421	0.067*
C6	0.55111 (16)	0.4662 (2)	0.05327 (13)	0.0518 (4)
C3	0.21126 (19)	0.3451 (2)	0.50901 (16)	0.0652 (5)
H3	0.2997	0.3982	0.5527	0.078*
C2	0.16017 (18)	0.1766 (2)	0.54594 (15)	0.0591 (4)
H2	0.2137	0.1190	0.6130	0.071*
C4	0.01328 (18)	0.3583 (2)	0.35553 (15)	0.0605 (4)
H4	−0.0391	0.4208	0.2899	0.073*
C7	0.5661 (2)	0.5712 (3)	0.16681 (15)	0.0701 (5)
H7A	0.5414	0.4897	0.2275	0.105*
H7B	0.4958	0.6754	0.1578	0.105*
H7C	0.6707	0.6158	0.1881	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0428 (7)	0.0475 (7)	0.0486 (7)	0.0018 (5)	0.0062 (5)	−0.0049 (6)
O1	0.0727 (8)	0.0700 (8)	0.0608 (7)	0.0253 (6)	−0.0076 (6)	−0.0006 (5)
N1	0.0600 (8)	0.0521 (7)	0.0671 (8)	−0.0065 (6)	0.0081 (6)	−0.0017 (6)
N2	0.0527 (7)	0.0553 (7)	0.0560 (7)	0.0087 (5)	0.0001 (5)	0.0000 (5)
C5	0.0513 (8)	0.0572 (8)	0.0550 (8)	−0.0064 (6)	−0.0020 (6)	0.0017 (7)
C6	0.0473 (7)	0.0539 (8)	0.0529 (8)	0.0050 (6)	0.0042 (6)	−0.0030 (6)
C3	0.0583 (9)	0.0607 (9)	0.0723 (11)	−0.0125 (7)	−0.0024 (8)	−0.0045 (8)
C2	0.0548 (8)	0.0562 (9)	0.0614 (9)	−0.0035 (7)	−0.0049 (7)	0.0018 (7)
C4	0.0621 (9)	0.0570 (9)	0.0596 (9)	−0.0021 (7)	0.0020 (7)	0.0063 (7)
C7	0.0760 (11)	0.0732 (11)	0.0567 (9)	0.0180 (9)	−0.0026 (8)	−0.0097 (8)

Geometric parameters (Å, º) top

C1—C5	1.384 (2)	C6—C6ⁱⁱ	1.474 (3)
C1—C2	1.391 (2)	C6—C7	1.493 (2)
C1—C1ⁱ	1.484 (3)	C3—C2	1.376 (2)
O1—N2	1.3941 (17)	C3—H3	0.9300
O1—H1	0.8200	C2—H2	0.9300
N1—C4	1.329 (2)	C4—H4	0.9300
N1—C3	1.329 (2)	C7—H7A	0.9600
N2—C6	1.2831 (18)	C7—H7B	0.9600
C5—C4	1.376 (2)	C7—H7C	0.9600
C5—H5	0.9300

C5—C1—C2	115.92 (14)	C2—C3—H3	118.2
C5—C1—C1ⁱ	121.91 (15)	C3—C2—C1	120.06 (15)
C2—C1—C1ⁱ	122.16 (16)	C3—C2—H2	120.0
N2—O1—H1	109.5	C1—C2—H2	120.0
C4—N1—C3	116.54 (14)	N1—C4—C5	123.68 (15)
C6—N2—O1	111.59 (12)	N1—C4—H4	118.2
C4—C5—C1	120.16 (14)	C5—C4—H4	118.2
C4—C5—H5	119.9	C6—C7—H7A	109.5
C1—C5—H5	119.9	C6—C7—H7B	109.5
N2—C6—C6ⁱⁱ	114.82 (16)	H7A—C7—H7B	109.5
N2—C6—C7	124.04 (14)	C6—C7—H7C	109.5
C6ⁱⁱ—C6—C7	121.13 (16)	H7A—C7—H7C	109.5
N1—C3—C2	123.61 (14)	H7B—C7—H7C	109.5
N1—C3—H3	118.2

C2—C1—C5—C4	1.8 (2)	N1—C3—C2—C1	0.1 (3)
C1ⁱ—C1—C5—C4	−177.95 (15)	C5—C1—C2—C3	−1.7 (2)
O1—N2—C6—C6ⁱⁱ	178.74 (15)	C1ⁱ—C1—C2—C3	178.06 (16)
O1—N2—C6—C7	−0.5 (2)	C3—N1—C4—C5	−1.3 (2)
C4—N1—C3—C2	1.4 (3)	C1—C5—C4—N1	−0.3 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱⁱⁱ	0.82	1.94	2.7459 (17)	169

Symmetry code: (iii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₂·C₄H₈N₂O₂
M_r	272.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.7247 (17), 7.1486 (14), 11.502 (2)
β (°)	99.44 (3)
V (Å³)	707.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.982, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	9684, 1636, 1265
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.133, 1.05
No. of reflections	1636
No. of parameters	93
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.13

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	1.94	2.7459 (17)	168.7

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Acknowledgements

This work was supported by the Qinghai Province International Science and Technology Cooperation Plan Projects (2011-H-808).

References

Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA. Google Scholar
Cervera, B., Ruiz, R., Lloret, F., Julve, M., Cano, J., Faus, J., Bois, C. & Mrozinski, J. (1997). J. Chem. Soc. Dalton Trans. pp. 395–401. CSD CrossRef Web of Science Google Scholar
Coropceanu, E., Croitor, L., Gdaniec, M., Wicher, B. & Fonari, M. (2009). Inorg. Chim. Acta, 362, 2151–2158. CrossRef CAS Google Scholar
Malinovskii, S. T., Bologa, O. A., Coropceanu, E. B., Luboradzki, R. & Gerbeleu, N. V. (2004). Russ. J. Coord. Chem. 30, 339–345. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar