(Acetonitrile)[bis­(2-pyridylmeth­yl)amine]bis­(perchlorato)copper(II)

Ray J Butcher; Yohannes T Tesema; Teshome B Yisgedu; Yilma Gultneh

doi:10.1107/S1600536807067001

. 2007 Dec 21;64(Pt 1):m233–m234. doi: 10.1107/S1600536807067001

(Acetonitrile)[bis(2-pyridylmethyl)amine]bis(perchlorato)copper(II)

Ray J Butcher ^a,^*, Yohannes T Tesema ^a, Teshome B Yisgedu ^a, Yilma Gultneh ^a

PMCID: PMC2915155 PMID: 21200577

Abstract

In the title compound, [Cu(ClO₄)₂(C₁₂H₁₃N₃)(C₂H₃N)], the Cu^II atom is six-coordinate in a Jahn–Teller distorted octahedral geometry, with coordination by the tridentate chelating ligand, an acetonitrile molecule, and two axial perchlorate anions. The tridentate ligand bis(2-pyridylmethyl)amine chelates meridionally and equatorially while an acetonitrile molecule is coordinated at the fourth equatorial site. The two perchlorate anions are disordered with site occupancy factors of 0.72/0.28. The amine H is involved in intramolecular hydrogen bonding to the perchlorate O atoms and there are extensive but weak intermolecular C—H⋯O interactions.

Related literature

For related literature, see: Belle et al. (2002 ▶); Gultneh et al. (1999 ▶); Humphreys et al. (2002 ▶); Palaniandavar et al. (1995 ▶).

Experimental

Crystal data

[Cu(ClO₄)₂(C₁₂H₁₃N₃)(C₂H₃N)]
M _r = 502.75
Monoclinic,
a = 8.3046 (16) Å
b = 31.453 (4) Å
c = 8.4978 (11) Å
β = 118.646 (10)°
V = 1948.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.45 mm⁻¹
T = 293 (2) K
0.45 × 0.21 × 0.07 mm

Data collection

Bruker P4S diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.757, T _max = 0.964 (expected range = 0.709–0.904)
4638 measured reflections
4347 independent reflections
2718 reflections with I > 2σ(I)
R _int = 0.030
3 standard reflections every 97 reflections intensity decay: <2%

Refinement

R[F ² > 2σ(F ²)] = 0.064
wR(F ²) = 0.193
S = 1.04
4347 reflections
320 parameters
92 restraints
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: XSCANS (Bruker, 1997 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 2000 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067001/bq2058sup1.cif

e-64-0m233-sup1.cif^{(24.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067001/bq2058Isup2.hkl

e-64-0m233-Isup2.hkl^{(213KB, hkl)}

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
N—H0A⋯O22A	0.91	2.45	2.89 (3)	110
N—H0A⋯O23	0.91	2.30	3.084 (12)	144
N—H0A⋯O23ⁱ	0.91	2.50	3.317 (10)	150
C2—H21⋯O13Aⁱⁱ	0.96	2.23	2.98 (2)	133
C2—H22⋯O14ⁱⁱⁱ	0.96	2.36	3.103 (14)	134
C1A—H1AA⋯O12ⁱⁱ	0.93	2.46	3.176 (9)	134
C3A—H3AA⋯O23^iv	0.93	2.53	3.376 (15)	152
C3A—H3AA⋯O23A^iv	0.93	2.29	2.993 (14)	133
C6A—H6AA⋯O21ⁱ	0.97	2.56	3.381 (9)	143
C2B—H2BA⋯O14A^v	0.93	2.35	3.112 (16)	140
C3B—H3BA⋯O11^vi	0.93	2.56	3.429 (10)	156
C4B—H4BA⋯O24A^vii	0.93	2.25	3.06 (3)	145
C6B—H6BA⋯O12	0.97	2.56	3.425 (13)	149
C6B—H6BB⋯O24A^vii	0.97	2.51	3.211 (16)	129

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

RJB acknowledges the Laboratory for the Structure of Matter at the Naval Research Laboratory, Washington, DC, USA, for access to their diffractometer.

supplementary crystallographic information

Comment

Bis(2-pyridylmethyl)amine (L¹) has been used as a chelating ligand for several metal ions, as a single unit, or as two or more units bridged by other groups (such as m-xylyl spaces or aliphatic hydrocarbon chains) through the amine N atom (Gultneh et al., 1999; Palaniandavar et al., 1995; Belle et al., 2002; Humphreys et al., 2002). We report here the structure of the copper (II) complex of the ligand L¹. The complex was synthesized by the reaction of L¹ with Cu(ClO₄)₂.6H₂O in acetonitrile.

The crystal structure shows that Cu^II is six-coordinate in a Jahn-Teller distorted geometry with coordination by the tridentate chelating ligand, an acetonitrile molecule, and two axial perchlorate anions (Fig. 1.). The tridentate ligand L¹ is chelating meridionally and equatorially while an acetonitrile molecule is coordinated at the fourth equatorial site. One axial perchlorate group is at a Cu^II—OClO₃^- distance of 2.455 (9) Å while the other is at 2.828 (5) Å consistent with its expected Jahn-Teller elongation (O—Cu—O angle 169.1 (2)°). The mutually trans Cu—N_py distances are 1.980 (5) Å and 1.984 (5) Å and span an angle of 165.3 (2)°. The Cu—N_amine bond distance is 1.991 (5) Å. The Cu—N_acetonitrile bond distance of 1.980 (5) Å is comparable to the Cu—N distances of the N atoms. The amine H is involved in intramolecular hydrogen bonding to the perchlorate O atoms and there are extensive but weak intermolecular C—H···O interactions. (Table 1.).

Experimental

The title compound, bis(2-pyridylmethyl)amine copper(II) acetonitrile bis(perchlorate), was obtained by refluxing bis(2-pyridylmethyl)amine (2 mmol) and copper(II) perchlorate hexahydrate (2 mmol) in 200 ml of acetonitrile for 1 h. The product deposited on cooling the solution. Suitable crystals suited for crystallographic structure determination were obtained by slow diffusion of diethyl ether into the nitromethane solution of the complex.