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Acta Cryst. (2009). E65, m1325    [ doi:10.1107/S1600536809040136 ]

Dimethyl(2,2':6',2''-terpyridine-[kappa]3N,N',N'')zinc(II)

T. Shalumova and J. M. Tanski

Abstract top

The title compound, [Zn(CH3)2(C15H11N3)], was synthesized by the addition of dimethylzinc to 2,2':6',2''-terpyridine and was crystallized by the slow evaporation of THF. The pentacoordinate ZnII atom, lying on a twofold rotation axis, displays a distorted trigonal-bipyramidal geometry, with two terminal N atoms at the axial positions and the central N atom and two methyl C atoms at the equatorial positions.

Comment top

The chelating ligand 2,2':6',2''-terpyridine coordinates to a variety of first-row transition metal Lewis acids. Specifically, it can coordinate to disubstituted zinc compounds, allowing for the formation of trigonal bipyramidal zinc(II) complexes (Harrison et al., 1986). The structure of terpyridine dichlorozinc(II) has been reported a number of times with different results (Corbridge & Cox, 1956; Einstein & Penfold, 1966; Vlasse et al., 1983). In addition to substituents on the zinc(II) center, substituents on the terpyridine are also known (Hou et al., 2004). The structure presented here is the first known structure in a class of terpyridine zinc(II) compounds with two alkyl groups bound directly to the metal center.

The title compound (Fig. 1) was obtained by the reaction of dimethylzinc with 2,2':6',2''-terpyridine. It exhibits a distorted trigonal bipyramidal geometry about the metal center and has the two terminal N atoms in the axial positions, with a bond length of 2.3381 (12) Å (Table 1). The central N atom, coordinated to the zinc via the equatorial position, has a slightly smaller bond length, 2.2603 (16) Å, due to the size of the ligand, which is not able to wrap around the metal 180°. The N1—Zn—N1i bond angle is 140.52 (6)° [symmetry code: (i) -x, y, 1/2-z], illustrating the degree to which the compound is distorted from a perfectly trigonal bipyramid. The Zn—C bond length is 2.0282 (15) Å, and the C1—Zn—C1i bond angle is 133.21 (9)°: slightly greater than the expected 120° between equatorial atoms. Interestingly, the Zn—N bond lengths shown here are about 0.2 Å longer than those reported for similar terpyridine zinc(II) complexes, while the Zn—C length is expectedly shorter than the Zn—Cl and Zn—S lengths (Harrison et al., 1986; Hou et al., 2004; Vlasse et al., 1983). However, the Zn—C bond length is similar to that reported for a bipyridine dimethylzinc(II) complex, characterized by Wessing et al. (1994). The terpyridyl N1—Zn—N1i and N1—Zn—N2 bond angles are in agreement with those reported in the literature (Harrison et al., 1986; Hou et al., 2004; Vlasse et al., 1983).

Related literature top

For the crystal structures of terpyridine dichlorozinc(II) compounds, see: Corbridge & Cox (1956); Einstein & Penfold (1966); Vlasse et al. (1983). For examples of other substituted terpyridine zinc(II) compounds, see: Harrison et al. (1986); Hou et al. (2004). The structure of a bipyridine dimethylzinc(II) compound was reported by Wissing et al. (1994).

Experimental top

Under a nitrogen atmosphere, dimethylzinc (2 M in toluene, 1.07 ml, 2.14 mmol) was added to a stirring solution of terpyridine (0.511 g, 2.19 mmol) in toluene (3.5 ml). The resulting orange precipitate, which is extremely sensitive to hydrolysis, was filtered and dried in vacuo (yield 65%, 0.46 g). Crystallization was achieved by slow evaporation of THF in a nitrogen filled glovebox, which yielded yellow plates within five days. Analysis, calculated for C17H17N3Zn: C 62.11, H 5.21, N 12.78%; found: C 59.18, H 5.09, N 12.12%. 1H NMR (300 MHz, C6D6): δ -0.529 (s, 6H, –CH3).

Refinement top

A suitable crystal was mounted in a nylon loop with Paratone-N cryoprotectant oil and data was collected on a Bruker APEXII CCD platform diffractometer. H atoms were included in calculated positions and were refined using a riding model, with C—H = 0.95 (aromatic) and 0.98 (methyl) Å and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C).

Computing details top

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

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, with displacement ellipsoids shown at the 50% probability level. [Symmetry code: (i) -x, y, 1/2-z.]
Dimethyl(2,2':6',2''-terpyridine-κ3N,N',N'')zinc(II) top
Crystal data top
[Zn(CH3)2(C15H11N3)]F(000) = 680
Mr = 328.71Dx = 1.469 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6987 reflections
a = 17.4250 (11) Åθ = 2.7–28.3°
b = 9.1083 (6) ŵ = 1.65 mm−1
c = 11.7595 (14) ÅT = 125 K
β = 127.193 (1)°Plate, yellow
V = 1486.8 (2) Å30.23 × 0.13 × 0.06 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer		1837 independent reflections
Radiation source: fine-focus sealed tube1710 reflections with I > 2σ(I)
graphiteRint = 0.025
φ and ω scansθmax = 28.3°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −23→23
Tmin = 0.703, Tmax = 0.908k = −12→12
9483 measured reflectionsl = −15→15
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0347P)2 + 0.7204P]
where P = (Fo2 + 2Fc2)/3
1837 reflections(Δ/σ)max < 0.001
98 parametersΔρmax = 0.41 e Å−3
0 restraintsΔρmin = −0.27 e Å−3
Crystal data top
[Zn(CH3)2(C15H11N3)]V = 1486.8 (2) Å3
Mr = 328.71Z = 4
Monoclinic, C2/cMo Kα radiation
a = 17.4250 (11) ŵ = 1.65 mm−1
b = 9.1083 (6) ÅT = 125 K
c = 11.7595 (14) Å0.23 × 0.13 × 0.06 mm
β = 127.193 (1)°
Data collection top
Bruker APEXII CCD
diffractometer		1837 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1710 reflections with I > 2σ(I)
Tmin = 0.703, Tmax = 0.908Rint = 0.025
9483 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.061Δρmax = 0.41 e Å−3
S = 1.09Δρmin = −0.27 e Å−3
1837 reflectionsAbsolute structure: ?
98 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn0.00000.27994 (2)0.25000.02138 (9)
N10.09270 (8)0.19322 (13)0.18122 (12)0.0217 (2)
N20.00000.03178 (17)0.25000.0181 (3)
C10.11086 (11)0.36835 (17)0.43838 (16)0.0282 (3)
H1A0.12920.46250.42070.042*
H1B0.16600.30130.48580.042*
H1C0.09090.38400.49960.042*
C20.13813 (11)0.28148 (17)0.14866 (16)0.0260 (3)
H2A0.13370.38460.15570.031*
C30.19141 (11)0.22995 (19)0.10513 (17)0.0291 (3)
H3A0.22370.29590.08450.035*
C40.19631 (10)0.0801 (2)0.09259 (16)0.0298 (3)
H4A0.23170.04130.06210.036*
C50.14921 (10)−0.01296 (17)0.12488 (15)0.0261 (3)
H5A0.1513−0.11630.11600.031*
C60.09862 (9)0.04762 (15)0.17079 (13)0.0197 (3)
C70.04737 (9)−0.04323 (15)0.21108 (13)0.0188 (3)
C80.04827 (10)−0.19665 (15)0.20904 (15)0.0239 (3)
H8A0.0814−0.24750.18010.029*
C90.0000−0.2732 (2)0.25000.0260 (4)
H9A0.0000−0.37750.25000.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.02557 (13)0.01758 (13)0.02424 (13)0.0000.01676 (11)0.000
N10.0219 (5)0.0236 (6)0.0222 (6)−0.0008 (4)0.0147 (5)−0.0004 (4)
N20.0182 (7)0.0178 (7)0.0176 (7)0.0000.0105 (6)0.000
C10.0330 (7)0.0234 (7)0.0303 (7)−0.0055 (6)0.0202 (7)−0.0032 (6)
C20.0259 (7)0.0279 (7)0.0261 (7)−0.0032 (6)0.0167 (6)0.0009 (6)
C30.0230 (7)0.0420 (9)0.0243 (7)−0.0018 (6)0.0154 (6)0.0048 (6)
C40.0236 (7)0.0461 (9)0.0247 (7)0.0082 (6)0.0173 (6)0.0050 (6)
C50.0252 (7)0.0299 (8)0.0253 (7)0.0066 (6)0.0164 (6)0.0020 (6)
C60.0172 (6)0.0242 (7)0.0161 (6)0.0021 (5)0.0093 (5)0.0006 (5)
C70.0177 (6)0.0195 (6)0.0167 (6)0.0016 (5)0.0091 (5)−0.0005 (5)
C80.0230 (7)0.0208 (7)0.0237 (7)0.0031 (5)0.0119 (6)−0.0023 (5)
C90.0262 (10)0.0171 (9)0.0276 (10)0.0000.0126 (9)0.000
Geometric parameters (Å, °) top
Zn—C1i2.0282 (15)C2—H2A0.9500
Zn—C12.0282 (15)C3—C41.381 (2)
Zn—N12.3381 (12)C3—H3A0.9500
Zn—N22.2603 (16)C4—C51.383 (2)
Zn—N1i2.3382 (12)C4—H4A0.9500
N1—C21.3364 (19)C5—C61.3958 (18)
N1—C61.3416 (18)C5—H5A0.9500
N2—C7i1.3470 (15)C6—C71.4893 (18)
N2—C71.3470 (15)C7—C81.3979 (19)
C1—H1A0.9800C8—C91.3838 (18)
C1—H1B0.9800C8—H8A0.9500
C1—H1C0.9800C9—C8i1.3838 (18)
C2—C31.385 (2)C9—H9A0.9500
C1i—Zn—C1133.21 (9)N1—C2—H2A118.4
C1i—Zn—N2113.39 (5)C3—C2—H2A118.4
C1—Zn—N2113.39 (5)C4—C3—C2118.22 (14)
C1i—Zn—N199.05 (5)C4—C3—H3A120.9
C1—Zn—N196.37 (5)C2—C3—H3A120.9
N2—Zn—N170.26 (3)C3—C4—C5119.41 (14)
C1i—Zn—N1i96.37 (5)C3—C4—H4A120.3
C1—Zn—N1i99.05 (5)C5—C4—H4A120.3
N2—Zn—N1i70.26 (3)C4—C5—C6118.83 (14)
N1—Zn—N1i140.52 (6)C4—C5—H5A120.6
C2—N1—C6118.48 (12)C6—C5—H5A120.6
C2—N1—Zn123.28 (10)N1—C6—C5121.84 (13)
C6—N1—Zn118.22 (9)N1—C6—C7115.22 (11)
C7i—N2—C7119.05 (16)C5—C6—C7122.93 (13)
C7i—N2—Zn120.48 (8)N2—C7—C8121.89 (13)
C7—N2—Zn120.47 (8)N2—C7—C6115.77 (12)
Zn—C1—H1A109.5C8—C7—C6122.34 (12)
Zn—C1—H1B109.5C9—C8—C7118.82 (14)
H1A—C1—H1B109.5C9—C8—H8A120.6
Zn—C1—H1C109.5C7—C8—H8A120.6
H1A—C1—H1C109.5C8—C9—C8i119.53 (19)
H1B—C1—H1C109.5C8—C9—H9A120.2
N1—C2—C3123.19 (14)C8i—C9—H9A120.2
C1i—Zn—N1—C268.69 (12)C2—C3—C4—C5−0.6 (2)
C1—Zn—N1—C2−66.99 (12)C3—C4—C5—C6−0.6 (2)
N2—Zn—N1—C2−179.60 (12)C2—N1—C6—C5−1.1 (2)
N1i—Zn—N1—C2−179.60 (12)Zn—N1—C6—C5177.37 (10)
C1i—Zn—N1—C6−109.70 (11)C2—N1—C6—C7179.08 (12)
C1—Zn—N1—C6114.62 (11)Zn—N1—C6—C7−2.45 (15)
N2—Zn—N1—C62.01 (9)C4—C5—C6—N11.5 (2)
N1i—Zn—N1—C62.01 (9)C4—C5—C6—C7−178.65 (12)
C1i—Zn—N2—C7i−89.74 (8)C7i—N2—C7—C80.42 (9)
C1—Zn—N2—C7i90.26 (8)Zn—N2—C7—C8−179.58 (9)
N1—Zn—N2—C7i178.72 (7)C7i—N2—C7—C6−179.48 (12)
N1i—Zn—N2—C7i−1.28 (7)Zn—N2—C7—C60.52 (12)
C1i—Zn—N2—C790.26 (8)N1—C6—C7—N21.31 (16)
C1—Zn—N2—C7−89.74 (8)C5—C6—C7—N2−178.51 (11)
N1—Zn—N2—C7−1.28 (7)N1—C6—C7—C8−178.59 (13)
N1i—Zn—N2—C7178.72 (7)C5—C6—C7—C81.6 (2)
C6—N1—C2—C3−0.3 (2)N2—C7—C8—C9−0.83 (19)
Zn—N1—C2—C3−178.64 (11)C6—C7—C8—C9179.07 (10)
N1—C2—C3—C41.1 (2)C7—C8—C9—C8i0.39 (9)
Symmetry codes: (i) −x, y, −z+1/2.
Table 1
Selected geometric parameters (Å) top
Zn—C12.0282 (15)Zn—N22.2603 (16)
Zn—N12.3381 (12)
Acknowledgements top

This work was supported by Vassar College. X-ray facilities were provided by the US National Science Foundation (grant No. 0521237 to JMT).

references
References top

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