Dimeth­yl(2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)zinc(II)

Shalumova, T.; Tanski, J.M.

doi:10.1107/S1600536809040136

metal-organic compounds

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Volume 65| Part 11| November 2009| Page m1325

https://doi.org/10.1107/S1600536809040136

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Dimethyl(2,2′:6′,2′′-terpyridine-κ³N,N′,N′′)zinc(II)

Tamila Shalumova ^a and Joseph M. Tanski ^a ^*

^aDepartment of Chemistry, Vassar College, Poughkeepsie, NY 12604, USA
^*Correspondence e-mail: jotanski@vassar.edu

(Received 21 September 2009; accepted 1 October 2009; online 7 October 2009)

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 Zn^II 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.

Related literature

For the crystal structures of terpyridine dichloridozinc(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

Crystal data

[Zn(CH₃)₂(C₁₅H₁₁N₃)]
M_r = 328.71
Monoclinic, C 2/c
a = 17.4250 (11) Å
b = 9.1083 (6) Å
c = 11.7595 (14) Å
β = 127.193 (1)°
V = 1486.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.65 mm⁻¹
T = 125 K
0.23 × 0.13 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.703, T_max = 0.908
9483 measured reflections
1837 independent reflections
1710 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.061
S = 1.09
1837 reflections
98 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn—C1	2.0282 (15)
Zn—N1	2.3381 (12)
Zn—N2	2.2603 (16)

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809040136/hy2233sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040136/hy2233Isup2.hkl

checkCIF report

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).

Structure description top

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

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
M_r = 328.71	D_x = 1.469 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6987 reflections
a = 17.4250 (11) Å	θ = 2.7–28.3°
b = 9.1083 (6) Å	µ = 1.65 mm⁻¹
c = 11.7595 (14) Å	T = 125 K
β = 127.193 (1)°	Plate, yellow
V = 1486.8 (2) Å³	0.23 × 0.13 × 0.06 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1837 independent reflections
Radiation source: fine-focus sealed tube	1710 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 28.3°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→23
T_min = 0.703, T_max = 0.908	k = −12→12
9483 measured reflections	l = −15→15

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0347P)² + 0.7204P] where P = (F_o² + 2F_c²)/3
1837 reflections	(Δ/σ)_max < 0.001
98 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Zn(CH₃)₂(C₁₅H₁₁N₃)]	V = 1486.8 (2) Å³
M_r = 328.71	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.4250 (11) Å	µ = 1.65 mm⁻¹
b = 9.1083 (6) Å	T = 125 K
c = 11.7595 (14) Å	0.23 × 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)
T_min = 0.703, T_max = 0.908	R_int = 0.025
9483 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.09	Δρ_max = 0.41 e Å⁻³
1837 reflections	Δρ_min = −0.27 e Å⁻³
98 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn	0.0000	0.27994 (2)	0.2500	0.02138 (9)
N1	0.09270 (8)	0.19322 (13)	0.18122 (12)	0.0217 (2)
N2	0.0000	0.03178 (17)	0.2500	0.0181 (3)
C1	0.11086 (11)	0.36835 (17)	0.43838 (16)	0.0282 (3)
H1A	0.1292	0.4625	0.4207	0.042*
H1B	0.1660	0.3013	0.4858	0.042*
H1C	0.0909	0.3840	0.4996	0.042*
C2	0.13813 (11)	0.28148 (17)	0.14866 (16)	0.0260 (3)
H2A	0.1337	0.3846	0.1557	0.031*
C3	0.19141 (11)	0.22995 (19)	0.10513 (17)	0.0291 (3)
H3A	0.2237	0.2959	0.0845	0.035*
C4	0.19631 (10)	0.0801 (2)	0.09259 (16)	0.0298 (3)
H4A	0.2317	0.0413	0.0621	0.036*
C5	0.14921 (10)	−0.01296 (17)	0.12488 (15)	0.0261 (3)
H5A	0.1513	−0.1163	0.1160	0.031*
C6	0.09862 (9)	0.04762 (15)	0.17079 (13)	0.0197 (3)
C7	0.04737 (9)	−0.04323 (15)	0.21108 (13)	0.0188 (3)
C8	0.04827 (10)	−0.19665 (15)	0.20904 (15)	0.0239 (3)
H8A	0.0814	−0.2475	0.1801	0.029*
C9	0.0000	−0.2732 (2)	0.2500	0.0260 (4)
H9A	0.0000	−0.3775	0.2500	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.02557 (13)	0.01758 (13)	0.02424 (13)	0.000	0.01676 (11)	0.000
N1	0.0219 (5)	0.0236 (6)	0.0222 (6)	−0.0008 (4)	0.0147 (5)	−0.0004 (4)
N2	0.0182 (7)	0.0178 (7)	0.0176 (7)	0.000	0.0105 (6)	0.000
C1	0.0330 (7)	0.0234 (7)	0.0303 (7)	−0.0055 (6)	0.0202 (7)	−0.0032 (6)
C2	0.0259 (7)	0.0279 (7)	0.0261 (7)	−0.0032 (6)	0.0167 (6)	0.0009 (6)
C3	0.0230 (7)	0.0420 (9)	0.0243 (7)	−0.0018 (6)	0.0154 (6)	0.0048 (6)
C4	0.0236 (7)	0.0461 (9)	0.0247 (7)	0.0082 (6)	0.0173 (6)	0.0050 (6)
C5	0.0252 (7)	0.0299 (8)	0.0253 (7)	0.0066 (6)	0.0164 (6)	0.0020 (6)
C6	0.0172 (6)	0.0242 (7)	0.0161 (6)	0.0021 (5)	0.0093 (5)	0.0006 (5)
C7	0.0177 (6)	0.0195 (6)	0.0167 (6)	0.0016 (5)	0.0091 (5)	−0.0005 (5)
C8	0.0230 (7)	0.0208 (7)	0.0237 (7)	0.0031 (5)	0.0119 (6)	−0.0023 (5)
C9	0.0262 (10)	0.0171 (9)	0.0276 (10)	0.000	0.0126 (9)	0.000

Geometric parameters (Å, º) top

Zn—C1ⁱ	2.0282 (15)	C2—H2A	0.9500
Zn—C1	2.0282 (15)	C3—C4	1.381 (2)
Zn—N1	2.3381 (12)	C3—H3A	0.9500
Zn—N2	2.2603 (16)	C4—C5	1.383 (2)
Zn—N1ⁱ	2.3382 (12)	C4—H4A	0.9500
N1—C2	1.3364 (19)	C5—C6	1.3958 (18)
N1—C6	1.3416 (18)	C5—H5A	0.9500
N2—C7ⁱ	1.3470 (15)	C6—C7	1.4893 (18)
N2—C7	1.3470 (15)	C7—C8	1.3979 (19)
C1—H1A	0.9800	C8—C9	1.3838 (18)
C1—H1B	0.9800	C8—H8A	0.9500
C1—H1C	0.9800	C9—C8ⁱ	1.3838 (18)
C2—C3	1.385 (2)	C9—H9A	0.9500

C1ⁱ—Zn—C1	133.21 (9)	N1—C2—H2A	118.4
C1ⁱ—Zn—N2	113.39 (5)	C3—C2—H2A	118.4
C1—Zn—N2	113.39 (5)	C4—C3—C2	118.22 (14)
C1ⁱ—Zn—N1	99.05 (5)	C4—C3—H3A	120.9
C1—Zn—N1	96.37 (5)	C2—C3—H3A	120.9
N2—Zn—N1	70.26 (3)	C3—C4—C5	119.41 (14)
C1ⁱ—Zn—N1ⁱ	96.37 (5)	C3—C4—H4A	120.3
C1—Zn—N1ⁱ	99.05 (5)	C5—C4—H4A	120.3
N2—Zn—N1ⁱ	70.26 (3)	C4—C5—C6	118.83 (14)
N1—Zn—N1ⁱ	140.52 (6)	C4—C5—H5A	120.6
C2—N1—C6	118.48 (12)	C6—C5—H5A	120.6
C2—N1—Zn	123.28 (10)	N1—C6—C5	121.84 (13)
C6—N1—Zn	118.22 (9)	N1—C6—C7	115.22 (11)
C7ⁱ—N2—C7	119.05 (16)	C5—C6—C7	122.93 (13)
C7ⁱ—N2—Zn	120.48 (8)	N2—C7—C8	121.89 (13)
C7—N2—Zn	120.47 (8)	N2—C7—C6	115.77 (12)
Zn—C1—H1A	109.5	C8—C7—C6	122.34 (12)
Zn—C1—H1B	109.5	C9—C8—C7	118.82 (14)
H1A—C1—H1B	109.5	C9—C8—H8A	120.6
Zn—C1—H1C	109.5	C7—C8—H8A	120.6
H1A—C1—H1C	109.5	C8—C9—C8ⁱ	119.53 (19)
H1B—C1—H1C	109.5	C8—C9—H9A	120.2
N1—C2—C3	123.19 (14)	C8ⁱ—C9—H9A	120.2

C1ⁱ—Zn—N1—C2	68.69 (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—C5	177.37 (10)
C1ⁱ—Zn—N1—C6	−109.70 (11)	C2—N1—C6—C7	179.08 (12)
C1—Zn—N1—C6	114.62 (11)	Zn—N1—C6—C7	−2.45 (15)
N2—Zn—N1—C6	2.01 (9)	C4—C5—C6—N1	1.5 (2)
N1ⁱ—Zn—N1—C6	2.01 (9)	C4—C5—C6—C7	−178.65 (12)
C1ⁱ—Zn—N2—C7ⁱ	−89.74 (8)	C7ⁱ—N2—C7—C8	0.42 (9)
C1—Zn—N2—C7ⁱ	90.26 (8)	Zn—N2—C7—C8	−179.58 (9)
N1—Zn—N2—C7ⁱ	178.72 (7)	C7ⁱ—N2—C7—C6	−179.48 (12)
N1ⁱ—Zn—N2—C7ⁱ	−1.28 (7)	Zn—N2—C7—C6	0.52 (12)
C1ⁱ—Zn—N2—C7	90.26 (8)	N1—C6—C7—N2	1.31 (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—C7	178.72 (7)	C5—C6—C7—C8	1.6 (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—C9	179.07 (10)
N1—C2—C3—C4	1.1 (2)	C7—C8—C9—C8ⁱ	0.39 (9)

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(CH₃)₂(C₁₅H₁₁N₃)]
M_r	328.71
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	125
a, b, c (Å)	17.4250 (11), 9.1083 (6), 11.7595 (14)
β (°)	127.193 (1)
V (Å³)	1486.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.65
Crystal size (mm)	0.23 × 0.13 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.703, 0.908
No. of measured, independent and observed [I > 2σ(I)] reflections	9483, 1837, 1710
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.061, 1.09
No. of reflections	1837
No. of parameters	98
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.27

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn—C1	2.0282 (15)	Zn—N2	2.2603 (16)
Zn—N1	2.3381 (12)

Acknowledgements

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

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