Bis­(benzene­thiol­ato)(2,2′-biquinoline)zinc(II)

Monroe, T.B.; Ikonen, A.; Maner, J.A.; Jones, D.S.; Striplin, D.R.

doi:10.1107/S1600536809041336

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page m1421

https://doi.org/10.1107/S1600536809041336

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Bis(benzenethiolato)(2,2′-biquinoline)zinc(II)

Thomas Blake Monroe,^a Anita Ikonen,^a Jonathon A. Maner,^b Daniel S. Jones ^a ^* and Durwin R. Striplin ^b ^*

^aDepartment of Chemistry, The University of North Carolina at Charlotte, 9201 University City Blvd, Charlotte, NC 28223, USA, and ^bDepartment of Chemistry, Davidson College, Davidson, NC 28035, USA
^*Correspondence e-mail: djones@uncc.edu, dustriplin@davidson.edu

(Received 27 August 2009; accepted 9 October 2009; online 23 October 2009)

The title compound, [Zn(C₆H₅S)₂(C₁₈H₁₂N₂)], was prepared as a model for future complexes that will be incorporated into light-harvesting arrays. The Zn^II atom lies on a twofold rotation axis and the ligands are arranged tetrahedrally around this atom. The benzenethiolate ligand and the biquinoline ligand are nearly perpendicular to one another, making a dihedral angle of 84.09 (5)°. The biquinoline ligand is nearly planar, with a maximum deviation of 0.055 (3) Å from the mean plane of the ring system. In the crystal, the molecules pack in a manner such that the biquinoline ligands are parallel to one another, with a π–π interaction [interplanar distance = 3.38 (1) Å] with the neighboring biquinoline ligand.

Related literature

For luminescent complexes of zinc(II), see: Koester (1975 ); Crosby et al. (1985 ); Highland et al. (1986 ). For related structures, see: Halvorsen et al. (1995 ); Anjali et al. (1999 ). For a study of π–π interactions involving quinoline ring systems, see: Janiak (2000 ). For details of the Cambridge Crystal Structure Database, see: Allen et al. (2002 ).

Experimental

Crystal data

[Zn(C₆H₅S)₂(C₁₈H₁₂N₂)]
M_r = 539.99
Monoclinic, C 2/c
a = 17.141 (2) Å
b = 11.5591 (8) Å
c = 12.8318 (14) Å
β = 93.811 (10)°
V = 2536.8 (4) Å³
Z = 4
Cu Kα radiation
μ = 3.04 mm⁻¹
T = 295 K
0.30 × 0.19 × 0.11 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: analytical (Alcock, 1970 ) T_min = 0.531, T_max = 0.796
4580 measured reflections
2294 independent reflections
1821 reflections with I > 2σ(I)
R_int = 0.025
3 standard reflections every 195 reflections intensity decay: 6%

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.076
S = 1.02
2294 reflections
160 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: DIRDIF (Beurskens et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809041336/su2141sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809041336/su2141Isup2.hkl

checkCIF report

Comment top

Deeply colored, luminescent complexes of zinc(II) arise when this d¹⁰ ion is coordinated with mixed ligands of benzenethiol anions and dinitrogenpolypyridyl ligands (Koester, 1975; Crosby et al., 1985; Highland et al., 1986). In many cases, the lowest-lying excited state of this class of molecules has been assigned to a charge transfer from the thiol to a π^* molecular orbital on the nitrogen heterocycle (Koester, 1975; Highland et al., 1986). The straightforward synthesis of the complexes, the cost, and the variety of ligand substitutions that are possible, enable numerous ways to tune the energy of this ligand-to-ligand charge transfer state. The closed-shell zinc(II) complex of this study absorbs strongly in the visible region of the spectrum and serves as a model for future complexes that will be incorporated into light-harvesting arrays.

The molecular structure of the title compound is illustrated in Fig. 1. The ligands are arranged tetrahedrally around the zinc atom, which lies on a 2-fold rotation axis. The benzenethiolate ligand and the biquinoline ligand are nearly perpendicular to one another, making a dihedral angle of 84.09 (5)°. The benzenethiolate ligands make a 72.30 (5)° angle with one another. The biquinoline ligand is nearly planar, with a maximum deviation of 0.055 (3) Å from the mean plane of the ring system.

In the crystal of the title compound the molecules pack in a manner such that the biquinoline ligands of all molecules are parallel. An exhaustive study has been made (Janiak, 2000) of structures in the Cambridge Structural Database (Allen, 2002) which show π-π interactions between quinoline ring systems. This study showed that parallel ring systems which interact are offset by an amount related to the distance between ring centroids. In the present study, the planes of the quinoline rings related by π-π interactions are ca. 3.38 Å apart. The centeroids of the pyridine ring and the benzene ring are ca. 3.68 Å apart, and the centroid-centroid line makes an angle of 23.3° with the normal to the plane of the quinoline rings. These values are in agreement with those found in the Janiak study. The π-π interactions may account for the near-planarity of the biquinoline ligand.

A search of the Cambridge Structural Database [CSD Version 5.30; Allen, 2002] yielded two chemically comparable structures: bis(Benzenethiolato)-(2,2'-bipyridine-N,N')-zinc (Anjali et al., 1999) and (1,2-Benzenedithiolato-S,S')-(2,2'-biquinolinato-N,N')-zinc(II) (Halvorsen et al., 1995).

Related literature top

For luminescent complexes of zinc(II), see: Koester (1975); Crosby et al. (1985); Highland et al. (1986). For related structures, see: Halvorsen et al. (1995); Anjali et al. (1999). For a study of π–π interactions involving quinoline ring systems, see: Janiak (2000). For details of the Cambridge Crystal Structure Database, see: Allen et al. (2002).

Experimental top

The complex was synthesized via a general procedure (Crosby et al., 1985). Zn(OAc)₂.2H₂O (0.0566 g) was dissolved in 5 ml absolute ethanol and heated. benzenethiol (0.0582 g) was dissolved in 4 ml absolute ethanol and heated. The benzenethiol solution was then added dropwise to the zinc(II) solution with vigorous stirring at reflux. 2,2'-biquinoline (0.0640 g) dissolved in 5 ml absolute ethanol was then slowly added to the refluxing solution. The solution turned orange and was allowed to sit overnight. An orange crystalline solid (0.0848 g) was collected in 47% yield via vacuum filtration and washed with cold ethanol. The compound was characterized by ¹H NMR, UV-VIS absorption spectroscopy, and room temperature and 77 K emission spectroscopy.

Structure description top

For luminescent complexes of zinc(II), see: Koester (1975); Crosby et al. (1985); Highland et al. (1986). For related structures, see: Halvorsen et al. (1995); Anjali et al. (1999). For a study of π–π interactions involving quinoline ring systems, see: Janiak (2000). For details of the Cambridge Crystal Structure Database, see: Allen et al. (2002).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: DIRDIF (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. View of the molecular structure of the title compound, with 50% probability displacement ellipsoids [Symmetry code: (i) -x, y, -z + 3/2]
	Fig. 2. Crystal packing diagram of the title compound, showing the π-π interactions between the biquinoline ligands.

Bis(benzenethiolato)(2,2'-biquinoline)zinc(II) top

Crystal data top

[Zn(C₆H₅S)₂(C₁₈H₁₂N₂)]	F(000) = 1112
M_r = 539.99	D_x = 1.414 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 17.141 (2) Å	θ = 9.8–42.1°
b = 11.5591 (8) Å	µ = 3.04 mm⁻¹
c = 12.8318 (14) Å	T = 295 K
β = 93.811 (10)°	Prism, orange
V = 2536.8 (4) Å³	0.30 × 0.19 × 0.11 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.025
Non–profiled ω/2θ scans	θ_max = 67.5°, θ_min = 4.6°
Absorption correction: analytical (Alcock, 1970)	h = −20→20
T_min = 0.531, T_max = 0.796	k = −13→0
4580 measured reflections	l = −15→15
2294 independent reflections	3 standard reflections every 195 reflections
1821 reflections with I > 2σ(I)	intensity decay: 6%

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0413P)² + 0.5756P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.027	(Δ/σ)_max < 0.001
wR(F²) = 0.076	Δρ_max = 0.25 e Å⁻³
S = 1.02	Δρ_min = −0.21 e Å⁻³
2294 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
160 parameters	Extinction coefficient: 0.00076 (7)
0 restraints

Crystal data top

[Zn(C₆H₅S)₂(C₁₈H₁₂N₂)]	V = 2536.8 (4) Å³
M_r = 539.99	Z = 4
Monoclinic, C2/c	Cu Kα radiation
a = 17.141 (2) Å	µ = 3.04 mm⁻¹
b = 11.5591 (8) Å	T = 295 K
c = 12.8318 (14) Å	0.30 × 0.19 × 0.11 mm
β = 93.811 (10)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1821 reflections with I > 2σ(I)
Absorption correction: analytical (Alcock, 1970)	R_int = 0.025
T_min = 0.531, T_max = 0.796	3 standard reflections every 195 reflections
4580 measured reflections	intensity decay: 6%
2294 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 1.02	Δρ_max = 0.25 e Å⁻³
2294 reflections	Δρ_min = −0.21 e Å⁻³
160 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.

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

	x	y	z	U_iso*/U_eq
Zn1	0.0000	0.23564 (3)	0.7500	0.03902 (14)
S1	0.10148 (4)	0.31521 (5)	0.84622 (4)	0.05310 (18)
C2	0.02308 (12)	−0.00711 (17)	0.70235 (14)	0.0373 (4)
N1	0.03843 (10)	0.09607 (14)	0.66414 (12)	0.0377 (4)
C11	0.13310 (13)	0.43928 (18)	0.78028 (16)	0.0431 (5)
C8	0.09842 (15)	0.2144 (2)	0.53830 (18)	0.0564 (6)
H8	0.0808	0.2807	0.5703	0.068*
C7	0.14180 (17)	0.2230 (3)	0.4526 (2)	0.0700 (8)
H7	0.1534	0.2957	0.4267	0.084*
C10	0.10770 (12)	0.0041 (2)	0.52807 (16)	0.0453 (5)
C9	0.08090 (12)	0.10452 (19)	0.57723 (15)	0.0409 (5)
C3	0.04840 (14)	−0.10960 (19)	0.65728 (17)	0.0487 (5)
H3	0.0371	−0.1810	0.6861	0.058*
C6	0.16875 (17)	0.1242 (3)	0.4038 (2)	0.0702 (8)
H6	0.1985	0.1318	0.3462	0.084*
C4	0.09000 (14)	−0.1033 (2)	0.57026 (17)	0.0514 (5)
H4	0.1066	−0.1708	0.5390	0.062*
C13	0.23087 (15)	0.5875 (2)	0.7683 (2)	0.0638 (7)
H13	0.2775	0.6210	0.7942	0.077*
C15	0.12222 (16)	0.5836 (2)	0.6443 (2)	0.0609 (7)
H15	0.0951	0.6146	0.5856	0.073*
C14	0.19151 (16)	0.6336 (2)	0.6820 (2)	0.0640 (7)
H14	0.2112	0.6980	0.6492	0.077*
C16	0.09275 (15)	0.4876 (2)	0.69300 (18)	0.0526 (6)
H16	0.0457	0.4551	0.6673	0.063*
C5	0.15209 (15)	0.0177 (3)	0.43955 (18)	0.0589 (6)
H5	0.1699	−0.0474	0.4057	0.071*
C12	0.20215 (14)	0.4915 (2)	0.8175 (2)	0.0551 (6)
H12	0.2296	0.4616	0.8764	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0495 (2)	0.0321 (2)	0.0360 (2)	0.000	0.00750 (15)	0.000
S1	0.0643 (4)	0.0479 (3)	0.0456 (3)	−0.0058 (2)	−0.0081 (3)	0.0087 (2)
C2	0.0443 (10)	0.0359 (10)	0.0317 (9)	0.0018 (8)	0.0014 (8)	−0.0010 (8)
N1	0.0427 (9)	0.0378 (8)	0.0332 (8)	−0.0015 (7)	0.0070 (7)	−0.0011 (7)
C11	0.0473 (11)	0.0395 (11)	0.0428 (11)	0.0013 (9)	0.0053 (9)	−0.0050 (9)
C8	0.0727 (15)	0.0512 (13)	0.0478 (12)	−0.0120 (12)	0.0220 (11)	−0.0036 (11)
C7	0.0817 (18)	0.0749 (18)	0.0565 (15)	−0.0219 (15)	0.0276 (13)	0.0013 (14)
C10	0.0416 (11)	0.0590 (13)	0.0350 (10)	0.0065 (10)	0.0014 (8)	−0.0100 (9)
C9	0.0427 (11)	0.0487 (11)	0.0319 (9)	−0.0024 (9)	0.0065 (8)	−0.0053 (8)
C3	0.0673 (14)	0.0376 (10)	0.0411 (11)	0.0069 (10)	0.0031 (10)	−0.0029 (9)
C6	0.0652 (16)	0.100 (2)	0.0484 (14)	−0.0113 (15)	0.0260 (12)	−0.0077 (14)
C4	0.0640 (14)	0.0471 (12)	0.0430 (12)	0.0137 (11)	0.0027 (10)	−0.0090 (10)
C13	0.0458 (13)	0.0585 (15)	0.088 (2)	−0.0082 (11)	0.0126 (13)	−0.0126 (14)
C15	0.0744 (17)	0.0461 (12)	0.0626 (16)	−0.0010 (12)	0.0081 (13)	0.0118 (12)
C14	0.0654 (16)	0.0470 (14)	0.0823 (18)	−0.0036 (12)	0.0257 (14)	0.0036 (13)
C16	0.0613 (14)	0.0447 (12)	0.0508 (12)	−0.0067 (10)	−0.0024 (11)	0.0027 (10)
C5	0.0553 (14)	0.0800 (17)	0.0426 (12)	0.0063 (13)	0.0132 (10)	−0.0136 (12)
C12	0.0485 (13)	0.0562 (14)	0.0603 (14)	0.0008 (11)	0.0020 (11)	−0.0058 (12)

Geometric parameters (Å, º) top

Zn1—N1ⁱ	2.0849 (16)	C10—C9	1.412 (3)
Zn1—N1	2.0849 (16)	C10—C5	1.417 (3)
Zn1—S1	2.2607 (6)	C3—C4	1.366 (3)
Zn1—S1ⁱ	2.2607 (6)	C3—H3	0.9300
S1—C11	1.768 (2)	C6—C5	1.351 (4)
C2—N1	1.323 (3)	C6—H6	0.9300
C2—C3	1.400 (3)	C4—H4	0.9300
C2—C2ⁱ	1.500 (4)	C13—C14	1.366 (4)
N1—C9	1.375 (2)	C13—C12	1.383 (4)
C11—C12	1.385 (3)	C13—H13	0.9300
C11—C16	1.393 (3)	C15—C14	1.380 (4)
C8—C7	1.371 (3)	C15—C16	1.386 (3)
C8—C9	1.405 (3)	C15—H15	0.9300
C8—H8	0.9300	C14—H14	0.9300
C7—C6	1.396 (4)	C16—H16	0.9300
C7—H7	0.9300	C5—H5	0.9300
C10—C4	1.396 (3)	C12—H12	0.9300

N1ⁱ—Zn1—N1	78.61 (9)	C4—C3—C2	119.0 (2)
N1ⁱ—Zn1—S1	106.55 (5)	C4—C3—H3	120.5
N1—Zn1—S1	110.17 (5)	C2—C3—H3	120.5
N1ⁱ—Zn1—S1ⁱ	110.17 (5)	C5—C6—C7	120.7 (2)
N1—Zn1—S1ⁱ	106.55 (5)	C5—C6—H6	119.7
S1—Zn1—S1ⁱ	131.98 (3)	C7—C6—H6	119.7
C11—S1—Zn1	108.53 (7)	C3—C4—C10	120.2 (2)
N1—C2—C3	122.36 (18)	C3—C4—H4	119.9
N1—C2—C2ⁱ	115.52 (11)	C10—C4—H4	119.9
C3—C2—C2ⁱ	122.11 (12)	C14—C13—C12	120.8 (2)
C2—N1—C9	119.58 (17)	C14—C13—H13	119.6
C2—N1—Zn1	115.11 (12)	C12—C13—H13	119.6
C9—N1—Zn1	125.20 (14)	C14—C15—C16	120.5 (2)
C12—C11—C16	118.0 (2)	C14—C15—H15	119.7
C12—C11—S1	118.08 (17)	C16—C15—H15	119.7
C16—C11—S1	123.91 (17)	C13—C14—C15	119.2 (2)
C7—C8—C9	119.4 (2)	C13—C14—H14	120.4
C7—C8—H8	120.3	C15—C14—H14	120.4
C9—C8—H8	120.3	C15—C16—C11	120.5 (2)
C8—C7—C6	120.9 (3)	C15—C16—H16	119.8
C8—C7—H7	119.5	C11—C16—H16	119.8
C6—C7—H7	119.5	C6—C5—C10	120.6 (2)
C4—C10—C9	118.17 (19)	C6—C5—H5	119.7
C4—C10—C5	123.5 (2)	C10—C5—H5	119.7
C9—C10—C5	118.4 (2)	C13—C12—C11	120.9 (2)
N1—C9—C8	119.33 (19)	C13—C12—H12	119.5
N1—C9—C10	120.6 (2)	C11—C12—H12	119.5
C8—C9—C10	120.04 (19)

Symmetry code: (i) −x, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Zn(C₆H₅S)₂(C₁₈H₁₂N₂)]
M_r	539.99
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	17.141 (2), 11.5591 (8), 12.8318 (14)
β (°)	93.811 (10)
V (Å³)	2536.8 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.04
Crystal size (mm)	0.30 × 0.19 × 0.11

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	Analytical (Alcock, 1970)
T_min, T_max	0.531, 0.796
No. of measured, independent and observed [I > 2σ(I)] reflections	4580, 2294, 1821
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.076, 1.02
No. of reflections	2294
No. of parameters	160
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.21

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), DIRDIF (Beurskens et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).

Acknowledgements

This work was supported in part by funds provided by the University of North Carolina at Charlotte and the Davidson College Faculty Study and Research Grants. Support for REU participant TBM was provided by the National Science Foundation, award number CHE-0851797.

References

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