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Acta Cryst. (2008). E64, m770    [ doi:10.1107/S1600536808011793 ]

(2-Methoxy-1,10-phenanthroline-[kappa]2N,N')bis(thiocyanato-[kappa]N)zinc(II)

H. Li, T. Q. Hu and S. G. Zhang

Abstract top

In the title complex, [Zn(NCS)2(C13H10N2O)], the ZnII ion is in a distorted tetrahdral ZnN2Cl2 coordination environment. In the crystal structure, there is a weak [pi]-[pi] stacking interaction between adjacent 1,10-phenanthroline rings, with a pyridine centroid-centroid distance of 3.6620 (15) Å.

Comment top

Derivatives of 1,10-phenanthroline play a pivotal role in the area of modern coordination chemistry (e.g. Zhang et al. 2006 and important references cited within), but no structures of complexes with 2-methoxy-1,10-phenanthroline as a ligand have been reported. Herein we report the crystal structure of the title complex (I).

The molecular structure of (I) is shown in Fig. 1. In this mononuclear complex atom Zn1 is in a distorted tetrahedral coordination geometry (Table 1). In the crystal structure, there are weak π-π stacking interactions between symmetry related 1,10-phenanthroline ligands, with the relevant distances being Cg1···Cg1i = 3.6620 (15) Å and a perpendicular distance of 3.563 Å [symmetry code: (i) 1/2-x, 3/2-y, 1-z; Cg1 is the centroid of the N1/C1/C3/C4/C5/C15 ring].

Related literature top

For a related structure, see: Zhang et al. (2006). For related literature, see: McMorran & Steel (2002).

Experimental top

A methanol solution (15ml) of Zn(ClO4).6H2O (0.2951 g, 0.792 mmol) was added into a 10 ml methanol solution containing 2-methoxy-1,10-phenanthroline (0.1666 g, 0.792 mmol), and the mixture was stirred for a few minutes. Then a 10 ml methanol solution of NaSCN (0.1296 g, 1.60 mmol) was added to the above mixture. Yellow single crystals were obtained after the solution had been allowed to stand at room temperature for two weeks.

Refinement top

H atoms were placed in calculated positions (C—H = 0.96 Å for methyl group and C—H = 0.93 Å for other H atoms) and refined as riding with Uiso = 1.5 Ueq(C) for methyl H and Uiso = 1.2 Ueq(C) for other H.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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
[Figure 1] Fig. 1. The molecular structure of (I), showing the the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level.
(2-Methoxy-1,10-phenanthroline-κ2N,N')bis(thiocyanato-κN)zinc(II) top
Crystal data top
[Zn(NCS)2(C13H10N2O)]F000 = 1584
Mr = 391.76Dx = 1.560 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4025 reflections
a = 26.360 (5) Åθ = 2.2–27.6º
b = 8.5949 (16) ŵ = 1.73 mm−1
c = 14.814 (3) ÅT = 298 (2) K
β = 96.266 (2)ºBar, yellow
V = 3336.3 (10) Å30.61 × 0.42 × 0.40 mm
Z = 8
Data collection top
Bruker SMART APEX CCD
diffractometer		3616 independent reflections
Radiation source: fine-focus sealed tube2974 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.040
T = 298(2) Kθmax = 27.0º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −33→26
Tmin = 0.418, Tmax = 0.545k = −9→10
9311 measured reflectionsl = −18→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.097  w = 1/[σ2(Fo2) + (0.0536P)2 + 0.2305P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
3616 reflectionsΔρmax = 0.33 e Å−3
209 parametersΔρmin = −0.49 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn(NCS)2(C13H10N2O)]V = 3336.3 (10) Å3
Mr = 391.76Z = 8
Monoclinic, C2/cMo Kα
a = 26.360 (5) ŵ = 1.73 mm−1
b = 8.5949 (16) ÅT = 298 (2) K
c = 14.814 (3) Å0.61 × 0.42 × 0.40 mm
β = 96.266 (2)º
Data collection top
Bruker SMART APEX CCD
diffractometer		3616 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2974 reflections with I > 2σ(I)
Tmin = 0.418, Tmax = 0.545Rint = 0.040
9311 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035209 parameters
wR(F2) = 0.097H-atom parameters constrained
S = 1.06Δρmax = 0.33 e Å−3
3616 reflectionsΔρmin = −0.49 e Å−3
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
xyzUiso*/Ueq
Zn10.130923 (10)1.01266 (3)0.392499 (16)0.04081 (11)
S20.07232 (4)1.52220 (8)0.35198 (6)0.0700 (2)
S30.15576 (3)0.73246 (10)0.13159 (4)0.0627 (2)
N10.19776 (7)0.98293 (19)0.47711 (12)0.0374 (4)
N20.10343 (6)0.8750 (2)0.48692 (10)0.0372 (4)
C50.19054 (7)0.8893 (2)0.54870 (12)0.0350 (4)
N30.10454 (8)1.2204 (3)0.38239 (13)0.0557 (5)
O10.02497 (6)0.8745 (2)0.41868 (12)0.0593 (4)
C40.22974 (8)0.8481 (3)0.61569 (13)0.0415 (5)
C80.13985 (8)0.8311 (2)0.55315 (13)0.0363 (4)
C60.21868 (10)0.7477 (3)0.68714 (15)0.0510 (6)
H60.24460.72050.73200.061*
C120.05651 (8)0.8226 (3)0.48815 (15)0.0446 (5)
N40.13885 (8)0.9127 (3)0.27851 (13)0.0580 (5)
C140.14584 (8)0.8383 (3)0.21771 (14)0.0424 (5)
C90.13065 (9)0.7316 (3)0.62413 (15)0.0435 (5)
C20.09073 (8)1.3458 (3)0.37012 (13)0.0422 (5)
C70.17119 (10)0.6909 (3)0.69101 (15)0.0530 (6)
H70.16500.62440.73810.064*
C110.04328 (10)0.7227 (3)0.55773 (17)0.0552 (6)
H110.00990.68780.55800.066*
C30.27856 (9)0.9092 (3)0.60652 (16)0.0517 (6)
H30.30590.88540.64940.062*
C100.07972 (10)0.6789 (3)0.62360 (16)0.0545 (6)
H100.07130.61300.66950.065*
C150.28561 (10)1.0030 (3)0.53490 (19)0.0543 (7)
H150.31771.04350.52860.065*
C10.24425 (9)1.0379 (3)0.47095 (17)0.0471 (5)
H10.24951.10200.42230.057*
C13−0.02649 (9)0.8142 (4)0.4045 (2)0.0721 (8)
H13A−0.02540.70270.40120.108*
H13B−0.04330.85480.34870.108*
H13C−0.04490.84500.45400.108*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.03960 (18)0.04250 (18)0.04019 (16)0.00072 (11)0.00369 (11)0.00223 (10)
S20.0862 (6)0.0478 (4)0.0775 (5)0.0193 (4)0.0155 (4)−0.0028 (3)
S30.0606 (4)0.0723 (5)0.0568 (4)0.0133 (3)0.0135 (3)−0.0126 (3)
N10.0323 (10)0.0394 (10)0.0409 (9)−0.0019 (7)0.0053 (7)−0.0012 (7)
N20.0320 (9)0.0377 (10)0.0427 (9)−0.0020 (8)0.0078 (7)−0.0029 (7)
C50.0357 (11)0.0319 (10)0.0383 (10)0.0010 (9)0.0080 (8)−0.0052 (8)
N30.0631 (14)0.0480 (13)0.0566 (12)0.0108 (11)0.0095 (10)0.0064 (9)
O10.0332 (9)0.0696 (12)0.0735 (11)−0.0053 (8)−0.0016 (7)0.0038 (9)
C40.0399 (12)0.0424 (12)0.0419 (11)0.0026 (10)0.0027 (9)−0.0043 (9)
C80.0378 (11)0.0344 (11)0.0380 (10)0.0001 (9)0.0099 (8)−0.0028 (8)
C60.0518 (15)0.0577 (15)0.0419 (12)0.0095 (12)−0.0021 (10)0.0045 (10)
C120.0355 (12)0.0456 (13)0.0533 (12)−0.0043 (10)0.0072 (9)−0.0080 (10)
N40.0637 (14)0.0639 (14)0.0467 (11)0.0039 (12)0.0065 (9)−0.0073 (11)
C140.0345 (11)0.0474 (13)0.0448 (12)0.0044 (10)0.0024 (9)0.0073 (10)
C90.0524 (14)0.0397 (12)0.0406 (11)−0.0023 (10)0.0145 (9)0.0000 (9)
C20.0395 (12)0.0512 (14)0.0369 (10)0.0001 (11)0.0089 (8)−0.0035 (9)
C70.0645 (17)0.0512 (15)0.0451 (12)0.0054 (12)0.0135 (11)0.0098 (11)
C110.0421 (13)0.0618 (16)0.0648 (15)−0.0143 (12)0.0205 (11)−0.0046 (12)
C30.0390 (12)0.0560 (15)0.0572 (13)0.0013 (11)−0.0072 (10)−0.0045 (12)
C100.0574 (15)0.0576 (15)0.0522 (13)−0.0120 (13)0.0220 (11)0.0036 (11)
C150.0366 (13)0.0585 (17)0.0672 (17)−0.0106 (11)0.0034 (12)−0.0008 (12)
C10.0373 (13)0.0486 (13)0.0561 (13)−0.0088 (11)0.0083 (10)0.0019 (10)
C130.0303 (13)0.086 (2)0.099 (2)−0.0058 (14)−0.0020 (13)−0.0092 (17)
Geometric parameters (Å, °) top
Zn1—N31.916 (2)C6—C71.351 (3)
Zn1—N41.926 (2)C6—H60.9300
Zn1—N22.0254 (16)C12—C111.414 (3)
Zn1—N12.0636 (19)N4—C141.136 (3)
S2—C21.606 (3)C9—C101.416 (3)
S3—C141.611 (2)C9—C71.419 (3)
N1—C11.326 (3)C7—H70.9300
N1—C51.361 (3)C11—C101.346 (4)
N2—C121.319 (3)C11—H110.9300
N2—C81.349 (3)C3—C151.361 (4)
C5—C41.398 (3)C3—H30.9300
C5—C81.435 (3)C10—H100.9300
N3—C21.145 (3)C15—C11.397 (4)
O1—C121.328 (3)C15—H150.9300
O1—C131.446 (3)C1—H10.9300
C4—C31.410 (3)C13—H13A0.9600
C4—C61.421 (3)C13—H13B0.9600
C8—C91.397 (3)C13—H13C0.9600
N3—Zn1—N4114.85 (9)N4—C14—S3179.9 (3)
N3—Zn1—N2116.36 (8)C8—C9—C10115.7 (2)
N4—Zn1—N2115.23 (9)C8—C9—C7119.8 (2)
N3—Zn1—N1116.20 (8)C10—C9—C7124.5 (2)
N4—Zn1—N1108.07 (8)N3—C2—S2178.9 (2)
N2—Zn1—N181.62 (7)C6—C7—C9120.8 (2)
C1—N1—C5118.2 (2)C6—C7—H7119.6
C1—N1—Zn1130.42 (16)C9—C7—H7119.6
C5—N1—Zn1111.33 (14)C10—C11—C12119.0 (2)
C12—N2—C8119.23 (18)C10—C11—H11120.5
C12—N2—Zn1128.04 (15)C12—C11—H11120.5
C8—N2—Zn1112.68 (13)C15—C3—C4119.9 (2)
N1—C5—C4123.20 (19)C15—C3—H3120.0
N1—C5—C8116.87 (18)C4—C3—H3120.0
C4—C5—C8119.93 (18)C11—C10—C9121.0 (2)
C2—N3—Zn1174.4 (2)C11—C10—H10119.5
C12—O1—C13119.4 (2)C9—C10—H10119.5
C5—C4—C3116.7 (2)C3—C15—C1119.5 (2)
C5—C4—C6119.1 (2)C3—C15—H15120.2
C3—C4—C6124.2 (2)C1—C15—H15120.2
N2—C8—C9123.38 (19)N1—C1—C15122.4 (2)
N2—C8—C5117.48 (17)N1—C1—H1118.8
C9—C8—C5119.14 (19)C15—C1—H1118.8
C7—C6—C4121.2 (2)O1—C13—H13A109.5
C7—C6—H6119.4O1—C13—H13B109.5
C4—C6—H6119.4H13A—C13—H13B109.5
N2—C12—O1112.55 (19)O1—C13—H13C109.5
N2—C12—C11121.6 (2)H13A—C13—H13C109.5
O1—C12—C11125.8 (2)H13B—C13—H13C109.5
C14—N4—Zn1171.4 (2)
N3—Zn1—N1—C1−64.6 (2)C4—C5—C8—C9−1.0 (3)
N4—Zn1—N1—C166.2 (2)C5—C4—C6—C70.4 (3)
N2—Zn1—N1—C1−179.9 (2)C3—C4—C6—C7−178.8 (2)
N3—Zn1—N1—C5116.32 (14)C8—N2—C12—O1−179.57 (18)
N4—Zn1—N1—C5−112.90 (14)Zn1—N2—C12—O1−2.3 (3)
N2—Zn1—N1—C51.00 (13)C8—N2—C12—C110.7 (3)
N3—Zn1—N2—C1266.0 (2)Zn1—N2—C12—C11177.98 (16)
N4—Zn1—N2—C12−72.75 (19)C13—O1—C12—N2173.2 (2)
N1—Zn1—N2—C12−178.84 (19)C13—O1—C12—C11−7.1 (4)
N3—Zn1—N2—C8−116.55 (14)N2—C8—C9—C10−0.6 (3)
N4—Zn1—N2—C8104.70 (15)C5—C8—C9—C10−179.83 (19)
N1—Zn1—N2—C8−1.40 (13)N2—C8—C9—C7179.9 (2)
C1—N1—C5—C4−0.2 (3)C5—C8—C9—C70.6 (3)
Zn1—N1—C5—C4179.00 (16)C4—C6—C7—C9−0.7 (4)
C1—N1—C5—C8−179.68 (19)C8—C9—C7—C60.2 (4)
Zn1—N1—C5—C8−0.5 (2)C10—C9—C7—C6−179.3 (2)
N1—C5—C4—C30.2 (3)N2—C12—C11—C10−0.8 (4)
C8—C5—C4—C3179.70 (19)O1—C12—C11—C10179.5 (2)
N1—C5—C4—C6−178.99 (19)C5—C4—C3—C15−0.1 (3)
C8—C5—C4—C60.5 (3)C6—C4—C3—C15179.1 (2)
C12—N2—C8—C90.1 (3)C12—C11—C10—C90.2 (4)
Zn1—N2—C8—C9−177.64 (16)C8—C9—C10—C110.5 (3)
C12—N2—C8—C5179.27 (18)C7—C9—C10—C11180.0 (2)
Zn1—N2—C8—C51.6 (2)C4—C3—C15—C10.0 (4)
N1—C5—C8—N2−0.7 (3)C5—N1—C1—C150.1 (3)
C4—C5—C8—N2179.77 (18)Zn1—N1—C1—C15−178.98 (17)
N1—C5—C8—C9178.51 (17)C3—C15—C1—N10.1 (4)
Table 1
Selected geometric parameters (Å, °) top
Zn1—N31.916 (2)Zn1—N22.0254 (16)
Zn1—N41.926 (2)Zn1—N12.0636 (19)
N3—Zn1—N4114.85 (9)N3—Zn1—N1116.20 (8)
N3—Zn1—N2116.36 (8)N4—Zn1—N1108.07 (8)
N4—Zn1—N2115.23 (9)N2—Zn1—N181.62 (7)
Acknowledgements top

The authors thank the Natural Science Foundation of Shandong Province of China for support (grant No. Y2007B26).

references
References top

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

McMorran, D. A. & Steel, P. J. (2002). Dalton Trans. pp. 3321–3326.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Zhang, J.-P., Lin, Y.-Y., Huang, X.-C. & Chen, X.-M. (2006). Eur. J. Inorg. Chem. pp. 3407–3412.