Acta Cryst. (2009). E65, m693 [ doi:10.1107/S1600536809019266 ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
3N,N',N'')zinc(II)In the title compound, [ZnBr2(C15H11N3)], the ZnII ion is five-coordinated by the three N atoms from a 2,2':6',2''-terpyridine ligand (terpy) and two bromide anions in a distorted trigonal bipyramidal configuration. Each molecule is situated on a twofold rotational axis that passes through the ZnII ion and the central ring of the terpy ligand. In the crystal structure, aromatic ![[pi]](/logos/entities/pi_rmgif.gif)
- interactions between terpy ligands [centroid-centroid distances = 3.6265 (9) Å] link molecules into stacks propagated in the [001] direction.
The title compound was synthesized hydrothermally in a Teflon-lined autoclave (25 mL) by heating a mixture of 2,2':6',2''-terpyridine (0.2 mmol), ZnBr2 (0.2 mmol) and one drop of Et3N (pH ≈ 8–9) in water (10 mL) at 393 K for 3 d. Crystals suitable for X-ray analysis were obtained.
All H atoms were included in calculated positions, with C—H distances fixed to 0.93 Å and were refined in the riding-model approximation, with Uiso(H) = 1.2 Ueq (C).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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).
![[Figure 1]](./cv2561fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with the atom-labelling scheme [symmetry code: (A) -x, + 1, y, -z + 1/2]. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius. |
![[Figure 2]](./cv2561fig2thm.gif)
| Fig. 2. A portion of the crystal packing showing the π–π interactions (dashed lines) between the aromatic rings. |
| [ZnBr2(C15H11N3)] | F000 = 888 |
| Mr = 458.46 | Dx = 2.042 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 1580 reflections |
| a = 17.0972 (5) Å | θ = 2.5–26.3º |
| b = 9.3528 (3) Å | µ = 7.00 mm−1 |
| c = 11.5334 (4) Å | T = 296 K |
| β = 126.0510 (10)º | Block, colourless |
| V = 1491.08 (8) Å3 | 0.20 × 0.18 × 0.16 mm |
| Z = 4 |
| Bruker SMART APEXII CCD diffractometer | 1457 independent reflections |
| Radiation source: fine-focus sealed tube | 1371 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.019 |
| T = 296 K | θmax = 26.0º |
| φ and ω scans | θmin = 2.6º |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −21→21 |
| Tmin = 0.335, Tmax = 0.401 | k = −11→11 |
| 9665 measured reflections | l = −14→14 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.015 | H-atom parameters constrained |
| wR(F2) = 0.039 | w = 1/[σ2(Fo2) + (0.0184P)2 + 1.2604P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.08 | (Δ/σ)max < 0.001 |
| 1457 reflections | Δρmax = 0.27 e Å−3 |
| 97 parameters | Δρmin = −0.29 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [ZnBr2(C15H11N3)] | V = 1491.08 (8) Å3 |
| Mr = 458.46 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 17.0972 (5) Å | µ = 7.00 mm−1 |
| b = 9.3528 (3) Å | T = 296 K |
| c = 11.5334 (4) Å | 0.20 × 0.18 × 0.16 mm |
| β = 126.0510 (10)º |
| Bruker SMART APEXII CCD diffractometer | 1457 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1371 reflections with I > 2σ(I) |
| Tmin = 0.335, Tmax = 0.401 | Rint = 0.019 |
| 9665 measured reflections |
| R[F2 > 2σ(F2)] = 0.015 | 97 parameters |
| wR(F2) = 0.039 | H-atom parameters constrained |
| S = 1.08 | Δρmax = 0.27 e Å−3 |
| 1457 reflections | Δρmin = −0.29 e Å−3 |
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. |
| x | y | z | Uiso*/Ueq | ||
| Br1 | 0.380531 (15) | 0.11870 (2) | 0.03979 (2) | 0.04022 (8) | |
| Zn1 | 0.5000 | 0.25499 (3) | 0.2500 | 0.02736 (8) | |
| N1 | 0.5000 | 0.4802 (2) | 0.2500 | 0.0253 (4) | |
| N2 | 0.58982 (11) | 0.31649 (16) | 0.18054 (15) | 0.0288 (3) | |
| C1 | 0.63375 (14) | 0.2248 (2) | 0.1474 (2) | 0.0352 (4) | |
| H1 | 0.6256 | 0.1272 | 0.1525 | 0.042* | |
| C2 | 0.69093 (14) | 0.2696 (2) | 0.1056 (2) | 0.0392 (4) | |
| H2 | 0.7210 | 0.2033 | 0.0838 | 0.047* | |
| C3 | 0.70254 (14) | 0.4137 (2) | 0.0970 (2) | 0.0394 (4) | |
| H3 | 0.7411 | 0.4461 | 0.0700 | 0.047* | |
| C4 | 0.65606 (13) | 0.5102 (2) | 0.12890 (18) | 0.0346 (4) | |
| H4 | 0.6620 | 0.6081 | 0.1219 | 0.042* | |
| C5 | 0.60056 (12) | 0.45792 (18) | 0.17152 (16) | 0.0268 (4) | |
| C6 | 0.54892 (12) | 0.55136 (18) | 0.21013 (16) | 0.0263 (3) | |
| C7 | 0.54910 (13) | 0.69976 (19) | 0.20701 (19) | 0.0337 (4) | |
| H7 | 0.5815 | 0.7485 | 0.1767 | 0.040* | |
| C8 | 0.5000 | 0.7736 (3) | 0.2500 | 0.0367 (6) | |
| H8 | 0.5000 | 0.8730 | 0.2500 | 0.044* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.04910 (14) | 0.03300 (12) | 0.03959 (12) | −0.01116 (8) | 0.02667 (10) | −0.00711 (7) |
| Zn1 | 0.03545 (17) | 0.01984 (14) | 0.03395 (16) | 0.000 | 0.02441 (14) | 0.000 |
| N1 | 0.0293 (10) | 0.0231 (10) | 0.0253 (9) | 0.000 | 0.0170 (9) | 0.000 |
| N2 | 0.0322 (8) | 0.0264 (8) | 0.0335 (7) | −0.0007 (6) | 0.0224 (7) | 0.0004 (6) |
| C1 | 0.0407 (11) | 0.0311 (10) | 0.0417 (10) | 0.0025 (8) | 0.0285 (9) | −0.0011 (8) |
| C2 | 0.0372 (11) | 0.0487 (12) | 0.0398 (10) | 0.0025 (9) | 0.0271 (9) | −0.0038 (9) |
| C3 | 0.0354 (10) | 0.0545 (12) | 0.0380 (10) | −0.0069 (9) | 0.0271 (9) | −0.0022 (9) |
| C4 | 0.0367 (10) | 0.0359 (10) | 0.0339 (9) | −0.0072 (8) | 0.0222 (8) | 0.0005 (8) |
| C5 | 0.0268 (9) | 0.0287 (9) | 0.0235 (7) | −0.0027 (7) | 0.0139 (7) | 0.0004 (7) |
| C6 | 0.0274 (9) | 0.0247 (8) | 0.0237 (7) | −0.0027 (7) | 0.0133 (7) | 0.0007 (6) |
| C7 | 0.0360 (10) | 0.0268 (9) | 0.0351 (9) | −0.0042 (8) | 0.0193 (8) | 0.0030 (7) |
| C8 | 0.0426 (16) | 0.0201 (12) | 0.0409 (14) | 0.000 | 0.0210 (13) | 0.000 |
| Br1—Zn1 | 2.4179 (2) | C2—H2 | 0.9300 |
| Zn1—N1 | 2.106 (2) | C3—C4 | 1.388 (3) |
| Zn1—N2i | 2.1861 (14) | C3—H3 | 0.9300 |
| Zn1—N2 | 2.1861 (14) | C4—C5 | 1.389 (2) |
| Zn1—Br1i | 2.4179 (2) | C4—H4 | 0.9300 |
| N1—C6i | 1.3441 (19) | C5—C6 | 1.485 (2) |
| N1—C6 | 1.3441 (19) | C6—C7 | 1.388 (3) |
| N2—C1 | 1.336 (2) | C7—C8 | 1.385 (2) |
| N2—C5 | 1.348 (2) | C7—H7 | 0.9300 |
| C1—C2 | 1.385 (3) | C8—C7i | 1.385 (2) |
| C1—H1 | 0.9300 | C8—H8 | 0.9300 |
| C2—C3 | 1.374 (3) | ||
| N1—Zn1—N2i | 74.75 (4) | C3—C2—H2 | 120.5 |
| N1—Zn1—N2 | 74.75 (4) | C1—C2—H2 | 120.5 |
| N2i—Zn1—N2 | 149.49 (8) | C2—C3—C4 | 119.27 (17) |
| N1—Zn1—Br1 | 121.815 (7) | C2—C3—H3 | 120.4 |
| N2i—Zn1—Br1 | 98.34 (4) | C4—C3—H3 | 120.4 |
| N2—Zn1—Br1 | 97.60 (4) | C3—C4—C5 | 118.78 (18) |
| N1—Zn1—Br1i | 121.815 (7) | C3—C4—H4 | 120.6 |
| N2i—Zn1—Br1i | 97.60 (4) | C5—C4—H4 | 120.6 |
| N2—Zn1—Br1i | 98.34 (4) | N2—C5—C4 | 121.69 (16) |
| Br1—Zn1—Br1i | 116.370 (14) | N2—C5—C6 | 114.99 (14) |
| C6i—N1—C6 | 120.6 (2) | C4—C5—C6 | 123.32 (16) |
| C6i—N1—Zn1 | 119.68 (10) | N1—C6—C7 | 121.01 (16) |
| C6—N1—Zn1 | 119.68 (10) | N1—C6—C5 | 114.25 (15) |
| C1—N2—C5 | 118.88 (15) | C7—C6—C5 | 124.74 (15) |
| C1—N2—Zn1 | 124.80 (12) | C8—C7—C6 | 118.57 (17) |
| C5—N2—Zn1 | 116.32 (11) | C8—C7—H7 | 120.7 |
| N2—C1—C2 | 122.43 (18) | C6—C7—H7 | 120.7 |
| N2—C1—H1 | 118.8 | C7i—C8—C7 | 120.2 (2) |
| C2—C1—H1 | 118.8 | C7i—C8—H8 | 119.9 |
| C3—C2—C1 | 118.93 (18) | C7—C8—H8 | 119.9 |
| N2i—Zn1—N1—C6i | 0.68 (9) | C1—C2—C3—C4 | −0.6 (3) |
| N2—Zn1—N1—C6i | −179.32 (9) | C2—C3—C4—C5 | 1.3 (3) |
| Br1—Zn1—N1—C6i | 91.12 (8) | C1—N2—C5—C4 | −0.1 (2) |
| Br1i—Zn1—N1—C6i | −88.88 (8) | Zn1—N2—C5—C4 | 179.88 (12) |
| N2i—Zn1—N1—C6 | −179.32 (9) | C1—N2—C5—C6 | 179.87 (15) |
| N2—Zn1—N1—C6 | 0.68 (9) | Zn1—N2—C5—C6 | −0.19 (18) |
| Br1—Zn1—N1—C6 | −88.88 (8) | C3—C4—C5—N2 | −0.9 (3) |
| Br1i—Zn1—N1—C6 | 91.12 (8) | C3—C4—C5—C6 | 179.12 (16) |
| N1—Zn1—N2—C1 | 179.71 (15) | C6i—N1—C6—C7 | −0.96 (12) |
| N2i—Zn1—N2—C1 | 179.71 (15) | Zn1—N1—C6—C7 | 179.04 (12) |
| Br1—Zn1—N2—C1 | −59.30 (14) | C6i—N1—C6—C5 | 179.02 (15) |
| Br1i—Zn1—N2—C1 | 58.90 (14) | Zn1—N1—C6—C5 | −0.98 (15) |
| N1—Zn1—N2—C5 | −0.23 (11) | N2—C5—C6—N1 | 0.74 (19) |
| N2i—Zn1—N2—C5 | −0.23 (11) | C4—C5—C6—N1 | −179.33 (14) |
| Br1—Zn1—N2—C5 | 120.76 (11) | N2—C5—C6—C7 | −179.29 (16) |
| Br1i—Zn1—N2—C5 | −121.05 (11) | C4—C5—C6—C7 | 0.6 (3) |
| C5—N2—C1—C2 | 0.8 (3) | N1—C6—C7—C8 | 1.9 (2) |
| Zn1—N2—C1—C2 | −179.16 (14) | C5—C6—C7—C8 | −178.10 (13) |
| N2—C1—C2—C3 | −0.4 (3) | C6—C7—C8—C7i | −0.91 (11) |
| Symmetry codes: (i) −x+1, y, −z+1/2. |
The authors are grateful to the Henan Administration of Science and Technology for financial support (grant No. 092300410031).
Alizadeh, R., Heidari, A., Ahmadi, R. & Amani, V. (2009). Acta Cryst. E65, m483–m484.
Bai, F. Q., Zhou, X., Xia, B. H., Liu, T., Zhang, J. P. & Zhang, H. X. (2009). J. Organomet. Chem. 694, 1848–1860.
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Huang, W., You, W., Wang, L. & Yao, C. (2009). Inorg. Chim. Acta, 362, 2127–2135.
Ma, Z., Xing, Y. P., Yang, M., Hua, M., Liu, B. Q., da Silva, M. F. C. G. & Pombeiro, A. J. L. (2009). Inorg. Chim. Acta, 362, 2921–2926.
Mahmoudi, A., Khalaj, M., Gao, S., Ng, S. W. & Mohammadgholiha, M. (2009). Acta Cryst. E65, m555.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
As a contribution to structural characterization of 2,2':6',2''-terpyridine complexes (Alizadeh et al., 2009; Huang et al., 2009; Ma et al., 2009; Bai et al., 2009) we present here the title complex (I).
In (I) (Fig. 1), the ZnII ion is five-coordinated in a distorted trigonal bipyramidal configuration by three N atoms from a 2,2':6',2''-terpyridine ligand and by two Br anions. The Zn–Br and Zn–N bond lengths are within normal ranges (Mahmoudi et al., 2009).
In the crystal structure, the π–π stacking interactions between aromatic rings of Cg1 and Cg2 [Cg1 and Cg2 are (N1, C6 — C8, C7i, C6i) and (N2, C1 — C5) ring centroids, respectively, symmetry code: (i) -x + 1, y, -z + 1/2] are observed, with a centroid–centroid distances of 3.6265 (9) Å.