Acta Cryst. (2007). E63, m3045 [ doi:10.1107/S1600536807051239 ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
N)zinc(II)]-![[mu]](/logos/entities/mu_rmgif.gif)
-1,4-bis(1,2,4-triazol-1-yl)butane]The structure of the title complex, [Zn(NCS)2(C8H12N6)]n, exhibits a one-dimensional zigzag chain through a 1,4-bis(1,2,4-triazol-1-yl)butane bridge, in which the ZnII atom, lying on a twofold rotation axis, is in a distorted tetrahedral environment formed by two N atoms of the triazoles and two N atoms from two thiocyanate ligands.
1,4-Bis(1,2,4-triazol-1-yl)butane (btb) was prepared according to literature method (Gromova et al., 2000). A 15 mL me thanol of ZnCl2(0.136 g, 1 mmol) was added to a 15 ml me thanol of KSCN (0.348 g, 2 mmol). The resulting precipitate of KCl was filtered off. A 15 ml aqueous solution of btb (0.192 g, 1 mmol) was added to the above filtrate. The reaction mixture was stirred at reflux temperature for 2 h. The colourless single crystals of the title complex were obtained by evaporating the reaction solution at room temperature for one week.
The H atoms were placed in a calculated positions, with C—H = 0.93 or 0.97 Å. All H atoms were included in the final cycle of refinement in riding mode, with Uiso(H) = 1.2Ueq(C,N,O).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).
![[Figure 1]](./at2425fig1thm.gif)
| Fig. 1. Molecular structure showing 50% probability displacement ellipsoids. |
![[Figure 2]](./at2425fig2thm.gif)
| Fig. 2. The extended structure of the title complex. |
| [Zn(NCS)2(C8H12N6)] | F000 = 760.00 |
| Mr = 373.76 | Dx = 1.519 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71069 Å |
| Hall symbol: -C 2yc | Cell parameters from 5666 reflections |
| a = 15.1950 (9) Å | θ = 4.0–27.4º |
| b = 5.8261 (2) Å | µ = 1.76 mm−1 |
| c = 18.8040 (7) Å | T = 298 (1) K |
| β = 100.893 (2)º | Platelet, colourless |
| V = 1634.68 (13) Å3 | 0.38 × 0.28 × 0.11 mm |
| Z = 4 |
| Rigaku R-AXIS RAPID diffractometer | 1473 reflections with F2 > 2σ(F2) |
| Detector resolution: 10.00 pixels mm-1 | Rint = 0.049 |
| ω scans | θmax = 27.5º |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −19→19 |
| Tmin = 0.515, Tmax = 0.824 | k = −7→7 |
| 7229 measured reflections | l = −24→23 |
| 1867 independent reflections |
| Refinement on F2 | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.034 | w = 1/[0.002Fo2 + σ(Fo2)]/(4Fo2) |
| wR(F2) = 0.132 | (Δ/σ)max < 0.001 |
| S = 1.00 | Δρmax = 0.50 e Å−3 |
| 1867 reflections | Δρmin = −0.46 e Å−3 |
| 96 parameters | Extinction correction: none |
| [Zn(NCS)2(C8H12N6)] | V = 1634.68 (13) Å3 |
| Mr = 373.76 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 15.1950 (9) Å | µ = 1.76 mm−1 |
| b = 5.8261 (2) Å | T = 298 (1) K |
| c = 18.8040 (7) Å | 0.38 × 0.28 × 0.11 mm |
| β = 100.893 (2)º |
| Rigaku R-AXIS RAPID diffractometer | 1867 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1473 reflections with F2 > 2σ(F2) |
| Tmin = 0.515, Tmax = 0.824 | Rint = 0.049 |
| 7229 measured reflections |
| R[F2 > 2σ(F2)] = 0.034 | ? restraints |
| wR(F2) = 0.132 | H-atom parameters constrained |
| S = 1.00 | Δρmax = 0.50 e Å−3 |
| 1867 reflections | Δρmin = −0.46 e Å−3 |
| 96 parameters |
Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
| x | y | z | Uiso*/Ueq | ||
| Zn1 | 0.5000 | 0.23651 (6) | 0.7500 | 0.04427 (14) | |
| S1 | 0.38748 (10) | −0.21390 (18) | 0.91869 (6) | 0.0815 (3) | |
| N1 | 0.40464 (14) | 0.4526 (3) | 0.69942 (11) | 0.0434 (5) | |
| N2 | 0.29337 (19) | 0.7082 (5) | 0.68471 (14) | 0.0552 (7) | |
| N3 | 0.34510 (17) | 0.7371 (3) | 0.63403 (12) | 0.0423 (5) | |
| N4 | 0.45101 (19) | 0.0641 (5) | 0.82138 (17) | 0.0697 (9) | |
| C1 | 0.33192 (19) | 0.5365 (5) | 0.72290 (14) | 0.0514 (8) | |
| C2 | 0.41033 (18) | 0.5847 (4) | 0.64281 (14) | 0.0452 (7) | |
| C3 | 0.3238 (2) | 0.9165 (4) | 0.57881 (14) | 0.0525 (7) | |
| C4 | 0.24236 (19) | 0.8540 (4) | 0.52201 (14) | 0.0468 (7) | |
| C5 | 0.4231 (2) | −0.0470 (5) | 0.86203 (17) | 0.0560 (8) | |
| H1 | 0.3114 | 0.4770 | 0.7627 | 0.063* | |
| H2 | 0.4535 | 0.5716 | 0.6140 | 0.055* | |
| H32 | 0.3118 | 1.0586 | 0.6021 | 0.061* | |
| H31 | 0.3748 | 0.9375 | 0.5553 | 0.061* | |
| H42 | 0.1926 | 0.8225 | 0.5462 | 0.055* | |
| H41 | 0.2275 | 0.9833 | 0.4895 | 0.055* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn1 | 0.0450 (2) | 0.0382 (2) | 0.0481 (3) | 0.0000 | 0.0050 (2) | 0.0000 |
| S1 | 0.0995 (8) | 0.0692 (6) | 0.0903 (7) | −0.0024 (5) | 0.0551 (6) | 0.0129 (5) |
| N1 | 0.0409 (11) | 0.0462 (11) | 0.0422 (11) | −0.0023 (9) | 0.0056 (9) | 0.0020 (9) |
| N2 | 0.0512 (14) | 0.0688 (16) | 0.0481 (13) | 0.0132 (11) | 0.0162 (11) | 0.0018 (11) |
| N3 | 0.0425 (12) | 0.0445 (12) | 0.0383 (11) | −0.0014 (9) | 0.0033 (9) | 0.0008 (9) |
| N4 | 0.0612 (17) | 0.0663 (17) | 0.0835 (19) | −0.0009 (13) | 0.0181 (14) | 0.0246 (15) |
| C1 | 0.0490 (16) | 0.0660 (18) | 0.0422 (13) | 0.0042 (13) | 0.0160 (11) | 0.0065 (13) |
| C2 | 0.0405 (13) | 0.0523 (15) | 0.0442 (13) | 0.0006 (11) | 0.0115 (10) | 0.0024 (11) |
| C3 | 0.0634 (18) | 0.0432 (14) | 0.0468 (14) | −0.0039 (13) | 0.0001 (12) | 0.0039 (12) |
| C4 | 0.0507 (15) | 0.0426 (14) | 0.0440 (12) | 0.0090 (11) | 0.0012 (11) | −0.0004 (12) |
| C5 | 0.0516 (17) | 0.0522 (16) | 0.0664 (18) | 0.0015 (13) | 0.0167 (13) | 0.0038 (15) |
| Zn1—N1 | 2.017 (2) | N3—C3 | 1.466 (3) |
| Zn1—N1i | 2.017 (2) | N4—C5 | 1.143 (4) |
| Zn1—N4 | 1.934 (3) | C3—C4 | 1.518 (3) |
| Zn1—N4i | 1.934 (3) | C4—C4ii | 1.510 (4) |
| S1—C5 | 1.610 (3) | C1—H1 | 0.930 |
| N1—C1 | 1.356 (3) | C2—H2 | 0.930 |
| N1—C2 | 1.330 (3) | C3—H32 | 0.970 |
| N2—N3 | 1.356 (4) | C3—H31 | 0.970 |
| N2—C1 | 1.304 (4) | C4—H42 | 0.970 |
| N3—C2 | 1.318 (3) | C4—H41 | 0.970 |
| N1—Zn1—N1i | 102.75 (8) | C3—C4—C4ii | 112.9 (2) |
| N1—Zn1—N4 | 108.35 (10) | S1—C5—N4 | 177.0 (3) |
| N1—Zn1—N4i | 109.46 (10) | N1—C1—H1 | 123.0 |
| N1i—Zn1—N4 | 109.46 (10) | N2—C1—H1 | 123.0 |
| N1i—Zn1—N4i | 108.35 (10) | N1—C2—H2 | 125.4 |
| N4—Zn1—N4i | 117.45 (13) | N3—C2—H2 | 125.4 |
| Zn1—N1—C1 | 128.93 (18) | N3—C3—H32 | 108.9 |
| Zn1—N1—C2 | 126.10 (19) | N3—C3—H31 | 108.9 |
| C1—N1—C2 | 103.4 (2) | C4—C3—H32 | 108.9 |
| N3—N2—C1 | 102.9 (2) | C4—C3—H31 | 108.9 |
| N2—N3—C2 | 110.5 (2) | H32—C3—H31 | 109.5 |
| N2—N3—C3 | 120.5 (2) | C3—C4—H42 | 108.6 |
| C2—N3—C3 | 129.0 (2) | C3—C4—H41 | 108.6 |
| Zn1—N4—C5 | 176.8 (3) | C4ii—C4—H42 | 108.6 |
| N1—C1—N2 | 114.0 (2) | C4ii—C4—H41 | 108.6 |
| N1—C2—N3 | 109.2 (2) | H42—C4—H41 | 109.5 |
| N3—C3—C4 | 111.6 (2) | ||
| N1—Zn1—N1i—C1i | −93.0 (2) | Zn1—N1—C1—N2 | 166.49 (19) |
| N1—Zn1—N1i—C2i | 70.5 (2) | Zn1—N1—C2—N3 | −166.57 (17) |
| N1i—Zn1—N1—C1 | −93.0 (2) | C1—N1—C2—N3 | 0.3 (2) |
| N1i—Zn1—N1—C2 | 70.5 (2) | C2—N1—C1—N2 | 0.2 (3) |
| N4—Zn1—N1—C1 | 22.8 (2) | N3—N2—C1—N1 | −0.5 (3) |
| N4—Zn1—N1—C2 | −173.7 (2) | C1—N2—N3—C2 | 0.7 (3) |
| N4i—Zn1—N1—C1 | 152.0 (2) | C1—N2—N3—C3 | 179.6 (2) |
| N4i—Zn1—N1—C2 | −44.5 (2) | N2—N3—C2—N1 | −0.6 (3) |
| N4—Zn1—N1i—C1i | 152.0 (2) | N2—N3—C3—C4 | −73.6 (3) |
| N4—Zn1—N1i—C2i | −44.5 (2) | C2—N3—C3—C4 | 105.1 (3) |
| N4i—Zn1—N1i—C1i | 22.8 (2) | C3—N3—C2—N1 | −179.4 (2) |
| N4i—Zn1—N1i—C2i | −173.7 (2) | N3—C3—C4—C4ii | −64.9 (3) |
| Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1/2, −y+3/2, −z+1. |
| Zn1—N1 | 2.017 (2) | N1—C1 | 1.356 (3) |
| Zn1—N4 | 1.934 (3) | N1—C2 | 1.330 (3) |
| S1—C5 | 1.610 (3) | N2—N3 | 1.356 (4) |
| N1—Zn1—N1i | 102.75 (8) | Zn1—N1—C1 | 128.93 (18) |
| N1—Zn1—N4 | 108.35 (10) | Zn1—N1—C2 | 126.10 (19) |
| N1—Zn1—N4i | 109.46 (10) | Zn1—N4—C5 | 176.8 (3) |
| N4—Zn1—N4i | 117.45 (13) | S1—C5—N4 | 177.0 (3) |
| Symmetry codes: (i) −x+1, y, −z+3/2. |
We express our gratitude to the Zhejiang Provincial Natural Science Foundation of China for financial support through project No. M203077
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Recently a new class of flexible ligands, [bis(1,2,4-triazol-1-yl)-alkanes], have been found to be very effective in the formation of various interesting extended structures. As bridging ligands, these 1,2,4-triazole derivatives show a great coordination diversity. Among these ligands, 1,4-bis(1,2,4-triazol-1-yl)butane(btb), with a appropriate length between two hetercyclic donors, is expected to play an important role in the construction of transition-metal supramolecular structures. To our knowledge, there are a few reports on the crystal structures of manganese(II) and cadmium(II) complexes with bridging 1,4-bis(1,2,4-triazol-1-yl)butane ligand [Li et al., 2006; Liu et al., 2006]. As part of our investigations of the coordination mode of the ligand in metal complexes incorporating 1,2,4-triazole derivatives, we here report the synthesis and crystal structure of a new polymeric Zn(II) with btb bridges.
The molecular structure of the title complex, with the atom-numbering scheme, is shown in Fig. 1. The Zn(II) atoms are surrounded by two triazoles and two NCS– ions, forming a distorted tetrahedral geometry. The Zn—N bond distances of btb [2.017 (2) Å] are slightly longer than the Zn—N from NCS [1.934 (3) Å]. The N—Zn—N angles around Zn centers range from 102.75 (8)o to 117.45 (13)o. The Zn—N—C angles are 176.8 (3)o, which deviating from 180º expected for sp hybrid orbital of the N atom. The NCS group is almost linear with a N(4)—C(5)—S(1) angle of 177.0 (3)o. The C—N distances [1.143 (4) Å] and C—S distances [1.610 (3) Å] in the SCN moiety show the normal structure of the thiocyanate in the complex.
As shown in Fig. 2, the Zn(II) ions are linked by btb ligands, building up coordination polymers to one-dimensional zigzag chain. The btb ligand adopts an anti-gauche conformation in this complex.