supplementary materials
Diaquabis[5-(pyrazin-2-yl)-5H-tetrazolato-![[kappa]](/logos/entities/kappa_rmgif.gif)
2N,N']copper(II) monohydrate
The CuII atom in the title compound, [Cu(C5H3N6)2(H2O)2]·H2O, is chelated by two pyrazinyltetrazolate ligands and, in addition, coordinated by two water molecules in a tetragonally elongated octahedral geometry [Cu-N = 1.990 (2) and 2.056 (2) Å, and Cu-O = 2.445 (2) Å]. The CuII atom lies on a center of inversion. In the crystal structure, molecules are linked by O-H
O and O-HN hydrogen bonds into a three-dimensional network. The free water molecule is disordered about a twofold axis.
Copper chloride dihydrate (34 mg, 0.2 mmol) and
2-(1H-tetrazol-5-yl)pyrazine (60 mg, 0.4 mmol) were dissolved in 10 ml
of a DMF–water (1:1) mixture. The clear solution was filtered; blue crystals
were isolated after a month in 30% yield.
Carbon-bound H atoms were placed at calculated positions [C—H = 0.93 Å; U(H)
= 1.2Ueq(C)]. The O2w atom is disordered about a twofold axis, and it
was allowed to refine off the symmetry element. The H atoms of the water
molecules were located in a difference Fourier map, and were refined with
distance restraints of O–H = 0.85±0.01 Å and H···H = 1.39±0.01 Å.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).
Diaquabis[5-(pyrazin-2-yl)-5
H-tetrazolato-
κ2N,
N']copper(II) monohydrate
top
Crystal data top
| [Cu(C5H3N6)2(H2O)2]·H2O | F(000) = 836 |
| Mr = 411.86 | Dx = 1.730 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2454 reflections |
| a = 13.045 (2) Å | θ = 3.2–26.3° |
| b = 7.341 (1) Å | µ = 1.43 mm−1 |
| c = 16.869 (2) Å | T = 294 K |
| β = 101.757 (2)° | Block, blue |
| V = 1581.5 (4) Å3 | 0.24 × 0.22 × 0.18 mm |
| Z = 4 | |
Data collection top
Bruker APEX area-detector
diffractometer | 1603 independent reflections |
| Radiation source: fine-focus sealed tube | 1375 reflections with I > 2σ(I) |
| graphite | Rint = 0.027 |
| φ and ω scans | θmax = 26.3°, θmin = 2.5° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | h = −15→16 |
| Tmin = 0.606, Tmax = 0.784 | k = −9→9 |
| 4287 measured reflections | l = −14→20 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.02 | w = 1/[σ2(Fo2) + (0.0428P)2 + 1.3231P]
where P = (Fo2 + 2Fc2)/3 |
| 1603 reflections | (Δ/σ)max = 0.001 |
| 136 parameters | Δρmax = 0.31 e Å−3 |
| 18 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
| [Cu(C5H3N6)2(H2O)2]·H2O | V = 1581.5 (4) Å3 |
| Mr = 411.86 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 13.045 (2) Å | µ = 1.43 mm−1 |
| b = 7.341 (1) Å | T = 294 K |
| c = 16.869 (2) Å | 0.24 × 0.22 × 0.18 mm |
| β = 101.757 (2)° | |
Data collection top
Bruker APEX area-detector
diffractometer | 1603 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | 1375 reflections with I > 2σ(I) |
| Tmin = 0.606, Tmax = 0.784 | Rint = 0.027 |
| 4287 measured reflections | θmax = 26.3° |
Refinement top
| R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.077 | Δρmax = 0.31 e Å−3 |
| S = 1.02 | Δρmin = −0.27 e Å−3 |
| 1603 reflections | Absolute structure: ? |
| 136 parameters | Flack parameter: ? |
| 18 restraints | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | Occ. (<1) |
| Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.02729 (14) | |
| O1W | 0.60924 (12) | 0.6371 (2) | 0.41419 (10) | 0.0387 (4) | |
| H11 | 0.6673 (11) | 0.582 (3) | 0.4237 (16) | 0.046* | |
| H12 | 0.6171 (17) | 0.7461 (16) | 0.4309 (15) | 0.046* | |
| O2W | 0.5303 (4) | 0.6846 (6) | 0.2457 (5) | 0.0821 (19) | 0.50 |
| H21 | 0.556 (5) | 0.660 (7) | 0.2958 (15) | 0.099* | 0.50 |
| H22 | 0.508 (7) | 0.583 (5) | 0.223 (3) | 0.099* | 0.50 |
| N1 | 0.40820 (12) | 0.7190 (2) | 0.48450 (10) | 0.0267 (4) | |
| N2 | 0.32571 (13) | 0.7878 (2) | 0.43186 (11) | 0.0322 (4) | |
| N3 | 0.30323 (14) | 0.9464 (3) | 0.45989 (12) | 0.0337 (4) | |
| N4 | 0.36960 (15) | 0.9853 (2) | 0.53077 (12) | 0.0318 (4) | |
| N5 | 0.57264 (12) | 0.6487 (2) | 0.59883 (10) | 0.0281 (4) | |
| N6 | 0.64382 (16) | 0.8787 (3) | 0.72971 (12) | 0.0460 (5) | |
| C1 | 0.43250 (14) | 0.8413 (2) | 0.54351 (12) | 0.0251 (4) | |
| C2 | 0.52281 (15) | 0.8057 (3) | 0.60846 (12) | 0.0261 (4) | |
| C3 | 0.55893 (18) | 0.9186 (3) | 0.67355 (14) | 0.0364 (5) | |
| H3 | 0.5230 | 1.0261 | 0.6784 | 0.044* | |
| C4 | 0.6933 (2) | 0.7251 (3) | 0.71873 (15) | 0.0474 (6) | |
| H4 | 0.7536 | 0.6941 | 0.7561 | 0.057* | |
| C5 | 0.65859 (17) | 0.6091 (3) | 0.65368 (14) | 0.0384 (5) | |
| H5 | 0.6956 | 0.5031 | 0.6484 | 0.046* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cu1 | 0.0274 (2) | 0.0203 (2) | 0.0296 (2) | 0.00697 (13) | −0.00475 (14) | −0.00489 (14) |
| O1W | 0.0332 (8) | 0.0308 (8) | 0.0497 (10) | 0.0062 (6) | 0.0030 (7) | −0.0004 (7) |
| O2W | 0.100 (5) | 0.073 (3) | 0.064 (3) | −0.024 (3) | −0.006 (4) | 0.005 (3) |
| N1 | 0.0247 (8) | 0.0226 (8) | 0.0306 (9) | 0.0042 (6) | 0.0005 (7) | 0.0001 (7) |
| N2 | 0.0278 (8) | 0.0293 (9) | 0.0368 (10) | 0.0066 (7) | 0.0003 (7) | 0.0029 (8) |
| N3 | 0.0300 (9) | 0.0277 (9) | 0.0425 (10) | 0.0070 (7) | 0.0051 (8) | 0.0039 (8) |
| N4 | 0.0310 (9) | 0.0233 (9) | 0.0416 (10) | 0.0048 (7) | 0.0089 (8) | 0.0007 (7) |
| N5 | 0.0274 (8) | 0.0234 (8) | 0.0310 (9) | 0.0018 (7) | −0.0001 (7) | −0.0036 (7) |
| N6 | 0.0512 (12) | 0.0410 (12) | 0.0397 (11) | −0.0005 (9) | −0.0054 (9) | −0.0108 (9) |
| C1 | 0.0246 (9) | 0.0203 (9) | 0.0315 (10) | 0.0020 (7) | 0.0080 (8) | −0.0003 (8) |
| C2 | 0.0267 (9) | 0.0222 (10) | 0.0298 (10) | −0.0013 (7) | 0.0064 (8) | −0.0014 (8) |
| C3 | 0.0414 (12) | 0.0305 (12) | 0.0366 (12) | 0.0019 (10) | 0.0066 (10) | −0.0067 (10) |
| C4 | 0.0448 (13) | 0.0423 (14) | 0.0449 (14) | 0.0044 (11) | −0.0149 (11) | −0.0082 (11) |
| C5 | 0.0357 (12) | 0.0320 (12) | 0.0412 (13) | 0.0057 (9) | −0.0068 (10) | −0.0035 (10) |
Geometric parameters (Å, °) top
| Cu1—N1 | 1.990 (2) | N3—N4 | 1.356 (3) |
| Cu1—N1i | 1.990 (2) | N4—C1 | 1.328 (2) |
| Cu1—N5 | 2.056 (2) | N5—C5 | 1.332 (3) |
| Cu1—N5i | 2.056 (2) | N5—C2 | 1.349 (2) |
| Cu1—O1w | 2.445 (2) | N6—C4 | 1.331 (3) |
| O1W—H11 | 0.84 (1) | N6—C3 | 1.335 (3) |
| O1W—H12 | 0.85 (1) | C1—C2 | 1.460 (3) |
| O2W—H21 | 0.86 (1) | C2—C3 | 1.380 (3) |
| O2W—H22 | 0.86 (1) | C3—H3 | 0.9300 |
| N1—C1 | 1.330 (2) | C4—C5 | 1.390 (3) |
| N1—N2 | 1.346 (2) | C4—H4 | 0.9300 |
| N2—N3 | 1.312 (3) | C5—H5 | 0.9300 |
| | | |
| N1i—Cu1—N1 | 180.000 (1) | C5—N5—C2 | 117.45 (18) |
| N1i—Cu1—N5i | 80.97 (6) | C5—N5—Cu1 | 129.11 (14) |
| N1—Cu1—N5i | 99.03 (6) | C2—N5—Cu1 | 113.42 (13) |
| N1i—Cu1—N5 | 99.03 (6) | C4—N6—C3 | 116.3 (2) |
| N1—Cu1—N5 | 80.97 (6) | N4—C1—N1 | 111.76 (17) |
| N5i—Cu1—N5 | 180.0 | N4—C1—C2 | 129.91 (18) |
| N1i—Cu1—O1W | 90.14 (6) | N1—C1—C2 | 118.27 (16) |
| N1—Cu1—O1W | 89.86 (6) | N5—C2—C3 | 120.95 (18) |
| N5i—Cu1—O1W | 88.07 (6) | N5—C2—C1 | 113.44 (17) |
| N5—Cu1—O1W | 91.93 (6) | C3—C2—C1 | 125.58 (18) |
| Cu1—O1W—H11 | 107.4 (18) | N6—C3—C2 | 122.1 (2) |
| Cu1—O1W—H12 | 103.7 (17) | N6—C3—H3 | 118.9 |
| H11—O1W—H12 | 110.1 (15) | C2—C3—H3 | 118.9 |
| H21—O2W—H22 | 106.4 (17) | N6—C4—C5 | 122.6 (2) |
| C1—N1—N2 | 106.08 (15) | N6—C4—H4 | 118.7 |
| C1—N1—Cu1 | 113.68 (12) | C5—C4—H4 | 118.7 |
| N2—N1—Cu1 | 140.23 (13) | N5—C5—C4 | 120.5 (2) |
| N3—N2—N1 | 107.61 (16) | N5—C5—H5 | 119.8 |
| N2—N3—N4 | 110.81 (16) | C4—C5—H5 | 119.8 |
| C1—N4—N3 | 103.74 (16) | | |
| | | |
| N5i—Cu1—N1—C1 | 176.48 (13) | Cu1—N1—C1—N4 | 179.87 (13) |
| N5—Cu1—N1—C1 | −3.52 (13) | N2—N1—C1—C2 | −177.69 (17) |
| O1W—Cu1—N1—C1 | −95.49 (14) | Cu1—N1—C1—C2 | 2.4 (2) |
| N5i—Cu1—N1—N2 | −3.3 (2) | C5—N5—C2—C3 | −1.1 (3) |
| N5—Cu1—N1—N2 | 176.7 (2) | Cu1—N5—C2—C3 | 177.58 (16) |
| O1W—Cu1—N1—N2 | 84.7 (2) | C5—N5—C2—C1 | 177.32 (18) |
| C1—N1—N2—N3 | 0.1 (2) | Cu1—N5—C2—C1 | −4.0 (2) |
| Cu1—N1—N2—N3 | 179.95 (16) | N4—C1—C2—N5 | −175.75 (19) |
| N1—N2—N3—N4 | 0.0 (2) | N1—C1—C2—N5 | 1.1 (3) |
| N2—N3—N4—C1 | −0.2 (2) | N4—C1—C2—C3 | 2.6 (3) |
| N1i—Cu1—N5—C5 | 2.7 (2) | N1—C1—C2—C3 | 179.5 (2) |
| N1—Cu1—N5—C5 | −177.3 (2) | C4—N6—C3—C2 | 1.3 (4) |
| O1W—Cu1—N5—C5 | −87.79 (19) | N5—C2—C3—N6 | −0.2 (3) |
| N1i—Cu1—N5—C2 | −175.81 (14) | C1—C2—C3—N6 | −178.4 (2) |
| N1—Cu1—N5—C2 | 4.19 (14) | C3—N6—C4—C5 | −1.3 (4) |
| O1W—Cu1—N5—C2 | 93.74 (14) | C2—N5—C5—C4 | 1.1 (3) |
| N3—N4—C1—N1 | 0.3 (2) | Cu1—N5—C5—C4 | −177.28 (18) |
| N3—N4—C1—C2 | 177.32 (19) | N6—C4—C5—N5 | 0.0 (4) |
| N2—N1—C1—N4 | −0.3 (2) | | |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1w—H11···N3ii | 0.84 (1) | 2.02 (1) | 2.857 (2) | 173 (3) |
| O1w—H12···N4iii | 0.85 (1) | 2.07 (1) | 2.919 (2) | 178 (2) |
| O2w—H21···O1w | 0.86 (1) | 1.98 (2) | 2.841 (9) | 172 (6) |
| Symmetry codes: (ii) x+1/2, y−1/2, z; (iii) −x+1, −y+2, −z+1. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1w—H11···N3i | 0.84 (1) | 2.02 (1) | 2.857 (2) | 173 (3) |
| O1w—H12···N4ii | 0.85 (1) | 2.07 (1) | 2.919 (2) | 178 (2) |
| O2w—H21···O1w | 0.86 (1) | 1.98 (2) | 2.841 (9) | 172 (6) |
| Symmetry codes: (i) x+1/2, y−1/2, z; (ii) −x+1, −y+2, −z+1. |
We thank Dalian Nationalities University and the University of Malaya for
supporting this study.
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
Bruker (1998). SMART (Version 5.051) and SAINT (Version 5.05). Bruker AXS Inc, Madison, Wisconsin, USA.
Li, J.-R., Bu, X.-H., Jian, G.-C. & Batten, S. R. (2007). J. Mol. Struct. 828, 142–146.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.
Westrip, S. P. (2007). publCIF. In preparation.
![[Figure 1]](./lh2383fig1thm.gif)
The Cambridge Structural Database (Version 5.28, November 2006; Allen, 2002) lists several examples of metal 5-(2-pyridyl)-5H-tetrazoles. A second nitrogen donor site in a pyrazine ring group could serve as a donor site, but this is not observed in the copper derivative, which crystallizes as a diaqua monohydrate. The second donor site in the pyrimidyl part of the anion is engaged in hydrogen bonding with the coordinated and lattice water molecules to form a three-dimensional network motif.