supplementary materials
Bis[![[mu]](/logos/entities/mu_rmgif.gif)
-5-(5-carboxylato-3-pyridyl)tetrazolato-![[kappa]](/logos/entities/kappa_rmgif.gif)
3N1,N5:N2]bis[triaquazinc(II)]
In the title complex, [Zn2(C7H3N5O2)2(H2O)6], the 5-(5-carboxylato-3-pyridyl)tetrazolate ligand chelates the ZnII center through one pyridyl N and one tetrazolate N atom, and uses another N atom to bridge to the second Zn atom, forming a centrosymmetric dinuclear unit. Three coordinated water molecules complete the distorted octahedral geometry of the ZnII atom. O-H
O and O-HN hydrogen bonds involving the coordinated water molecules, tetrazolate N atoms and the carboxylate group result in a three-dimensional structure.
A mixture of Zn(NO3)2.6H2O (149 mg, 0.5 mmol), sodium azide(33 mg, 0.5 mmol) and 6-cyanopyridine-3-carboxylic acid (74 mg, 0.5 mmol) was suspended in
water (10 ml) and heated in a teflon-lined steel bomb at 160 ° C for 3 days.
The colorless crystals were obtained.
H atoms bonded to C were located geometrically (C—H = 0.95 Å) with
Uiso(H) = 1.2 Ueq(C). H atoms bonded to O were located by
difference maps and refined with a distance restraint of O—H = 0.85 (1) Å.
The displacement factors were freely refined.
Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
Bis[µ-5-(5-carboxylato-3-pyridyl)tetrazolato-
κ3N1,
N5:
N2]bis[triaquazinc(II)]
top
Crystal data top
| [Zn2(C7H3N5O2)2(H2O)6] | F(000) = 624 |
| Mr = 617.12 | Dx = 1.875 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2535 reflections |
| a = 12.751 (5) Å | θ = 3.2–27.5° |
| b = 12.685 (4) Å | µ = 2.27 mm−1 |
| c = 6.992 (3) Å | T = 295 K |
| β = 104.914 (4)° | Prism, colorless |
| V = 1092.9 (7) Å3 | 0.12 × 0.08 × 0.08 mm |
| Z = 2 | |
Data collection top
Rigaku Mercury CCD
diffractometer | 2502 independent reflections |
| Radiation source: fine-focus sealed tube | 2146 reflections with I > 2σ(I) |
| graphite | Rint = 0.031 |
| Detector resolution: 14.6306 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
| CCD_Profile_fitting scans | h = −13→16 |
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000) | k = −16→13 |
| Tmin = 0.880, Tmax = 1.000 | l = −9→8 |
| 8378 measured reflections | |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.10 | w = 1/[σ2(Fo2) + (0.0236P)2 + 0.4632P]
where P = (Fo2 + 2Fc2)/3 |
| 2502 reflections | (Δ/σ)max = 0.001 |
| 187 parameters | Δρmax = 0.44 e Å−3 |
| 6 restraints | Δρmin = −0.31 e Å−3 |
Crystal data top
| [Zn2(C7H3N5O2)2(H2O)6] | V = 1092.9 (7) Å3 |
| Mr = 617.12 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 12.751 (5) Å | µ = 2.27 mm−1 |
| b = 12.685 (4) Å | T = 295 K |
| c = 6.992 (3) Å | 0.12 × 0.08 × 0.08 mm |
| β = 104.914 (4)° | |
Data collection top
Rigaku Mercury CCD
diffractometer | 2502 independent reflections |
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000) | 2146 reflections with I > 2σ(I) |
| Tmin = 0.880, Tmax = 1.000 | Rint = 0.031 |
| 8378 measured reflections | θmax = 27.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.064 | Δρmax = 0.44 e Å−3 |
| S = 1.10 | Δρmin = −0.31 e Å−3 |
| 2502 reflections | Absolute structure: ? |
| 187 parameters | Flack parameter: ? |
| 6 restraints | Rogers parameter: ? |
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| | x | y | z | Uiso*/Ueq | |
| Zn1 | 0.16114 (2) | 0.451195 (18) | 0.04261 (4) | 0.01891 (9) | |
| N1 | 0.29843 (15) | 0.55236 (13) | 0.1954 (3) | 0.0199 (4) | |
| O2 | 0.62383 (14) | 0.48266 (13) | 0.2838 (3) | 0.0345 (4) | |
| O1 | 0.67185 (13) | 0.64838 (12) | 0.3616 (2) | 0.0273 (4) | |
| N2 | 0.08352 (15) | 0.59050 (14) | 0.1144 (3) | 0.0184 (4) | |
| C1 | 0.60194 (19) | 0.57469 (18) | 0.3163 (3) | 0.0219 (5) | |
| C4 | 0.3458 (2) | 0.72742 (18) | 0.3169 (4) | 0.0258 (5) | |
| H4 | 0.3239 | 0.7953 | 0.3491 | 0.031* | |
| C6 | 0.26966 (19) | 0.65036 (16) | 0.2412 (3) | 0.0196 (5) | |
| C3 | 0.4544 (2) | 0.70372 (18) | 0.3447 (4) | 0.0260 (5) | |
| H3 | 0.5079 | 0.7557 | 0.3958 | 0.031* | |
| C2 | 0.48558 (18) | 0.60427 (17) | 0.2980 (3) | 0.0193 (5) | |
| C5 | 0.40336 (19) | 0.53119 (17) | 0.2249 (3) | 0.0217 (5) | |
| H5 | 0.4236 | 0.4624 | 0.1944 | 0.026* | |
| O3 | 0.26729 (15) | 0.34205 (13) | −0.0178 (3) | 0.0278 (4) | |
| O4 | 0.16780 (16) | 0.52386 (13) | −0.2289 (3) | 0.0277 (4) | |
| C7 | 0.15272 (19) | 0.66661 (16) | 0.1971 (3) | 0.0184 (5) | |
| O5 | 0.16098 (16) | 0.37901 (15) | 0.3062 (3) | 0.0353 (5) | |
| N5 | −0.01525 (15) | 0.63182 (14) | 0.0916 (3) | 0.0195 (4) | |
| N4 | −0.00558 (16) | 0.72963 (15) | 0.1574 (3) | 0.0250 (4) | |
| N3 | 0.09973 (16) | 0.75412 (15) | 0.2242 (3) | 0.0245 (4) | |
| H4A | 0.141 (2) | 0.5845 (12) | −0.254 (4) | 0.041 (9)* | |
| H3A | 0.289 (2) | 0.2851 (13) | 0.042 (4) | 0.040 (8)* | |
| H4B | 0.2293 (14) | 0.527 (2) | −0.254 (5) | 0.047 (9)* | |
| H3B | 0.279 (2) | 0.339 (2) | −0.132 (2) | 0.045 (9)* | |
| H5A | 0.114 (2) | 0.336 (2) | 0.320 (5) | 0.058 (10)* | |
| H5B | 0.2086 (18) | 0.383 (2) | 0.415 (2) | 0.040 (8)* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Zn1 | 0.01593 (16) | 0.01373 (14) | 0.02694 (15) | −0.00018 (10) | 0.00528 (11) | −0.00126 (10) |
| N1 | 0.0160 (10) | 0.0159 (9) | 0.0274 (10) | −0.0006 (7) | 0.0051 (8) | −0.0027 (8) |
| O2 | 0.0210 (10) | 0.0243 (9) | 0.0606 (12) | 0.0007 (7) | 0.0146 (9) | −0.0065 (8) |
| O1 | 0.0170 (9) | 0.0271 (9) | 0.0372 (10) | −0.0048 (7) | 0.0059 (8) | −0.0073 (7) |
| N2 | 0.0140 (10) | 0.0172 (9) | 0.0240 (10) | 0.0005 (7) | 0.0051 (8) | −0.0017 (7) |
| C1 | 0.0166 (13) | 0.0276 (13) | 0.0222 (12) | −0.0001 (9) | 0.0061 (10) | −0.0008 (9) |
| C4 | 0.0196 (13) | 0.0194 (11) | 0.0382 (14) | 0.0004 (9) | 0.0071 (11) | −0.0072 (10) |
| C6 | 0.0188 (13) | 0.0170 (11) | 0.0228 (11) | 0.0007 (9) | 0.0051 (10) | −0.0022 (9) |
| C3 | 0.0206 (13) | 0.0215 (12) | 0.0344 (14) | −0.0052 (10) | 0.0042 (11) | −0.0072 (10) |
| C2 | 0.0146 (12) | 0.0207 (11) | 0.0222 (12) | −0.0003 (9) | 0.0039 (9) | −0.0007 (9) |
| C5 | 0.0173 (13) | 0.0192 (11) | 0.0288 (12) | 0.0011 (9) | 0.0063 (10) | −0.0016 (9) |
| O3 | 0.0332 (11) | 0.0185 (9) | 0.0347 (10) | 0.0079 (7) | 0.0141 (9) | 0.0029 (8) |
| O4 | 0.0258 (11) | 0.0238 (9) | 0.0367 (10) | 0.0053 (7) | 0.0139 (9) | 0.0075 (8) |
| C7 | 0.0168 (12) | 0.0167 (10) | 0.0218 (11) | −0.0013 (8) | 0.0050 (9) | −0.0036 (9) |
| O5 | 0.0301 (12) | 0.0394 (11) | 0.0302 (10) | −0.0183 (9) | −0.0033 (9) | 0.0129 (8) |
| N5 | 0.0135 (10) | 0.0175 (9) | 0.0273 (10) | 0.0009 (7) | 0.0050 (8) | −0.0028 (8) |
| N4 | 0.0185 (11) | 0.0199 (10) | 0.0363 (12) | 0.0006 (8) | 0.0067 (9) | −0.0077 (8) |
| N3 | 0.0170 (11) | 0.0202 (10) | 0.0353 (11) | 0.0011 (8) | 0.0048 (9) | −0.0089 (8) |
Geometric parameters (Å, °) top
| Zn1—O3 | 2.0547 (18) | C6—C7 | 1.457 (3) |
| Zn1—O5 | 2.0587 (19) | C3—C2 | 1.386 (3) |
| Zn1—O4 | 2.1317 (18) | C3—H3 | 0.9500 |
| Zn1—N5i | 2.1333 (19) | C2—C5 | 1.394 (3) |
| Zn1—N2 | 2.1470 (18) | C5—H5 | 0.9500 |
| Zn1—N1 | 2.2114 (19) | O3—H3A | 0.846 (10) |
| N1—C5 | 1.328 (3) | O3—H3B | 0.849 (10) |
| N1—C6 | 1.358 (3) | O4—H4A | 0.841 (10) |
| O2—C1 | 1.235 (3) | O4—H4B | 0.846 (10) |
| O1—C1 | 1.274 (3) | C7—N3 | 1.338 (3) |
| N2—C7 | 1.335 (3) | O5—H5A | 0.841 (10) |
| N2—N5 | 1.335 (2) | O5—H5B | 0.844 (10) |
| C1—C2 | 1.504 (3) | N5—N4 | 1.318 (3) |
| C4—C3 | 1.381 (3) | N5—Zn1i | 2.1333 (19) |
| C4—C6 | 1.384 (3) | N4—N3 | 1.340 (3) |
| C4—H4 | 0.9500 | | |
| | | |
| O3—Zn1—O5 | 92.12 (8) | N1—C6—C7 | 113.79 (19) |
| O3—Zn1—O4 | 85.92 (7) | C4—C6—C7 | 124.1 (2) |
| O5—Zn1—O4 | 177.71 (8) | C4—C3—C2 | 120.2 (2) |
| O3—Zn1—N5i | 97.06 (7) | C4—C3—H3 | 119.9 |
| O5—Zn1—N5i | 88.43 (7) | C2—C3—H3 | 119.9 |
| O4—Zn1—N5i | 92.97 (7) | C3—C2—C5 | 117.2 (2) |
| O3—Zn1—N2 | 166.01 (7) | C3—C2—C1 | 122.9 (2) |
| O5—Zn1—N2 | 92.86 (8) | C5—C2—C1 | 119.8 (2) |
| O4—Zn1—N2 | 88.79 (7) | N1—C5—C2 | 123.7 (2) |
| N5i—Zn1—N2 | 96.13 (7) | N1—C5—H5 | 118.1 |
| O3—Zn1—N1 | 90.51 (7) | C2—C5—H5 | 118.1 |
| O5—Zn1—N1 | 90.49 (7) | Zn1—O3—H3A | 128.6 (19) |
| O4—Zn1—N1 | 88.35 (7) | Zn1—O3—H3B | 121 (2) |
| N5i—Zn1—N1 | 172.39 (7) | H3A—O3—H3B | 108 (3) |
| N2—Zn1—N1 | 76.39 (7) | Zn1—O4—H4A | 118.2 (19) |
| C5—N1—C6 | 118.12 (19) | Zn1—O4—H4B | 117 (2) |
| C5—N1—Zn1 | 126.76 (14) | H4A—O4—H4B | 105 (3) |
| C6—N1—Zn1 | 114.64 (15) | N2—C7—N3 | 111.1 (2) |
| C7—N2—N5 | 105.42 (17) | N2—C7—C6 | 121.04 (19) |
| C7—N2—Zn1 | 113.79 (15) | N3—C7—C6 | 127.8 (2) |
| N5—N2—Zn1 | 140.58 (14) | Zn1—O5—H5A | 124 (2) |
| O2—C1—O1 | 124.2 (2) | Zn1—O5—H5B | 128 (2) |
| O2—C1—C2 | 119.0 (2) | H5A—O5—H5B | 108 (3) |
| O1—C1—C2 | 116.8 (2) | N4—N5—N2 | 109.10 (17) |
| C3—C4—C6 | 118.7 (2) | N4—N5—Zn1i | 127.65 (14) |
| C3—C4—H4 | 120.7 | N2—N5—Zn1i | 123.21 (13) |
| C6—C4—H4 | 120.7 | N5—N4—N3 | 109.59 (17) |
| N1—C6—C4 | 122.1 (2) | C7—N3—N4 | 104.80 (18) |
| Symmetry codes: (i) −x, −y+1, −z. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4B···O2ii | 0.85 (1) | 1.94 (1) | 2.782 (3) | 172 (3) |
| O4—H4A···N3iii | 0.84 (1) | 2.11 (1) | 2.940 (3) | 169 (3) |
| O3—H3B···O1ii | 0.85 (1) | 1.88 (1) | 2.712 (3) | 169 (3) |
| O3—H3A···O1iv | 0.85 (1) | 1.88 (1) | 2.719 (2) | 171 (3) |
| O5—H5B···O1v | 0.84 (1) | 1.92 (1) | 2.740 (3) | 163 (3) |
| O5—H5A···N4vi | 0.84 (1) | 1.96 (1) | 2.800 (3) | 177 (3) |
| Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x, −y+3/2, z−1/2; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, −y+1, −z+1; (vi) −x, y−1/2, −z+1/2. |
Table 1
Selected geometric parameters (Å, °) top| Zn1—O3 | 2.0547 (18) | Zn1—N5i | 2.1333 (19) |
| Zn1—O5 | 2.0587 (19) | Zn1—N2 | 2.1470 (18) |
| Zn1—O4 | 2.1317 (18) | Zn1—N1 | 2.2114 (19) |
| | | |
| O3—Zn1—O5 | 92.12 (8) | O5—Zn1—O4 | 177.71 (8) |
| O3—Zn1—O4 | 85.92 (7) | | |
| Symmetry codes: (i) −x, −y+1, −z. |
Table 2
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4B···O2ii | 0.85 (1) | 1.94 (1) | 2.782 (3) | 172 (3) |
| O4—H4A···N3iii | 0.84 (1) | 2.11 (1) | 2.940 (3) | 169 (3) |
| O3—H3B···O1ii | 0.85 (1) | 1.88 (1) | 2.712 (3) | 169 (3) |
| O3—H3A···O1iv | 0.85 (1) | 1.88 (1) | 2.719 (2) | 171 (3) |
| O5—H5B···O1v | 0.84 (1) | 1.92 (1) | 2.740 (3) | 163 (3) |
| O5—H5A···N4vi | 0.84 (1) | 1.96 (1) | 2.800 (3) | 177 (3) |
| Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x, −y+3/2, z−1/2; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, −y+1, −z+1; (vi) −x, y−1/2, −z+1/2. |
The authors acknowledge financial support from Zhejiang Provincial Natural
Science Foundation of China (Y4080093 and Y407189).
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
Li, J.-T., Tao, J., Huang, R.-B. & Zhang, L.-S. (2005). Acta Cryst. E61, m984–m985.
Rigaku (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sun, Z.-H., Meng, L.-B. & Lin, H. (2009). Acta Cryst. E65, m280.
![[Figure 1]](./ng2558fig1thm.gif)
![[Figure 2]](./ng2558fig2thm.gif)
Metal complexes based on tetrazol ligands have attracted great interests (Li et al. 2005; Sun et al. 2009). In the contribution, we report the title binuclear complex (I) based on tetrazol ligand obtained by in situ ligand synthesis.
In the structure of (I), 3-carboxylatopyridyl-6-tetrazolato ligand chelates ZnII center through one pyridyl N and one tetrazolato N and another bridging tetrazolato N atom results in a centrosymmetrical binuclear unit. Three coordinated water molecules complete the distorted octahedral geometry of ZnII center (Fig.1). There exist various hydrogen-bonding interactions between coordinated water molecules and tetrazol N, carboxylate group of the ligand (Table. 2). The hydrogen bonds connect binuclear complex into a three-dimensional structure (Fig.2).