supplementary materials
Diaquabis[5-(5-carboxy-2-pyridyl)tetrazolato-![[kappa]](/logos/entities/kappa_rmgif.gif)
2N1,N5]cadmium(II) dihydrate
A mixture of Cd(NO3)2.4H2O (77 mg, 0.25 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 = 0.87 (3) 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).
Diaquabis[5-(5-carboxy-2-pyridyl)tetrazolato-
κ2N1,
N5]cadmium(II) dihydrate
top
Crystal data top
| [Cd(C7H4N5O2)2(H2O)2]·2H2O | Z = 1 |
| Mr = 564.77 | F(000) = 282 |
| Triclinic, P1 | Dx = 1.855 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.1018 (2) Å | Cell parameters from 612 reflections |
| b = 7.3805 (1) Å | θ = 3.0–27.5° |
| c = 12.383 (2) Å | µ = 1.15 mm−1 |
| α = 84.17 (3)° | T = 293 K |
| β = 88.91 (3)° | Prism, colorless |
| γ = 65.71 (2)° | 0.20 × 0.20 × 0.20 mm |
| V = 505.51 (8) Å3 | |
Data collection top
Rigaku Mercury CCD
diffractometer | 2286 independent reflections |
| Radiation source: fine-focus sealed tube | 2104 reflections with I > 2σ(I) |
| graphite | Rint = 0.027 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.4°, θmin = 3.0° |
| CCD_Profile_fitting scans | h = −7→7 |
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000) | k = −7→9 |
| Tmin = 0.773, Tmax = 1.000 | l = −15→15 |
| 3817 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.10 | w = 1/[σ2(Fo2) + (0.0287P)2 + 0.1909P]
where P = (Fo2 + 2Fc2)/3 |
| 2286 reflections | (Δ/σ)max = 0.001 |
| 171 parameters | Δρmax = 0.39 e Å−3 |
| 5 restraints | Δρmin = −0.70 e Å−3 |
Crystal data top
| [Cd(C7H4N5O2)2(H2O)2]·2H2O | γ = 65.71 (2)° |
| Mr = 564.77 | V = 505.51 (8) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 6.1018 (2) Å | Mo Kα radiation |
| b = 7.3805 (1) Å | µ = 1.15 mm−1 |
| c = 12.383 (2) Å | T = 293 K |
| α = 84.17 (3)° | 0.20 × 0.20 × 0.20 mm |
| β = 88.91 (3)° | |
Data collection top
Rigaku Mercury CCD
diffractometer | 2286 independent reflections |
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000) | 2104 reflections with I > 2σ(I) |
| Tmin = 0.773, Tmax = 1.000 | Rint = 0.027 |
| 3817 measured reflections | θmax = 27.4° |
Refinement top
| R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.078 | Δρmax = 0.39 e Å−3 |
| S = 1.10 | Δρmin = −0.70 e Å−3 |
| 2286 reflections | Absolute structure: ? |
| 171 parameters | Flack parameter: ? |
| 5 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 | |
| Cd1 | 0.5000 | 0.0000 | 0.5000 | 0.03880 (13) | |
| O1 | −0.1058 (5) | −0.1234 (4) | 0.1759 (2) | 0.0614 (8) | |
| N1 | 0.3050 (5) | 0.1080 (4) | 0.32445 (19) | 0.0328 (6) | |
| C1 | −0.1196 (6) | 0.0465 (5) | 0.1283 (3) | 0.0401 (7) | |
| H1 | −0.217 (7) | −0.160 (7) | 0.152 (4) | 0.098 (17)* | |
| O2 | −0.2500 (5) | 0.1386 (4) | 0.0504 (2) | 0.0580 (7) | |
| N2 | 0.5549 (5) | 0.4825 (4) | 0.2873 (2) | 0.0404 (6) | |
| C2 | 0.0443 (6) | 0.1228 (4) | 0.1777 (2) | 0.0338 (7) | |
| O3 | 0.1539 (5) | 0.2229 (4) | 0.5726 (2) | 0.0512 (6) | |
| N3 | 0.7080 (5) | 0.4857 (4) | 0.3617 (2) | 0.0461 (7) | |
| C3 | 0.0743 (6) | 0.2851 (5) | 0.1257 (3) | 0.0425 (8) | |
| H3 | −0.0060 | 0.3468 | 0.0581 | 0.051* | |
| H3A | 0.195 (6) | 0.321 (4) | 0.587 (2) | 0.031 (8)* | |
| H3B | 0.015 (5) | 0.273 (5) | 0.540 (3) | 0.052 (11)* | |
| O4 | 0.6141 (5) | 0.7305 (4) | 0.1064 (2) | 0.0579 (7) | |
| N4 | 0.7355 (5) | 0.3463 (4) | 0.4431 (2) | 0.0450 (7) | |
| C4 | 0.2210 (6) | 0.3572 (5) | 0.1722 (3) | 0.0424 (8) | |
| H4 | 0.2453 | 0.4676 | 0.1367 | 0.051* | |
| H4A | 0.492 (6) | 0.781 (6) | 0.063 (3) | 0.062 (12)* | |
| H4B | 0.571 (7) | 0.666 (6) | 0.157 (3) | 0.068 (13)* | |
| N5 | 0.6029 (5) | 0.2491 (4) | 0.4230 (2) | 0.0354 (6) | |
| C5 | 0.1627 (6) | 0.0381 (5) | 0.2777 (2) | 0.0366 (7) | |
| H5 | 0.1418 | −0.0732 | 0.3141 | 0.044* | |
| C6 | 0.3338 (5) | 0.2658 (4) | 0.2722 (2) | 0.0326 (6) | |
| C7 | 0.4943 (6) | 0.3343 (4) | 0.3263 (2) | 0.0340 (7) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cd1 | 0.0443 (2) | 0.0424 (2) | 0.03052 (19) | −0.02092 (16) | −0.00857 (14) | 0.00836 (13) |
| O1 | 0.075 (2) | 0.0752 (19) | 0.0503 (16) | −0.0506 (17) | −0.0210 (14) | 0.0103 (13) |
| N1 | 0.0369 (15) | 0.0352 (13) | 0.0274 (13) | −0.0169 (12) | 0.0003 (10) | 0.0014 (10) |
| C1 | 0.0366 (19) | 0.054 (2) | 0.0307 (16) | −0.0186 (16) | 0.0024 (13) | −0.0080 (14) |
| O2 | 0.0524 (17) | 0.0714 (17) | 0.0467 (15) | −0.0237 (14) | −0.0215 (12) | 0.0051 (12) |
| N2 | 0.0446 (17) | 0.0393 (15) | 0.0422 (16) | −0.0237 (13) | −0.0003 (12) | 0.0031 (11) |
| C2 | 0.0324 (17) | 0.0403 (16) | 0.0252 (15) | −0.0118 (13) | −0.0002 (12) | −0.0016 (12) |
| O3 | 0.0495 (18) | 0.0497 (15) | 0.0547 (16) | −0.0199 (14) | −0.0028 (13) | −0.0076 (12) |
| N3 | 0.0491 (19) | 0.0470 (16) | 0.0503 (18) | −0.0276 (15) | 0.0015 (14) | −0.0062 (13) |
| C3 | 0.042 (2) | 0.0482 (19) | 0.0329 (17) | −0.0168 (16) | −0.0089 (14) | 0.0099 (14) |
| O4 | 0.0610 (19) | 0.0764 (19) | 0.0474 (16) | −0.0446 (16) | −0.0197 (14) | 0.0201 (14) |
| N4 | 0.0446 (18) | 0.0470 (16) | 0.0478 (17) | −0.0231 (14) | −0.0064 (13) | −0.0032 (13) |
| C4 | 0.046 (2) | 0.0419 (18) | 0.0370 (18) | −0.0190 (16) | −0.0024 (14) | 0.0105 (13) |
| N5 | 0.0352 (15) | 0.0353 (13) | 0.0381 (14) | −0.0178 (12) | −0.0034 (11) | 0.0014 (11) |
| C5 | 0.0393 (19) | 0.0405 (17) | 0.0315 (16) | −0.0194 (15) | −0.0029 (13) | 0.0032 (12) |
| C6 | 0.0321 (17) | 0.0321 (15) | 0.0312 (16) | −0.0114 (13) | 0.0011 (12) | 0.0000 (12) |
| C7 | 0.0345 (17) | 0.0319 (15) | 0.0336 (16) | −0.0128 (13) | 0.0034 (12) | 0.0017 (12) |
Geometric parameters (Å, °) top
| Cd1—N5 | 2.293 (2) | C2—C5 | 1.398 (4) |
| Cd1—N5i | 2.293 (2) | O3—H3A | 0.90 (2) |
| Cd1—O3i | 2.312 (3) | O3—H3B | 0.86 (2) |
| Cd1—O3 | 2.312 (3) | N3—N4 | 1.325 (4) |
| Cd1—N1 | 2.396 (2) | C3—C4 | 1.374 (5) |
| Cd1—N1i | 2.396 (2) | C3—H3 | 0.9500 |
| O1—C1 | 1.301 (4) | O4—H4A | 0.85 (3) |
| O1—H1 | 0.89 (3) | O4—H4B | 0.85 (3) |
| N1—C5 | 1.342 (4) | N4—N5 | 1.324 (4) |
| N1—C6 | 1.348 (4) | C4—C6 | 1.394 (4) |
| C1—O2 | 1.215 (4) | C4—H4 | 0.9500 |
| C1—C2 | 1.499 (4) | N5—C7 | 1.343 (4) |
| N2—N3 | 1.332 (4) | C5—H5 | 0.9500 |
| N2—C7 | 1.336 (4) | C6—C7 | 1.472 (4) |
| C2—C3 | 1.379 (4) | | |
| | | |
| N5—Cd1—N5i | 180.0 | C5—C2—C1 | 121.8 (3) |
| N5—Cd1—O3i | 87.03 (10) | Cd1—O3—H3A | 103 (2) |
| N5i—Cd1—O3i | 92.97 (10) | Cd1—O3—H3B | 124 (3) |
| N5—Cd1—O3 | 92.97 (10) | H3A—O3—H3B | 109 (3) |
| N5i—Cd1—O3 | 87.03 (10) | N4—N3—N2 | 109.7 (3) |
| O3i—Cd1—O3 | 180.0 | C4—C3—C2 | 119.7 (3) |
| N5—Cd1—N1 | 72.97 (9) | C4—C3—H3 | 120.2 |
| N5i—Cd1—N1 | 107.03 (9) | C2—C3—H3 | 120.2 |
| O3i—Cd1—N1 | 91.55 (9) | H4A—O4—H4B | 103 (4) |
| O3—Cd1—N1 | 88.45 (9) | N5—N4—N3 | 109.3 (3) |
| N5—Cd1—N1i | 107.03 (9) | C3—C4—C6 | 119.0 (3) |
| N5i—Cd1—N1i | 72.97 (9) | C3—C4—H4 | 120.5 |
| O3i—Cd1—N1i | 88.45 (9) | C6—C4—H4 | 120.5 |
| O3—Cd1—N1i | 91.55 (9) | N4—N5—C7 | 105.1 (2) |
| N1—Cd1—N1i | 180.00 (5) | N4—N5—Cd1 | 140.8 (2) |
| C1—O1—H1 | 113 (3) | C7—N5—Cd1 | 114.08 (19) |
| C5—N1—C6 | 118.3 (2) | N1—C5—C2 | 122.5 (3) |
| C5—N1—Cd1 | 127.62 (19) | N1—C5—H5 | 118.7 |
| C6—N1—Cd1 | 113.95 (18) | C2—C5—H5 | 118.7 |
| O2—C1—O1 | 124.7 (3) | N1—C6—C4 | 122.1 (3) |
| O2—C1—C2 | 121.4 (3) | N1—C6—C7 | 116.0 (2) |
| O1—C1—C2 | 113.9 (3) | C4—C6—C7 | 121.9 (3) |
| N3—N2—C7 | 104.7 (3) | N2—C7—N5 | 111.3 (3) |
| C3—C2—C5 | 118.4 (3) | N2—C7—C6 | 126.0 (3) |
| C3—C2—C1 | 119.8 (3) | N5—C7—C6 | 122.7 (3) |
| Symmetry codes: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4B···N2 | 0.85 (3) | 2.02 (3) | 2.860 (4) | 166 (4) |
| O4—H4A···O2ii | 0.85 (3) | 1.92 (3) | 2.767 (4) | 170 (4) |
| O1—H1···O4iii | 0.89 (3) | 1.68 (3) | 2.566 (4) | 170 (5) |
| O3—H3B···N4iv | 0.86 (2) | 1.96 (3) | 2.804 (4) | 168 (4) |
| O3—H3A···N3v | 0.90 (2) | 1.92 (2) | 2.806 (4) | 172 (3) |
| Symmetry codes: (ii) −x, −y+1, −z; (iii) x−1, y−1, z; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1. |
Table 1
Selected geometric parameters (Å, °) top| Cd1—N5 | 2.293 (2) | Cd1—O3 | 2.312 (3) |
| Cd1—O3i | 2.312 (3) | Cd1—N1 | 2.396 (2) |
| | | |
| N5—Cd1—N1 | 72.97 (9) | | |
| Symmetry codes: (i) −x+1, −y, −z+1. |
Table 2
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4B···N2 | 0.85 (3) | 2.02 (3) | 2.860 (4) | 166 (4) |
| O4—H4A···O2ii | 0.85 (3) | 1.92 (3) | 2.767 (4) | 170 (4) |
| O1—H1···O4iii | 0.89 (3) | 1.68 (3) | 2.566 (4) | 170 (5) |
| O3—H3B···N4iv | 0.86 (2) | 1.96 (3) | 2.804 (4) | 168 (4) |
| O3—H3A···N3v | 0.90 (2) | 1.92 (2) | 2.806 (4) | 172 (3) |
| Symmetry codes: (ii) −x, −y+1, −z; (iii) x−1, y−1, z; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1. |
The authors acknowledge financial support from the Zhejiang Provincial Natural
Science Foundation of China (grant Nos.Y4080093 and Y407189).
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
Rigaku (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Xiong, R. G., Xue, X., Zhao, H., You, X. Z., Abrahams, B. F. & Xue, Z. (2002). Angew. Chem. Int. Ed. 41, 3800–3803
symmetry) is coordinated by four N atoms from two symmetry-related 3-carboxypyidyl-6-tetrazolato ligands, forming a distorted octahedral complex. The uncoordinated water molecules connect the mononuclear units into a layer structure through O-H
N and O-H![[Figure 1]](./ng2554fig1thm.gif)
![[Figure 2]](./ng2554fig2thm.gif)
Hydrothermal reactions involving in situ ligand synthesis have attracted great interests (Xiong et al., 2002). In the contribution, we report the title mononuclear complex (I) based on tetrazol ligand obtained by in situ ligand synthesis.
In the structure of (I), the ligand chelates Cd(II) center through pyridyl N and tetrazol N to form a centrosymmetrical mononuclear complex. Two coordinated water molecules complete the octahedral geometry of Cd(II) center (Fig.1). Two solvent water molecules and carboxylic groups of the ligands form a synthon R44(12) which connects mononuclear unit into a two-dimensional layer structure through hydrogen bonds between solvent water and tetrazol groups (Table. 2). The hydrogen bonds between coordinated water molecules and tetrazol groups result in a three-dimensional structure (Fig.2).