supplementary materials
(Nitrato-![[kappa]](/logos/entities/kappa_rmgif.gif)
2O,O')bis[(E)-N-(pyridin-4-ylmethylidene-N)hydroxyamine]silver(I)
In the mononuclear title compound, [Ag(NO3)(C6H6N2O)2], the AgI atom is located on a twofold rotation axis and the nitrate-chelated AgI atom is further coordinated by two aromatic N atoms of hydroxylamine ligands in a distorted tetrahedral geometry. In the crystal, the nitrate ion has 2 symmetry with the N atom and one O atom located on the twofold rotation axis, and is linked to hydroxy groups of the hydroxylamine ligands by O-H
O hydrogen bonds, generating a chain running along the b axis.
Isonicotinaldehyde oxime was synthesized from the reaction of isonicotinaldehyde
and hydroxylamine. Silver nitrate (1 mmol) dissolved in water (5 ml) was added
to picolinaldehyde oxime (1 mmol) dissolved in ethanol (5 ml). The solution
was filtered and set aside, away from light, for the growth of colorless
crystals.
Carbon- and oxygen-bound H-atoms were placed in calculated positions (C–H 0.93 Å, O–H 0.84 Å) and were included in the refinement in the riding model
approximation, with U(H) set to 1.2–1.5U(C,O).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); 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: publCIF (Westrip, 2010).
(Nitrato-
κ2O,
O')bis[(
E)-
N-(pyridin-4-
ylmethylidene-
κN)hydroxyamine]silver(I)
top
Crystal data top
| [Ag(NO3)(C6H6N2O)2] | F(000) = 824 |
| Mr = 414.14 | Dx = 1.838 Mg m−3 |
| Orthorhombic, Pccn | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ab 2ac | Cell parameters from 4605 reflections |
| a = 18.027 (3) Å | θ = 3.2–27.5° |
| b = 4.6907 (6) Å | µ = 1.38 mm−1 |
| c = 17.7020 (19) Å | T = 293 K |
| V = 1496.9 (3) Å3 | Prism, colorless |
| Z = 4 | 0.20 × 0.12 × 0.12 mm |
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer | 1705 independent reflections |
| Radiation source: fine-focus sealed tube | 1038 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.082 |
| ω scan | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995) | h = −23→23 |
| Tmin = 0.770, Tmax = 0.852 | k = −5→6 |
| 13223 measured reflections | l = −21→22 |
Refinement top
| 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)] = 0.050 | H-atom parameters constrained |
| wR(F2) = 0.162 | w = 1/[σ2(Fo2) + (0.073P)2 + 1.2436P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.13 | (Δ/σ)max = 0.001 |
| 1705 reflections | Δρmax = 0.92 e Å−3 |
| 108 parameters | Δρmin = −0.67 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0096 (16) |
Crystal data top
| [Ag(NO3)(C6H6N2O)2] | V = 1496.9 (3) Å3 |
| Mr = 414.14 | Z = 4 |
| Orthorhombic, Pccn | Mo Kα radiation |
| a = 18.027 (3) Å | µ = 1.38 mm−1 |
| b = 4.6907 (6) Å | T = 293 K |
| c = 17.7020 (19) Å | 0.20 × 0.12 × 0.12 mm |
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer | 1705 independent reflections |
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995) | 1038 reflections with I > 2σ(I) |
| Tmin = 0.770, Tmax = 0.852 | Rint = 0.082 |
| 13223 measured reflections | θmax = 27.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
| wR(F2) = 0.162 | Δρmax = 0.92 e Å−3 |
| S = 1.13 | Δρmin = −0.67 e Å−3 |
| 1705 reflections | Absolute structure: ? |
| 108 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| Ag1 | 0.2500 | 0.2500 | 0.18639 (3) | 0.0532 (4) | |
| O1 | 0.5757 (2) | 1.5200 (8) | 0.0886 (2) | 0.0584 (11) | |
| H1 | 0.6143 | 1.5575 | 0.1132 | 0.088* | |
| O2 | 0.3058 (3) | 0.1732 (13) | 0.3234 (2) | 0.0789 (15) | |
| O3 | 0.2500 | 0.2500 | 0.4306 (3) | 0.093 (3) | |
| N1 | 0.3325 (2) | 0.5683 (9) | 0.1548 (2) | 0.0454 (11) | |
| N2 | 0.5350 (3) | 1.3109 (9) | 0.1264 (2) | 0.0487 (11) | |
| N3 | 0.2500 | 0.2500 | 0.3606 (4) | 0.067 (2) | |
| C1 | 0.3371 (3) | 0.6602 (14) | 0.0824 (3) | 0.0487 (13) | |
| H1A | 0.3067 | 0.5752 | 0.0464 | 0.058* | |
| C2 | 0.3841 (3) | 0.8714 (12) | 0.0598 (2) | 0.0426 (12) | |
| H2 | 0.3840 | 0.9318 | 0.0098 | 0.051* | |
| C3 | 0.4321 (2) | 0.9961 (10) | 0.1113 (3) | 0.0397 (11) | |
| C4 | 0.4286 (3) | 0.9016 (12) | 0.1858 (3) | 0.0466 (13) | |
| H4 | 0.4601 | 0.9782 | 0.2222 | 0.056* | |
| C5 | 0.3783 (3) | 0.6940 (12) | 0.2050 (3) | 0.0454 (13) | |
| H5 | 0.3756 | 0.6371 | 0.2552 | 0.055* | |
| C6 | 0.4830 (3) | 1.2177 (11) | 0.0848 (3) | 0.0459 (13) | |
| H6 | 0.4771 | 1.2919 | 0.0365 | 0.055* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Ag1 | 0.0461 (5) | 0.0541 (5) | 0.0594 (5) | −0.0093 (3) | 0.000 | 0.000 |
| O1 | 0.051 (2) | 0.064 (3) | 0.060 (2) | −0.022 (2) | −0.0052 (18) | 0.007 (2) |
| O2 | 0.054 (3) | 0.124 (4) | 0.059 (3) | 0.037 (3) | 0.006 (2) | 0.002 (2) |
| O3 | 0.084 (6) | 0.155 (10) | 0.040 (3) | 0.050 (5) | 0.000 | 0.000 |
| N1 | 0.038 (2) | 0.047 (3) | 0.051 (2) | −0.007 (2) | 0.0030 (19) | −0.003 (2) |
| N2 | 0.049 (3) | 0.050 (3) | 0.046 (2) | −0.009 (2) | 0.003 (2) | 0.0004 (19) |
| N3 | 0.057 (5) | 0.084 (6) | 0.061 (5) | 0.020 (4) | 0.000 | 0.000 |
| C1 | 0.040 (3) | 0.061 (3) | 0.045 (3) | 0.002 (3) | −0.002 (2) | −0.005 (3) |
| C2 | 0.039 (3) | 0.050 (3) | 0.039 (3) | 0.000 (3) | 0.000 (2) | 0.003 (2) |
| C3 | 0.034 (2) | 0.040 (3) | 0.045 (3) | 0.002 (2) | 0.003 (2) | 0.001 (2) |
| C4 | 0.047 (3) | 0.045 (3) | 0.047 (3) | −0.004 (3) | −0.004 (2) | 0.000 (2) |
| C5 | 0.043 (3) | 0.053 (3) | 0.041 (3) | −0.009 (2) | −0.001 (2) | −0.002 (2) |
| C6 | 0.046 (3) | 0.051 (3) | 0.041 (2) | 0.002 (2) | −0.005 (2) | 0.000 (2) |
Geometric parameters (Å, º) top
| Ag1—N1i | 2.180 (4) | N3—O2i | 1.256 (6) |
| Ag1—N1 | 2.180 (4) | C1—C2 | 1.364 (9) |
| Ag1—O2 | 2.651 (4) | C1—H1A | 0.9300 |
| Ag1—O2i | 2.651 (4) | C2—C3 | 1.386 (7) |
| O1—N2 | 1.396 (5) | C2—H2 | 0.9300 |
| O1—H1 | 0.8400 | C3—C4 | 1.393 (6) |
| O2—N3 | 1.256 (6) | C3—C6 | 1.463 (7) |
| O3—N3 | 1.239 (9) | C4—C5 | 1.374 (8) |
| N1—C5 | 1.349 (6) | C4—H4 | 0.9300 |
| N1—C1 | 1.354 (6) | C5—H5 | 0.9300 |
| N2—C6 | 1.270 (7) | C6—H6 | 0.9300 |
| | | |
| N1i—Ag1—N1 | 150.3 (2) | C2—C1—H1A | 118.4 |
| N1i—Ag1—O2 | 113.62 (18) | C1—C2—C3 | 120.1 (4) |
| N1—Ag1—O2 | 93.94 (18) | C1—C2—H2 | 119.9 |
| N1i—Ag1—O2i | 93.94 (18) | C3—C2—H2 | 119.9 |
| N1—Ag1—O2i | 113.62 (18) | C2—C3—C4 | 117.4 (4) |
| O2—Ag1—O2i | 47.57 (19) | C2—C3—C6 | 118.7 (4) |
| N2—O1—H1 | 109.5 | C4—C3—C6 | 123.9 (4) |
| N3—O2—Ag1 | 97.9 (4) | C5—C4—C3 | 119.3 (5) |
| C5—N1—C1 | 116.5 (5) | C5—C4—H4 | 120.3 |
| C5—N1—Ag1 | 123.2 (3) | C3—C4—H4 | 120.3 |
| C1—N1—Ag1 | 120.2 (3) | N1—C5—C4 | 123.5 (5) |
| C6—N2—O1 | 110.6 (4) | N1—C5—H5 | 118.3 |
| O3—N3—O2i | 121.6 (4) | C4—C5—H5 | 118.3 |
| O3—N3—O2 | 121.6 (4) | N2—C6—C3 | 121.4 (5) |
| O2i—N3—O2 | 116.7 (7) | N2—C6—H6 | 119.3 |
| N1—C1—C2 | 123.2 (5) | C3—C6—H6 | 119.3 |
| N1—C1—H1A | 118.4 | | |
| | | |
| N1i—Ag1—O2—N3 | −72.7 (4) | Ag1—N1—C1—C2 | 175.7 (4) |
| N1—Ag1—O2—N3 | 118.8 (3) | N1—C1—C2—C3 | 2.3 (9) |
| O2i—Ag1—O2—N3 | 0.000 (1) | C1—C2—C3—C4 | −1.5 (8) |
| N1i—Ag1—N1—C5 | −171.4 (4) | C1—C2—C3—C6 | 178.7 (5) |
| O2—Ag1—N1—C5 | −12.8 (4) | C2—C3—C4—C5 | −0.5 (8) |
| O2i—Ag1—N1—C5 | 32.1 (5) | C6—C3—C4—C5 | 179.4 (5) |
| N1i—Ag1—N1—C1 | 12.1 (4) | C1—N1—C5—C4 | −1.1 (8) |
| O2—Ag1—N1—C1 | 170.6 (4) | Ag1—N1—C5—C4 | −177.7 (4) |
| O2i—Ag1—N1—C1 | −144.4 (4) | C3—C4—C5—N1 | 1.8 (9) |
| Ag1—O2—N3—O3 | 180.0 | O1—N2—C6—C3 | 179.9 (4) |
| Ag1—O2—N3—O2i | 0.000 (1) | C2—C3—C6—N2 | −170.0 (5) |
| C5—N1—C1—C2 | −1.0 (8) | C4—C3—C6—N2 | 10.2 (8) |
| Symmetry code: (i) −x+1/2, −y+1/2, z. |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O2ii | 0.84 | 1.90 | 2.740 (6) | 173 |
| Symmetry code: (ii) −x+1, y+3/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O2i | 0.84 | 1.90 | 2.740 (6) | 172.8 |
| Symmetry code: (i) −x+1, y+3/2, −z+1/2. |
We thank the Key Project of the Natural Science Foundation of Heilongjiang
Province (No. ZD200903), the Key Project of the Education Bureau of
Heilongjiang Province (Nos. 12511z023 and 2011CJHB006), the Innovation Team
of Education Bureau of Heilongjiang Province (No. 2010 t d03),
Heilongjiang
University (Hdtd2010–04) and the Ministry of Higher Education of Malaysia
(grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.
Abu-Youssef, M. A., Soliman, S. V., Langer, V., Gohar, Y. M., Hasanen, A. A., Makhyoun, M. A., Zaky, A. H. & Öhrström, L. R. (2010). Inorg. Chem. 49, 9788–9797.
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
![[Figure 1]](./xu5647fig1thm.gif)
![[Figure 2]](./xu5647fig2thm.gif)
Picolinylaldehyde oxime reacts with silver nitrate to yield a monomeric adduct in which the metal atom is N,N'-chelated by the ligand. The nitrate ion is also involved in coordination (Abu-Youssef et al., 2010). The corresponding reaction with isonicotinylaldehyde in place of picolinylaldehyde yields a bis adduct (Scheme I). The nitrate-chelated AgI atom in mononuclear Ag(NO3)(C6H6N2O)2 is coordinated to the hydroxylamine through its aromatic N atom, and it exists in an approximate tetrahedral geometry (Fig. 1). The hydroxyl OH group forms a hydrogen bond with a nitrate O atom to generate a chain running along the longest axis of the orthorhombic unit cell (Table 1).