metal-organic compounds
Bis(nitrilotriacetamide-κ4N,O,O′,O′′)silver(I) nitrate
aCollege of Chemistry and Chemical Engineering, Huanggang Normal University, Huanggang 438000, People's Republic of China, Hubei Key Laboratory for Processing and Application of Catalytic Materials
*Correspondence e-mail: ranjw@126.com
In the centrosymmetric cation of the title compound, [Ag(C6H12N4O3)2]NO3, the AgI ion, lying on a threefold rotoinversion axis, is coordinated by two N atoms and six O atoms from two nitrilotriacetamide ligands, forming a distorted dodecahedral environment. In the crystal, cations and anions are linked through N—H⋯O hydrogen-bonding interactions, leading to a three-dimensional network structure.
Keywords: crystal structure; silver; nitrate ligand; disorder.
CCDC reference: 1817527
Structure description
Nitrilotriacetamide (NTA) as a ligand is able to coordinate through various coordination sites. Synthetic aspects of the coordination chemistry of transition metals with nitrilotriacetamide ligands were given in detail some time ago (Smith et al., 1992, 1995). A silver complex of the derivative nitrilotris(N-benzylacetamide) as a ligand was reported by Kang et al. (2007) where the AgI ion is coordinated by the tetradentate ligand and by a bidentate nitrate anion. The resulting coordination environment is distorted octahedral. As an extension of the structural characterization of silver compounds with mixed ligands derived from NTA and nitrate, we report here on the synthesis and of a new mononuclear silver(I) compound, [Ag(C6H12N4O3)2]+·NO3−.
The AgI atom of the cation (Fig. 1) is located on a site with symmetry . (Wyckoff position 1a) and is linearly coordinated by the central N atoms of two symmetry-related NTA ligands at distances of 2.417 (2) Å. In comparison with a true twofold coordination by N atoms (Ag—N ≃ 2.15 Å), the Ag—N bonds are elongated. The overall coordination sphere is supplemented by six symmetry-related O atoms from the two NTA ligands [Ag—O = 2.7774 (14) Å], leading to a distorted dodecahedral coordination environment. The nitrate anion is disordered around a axis and is not involved in coordination to the silver cation.
N—H⋯O hydrogen-bonding interactions (including a trifurcated hydrogen bond) between the amino functions as donor groups and the weakly bound amide O atoms and nitrate O atoms as acceptor groups consolidate the molecular packing within the three-dimensional network structure (Fig. 2Synthesis and crystallization
The NTA ligand was prepared according to a literature method (Smith et al., 1995). The title compound was synthesized by adding an aqueous solution of AgNO3 (340 mg, 2 mmol) to a solution of the ligand (752 mg, 4 mmol) in water (20 ml). The mixture was stirred for 30 min at room temperature. The solution was then filtered and the filtrate was allowed to stand in air for one week. Colourless crystals were formed at the bottom of the vessel on slow evaporation of the solvent at room temperature (yield: 41.5%). Selected IR data (cm−1): 3416 (vs), 1677 (vs), 1358 (m), 605 (m), 1617 (w), 1264 (w).
Refinement
Crystal data, data collection and structure . The N atom of the nitrate group is located on a position with symmetry . (Wyckoff position 1b). Hence the unique O atom of the nitrate group is equally disordered around the axis and was treated with half-occupancy.
details are summarized in Table 2Structural data
CCDC reference: 1817527
https://doi.org/10.1107/S2414314618001013/wm4063sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618001013/wm4063Isup2.hkl
Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).[Ag(C6H12N4O3)2]NO3 | Dx = 1.838 Mg m−3 Dm = 1.838 Mg m−3 Dm measured by not measured |
Mr = 546.27 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 761 reflections |
a = 11.6518 (16) Å | θ = 1.0–27.5° |
c = 12.590 (3) Å | µ = 1.09 mm−1 |
V = 1480.3 (5) Å3 | T = 291 K |
Z = 3 | Cuboid, colorless |
F(000) = 834 | 0.30 × 0.26 × 0.24 mm |
Bruker APEXII CCD diffractometer | 748 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
φ and ω scans | θmax = 27.5°, θmin = 3.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −15→15 |
Tmin = 0.736, Tmax = 0.780 | k = −15→14 |
4800 measured reflections | l = −16→15 |
761 independent reflections |
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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0383P)2 + 1.4406P] where P = (Fo2 + 2Fc2)/3 |
761 reflections | (Δ/σ)max < 0.001 |
48 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ag1 | 0.0000 | 0.0000 | 0.0000 | 0.03254 (13) | |
O1 | 0.17358 (13) | −0.06869 (14) | 0.09278 (10) | 0.0376 (3) | |
N1 | 0.0000 | 0.0000 | 0.19194 (18) | 0.0229 (4) | |
N2 | 0.29870 (16) | −0.01709 (18) | 0.24078 (15) | 0.0418 (4) | |
H2A | 0.3432 | −0.0526 | 0.2178 | 0.050* | |
H2B | 0.3155 | 0.0195 | 0.3024 | 0.050* | |
C1 | 0.13626 (15) | 0.05180 (16) | 0.23128 (13) | 0.0279 (3) | |
H1A | 0.1341 | 0.0411 | 0.3078 | 0.033* | |
H1B | 0.1879 | 0.1458 | 0.2158 | 0.033* | |
C2 | 0.20369 (15) | −0.01821 (15) | 0.18150 (13) | 0.0269 (3) | |
N3 | 1.0000 | 0.0000 | 0.5000 | 0.0288 (7) | |
O2 | 0.9536 (3) | 0.0759 (3) | 0.5023 (2) | 0.0452 (6)* | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.04075 (16) | 0.04075 (16) | 0.01610 (17) | 0.02038 (8) | 0.000 | 0.000 |
O1 | 0.0383 (6) | 0.0522 (8) | 0.0289 (6) | 0.0275 (6) | −0.0018 (5) | −0.0065 (5) |
N1 | 0.0229 (6) | 0.0229 (6) | 0.0230 (10) | 0.0114 (3) | 0.000 | 0.000 |
N2 | 0.0368 (8) | 0.0525 (9) | 0.0434 (9) | 0.0278 (7) | −0.0116 (7) | −0.0045 (7) |
C1 | 0.0266 (7) | 0.0311 (7) | 0.0252 (7) | 0.0140 (6) | −0.0047 (6) | −0.0037 (6) |
C2 | 0.0226 (7) | 0.0271 (7) | 0.0280 (7) | 0.0102 (6) | 0.0012 (6) | 0.0042 (6) |
N3 | 0.0328 (10) | 0.0328 (10) | 0.0209 (15) | 0.0164 (5) | 0.000 | 0.000 |
Ag1—N1i | 2.417 (2) | N2—H2A | 0.8593 |
Ag1—N1 | 2.417 (2) | N2—H2B | 0.8591 |
Ag1—O1ii | 2.7774 (14) | C1—C2 | 1.522 (2) |
Ag1—O1i | 2.7774 (14) | C1—H1A | 0.9700 |
Ag1—O1iii | 2.7774 (14) | C1—H1B | 0.9700 |
Ag1—O1iv | 2.7774 (14) | N3—O2vi | 1.247 (3) |
Ag1—O1 | 2.7774 (14) | N3—O2vii | 1.247 (3) |
Ag1—O1v | 2.7774 (14) | N3—O2viii | 1.247 (3) |
O1—C2 | 1.229 (2) | N3—O2ix | 1.247 (3) |
N1—C1v | 1.4737 (17) | N3—O2x | 1.247 (3) |
N1—C1 | 1.4737 (17) | N3—O2 | 1.247 (3) |
N1—C1ii | 1.4738 (17) | O2—O2viii | 1.248 (3) |
N2—C2 | 1.330 (2) | O2—O2vi | 1.248 (3) |
N1—Ag1—N1i | 180.0 | O2vi—N3—O2vii | 180.0 |
C1v—N1—C1 | 109.31 (11) | O2vi—N3—O2viii | 119.947 (12) |
C1v—N1—C1ii | 109.30 (11) | O2vii—N3—O2viii | 60.053 (12) |
C1—N1—C1ii | 109.31 (11) | O2vi—N3—O2ix | 60.053 (12) |
C1v—N1—Ag1 | 109.64 (10) | O2vii—N3—O2ix | 119.947 (12) |
C1—N1—Ag1 | 109.64 (10) | O2viii—N3—O2ix | 180.0 (3) |
C1ii—N1—Ag1 | 109.64 (10) | O2vi—N3—O2x | 119.947 (13) |
C2—N2—H2A | 120.4 | O2vii—N3—O2x | 60.053 (12) |
C2—N2—H2B | 119.6 | O2viii—N3—O2x | 119.947 (12) |
H2A—N2—H2B | 120.0 | O2ix—N3—O2x | 60.053 (12) |
N1—C1—C2 | 112.41 (13) | O2vi—N3—O2 | 60.054 (12) |
N1—C1—H1A | 109.1 | O2vii—N3—O2 | 119.946 (12) |
C2—C1—H1A | 109.1 | O2viii—N3—O2 | 60.052 (12) |
N1—C1—H1B | 109.1 | O2ix—N3—O2 | 119.948 (13) |
C2—C1—H1B | 109.1 | O2x—N3—O2 | 180.0 (2) |
H1A—C1—H1B | 107.9 | N3—O2—O2viii | 59.974 (6) |
O1—C2—N2 | 123.50 (16) | N3—O2—O2vi | 59.973 (6) |
O1—C2—C1 | 122.03 (14) | O2viii—O2—O2vi | 119.79 (5) |
N2—C2—C1 | 114.46 (15) | ||
C1v—N1—C1—C2 | 68.5 (2) | O2vii—N3—O2—O2viii | −4.6 (5) |
C1ii—N1—C1—C2 | −171.88 (13) | O2ix—N3—O2—O2viii | 180.0 |
Ag1—N1—C1—C2 | −51.68 (13) | O2vii—N3—O2—O2vi | 180.0 |
N1—C1—C2—O1 | 27.5 (2) | O2viii—N3—O2—O2vi | −175.4 (5) |
N1—C1—C2—N2 | −153.92 (16) | O2ix—N3—O2—O2vi | 4.6 (5) |
O2vi—N3—O2—O2viii | 175.4 (5) |
Symmetry codes: (i) −x, −y, −z; (ii) −y, x−y, z; (iii) y, −x+y, −z; (iv) x−y, x, −z; (v) −x+y, −x, z; (vi) y+1, −x+y+1, −z+1; (vii) −y+1, x−y−1, z; (viii) x−y, x−1, −z+1; (ix) −x+y+2, −x+1, z; (x) −x+2, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O1xi | 0.86 | 2.15 | 2.969 (2) | 159 |
N2—H2A···O2xii | 0.86 | 2.42 | 3.256 (4) | 163 |
N2—H2A···O2xiii | 0.86 | 2.22 | 2.880 (4) | 133 |
N2—H2A···O1xiv | 0.86 | 2.59 | 3.058 (2) | 115 |
Symmetry codes: (xi) −x+y+2/3, −x+1/3, z+1/3; (xii) y+1/3, −x+y+2/3, −z+2/3; (xiii) x−2/3, y−1/3, z−1/3; (xiv) y+2/3, −x+y+1/3, −z+1/3. |
Funding information
This research was supported by the Natural Science Foundation of Hubei Provincial Department of Education 77 (D20152901).
References
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kang, D., Park, K.-M., Lee, S. Y., Lee, S. S. & Choi, K. S. (2007). Bull. Korean Chem. Soc. 28, 2546–2548. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Smith, D. A., Sucheck, S. & Pinkerton, A. A. (1992). J. Chem. Soc. Chem. Commun. pp. 367–368. CSD CrossRef CAS Google Scholar
Smith, D. A., Sucheck, S., Cramer, S. & Baker, D. (1995). Synth. Commun. 25, 4123–4132. CrossRef CAS Web of Science Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
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