Bis(nitrilo­triacetamide-κ4N,O,O′,O′′)silver(I) nitrate

Ren, M.; Yue, M.; Ran, J.

doi:10.1107/S2414314618001013

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 1| January 2018| x180101

https://doi.org/10.1107/S2414314618001013

Open

access

Bis(nitrilotriacetamide-κ⁴N,O,O′,O′′)silver(I) nitrate

Min Ren,^a Ming Yue ^a and Jingwen Ran ^a ^*

^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

Edited by M. Weil, Vienna University of Technology, Austria (Received 1 December 2017; accepted 17 January 2018; online 22 January 2018)

In the centrosymmetric cation of the title compound, [Ag(C₆H₁₂N₄O₃)₂]NO₃, the Ag^I 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 Ag^I 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 crystal structure of a new mononuclear silver(I) compound, [Ag(C₆H₁₂N₄O₃)₂]⁺·NO₃⁻.

The Ag^I atom of the cation (Fig. 1) is located on a site with point group symmetry $[\overline{3}]$ . (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 $[\overline{3}]$ axis and is not involved in coordination to the silver cation.

Figure 1
The molecular entities in the complex title salt. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (1) −x, −y, −z; (2) −y, x − y, z; (3) y, −x + y, −z; (4) x − y, x, −z; (5) −x + y, −x, z.]

In the crystal structure, 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. 2, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O1ⁱ	0.86	2.15	2.969 (2)	159
N2—H2A⋯O2ⁱⁱ	0.86	2.42	3.256 (4)	163
N2—H2A⋯O2ⁱⁱⁱ	0.86	2.22	2.880 (4)	133
N2—H2A⋯O1^iv	0.86	2.59	3.058 (2)	115
Symmetry codes: (i) $[-x+y+{\script{2\over 3}}, -x+{\script{1\over 3}}, z+{\script{1\over 3}}]$ ; (ii) $[y+{\script{1\over 3}}, -x+y+{\script{2\over 3}}, -z+{\script{2\over 3}}]$ ; (iii) $[x-{\script{2\over 3}}, y-{\script{1\over 3}}, z-{\script{1\over 3}}]$ ; (iv) $[y+{\script{2\over 3}}, -x+y+{\script{1\over 3}}, -z+{\script{1\over 3}}]$ .

Figure 2
The packing diagram for the title compound, viewed along the c axis, with hydrogen bonds drawn as dashed lines.

Synthesis 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 refinement details are summarized in Table 2. The N atom of the nitrate group is located on a position with point group symmetry $[\overline{3}]$ . (Wyckoff position 1b). Hence the unique O atom of the nitrate group is equally disordered around the $[\overline{3}]$ axis and was treated with half-occupancy.

Table 2
Experimental details

Crystal data
Chemical formula	[Ag(C₆H₁₂N₄O₃)₂]NO₃
M_r	546.27
Crystal system, space group	Trigonal, R $[\overline{3}]$
Temperature (K)	291
a, c (Å)	11.6518 (16), 12.590 (3)
V (Å³)	1480.3 (5)
Z	3
Radiation type	Mo Kα
μ (mm⁻¹)	1.09
Crystal size (mm)	0.30 × 0.26 × 0.24

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005 )
T_min, T_max	0.736, 0.780
No. of measured, independent and observed [I > 2σ(I)] reflections	4800, 761, 748
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.059, 1.12
No. of reflections	761
No. of parameters	48
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.31
Computer programs: APEX2 and SAINT (Bruker, 2005), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1817527

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618001013/wm4063sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618001013/wm4063Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: 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).

Bis(nitrilotriacetamide-κ⁴N,O,O',O'')silver(I) nitrate top

Crystal data top

[Ag(C₆H₁₂N₄O₃)₂]NO₃	D_x = 1.838 Mg m⁻³ D_m = 1.838 Mg m⁻³ D_m measured by not measured
M_r = 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

Data collection top

Bruker APEXII CCD diffractometer	748 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
φ and ω scans	θ_max = 27.5°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −15→15
T_min = 0.736, T_max = 0.780	k = −15→14
4800 measured reflections	l = −16→15
761 independent 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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.059	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0383P)² + 1.4406P] where P = (F_o² + 2F_c²)/3
761 reflections	(Δ/σ)_max < 0.001
48 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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

Geometric parameters (Å, º) top

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—O1^iv	2.7774 (14)	N3—O2^vi	1.247 (3)
Ag1—O1	2.7774 (14)	N3—O2^vii	1.247 (3)
Ag1—O1^v	2.7774 (14)	N3—O2^viii	1.247 (3)
O1—C2	1.229 (2)	N3—O2^ix	1.247 (3)
N1—C1^v	1.4737 (17)	N3—O2^x	1.247 (3)
N1—C1	1.4737 (17)	N3—O2	1.247 (3)
N1—C1ⁱⁱ	1.4738 (17)	O2—O2^viii	1.248 (3)
N2—C2	1.330 (2)	O2—O2^vi	1.248 (3)

N1—Ag1—N1ⁱ	180.0	O2^vi—N3—O2^vii	180.0
C1^v—N1—C1	109.31 (11)	O2^vi—N3—O2^viii	119.947 (12)
C1^v—N1—C1ⁱⁱ	109.30 (11)	O2^vii—N3—O2^viii	60.053 (12)
C1—N1—C1ⁱⁱ	109.31 (11)	O2^vi—N3—O2^ix	60.053 (12)
C1^v—N1—Ag1	109.64 (10)	O2^vii—N3—O2^ix	119.947 (12)
C1—N1—Ag1	109.64 (10)	O2^viii—N3—O2^ix	180.0 (3)
C1ⁱⁱ—N1—Ag1	109.64 (10)	O2^vi—N3—O2^x	119.947 (13)
C2—N2—H2A	120.4	O2^vii—N3—O2^x	60.053 (12)
C2—N2—H2B	119.6	O2^viii—N3—O2^x	119.947 (12)
H2A—N2—H2B	120.0	O2^ix—N3—O2^x	60.053 (12)
N1—C1—C2	112.41 (13)	O2^vi—N3—O2	60.054 (12)
N1—C1—H1A	109.1	O2^vii—N3—O2	119.946 (12)
C2—C1—H1A	109.1	O2^viii—N3—O2	60.052 (12)
N1—C1—H1B	109.1	O2^ix—N3—O2	119.948 (13)
C2—C1—H1B	109.1	O2^x—N3—O2	180.0 (2)
H1A—C1—H1B	107.9	N3—O2—O2^viii	59.974 (6)
O1—C2—N2	123.50 (16)	N3—O2—O2^vi	59.973 (6)
O1—C2—C1	122.03 (14)	O2^viii—O2—O2^vi	119.79 (5)
N2—C2—C1	114.46 (15)

C1^v—N1—C1—C2	68.5 (2)	O2^vii—N3—O2—O2^viii	−4.6 (5)
C1ⁱⁱ—N1—C1—C2	−171.88 (13)	O2^ix—N3—O2—O2^viii	180.0
Ag1—N1—C1—C2	−51.68 (13)	O2^vii—N3—O2—O2^vi	180.0
N1—C1—C2—O1	27.5 (2)	O2^viii—N3—O2—O2^vi	−175.4 (5)
N1—C1—C2—N2	−153.92 (16)	O2^ix—N3—O2—O2^vi	4.6 (5)
O2^vi—N3—O2—O2^viii	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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1^xi	0.86	2.15	2.969 (2)	159
N2—H2A···O2^xii	0.86	2.42	3.256 (4)	163
N2—H2A···O2^xiii	0.86	2.22	2.880 (4)	133
N2—H2A···O1^xiv	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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.