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In the title metal-organic framework (MOF), {[Ag3(C6H10N3)2]NO3}n, the AgI cation is coordinated by two N atoms from two different 3,5-diethyl-1,2,4-triazolate (detz) ligands in a linear configuration. Each AgI cation is then connected to two adjacent AgI cations via a [mu]3-N1:N2:N4-detrz ligand, resulting in a three-dimensional chiral silver-triazolate structure showing an SrSi2 (srs) net with 103 topology.

Supporting information


Crystallographic Information File (CIF)
Contains datablock I


Structure factor file (CIF format)
Contains datablock I

CCDC reference: 969491

Introduction top

Metal–organic frameworks (MOFs), which consist of metal ions and organic struts connected via coordination bonds, have drawn considerable inter­est during the past decades because of their fascinating architectures as well as their promising applications, relating to their structure such as gas storage and separation, catalysis, sensors, and so on (Kitagawa et al., 2004; Biradha et al., 2011; Sumida et al., 2012; Jiang et al., 2011; Cui et al., 2012). Compared with other artificially synthesized crystalline materials, one of the unique properties of MOFs is the infinite structural possibilities based on the variety of nodes and linkers that can be derived from combining the various inorganic and organic fragments, respectively (Bonneau et al., 2004; Ockwig et al., 2005). A variety of structural networks in MOFs have been observed. Not only well known networks, such as dia, pcu, pts, rho and rlt (O'Keeffe, et al., 2008), but also unprecedented novel frameworks, such as xmz (Zhang et al., 2007), zxc (Chen et al., 2010) and fly (Yang et al. 2013), that are based on carefully designed multidentate ligands have been isolated. Due to the importance of the topologies in the synthesis of functional crystalline materials, more and more inter­est therefore has been paid to the pursuit of novel structures and topologies in the self-assembled systems.

3,5-Disubstituted-1,2,4-triazolates are rigid conjugated ligands with simple coordination geometry, generally showing exodentate µ3-N1:N2:N4-coordi­antion (Zhang et al., 2012). The silver(I) ion is one of the metal ions that shows simple coordination geometries, such as linear, T- or Y-shaped and square-planar or tetra­hedral coordinations for 2-, 3- and 4-coordinated AgI atoms. Although the AgI and 3,5-disubstituted-1,2,4-triazolates are very simple in their coordination geometries, a diverse range of structures based on them have been successfully isolated previously, including dia, CdSO4 and nbo (Zhang et al., 2012; Yang et al., 2009; Ling et al., 2011). It has been shown that alongside the reaction conditions (such as temperature, solvent etc.), the 3,5-disubstituted groups also play a significant role in determining the resulting coordination configuration of the silver–triazolates (Zhang et al., 2012), thus leading to differences in their topologies. However, to the best of our knowledge, chiral structures built of silver ions and achiral triazolates are not known. Herein we report the synthesis and structure of a novel three-dimensional chiral structure built of silver and 3,5-di­ethyl-4H-1,2,4-triazole (Hdetz), the title compound, poly[bis­(µ3-3,5-di­ethyl-1,2,4-triazolato-κ3N1:N2:N4)tris­ilver nitrate], (I), which forms a 3-connected SrSi2 net with 103 topology.

Experimental top

Synthesis and crystallization top

3,5-Di­ethyl-4H-1,2,4-triazole (Hdetz) was prepared according to previously reported methods (Yang et al., 2009). Hdetz (0.0252 g, 0.2 mmol) was dissolved in the aceto­nitrile (5 ml), then the solution was added to the aqueous soultion (5 ml) containing silver nitrate (0.052 g, 0.3 mmol). The mixture was stirred at room temperature for 30 min. Then toluene (1 ml) was added. The mixture was then transferred into a 15 ml Teflon-lined Parr bomb and heated at 433 K for 3 d. The reaction mixture was allowed to cool to room temperature. Needle-like colourless crystals of (I) were obtained by filtration (yield: 45%, based on Hdetz). Analysis calculated (found) for C12H20Ag3N7O3 (%): C 22.74 (22.67), H 3.18 (3.23), N 15.47 (15.53). IR spectrum for (I) (KBr, cm-1): 2960 (m), 2920 (w), 2860 (w), 1580 (m), 1500 (m), 1470 (s), 1440 (m), 1360(m), 1311 (m), 1287 (m), 1240 (m), 1050 (m), 970 (w), 864 (w), 787 (w), 742 (w).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.96 Å and Uiso(H) = 1.2Ueq(C) for methyl H atoms, and C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for methyl­ene H atoms.

Results and discussion top

Compound (I) crystallizes in the tetra­gonal crystal system, in the chiral P43212 space group. The asymmetric unit contains one and a half crystallographically unique AgI atoms, one detz ligand and a half an NO3- anion. The structural motif of (I) with the coordination environment of the AgI cations is shown in Fig. 1. Ag1 is coordinated by two N atoms from two detz ligands. The Ag1—N1 and Ag1—N2i [symmetry code: (i) y+1/2, -x+1/2, z+1/4] bond lengths are 2.137 (4) and 2.124 (4) Å, respectively. The N1—Ag1—N2i angle of 157.09 (15)° indicates that the coordination mode of Ag1 deviates from the ideal linear environment. The distance of Ag2—N3 is 2.118 (3) Å and the N3—Ag2—N3ii [symmetry code: (ii) y, x, -z] angle is 161.4 (2)°. All the Ag—N bond lengths are in agreement with those observed previously in silver–triazolate compounds (Ling et al.,2011; Yang et al., 2009). The distance between Ag atoms connected by detz ligands in a µ1,4-mode is 6.2455 (23) Å and the Ag···Ag distance between AgI ions bridged by detz in a µ1,2-mode is 3.600 (3) Å. The connections of Ag1—N by detz in a µ1,4-mode generate an one dimensional chain (Fig. 2). These chains are further connected to each other by Ag2—N bonds, resulting in the generation of a three-dimensional cationic framework. It is inter­esting to note that the NO3- anion is weakly chelated to the neighbouring three AgI ions, with the average Ag···O distance of ca. 2.84 Å, thus forming a trinuclear silver–nitrate motif. The 3,5-disubsitituted ethyl groups on the triazolate stretch into the channel running along the [110] direction. The Flack parameter is -0.02 (4), confirming the chirality of the crystal structure of (I). To structurally analyze the network of (I), the infinite three-dimensional framework is best described as a 3-connected network with point symbol of 103. The TOPOS program (Blatov, 2006) regards this network as SrSi2 net, considering detz ligands as 3-connected nodes and AgI ions as linear linkers (Fig. 3). This structure is different from a previously reported Ag–detz compound, (II), which is crystallizes in the C2/c space group and has a (4,6)-connected net (Yang et al., 2009). The difference can be ascribed to different coordination geometry of AgI ions, which is almost linear in (I) and Y-shaped in (II).

Thus, the title compound is a new example of a silver–triazolate compound showing a chiral structure consisting of achiral ligand and featuring the SrSi2 net with point symbol of 103.

Related literature top

For related literature, see: Biradha et al. (2011); Blatov (2006); Bonneau et al. (2004); Brandenburg & Berndt (2005); Bruker (2003); Chen et al. (2010); Cui et al. (2012); Jiang & Xu (2011); Kitagawa et al. (2004); Ling et al. (2011); O'Keeffe et al. (2008); Ockwig et al. (2005); Sheldrick (2008, 2008); Sumida et al. (2012); Westrip (2010); Yang et al. (2009, 2013); Zhang et al. (2007, 2012).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The coordination environment of the Ag1 and Ag 2 cations in (I), showing the atomic labels. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity. [Symmetry codes: (i) x, y, -z; (ii) y+1/2, -x+1/4, z+1/4.]
[Figure 2] Fig. 2. (a) A view of the structure of (I) along the [110] direction, showing the three-dimensional framework. H atoms and ethyl groups have been omitted for clarity. (b) A view the one-dimensional chain linked by Ag1—N bonds, with only the triazolate groups shown for simplicity. (c) The trinuclear silver motif with the nitrate anion. [Symmetry codes: (iii) -y+1/2, x-1/2, z-1/4; (iv) x-1/2, -y+3/2, -z+1/4; (v) -y, -x+1, -z+1/2.]
[Figure 3] Fig. 3. A schematic representation of the typical for SrSi2 net topology of (I) showing along the c axis.
Poly[bis(µ3-3,5-diethyl-1,2,4-triazolato-κ3N1:N2:N4)trisilver nitrate] top
Crystal data top
[Ag3(C6H10N3)2]NO3Dx = 2.297 Mg m3
Mr = 633.96Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212Cell parameters from 907 reflections
a = 8.628 (3) Åθ = 2.6–27.7°
c = 24.621 (10) ŵ = 3.20 mm1
V = 1832.8 (15) Å3T = 293 K
Z = 4Needle, colourless
F(000) = 12240.18 × 0.15 × 0.12 mm
Data collection top
Bruker SMART CCD area-detector
1606 reflections with I > 2σ(I)
phi and ω scansRint = 0.088
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
θmax = 25.2°, θmin = 2.5°
Tmin = 0.721, Tmax = 1.000h = 1010
9189 measured reflectionsk = 710
1656 independent reflectionsl = 2829
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.029 w = 1/[σ2(Fo2) + (0.0301P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.063(Δ/σ)max < 0.001
S = 1.06Δρmax = 0.64 e Å3
1656 reflectionsΔρmin = 0.72 e Å3
115 parametersAbsolute structure: Flack x determined using 577 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
0 restraintsAbsolute structure parameter: 0.02 (4)
Crystal data top
[Ag3(C6H10N3)2]NO3Z = 4
Mr = 633.96Mo Kα radiation
Tetragonal, P43212µ = 3.20 mm1
a = 8.628 (3) ÅT = 293 K
c = 24.621 (10) Å0.18 × 0.15 × 0.12 mm
V = 1832.8 (15) Å3
Data collection top
Bruker SMART CCD area-detector
1656 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
1606 reflections with I > 2σ(I)
Tmin = 0.721, Tmax = 1.000Rint = 0.088
9189 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.063Δρmax = 0.64 e Å3
S = 1.06Δρmin = 0.72 e Å3
1656 reflectionsAbsolute structure: Flack x determined using 577 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
115 parametersAbsolute structure parameter: 0.02 (4)
0 restraints
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
Ag10.38813 (6)0.04977 (6)0.23870 (2)0.04307 (17)
Ag20.25605 (6)0.25605 (6)0.00000.0473 (2)
C10.4257 (7)0.0585 (7)0.11530 (19)0.0365 (14)
C20.5055 (11)0.2094 (9)0.1280 (3)0.062 (2)
C30.5659 (12)0.2331 (10)0.1814 (3)0.090 (3)
C40.3092 (7)0.1567 (7)0.1214 (2)0.0361 (14)
C50.2365 (9)0.2986 (9)0.1433 (2)0.0544 (19)
C60.3507 (11)0.4053 (10)0.1710 (4)0.080 (3)
N10.3708 (6)0.0431 (6)0.15213 (17)0.0344 (11)
N20.4020 (6)0.0100 (5)0.06543 (16)0.0343 (11)
N30.3278 (6)0.1284 (6)0.06898 (16)0.0370 (11)
N40.0304 (7)0.0304 (7)0.25000.0490 (19)
O10.1082 (6)0.0668 (6)0.2428 (2)0.0726 (15)
O20.1319 (6)0.1319 (6)0.25000.0586 (18)
Atomic displacement parameters (Å2) top
Ag10.0604 (3)0.0516 (3)0.0172 (2)0.0044 (2)0.0073 (2)0.00063 (18)
Ag20.0601 (3)0.0601 (3)0.0216 (3)0.0142 (4)0.00787 (18)0.00787 (18)
C10.048 (4)0.039 (3)0.023 (3)0.003 (3)0.006 (2)0.001 (2)
C20.105 (7)0.040 (4)0.041 (4)0.012 (5)0.012 (4)0.001 (3)
C30.120 (9)0.069 (6)0.082 (5)0.033 (6)0.052 (6)0.010 (5)
C40.038 (3)0.050 (4)0.020 (2)0.003 (3)0.002 (2)0.002 (2)
C50.067 (5)0.063 (5)0.034 (3)0.022 (4)0.001 (3)0.003 (3)
C60.107 (8)0.050 (5)0.084 (6)0.014 (5)0.007 (5)0.015 (5)
N10.045 (3)0.041 (3)0.0166 (19)0.000 (2)0.002 (2)0.0032 (19)
N20.051 (3)0.037 (3)0.0145 (19)0.001 (2)0.0023 (19)0.0022 (18)
N30.046 (3)0.047 (3)0.0182 (19)0.008 (2)0.0062 (19)0.002 (2)
N40.056 (3)0.056 (3)0.034 (4)0.007 (4)0.000 (2)0.000 (2)
O10.049 (3)0.079 (4)0.090 (4)0.015 (3)0.000 (3)0.011 (3)
O20.055 (3)0.055 (3)0.065 (4)0.002 (4)0.003 (2)0.003 (2)
Geometric parameters (Å, º) top
Ag1—N2i2.125 (4)C4—N11.348 (7)
Ag1—N12.137 (4)C4—C51.477 (9)
Ag2—N32.117 (4)C5—C61.510 (11)
Ag2—N3ii2.117 (4)C5—H5A0.9700
C1—N21.313 (7)C5—H5B0.9700
C1—N11.347 (7)C6—H6A0.9600
C1—C21.506 (10)C6—H6B0.9600
C2—C31.429 (10)C6—H6C0.9600
C2—H2A0.9700N2—N31.358 (7)
C2—H2B0.9700N2—Ag1iii2.125 (4)
C3—H3A0.9600N4—O21.237 (11)
C3—H3B0.9600N4—O11.249 (6)
C3—H3C0.9600N4—O1iv1.249 (6)
C4—N31.324 (7)
N2i—Ag1—N1157.06 (19)C6—C5—H5A109.0
N3—Ag2—N3ii161.4 (3)C4—C5—H5B109.0
N2—C1—N1111.6 (5)C6—C5—H5B109.0
N2—C1—C2122.7 (5)H5A—C5—H5B107.8
N1—C1—C2125.7 (5)C5—C6—H6A109.5
C3—C2—C1118.8 (6)C5—C6—H6B109.5
H2A—C2—H2B107.0C1—N1—C4103.6 (5)
C2—C3—H3A109.5C1—N1—Ag1131.6 (4)
C2—C3—H3B109.5C4—N1—Ag1124.6 (4)
H3A—C3—H3B109.5C1—N2—N3107.1 (4)
C2—C3—H3C109.5C1—N2—Ag1iii132.0 (4)
H3A—C3—H3C109.5N3—N2—Ag1iii120.9 (3)
H3B—C3—H3C109.5C4—N3—N2106.4 (4)
N3—C4—N1111.4 (5)C4—N3—Ag2130.6 (4)
N3—C4—C5124.1 (5)N2—N3—Ag2123.0 (3)
N1—C4—C5124.4 (5)O2—N4—O1120.0 (4)
C4—C5—C6113.1 (6)O2—N4—O1iv120.0 (4)
C4—C5—H5A109.0O1—N4—O1iv120.1 (9)
Symmetry codes: (i) y+1/2, x+1/2, z+1/4; (ii) y, x, z; (iii) y+1/2, x1/2, z1/4; (iv) y, x, z+1/2.

Experimental details

Crystal data
Chemical formula[Ag3(C6H10N3)2]NO3
Crystal system, space groupTetragonal, P43212
Temperature (K)293
a, c (Å)8.628 (3), 24.621 (10)
V3)1832.8 (15)
Radiation typeMo Kα
µ (mm1)3.20
Crystal size (mm)0.18 × 0.15 × 0.12
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.721, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
9189, 1656, 1606
(sin θ/λ)max1)0.599
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.063, 1.06
No. of reflections1656
No. of parameters115
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.64, 0.72
Absolute structureFlack x determined using 577 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
Absolute structure parameter0.02 (4)

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXL2013 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 2005), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).


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