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2-Amino­pyrimidine (L1) and 2-amino-4,6-dimethyl­pyrimidine (L2) have been used to create the two novel title complexes, [Ag2(NCS)2(C4H5N3)]n, (I), and [Ag(NCS)(C6H9N3)]n, (II). The structures of complexes (I) and (II) are mainly directed by the steric properties of the ligands. In (I), the L1 ligand is bisected by a twofold rotation axis running through the amine N atom and opposite C atoms of the pyrimidine ring. The thio­cyanate anion adopts the rare [mu]3-[kappa]3S coordination mode to link three tetra­hedrally coordinated AgI ions into a two-dimensional honeycomb-like 63 net. The L1 ligands further extend the two-dimensional sheet to form a three-dimensional framework by bridging AgI ions in adjacent layers. In (II), with three formula units in the asymmetric unit, the L2 ligand bonds to a single AgI ion in a monodentate fashion, while the thio­cyanate anions adopt a [mu]3-[kappa]1N,[kappa]2S coordination mode to link the AgL2 subunits to form two-dimensional sheets. These layers are linked by N-H...N hydrogen bonds between the noncoordinated amino H atoms and both thio­cyanate and pyrimidine N atoms.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109032934/sq3210sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109032934/sq3210Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109032934/sq3210IIsup3.hkl
Contains datablock II

CCDC references: 740120; 755980

Comment top

The rational design and construction of novel discrete and polymeric metal–organic complexes have been the subject of intense study in recent years, not only due to their structural and topological novelty (Fujita et al., 2004; Wang et al., 2005, 2006), but also because of their potential applications as functional materials in areas such as catalysis, molecular recognition, separation and nonlinear optics (Fujita et al., 1994; Evans & Lin, 2002; Kasai et al., 2000; Kitagawa et al., 2004). The structure of metal–organic complexes is greatly influenced by many factors, such as the coordination geometry of the metal ion, the structure of the organic ligand, the solvent system, the counteranion and the ratio of ligands to metal ions (Khlobystov et al., 2003; Oxtoby & Champness, 2005). In addition, secondary forces such as hydrogen-bonding, ππ stacking and metal···metal interactions must be considered as well (Blake et al., 1999, 2000).

The SCN- anion is reported to show a rich variety of coordination modes through either the N or the S atom, or both, giving rise to linkage isomers or polymers. Silver(I) is a good candidate to be paired with thiocyanate as a soft acid favouring coordination to soft bases containing S and N atoms (Krautscheid et al., 1998). Although the formation and crystal structures of complexes of AgSCN with various N-donor ligands such as substituted pyridine and polyamine ligands have been reported (Morpurgo et al., 1984; Healy et al., 1984, 1991; Ren et al., 2001), complexes of AgSCN incorporating multidentate aminopyrimidine ligands have not appeared in the literature until now. Aminopyrimidine and its derivatives are considered interesting ligands from a supramolecular chemistry point of view, due to the presence of one acceptor and two donor N atoms. This makes them well suited to developing polymeric metal–organic hybrid frameworks (Delgado et al., 2003; Smith et al., 1998; Chi et al., 2006). In our recent investigations, 2-aminopyrimidine and its derivatives and/or other auxiliary ligands have been successfully used to construct a series of AgI complexes with structures spanning from zero- to three-dimensional (Luo, Huang, Chen et al., 2008; Luo, Huang, Zhang et al., 2008; Luo et al., 2009; Sun, Luo, Zhang et al., 2009; Sun, Luo, Huang et al., 2009). As a continuation of our work, we now report the two title novel silver(I) coordination polymers, (I) and (II), with different dimensionalities, based on the SCN- anion and the ligands 2-aminopyrimidine (L1) or 4,6-dimethyl-2-aminopyrimidine (L2).

The crystal structure of complex (I) consists of a silver(I) thiocyanate–L1 adduct in 2:1 stoichiometry (Fig. 1). The L1 ligand sits on a special position with the twofold rotation axis running through atoms N1, C1 and C3 of the pyrimidine ring. Each AgI ion is coordinated to one pyrimidine N atom of L1 and three different thiocyanate S atoms, resulting in a distorted tetrahedral coordination geometry, with one S—Ag—N bond angle opened up to 133.68 (8)° while the remaining angles vary from 93.14 (10) to 114.60 (8)° (Table 1). The Ag—S bond lengths fall in the range 2.543 (2)–2.816 (2) Å, comparable with those found in other AgSCN-containing complexes (Corradi Bonamartini et al., 1987). Each thiocyanate anion adopts a µ3-k3S coordination mode to link three silver(I) ions to form an Ag3S3 boat-like six-membered ring (Fig. 2). This repeat unit shares the Ag—S edges to extend the structure into a two-dimensional honeycomb-like 63 net parallel to the bc plane. To the best of our knowledge, (I) is the first complex containing a thiocyanate anion with a µ3-k3S coordination mode, and the characteristic IR spectroscopic absorption for a µ3-k3S SCN- anion occurs at \sim 2130 cm-1. The coordination mode of the thiocyanate anion in (I) obviously follows Pearson's principle of hard and soft Lewis acids and bases (HSAB), according to which the `soft' AgI ions should bind preferentially to the `softer' S atoms of the thiocyanate groups (Pearson, 1963). Adjacent two-dimensional nets stacked along the a axis are linked by L1 ligands with µ2-N,N' coordination modes to create a three-dimensional framework (Fig. 3). Since the thiocyanate anions use only their S atoms to bind to the silver(I) atoms, the uncoordinated N atoms are available to act as acceptors to form hydrogen bonds with the amino groups of L1, which further stabilizes the resulting framework (Table 2, Fig. 3).

Complex (II) contains three crystallographically independent silver(I) atoms and the stoichiometry for the silver(I) thiocyanate–L2 adduct is 1:1 (Fig. 4). Each AgI atom is coordinated by one N atom from L2, and two S atoms and one N atom from three different thiocyanate anions, resulting in a tetrahedral coordination geometry with bond angles ranging from 100.6 (4) to 130.84 (14)° (Table 3). Each thiocyanate anion adopts a µ3-k1N, k2S coordination mode to link three silver(I) atoms to form a saddle-like ten-membered ring (Fig. 5), and these repeat units are fused together to form a wave-shaped two-dimensional net in the ab plane. IR spectroscopic absorption in the range 2100–2107 cm-1 indicates the existence of bridging µ3-k1N,k2S SCN- anions in (II) (Shen & Xu, 2001). The L2 ligands only adopt a monodentate coordination mode to project off the two-dimensional net and do not extend the net to a higher dimension as in (I), which may be due to the more intense steric effects in L2 than in L1. Adjacent nets are joined together to form a three-dimensional framework by N–H···N hydrogen bonds from the amino groups to the non-coordinated pyrimidine N atoms of the L2 ligands and coordinated N atoms of the thiocyanate anions (Fig. 6).

In this work, we have successfully assembled two different silver(I) coordination polymers from 2-aminopyrimidyl derivatives (ligands L1 and L2) and AgSCN. Moreover, the structures of the two title complexes are governed by the nature of the aminopyrimidyl derivatives and the different coordination modes of the SCN- anions. Recently, we found that trigonal NO3- as a chelating counteranion reacts with AgI and L1 to give [Ag(L1)(NO3)]n in the form of a one-dimensional zigzag chain structure (Luo, Huang, Zhang et al., 2008). By contrast, in (I) the linear SCN- anions possess two kinds of potential terminal coordination atoms and the `softer' µ3-S atoms link the soft AgI atoms to form a two-dimensional honeycomb structure. When trigonal NO3- and tetrahedral ClO4- counteranions were chosen to react with AgI and L2, the result was tetranuclear [Ag4(L2)6(NO3)4] and dinuclear [Ag2(L2)4(ClO4)2] zero-dimensional molecular structures, respectively (Luo, Huang, Chen et al., 2008; Luo, Huang, Zhang et al., 2008). In (II), SCN- anions with two different coordinated atoms link the Ag atoms to form a two-dimensional rectangular net structure. Thus, it is evident that the thiocyanate anion promotes higher dimensionalities in these systems.

Experimental top

All reagents and solvents were commercially available and were used as received. For (I), AgSCN (0.5 mmol, 83 mg) was dissolved in a saturated aqueous solution of KSCN (5 ml), and then L1 (0.5 mmol, 48 mg) in acetonitrile (5 ml) was carefully layered on top. The whole reaction system was kept in darkness at room temperature, and colourless block crystals of (I) were obtained after 3 d. The crystals were filtered off, washed with distilled water and acetonitrile, and left to dry in darkness at room temperature (yield 66 mg, 62%). Analysis calculated for C6H4Ag2N5S2: C 16.92, H 0.95, N 16.44%; found: C 16.99, H 1.05, N 16.36%. IR (KBr, ν, cm-1): 3450 (w), 3339 (w), 2130 (s), 1612 (s), 1580 (s), 1463 (s), 1423 (w), 1358 (m), 1312 (w), 1222 (m), 1165 (w), 1163 (w), 1100 (w), 1064 (w), 965 (w), 792 (m), 777 (s), 739 (m), 662 (m), 634 (w), 412 (w), 409 (w).

The synthesis of (II) was similar to that of (I), but with L2 (0.5 mol, 65 mg) in the place of L1 (yield 75 mg, 52%). Analysis calculated for C21H27Ag3N12S3: C 29.08, H 3.14, N 19.38%; found: C 29.12, H 3.08, N 19.45%. IR (KBr, ν, cm-1): 3396 (w), 3302 (w), 2107 (s), 2100 (s), 1623 (s), 1582 (s), 1465 (s), 1427 (w), 1360 (m), 1324 (w), 1225 (m), 1168 (w), 1160 (w), 1101 (w), 1006 (w), 828 (m), 822 (w), 789 (m), 782 (m), 757 (w), 747 (w), 732 (w), 693 (w), 675 (w), 666 (m), 619 (w), 474 (w), 434 (w), 452 (w).

Refinement top

For both compounds, all H atoms were refined using a riding model, with C—H = 0.95 (aromatic) or 0.98Å (CH2), N—H = 0.86 [for (I)] or 0.88Å [for (II)], with Uiso(H) = 1.2Ueq(C or N).

Computing details top

For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), along with a symmetry-generated portion of 2-aminopyrimidine and an adjacent Ag atom, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted. [Symmetry code: (iii) 1 - x, y, 1/2 - z.]
[Figure 2] Fig. 2. The two-dimensional honeycomb-like net bridged by SCN- in (I), viewed along the a axis.
[Figure 3] Fig. 3. The three-dimensional framework of (I), with the N—H···N hydrogen bonds shown as dashed lines.
[Figure 4] Fig. 4. The asymmetric unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted.
[Figure 5] Fig. 5. The two-dimensional saddle-like net in (II), viewed along two different axes.
[Figure 6] Fig. 6. The three-dimensional framework of (II), with the hydrogen bonds shown as dashed lines.
(I) poly[(µ2-2-aminopyrimidine-κ2N1:N3)bis(µ3- thiocyanato-κ3S:S:S)disilver(I)] top
Crystal data top
[Ag2(NCS)2(C4H5N3)]F(000) = 808
Mr = 427.01Dx = 2.678 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 3087 reflections
a = 17.719 (6) Åθ = 5.5–56.8°
b = 8.159 (3) ŵ = 4.06 mm1
c = 7.326 (2) ÅT = 298 K
V = 1059.1 (6) Å3Block, colourless
Z = 40.10 × 0.05 × 0.05 mm
Data collection top
Oxford Gemini S Ultra
diffractometer
1034 independent reflections
Radiation source: fine-focus sealed tube992 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
Detector resolution: 16.1903 pixels mm-1θmax = 26.0°, θmin = 2.3°
ω scansh = 2121
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
k = 910
Tmin = 0.687, Tmax = 0.823l = 93
4766 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0353P)2 + 3.1955P]
where P = (Fo2 + 2Fc2)/3
S = 1.22(Δ/σ)max < 0.001
1034 reflectionsΔρmax = 0.95 e Å3
71 parametersΔρmin = 0.61 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0019 (5)
Crystal data top
[Ag2(NCS)2(C4H5N3)]V = 1059.1 (6) Å3
Mr = 427.01Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 17.719 (6) ŵ = 4.06 mm1
b = 8.159 (3) ÅT = 298 K
c = 7.326 (2) Å0.10 × 0.05 × 0.05 mm
Data collection top
Oxford Gemini S Ultra
diffractometer
1034 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
992 reflections with I > 2σ(I)
Tmin = 0.687, Tmax = 0.823Rint = 0.046
4766 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.104H-atom parameters constrained
S = 1.22Δρmax = 0.95 e Å3
1034 reflectionsΔρmin = 0.61 e Å3
71 parameters
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 > 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
xyzUiso*/Ueq
Ag10.68299 (3)0.14887 (6)0.20060 (7)0.0488 (3)
C10.50000.1063 (9)0.25000.0286 (15)
C20.5638 (4)0.1372 (7)0.2077 (9)0.0424 (14)
H2A0.60750.19400.17730.051*
C30.50000.2253 (11)0.25000.050 (2)
H3A0.50000.33930.25000.060*
C40.8316 (3)0.0180 (6)0.0363 (7)0.0314 (11)
N10.50000.2711 (8)0.25000.0437 (17)
H10.45930.32380.27580.052*
N20.5657 (2)0.0277 (6)0.2083 (6)0.0327 (10)
N30.8825 (3)0.0526 (7)0.0194 (7)0.0503 (13)
S10.75465 (8)0.12005 (16)0.11137 (18)0.0331 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0350 (4)0.0494 (4)0.0621 (4)0.0041 (2)0.0083 (2)0.0129 (2)
C10.028 (4)0.029 (4)0.029 (3)0.0000.002 (3)0.000
C20.037 (3)0.033 (3)0.057 (4)0.006 (2)0.006 (3)0.006 (2)
C30.043 (5)0.027 (4)0.080 (6)0.0000.010 (5)0.000
C40.034 (3)0.027 (3)0.032 (3)0.000 (2)0.005 (2)0.002 (2)
N10.035 (4)0.025 (3)0.071 (5)0.0000.018 (3)0.000
N20.027 (2)0.032 (2)0.039 (2)0.0016 (18)0.0003 (19)0.0037 (18)
N30.046 (3)0.053 (3)0.052 (3)0.017 (3)0.002 (2)0.009 (3)
S10.0343 (7)0.0290 (7)0.0361 (7)0.0026 (5)0.0010 (6)0.0025 (5)
Geometric parameters (Å, º) top
Ag1—N22.303 (4)C2—H2A0.9300
Ag1—S1i2.5832 (15)C3—C2iii1.375 (8)
Ag1—S12.6252 (16)C3—H3A0.9300
Ag1—S1ii2.8851 (16)C4—N31.146 (7)
C1—N11.344 (10)C4—S11.689 (6)
C1—N2iii1.363 (6)N1—H10.8600
C1—N21.363 (6)S1—Ag1iv2.5832 (15)
C2—N21.346 (7)S1—Ag1v2.8851 (16)
C2—C31.375 (8)
N2—Ag1—S1i133.35 (11)C2—C3—H3A121.5
N2—Ag1—S1114.81 (11)C2iii—C3—H3A121.5
N2—Ag1—S1ii93.39 (12)N3—C4—S1177.9 (5)
S1i—Ag1—S1108.83 (3)C1—N1—H1120.0
S1i—Ag1—S1ii96.44 (4)C2—N2—C1116.8 (5)
S1—Ag1—S1ii97.74 (4)C2—N2—Ag1116.8 (4)
N1—C1—N2iii118.1 (3)C1—N2—Ag1125.0 (4)
N1—C1—N2118.1 (3)C4—S1—Ag1iv100.86 (18)
N2iii—C1—N2123.8 (7)C4—S1—Ag198.68 (18)
N2—C2—C3122.8 (6)Ag1iv—S1—Ag1127.28 (5)
N2—C2—H2A118.6C4—S1—Ag1v97.80 (19)
C3—C2—H2A118.6Ag1iv—S1—Ag1v119.26 (6)
C2—C3—C2iii117.0 (8)Ag1—S1—Ag1v105.72 (5)
Symmetry codes: (i) x+3/2, y+1/2, z+1/2; (ii) x, y, z+1/2; (iii) x+1, y, z+1/2; (iv) x+3/2, y+1/2, z1/2; (v) x, y, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N3vi0.862.263.042 (6)151
Symmetry code: (vi) x+3/2, y+1/2, z.
(II) poly[(2-amino-4,6-dimethylpyrimidine-κN)(µ3- thiocyanato-κ3N:S:S)silver(I)] top
Crystal data top
[Ag(NCS)(C6H9N3)]F(000) = 3408
Mr = 289.11Dx = 2.017 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 4693 reflections
a = 20.955 (4) Åθ = 4.4–56.3°
b = 11.282 (2) ŵ = 2.29 mm1
c = 24.166 (5) ÅT = 173 K
V = 5713 (2) Å3Block, colourless
Z = 240.13 × 0.10 × 0.08 mm
Data collection top
Oxford Gemini S Ultra
diffractometer
5603 independent reflections
Radiation source: fine-focus sealed tube3440 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.115
Detector resolution: 16.1903 pixels mm-1θmax = 26.0°, θmin = 1.7°
ω scansh = 2525
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
k = 137
Tmin = 0.755, Tmax = 0.838l = 2927
29723 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125H-atom parameters constrained
S = 0.90 w = 1/[σ2(Fo2) + (0.0627P)2]
where P = (Fo2 + 2Fc2)/3
5603 reflections(Δ/σ)max = 0.001
358 parametersΔρmax = 1.39 e Å3
0 restraintsΔρmin = 0.72 e Å3
Crystal data top
[Ag(NCS)(C6H9N3)]V = 5713 (2) Å3
Mr = 289.11Z = 24
Orthorhombic, PbcaMo Kα radiation
a = 20.955 (4) ŵ = 2.29 mm1
b = 11.282 (2) ÅT = 173 K
c = 24.166 (5) Å0.13 × 0.10 × 0.08 mm
Data collection top
Oxford Gemini S Ultra
diffractometer
5603 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
3440 reflections with I > 2σ(I)
Tmin = 0.755, Tmax = 0.838Rint = 0.115
29723 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.125H-atom parameters constrained
S = 0.90Δρmax = 1.39 e Å3
5603 reflectionsΔρmin = 0.72 e Å3
358 parameters
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 > 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
xyzUiso*/Ueq
Ag10.52093 (3)0.36852 (5)0.79944 (2)0.03338 (17)
Ag20.35091 (3)0.36915 (5)0.71765 (2)0.03165 (17)
Ag30.17515 (3)0.37154 (5)0.62053 (2)0.03153 (16)
C10.3385 (3)0.3752 (6)0.8511 (3)0.0253 (15)
C20.3097 (3)0.2338 (6)0.9123 (3)0.0230 (15)
C30.2992 (3)0.1550 (6)0.8702 (3)0.0268 (16)
H3A0.28500.07660.87750.032*
C40.3100 (3)0.1940 (6)0.8161 (3)0.0221 (15)
C50.3021 (3)0.1147 (6)0.7678 (3)0.0340 (18)
H5A0.27390.15240.74060.041*
H5B0.28330.03950.77990.041*
H5C0.34380.09970.75090.041*
C60.3013 (3)0.1991 (6)0.9721 (3)0.0290 (16)
H6A0.27410.25750.99060.035*
H6B0.34300.19650.99030.035*
H6C0.28120.12070.97410.035*
C70.1454 (3)0.3766 (6)0.4905 (3)0.0240 (15)
C80.1454 (3)0.1859 (6)0.5241 (2)0.0202 (14)
C90.1418 (3)0.1451 (6)0.4708 (3)0.0272 (16)
H9A0.14040.06240.46350.033*
C100.1403 (3)0.2253 (6)0.4281 (3)0.0229 (15)
C110.1383 (3)0.1870 (6)0.3687 (3)0.0315 (17)
H11A0.09960.21840.35120.038*
H11B0.13790.10030.36680.038*
H11C0.17590.21740.34930.038*
C120.1471 (3)0.1051 (6)0.5722 (3)0.0319 (17)
H12A0.18770.11440.59180.038*
H12B0.14270.02300.55950.038*
H12C0.11180.12420.59730.038*
C130.4983 (3)0.3740 (6)0.9306 (2)0.0222 (14)
C140.4758 (3)0.2293 (6)0.9926 (2)0.0215 (15)
C150.4727 (3)0.1487 (6)0.9494 (3)0.0230 (15)
H15A0.46430.06740.95660.028*
C160.4818 (3)0.1875 (6)0.8963 (3)0.0238 (15)
C170.4785 (3)0.1073 (6)0.8478 (3)0.0308 (17)
H17A0.44200.12930.82460.037*
H17B0.47340.02530.86050.037*
H17C0.51790.11410.82630.037*
C180.4673 (3)0.1927 (6)1.0520 (3)0.0310 (17)
H18A0.50000.23091.07480.037*
H18B0.47130.10641.05500.037*
H18C0.42490.21711.06480.037*
C190.3110 (3)0.1749 (7)0.6221 (3)0.0225 (15)
C200.4741 (3)0.1720 (6)0.7037 (3)0.0245 (15)
C210.6414 (3)0.1749 (7)0.7817 (3)0.0252 (16)
N10.3590 (3)0.4856 (5)0.8419 (2)0.0348 (15)
H1A0.36660.53320.87000.042*
H1B0.36490.51070.80780.042*
N20.3304 (3)0.3418 (5)0.9036 (2)0.0236 (13)
N30.3298 (2)0.3043 (5)0.8063 (2)0.0227 (12)
N40.5093 (3)0.4879 (5)0.9220 (2)0.0326 (15)
H4A0.51060.53730.95020.039*
H4B0.51540.51430.88820.039*
N50.4895 (3)0.3412 (5)0.9834 (2)0.0230 (13)
N60.4953 (2)0.3018 (5)0.88608 (19)0.0192 (12)
N70.1486 (3)0.4925 (5)0.4986 (2)0.0321 (14)
H7A0.15230.52080.53240.038*
H7B0.14700.54130.47020.038*
N80.1479 (2)0.3036 (5)0.53461 (19)0.0205 (12)
N90.1417 (3)0.3404 (5)0.4372 (2)0.0246 (13)
N100.3184 (3)0.0746 (6)0.6181 (2)0.0351 (15)
N110.4773 (3)0.0720 (5)0.7006 (2)0.0338 (15)
N120.6408 (3)0.0727 (5)0.7811 (2)0.0324 (15)
S10.64404 (8)0.32168 (15)0.78202 (7)0.0261 (4)
S20.47375 (8)0.31996 (15)0.70592 (7)0.0250 (4)
S30.30163 (8)0.32137 (15)0.62529 (7)0.0247 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0596 (4)0.0188 (3)0.0217 (3)0.0001 (3)0.0015 (2)0.0020 (2)
Ag20.0514 (4)0.0220 (3)0.0216 (3)0.0018 (3)0.0006 (2)0.0024 (2)
Ag30.0531 (4)0.0206 (3)0.0209 (3)0.0011 (3)0.0016 (2)0.0022 (2)
C10.030 (4)0.018 (4)0.028 (4)0.004 (3)0.004 (3)0.008 (3)
C20.022 (4)0.027 (4)0.020 (4)0.007 (3)0.003 (3)0.001 (3)
C30.031 (4)0.021 (4)0.028 (4)0.005 (3)0.001 (3)0.003 (3)
C40.020 (4)0.019 (4)0.027 (4)0.001 (3)0.006 (3)0.002 (3)
C50.039 (4)0.027 (4)0.037 (4)0.001 (4)0.003 (3)0.002 (3)
C60.032 (4)0.032 (4)0.023 (4)0.002 (3)0.003 (3)0.003 (3)
C70.023 (4)0.015 (3)0.034 (4)0.000 (3)0.000 (3)0.002 (3)
C80.023 (4)0.026 (4)0.012 (3)0.001 (3)0.000 (3)0.002 (3)
C90.035 (4)0.019 (4)0.027 (4)0.002 (3)0.005 (3)0.000 (3)
C100.024 (4)0.025 (4)0.019 (3)0.003 (3)0.004 (3)0.004 (3)
C110.040 (5)0.027 (4)0.028 (4)0.001 (3)0.002 (3)0.005 (3)
C120.045 (5)0.023 (4)0.027 (4)0.002 (3)0.016 (3)0.008 (3)
C130.029 (4)0.016 (3)0.021 (4)0.000 (3)0.004 (3)0.002 (3)
C140.024 (4)0.021 (4)0.020 (3)0.002 (3)0.000 (3)0.004 (3)
C150.026 (4)0.019 (4)0.024 (4)0.005 (3)0.002 (3)0.004 (3)
C160.023 (4)0.017 (4)0.032 (4)0.004 (3)0.003 (3)0.002 (3)
C170.042 (4)0.022 (4)0.028 (4)0.006 (3)0.001 (3)0.004 (3)
C180.042 (5)0.020 (4)0.030 (4)0.006 (3)0.003 (3)0.009 (3)
C190.023 (4)0.028 (4)0.017 (3)0.003 (3)0.003 (3)0.005 (3)
C200.031 (4)0.028 (4)0.015 (3)0.003 (3)0.005 (3)0.008 (3)
C210.028 (4)0.031 (4)0.017 (3)0.001 (3)0.001 (3)0.004 (3)
N10.067 (5)0.022 (3)0.016 (3)0.013 (3)0.004 (3)0.004 (2)
N20.030 (3)0.025 (3)0.015 (3)0.004 (3)0.002 (2)0.004 (2)
N30.028 (3)0.021 (3)0.019 (3)0.006 (3)0.000 (2)0.002 (2)
N40.067 (4)0.014 (3)0.017 (3)0.001 (3)0.001 (3)0.001 (2)
N50.036 (3)0.022 (3)0.011 (3)0.002 (3)0.005 (2)0.002 (2)
N60.026 (3)0.022 (3)0.010 (3)0.002 (2)0.001 (2)0.001 (2)
N70.064 (4)0.016 (3)0.015 (3)0.003 (3)0.001 (3)0.004 (2)
N80.022 (3)0.026 (3)0.014 (3)0.004 (2)0.003 (2)0.004 (2)
N90.033 (3)0.026 (3)0.015 (3)0.003 (3)0.004 (2)0.000 (2)
N100.055 (4)0.023 (4)0.028 (3)0.006 (3)0.001 (3)0.002 (3)
N110.058 (4)0.014 (3)0.030 (3)0.003 (3)0.007 (3)0.000 (3)
N120.042 (4)0.017 (3)0.039 (4)0.000 (3)0.006 (3)0.004 (3)
S10.0386 (11)0.0177 (9)0.0221 (9)0.0013 (8)0.0061 (7)0.0016 (7)
S20.0348 (10)0.0157 (9)0.0243 (9)0.0009 (8)0.0009 (7)0.0006 (7)
S30.0336 (10)0.0188 (9)0.0218 (9)0.0009 (8)0.0017 (7)0.0006 (7)
Geometric parameters (Å, º) top
Ag1—N62.289 (5)C11—H11A0.9800
Ag1—N11i2.296 (6)C11—H11B0.9800
Ag1—S12.667 (2)C11—H11C0.9800
Ag1—S22.5269 (18)C12—H12A0.9800
Ag2—N12i2.303 (6)C12—H12B0.9800
Ag2—N32.307 (5)C12—H12C0.9800
Ag2—S22.6485 (19)C13—N41.322 (8)
Ag2—S32.5176 (17)C13—N51.342 (7)
Ag3—N82.286 (5)C13—N61.351 (7)
Ag3—N10ii2.295 (6)C14—N51.313 (8)
Ag3—S1iii2.5075 (17)C14—C151.385 (8)
Ag3—S32.7126 (19)C14—C181.505 (8)
C1—N21.335 (8)C15—C161.369 (8)
C1—N11.335 (8)C15—H15A0.9500
C1—N31.358 (8)C16—N61.342 (8)
C2—N21.311 (8)C16—C171.483 (9)
C2—C31.369 (9)C17—H17A0.9800
C2—C61.507 (8)C17—H17B0.9800
C3—C41.398 (9)C17—H17C0.9800
C3—H3A0.9500C18—H18A0.9800
C4—N31.333 (8)C18—H18B0.9800
C4—C51.480 (9)C18—H18C0.9800
C5—H5A0.9800C19—N101.147 (9)
C5—H5B0.9800C19—S31.666 (8)
C5—H5C0.9800C20—N111.132 (8)
C6—H6A0.9800C20—S21.671 (7)
C6—H6B0.9800C21—N121.154 (9)
C6—H6C0.9800C21—S11.657 (8)
C7—N71.324 (8)N1—H1A0.8800
C7—N81.348 (8)N1—H1B0.8800
C7—N91.354 (8)N4—H4A0.8800
C8—N81.353 (8)N4—H4B0.8800
C8—C91.369 (8)N7—H7A0.8800
C8—C121.479 (8)N7—H7B0.8800
C9—C101.372 (8)N10—Ag3iv2.295 (6)
C9—H9A0.9500N11—Ag1v2.296 (6)
C10—N91.318 (8)N12—Ag2v2.303 (6)
C10—C111.500 (8)S1—Ag3vi2.5075 (17)
N6—Ag1—N11i109.5 (2)C8—C12—H12C109.5
N6—Ag1—S2130.90 (14)H12A—C12—H12C109.5
N6—Ag1—S1107.85 (13)H12B—C12—H12C109.5
N11i—Ag1—S1100.49 (16)N4—C13—N5116.2 (6)
N11i—Ag1—S2102.86 (15)N4—C13—N6118.0 (5)
N3—Ag2—N12i108.61 (19)N5—C13—N6125.8 (6)
N3—Ag2—S2102.64 (13)N5—C14—C15121.0 (6)
N3—Ag2—S3132.61 (15)N5—C14—C18116.7 (6)
N12i—Ag2—S3104.82 (15)C15—C14—C18122.2 (6)
N12i—Ag2—S297.85 (15)C16—C15—C14119.3 (6)
N8—Ag3—N10ii109.0 (2)C16—C15—H15A120.4
N8—Ag3—S1iii135.47 (14)C14—C15—H15A120.4
N8—Ag3—S3102.29 (13)N6—C16—C15120.6 (6)
N10ii—Ag3—S1iii105.26 (15)N6—C16—C17116.8 (6)
N10ii—Ag3—S398.72 (16)C15—C16—C17122.6 (6)
S1—Ag1—S2101.20 (6)C16—C17—H17A109.5
S1iii—Ag3—S399.63 (6)C16—C17—H17B109.5
S2—Ag2—S3105.00 (6)H17A—C17—H17B109.5
N2—C1—N1117.5 (6)C16—C17—H17C109.5
N2—C1—N3125.0 (6)H17A—C17—H17C109.5
N1—C1—N3117.4 (6)H17B—C17—H17C109.5
N2—C2—C3122.6 (6)C14—C18—H18A109.5
N2—C2—C6115.7 (6)C14—C18—H18B109.5
C3—C2—C6121.6 (6)H18A—C18—H18B109.5
C2—C3—C4117.7 (6)C14—C18—H18C109.5
C2—C3—H3A121.2H18A—C18—H18C109.5
C4—C3—H3A121.2H18B—C18—H18C109.5
N3—C4—C3120.7 (6)N10—C19—S3177.6 (6)
N3—C4—C5117.3 (6)N11—C20—S2176.4 (7)
C3—C4—C5122.0 (6)N12—C21—S1178.7 (7)
C4—C5—H5A109.5C1—N1—H1A120.0
C4—C5—H5B109.5C1—N1—H1B120.0
H5A—C5—H5B109.5H1A—N1—H1B120.0
C4—C5—H5C109.5C2—N2—C1117.2 (6)
H5A—C5—H5C109.5C4—N3—C1116.8 (6)
H5B—C5—H5C109.5C4—N3—Ag2121.4 (4)
C2—C6—H6A109.5C1—N3—Ag2121.8 (4)
C2—C6—H6B109.5C13—N4—H4A120.0
H6A—C6—H6B109.5C13—N4—H4B120.0
C2—C6—H6C109.5H4A—N4—H4B120.0
H6A—C6—H6C109.5C14—N5—C13117.1 (6)
H6B—C6—H6C109.5C16—N6—C13116.2 (5)
N7—C7—N8119.0 (6)C16—N6—Ag1122.3 (4)
N7—C7—N9116.2 (6)C13—N6—Ag1121.3 (4)
N8—C7—N9124.8 (6)C7—N7—H7A120.0
N8—C8—C9120.6 (6)C7—N7—H7B120.0
N8—C8—C12117.1 (5)H7A—N7—H7B120.0
C9—C8—C12122.3 (6)C7—N8—C8116.7 (5)
C8—C9—C10119.1 (6)C7—N8—Ag3121.5 (4)
C8—C9—H9A120.5C8—N8—Ag3120.6 (4)
C10—C9—H9A120.5C10—N9—C7117.1 (5)
N9—C10—C9121.7 (6)C19—N10—Ag3iv172.4 (6)
N9—C10—C11116.3 (6)C20—N11—Ag1v175.6 (6)
C9—C10—C11122.0 (6)C21—N12—Ag2v174.7 (6)
C10—C11—H11A109.5C21—S1—Ag3vi103.7 (2)
C10—C11—H11B109.5C21—S1—Ag199.6 (2)
H11A—C11—H11B109.5Ag3vi—S1—Ag193.37 (6)
C10—C11—H11C109.5C20—S2—Ag1104.1 (2)
H11A—C11—H11C109.5C20—S2—Ag2102.5 (2)
H11B—C11—H11C109.5Ag1—S2—Ag2103.83 (6)
C8—C12—H12A109.5C19—S3—Ag2101.8 (2)
C8—C12—H12B109.5C19—S3—Ag3108.7 (2)
H12A—C12—H12B109.5Ag2—S3—Ag3113.18 (6)
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1/2, y+1/2, z; (iii) x1/2, y, z+3/2; (iv) x+1/2, y1/2, z; (v) x+1, y1/2, z+3/2; (vi) x+1/2, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N9vii0.882.173.025 (7)165
N1—H1B···N12i0.882.263.133 (8)169
N4—H4A···N5viii0.882.112.989 (7)178
N4—H4B···N11i0.882.253.125 (8)175
N7—H7A···N10ii0.882.243.110 (8)168
N7—H7B···N2ix0.882.132.993 (7)165
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1/2, y+1/2, z; (vii) x+1/2, y+1, z+1/2; (viii) x+1, y+1, z+2; (ix) x+1/2, y+1, z1/2.

Experimental details

(I)(II)
Crystal data
Chemical formula[Ag2(NCS)2(C4H5N3)][Ag(NCS)(C6H9N3)]
Mr427.01289.11
Crystal system, space groupOrthorhombic, PbcnOrthorhombic, Pbca
Temperature (K)298173
a, b, c (Å)17.719 (6), 8.159 (3), 7.326 (2)20.955 (4), 11.282 (2), 24.166 (5)
V3)1059.1 (6)5713 (2)
Z424
Radiation typeMo KαMo Kα
µ (mm1)4.062.29
Crystal size (mm)0.10 × 0.05 × 0.050.13 × 0.10 × 0.08
Data collection
DiffractometerOxford Gemini S Ultra
diffractometer
Oxford Gemini S Ultra
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2008)
Multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
Tmin, Tmax0.687, 0.8230.755, 0.838
No. of measured, independent and
observed [I > 2σ(I)] reflections
4766, 1034, 992 29723, 5603, 3440
Rint0.0460.115
(sin θ/λ)max1)0.6170.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.104, 1.22 0.054, 0.125, 0.90
No. of reflections10345603
No. of parameters71358
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.95, 0.611.39, 0.72

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2009).

Selected geometric parameters (Å, º) for (I) top
Ag1—N22.303 (4)Ag1—S12.6252 (16)
Ag1—S1i2.5832 (15)Ag1—S1ii2.8851 (16)
N2—Ag1—S1i133.35 (11)S1i—Ag1—S1108.83 (3)
N2—Ag1—S1114.81 (11)S1i—Ag1—S1ii96.44 (4)
N2—Ag1—S1ii93.39 (12)S1—Ag1—S1ii97.74 (4)
Symmetry codes: (i) x+3/2, y+1/2, z+1/2; (ii) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N3iii0.862.263.042 (6)150.8
Symmetry code: (iii) x+3/2, y+1/2, z.
Selected geometric parameters (Å, º) for (II) top
Ag1—N62.289 (5)Ag2—S22.6485 (19)
Ag1—N11i2.296 (6)Ag2—S32.5176 (17)
Ag1—S12.667 (2)Ag3—N82.286 (5)
Ag1—S22.5269 (18)Ag3—N10ii2.295 (6)
Ag2—N12i2.303 (6)Ag3—S1iii2.5075 (17)
Ag2—N32.307 (5)Ag3—S32.7126 (19)
N6—Ag1—N11i109.5 (2)N12i—Ag2—S297.85 (15)
N6—Ag1—S2130.90 (14)N8—Ag3—N10ii109.0 (2)
N6—Ag1—S1107.85 (13)N8—Ag3—S1iii135.47 (14)
N11i—Ag1—S1100.49 (16)N8—Ag3—S3102.29 (13)
N11i—Ag1—S2102.86 (15)N10ii—Ag3—S1iii105.26 (15)
N3—Ag2—N12i108.61 (19)N10ii—Ag3—S398.72 (16)
N3—Ag2—S2102.64 (13)S1—Ag1—S2101.20 (6)
N3—Ag2—S3132.61 (15)S1iii—Ag3—S399.63 (6)
N12i—Ag2—S3104.82 (15)S2—Ag2—S3105.00 (6)
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1/2, y+1/2, z; (iii) x1/2, y, z+3/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N9iv0.882.173.025 (7)164.7
N1—H1B···N12i0.882.263.133 (8)168.9
N4—H4A···N5v0.882.112.989 (7)177.8
N4—H4B···N11i0.882.253.125 (8)174.6
N7—H7A···N10ii0.882.243.110 (8)168.2
N7—H7B···N2vi0.882.132.993 (7)165.0
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1/2, y+1/2, z; (iv) x+1/2, y+1, z+1/2; (v) x+1, y+1, z+2; (vi) x+1/2, y+1, z1/2.
 

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