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The title compound, {(C6H14N2)[Ag(NCS)3]}n, is a polymeric silver(I) complex. The AgI atom is hexacoordinated by the S atoms of six thio­cyanate anions, with each thio­cyanate S atom acting in a bridging mode to link the Ag atoms together. The unique AgI atom lies at a cell origin and has crystallo­graphically imposed \overline3 symmetry. The diazonia[2.2.2]octane molecule lies about a site with \overline6 imposed symmetry with the unique N atom on a threefold axis. The S and N atoms of the thio­cyanate ligands sit on a mirror plane and a threefold axis, respectively. The crystal structure consists of one-dimensional chains, which are stabilized by N—H...N hydrogen bonds to form a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010401772X/av1193sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010401772X/av1193Isup2.hkl
Contains datablock I

CCDC reference: 251294

Comment top

Because silver(I) is good candidate as a soft acid favouring coordination to soft bases, such as ligands containing S and N atoms, we and others have exploited the coordination flexibility of silver(I) in the construction of a large number of coordination polymers, which exhibit interesting structural diversity (Yang et al., 2000; Zhu Zhang et al., 2003; Zhu et al., 2004). Thiocyanate is a potential bridging ligand. Thus, many complexes containing AgSCN units have been reported (Cotton & Wilkinson, 1988; Krautscheid et al., 1998; Ren et al., 2001). In this paper we report the title novel silver(I) thiocyanate salt, (I). \sch

Compound (I) is a polymeric silver(I) complex. The AgI atoms sit on a sixfold axis, and their site occupancy factors are 1/6 or 0.16667. The other 5/6 of each atom is generated by the symmetry elements that pass through those special positons. The S and N atoms of the thiocyanate ligands sit on the mirror plane and threefold axis, respectively, with site occupancy factors of 1/2 and 1/3, respectively.

The Ag atom is pseudo-octahedrally six-coordinated by three pairs of bridging S atoms which link the Ag atoms together, forming a one-dimensional polymeric chain (Fig. 1). The smallest repeat unit consists of a silver-thiocyanate-1,4-diazonia[2.2.2]octane adduct in 1:3:1 stoichiometry, in which 1,4-diazonia[2.2.2]octane acts as a cation, not as a coordination ligand to the Ag atom. The six Ag—S bonds are the same [2.7993 (15) Å] and are normal by comparison with those in a similar complex (Zhu Liu & Meng, 2003). The bond angles are in the range 83.35 (4)–96.65 (4)° at the Ag atom, so each Ag atom lies almost in the centre of a slightly distorted octahedron. The thiocyanate group is almost linear [S—C 1.645 (8) and C—N 1.490 (5) Å, and S—C—N 179.5 (7)°]. The Ag—S—Ag angle is 79.69 (5)°. The remaining C—S—Ag angles about the S atom are both 106.89 (19)°, so that the geometry at the S atom is a slightly distorted pyramid.

In the crystal of (I), the 1,4-diazonia[2.2.2]octane cations are located between the chains. The bridging S atoms link the Ag atoms into a linear chain along the c axis. Adjacent chains interact with the cations via three equivalent hydrogen bonds [N2—H3 0.91 (2), H3···A 2.443 (14) and N2···A 3.070 (7) Å, and N2—H3···A 125.9 (4)°, where A is N1i, N1ii and N1iii; symmetry codes: (i) 1 − x, 1 − y, −z; (ii) x-y, x, −z; (iii) y, 1 − x + y, −z], forming a three-dimensional structure (Fig.2)

Experimental top

AgNO3 (0.170 g, 1 mmol) and 1,4-diazabicyclo[2.2.2]octane (0.5 ml) were dissolved in ammonia solution (10 ml, 30%), and the mixture was stirred for about 30 min at room temperature. The resulting clear colourless solution was allowed to stand in air and, after slow evaporation of the solvent over 15 d, large colourless crystals of (I) were formed at the bottom of the vessel. The crystals were isolated, washed three times with water and dried in a vacuum desiccator using CaCl2 (yield 52.8%). Analysis, found: C 27.32, H 3.48, N 17.62, S 24.31%; calculated for C9H14AgN5S3: C 27.28, H 3.56, N 17.67, S 24.27%.

Refinement top

All H atoms were located in difference Fourier maps and were refined isotropically.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of (I) along the a axis. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The crystal packing of (I), showing the N—H···N hydrogen-bonding interactions as dashed lines. H atoms not involved in the hydrogen bonds have been omitted for clarity.
catena-Poly[1,4-diazonia[2.2.2]octane [silver(I)-tri-µ-thiocyanato-κ6S:S]] top
Crystal data top
(C6H14N2)[Ag(NCS)3]Dx = 2.030 Mg m3
Mr = 396.30Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63/mCell parameters from 506 reflections
a = 10.2148 (14) Åθ = 3–28°
c = 7.1740 (14) ŵ = 2.03 mm1
V = 648.26 (18) Å3T = 293 K
Z = 2Needle, colourless
F(000) = 3960.30 × 0.10 × 0.08 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer
506 independent reflections
Radiation source: fine-focus sealed tube489 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.160
ϕ and ω scansθmax = 27.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 138
Tmin = 0.582, Tmax = 0.855k = 1213
3024 measured reflectionsl = 98
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)] = 0.067Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168All H-atom parameters refined
S = 1.06 w = 1/[σ2(Fo2) + (0.0632P)2 + 3.05P]
where P = (Fo2 + 2Fc2)/3
506 reflections(Δ/σ)max < 0.001
43 parametersΔρmax = 0.81 e Å3
1 restraintΔρmin = 0.69 e Å3
Crystal data top
(C6H14N2)[Ag(NCS)3]Z = 2
Mr = 396.30Mo Kα radiation
Hexagonal, P63/mµ = 2.03 mm1
a = 10.2148 (14) ÅT = 293 K
c = 7.1740 (14) Å0.30 × 0.10 × 0.08 mm
V = 648.26 (18) Å3
Data collection top
Siemens SMART CCD area-detector
diffractometer
506 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
489 reflections with I > 2σ(I)
Tmin = 0.582, Tmax = 0.855Rint = 0.160
3024 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0671 restraint
wR(F2) = 0.168All H-atom parameters refined
S = 1.06Δρmax = 0.81 e Å3
506 reflectionsΔρmin = 0.69 e Å3
43 parameters
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.

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
Ag11.00001.00000.00000.0510 (5)
S10.7928 (2)0.7865 (2)0.25000.0352 (6)
N20.33330.66670.0774 (9)0.0213 (14)
C20.1800 (5)0.6260 (6)0.1463 (7)0.0256 (11)
N10.8424 (8)0.5408 (8)0.25000.0379 (16)
C10.8227 (8)0.6425 (8)0.25000.0268 (15)
H10.115 (5)0.538 (6)0.104 (7)0.009 (11)*
H20.163 (6)0.690 (7)0.092 (8)0.022 (13)*
H30.33330.66670.050 (3)0.03 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0514 (6)0.0514 (6)0.0503 (8)0.0257 (3)0.0000.000
S10.0249 (10)0.0292 (10)0.0530 (12)0.0145 (8)0.0000.000
N20.019 (2)0.019 (2)0.025 (3)0.0097 (10)0.0000.000
C20.016 (2)0.027 (2)0.033 (3)0.010 (2)0.0035 (19)0.001 (2)
N10.040 (4)0.031 (4)0.040 (3)0.015 (3)0.0000.000
C10.022 (3)0.028 (4)0.027 (3)0.011 (3)0.0000.000
Geometric parameters (Å, º) top
Ag1—S1i2.7993 (15)N2—C21.490 (5)
Ag1—S1ii2.7993 (15)N2—C2vii1.490 (5)
Ag1—S1iii2.7993 (15)N2—C2viii1.490 (5)
Ag1—S1iv2.7993 (15)N2—H30.91 (2)
Ag1—S1v2.7993 (15)C2—C2ix1.489 (10)
Ag1—S12.7993 (15)C2—H10.86 (5)
S1—C11.645 (8)C2—H20.86 (6)
S1—Ag1vi2.7993 (15)N1—C11.152 (10)
S1i—Ag1—S1ii96.65 (4)C1—S1—Ag1106.89 (19)
S1i—Ag1—S1iii83.35 (4)Ag1vi—S1—Ag179.69 (5)
S1ii—Ag1—S1iii180.0C2—N2—C2vii109.6 (3)
S1i—Ag1—S1iv96.65 (4)C2—N2—C2viii109.6 (3)
S1ii—Ag1—S1iv83.35 (4)C2vii—N2—C2viii109.6 (3)
S1iii—Ag1—S1iv96.65 (4)C2—N2—H3109.4 (3)
S1i—Ag1—S1v180.0C2vii—N2—H3109.4 (3)
S1ii—Ag1—S1v83.35 (4)C2viii—N2—H3109.4 (3)
S1iii—Ag1—S1v96.65 (4)C2ix—C2—N2109.4 (3)
S1iv—Ag1—S1v83.35 (4)C2ix—C2—H1111 (3)
S1i—Ag1—S183.35 (4)N2—C2—H1109 (3)
S1ii—Ag1—S196.65 (4)C2ix—C2—H2117 (4)
S1iii—Ag1—S183.35 (4)N2—C2—H2103 (4)
S1iv—Ag1—S1180.0H1—C2—H2107 (5)
S1v—Ag1—S196.65 (4)N1—C1—S1179.5 (7)
C1—S1—Ag1vi106.89 (19)
S1i—Ag1—S1—C162.66 (19)S1iii—Ag1—S1—Ag1vi42.023 (15)
S1ii—Ag1—S1—C133.30 (18)S1iv—Ag1—S1—Ag1vi99.40 (12)
S1iii—Ag1—S1—C1146.70 (18)S1v—Ag1—S1—Ag1vi137.977 (15)
S1iv—Ag1—S1—C1156 (46)C2vii—N2—C2—C2ix60.1 (4)
S1v—Ag1—S1—C1117.34 (19)C2viii—N2—C2—C2ix60.1 (4)
S1i—Ag1—S1—Ag1vi42.023 (15)Ag1vi—S1—C1—N1137.96 (6)
S1ii—Ag1—S1—Ag1vi137.977 (15)Ag1—S1—C1—N1137.96 (6)
Symmetry codes: (i) y+2, xy+1, z; (ii) xy+1, x, z; (iii) x+y+1, x+2, z; (iv) x+2, y+2, z; (v) y, x+y+1, z; (vi) x+2, y+2, z+1/2; (vii) x+y, x+1, z; (viii) y+1, xy+1, z; (ix) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H3···N1x0.91 (2)2.44 (1)3.070 (7)126 (1)
Symmetry code: (x) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula(C6H14N2)[Ag(NCS)3]
Mr396.30
Crystal system, space groupHexagonal, P63/m
Temperature (K)293
a, c (Å)10.2148 (14), 7.1740 (14)
V3)648.26 (18)
Z2
Radiation typeMo Kα
µ (mm1)2.03
Crystal size (mm)0.30 × 0.10 × 0.08
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.582, 0.855
No. of measured, independent and
observed [I > 2σ(I)] reflections
3024, 506, 489
Rint0.160
(sin θ/λ)max1)0.638
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.168, 1.06
No. of reflections506
No. of parameters43
No. of restraints1
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.81, 0.69

Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H3···N1i0.91 (2)2.443 (14)3.070 (7)125.9 (4)
Symmetry code: (i) x+1, y+1, z.
 

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