Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010401772X/av1193sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010401772X/av1193Isup2.hkl |
CCDC reference: 251294
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%.
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.
(C6H14N2)[Ag(NCS)3] | Dx = 2.030 Mg m−3 |
Mr = 396.30 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P63/m | Cell parameters from 506 reflections |
a = 10.2148 (14) Å | θ = 3–28° |
c = 7.1740 (14) Å | µ = 2.03 mm−1 |
V = 648.26 (18) Å3 | T = 293 K |
Z = 2 | Needle, colourless |
F(000) = 396 | 0.30 × 0.10 × 0.08 mm |
Siemens SMART CCD area-detector diffractometer | 506 independent reflections |
Radiation source: fine-focus sealed tube | 489 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.160 |
ϕ and ω scans | θmax = 27.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→8 |
Tmin = 0.582, Tmax = 0.855 | k = −12→13 |
3024 measured reflections | l = −9→8 |
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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.168 | All 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 parameters | Δρmax = 0.81 e Å−3 |
1 restraint | Δρmin = −0.69 e Å−3 |
(C6H14N2)[Ag(NCS)3] | Z = 2 |
Mr = 396.30 | Mo Kα radiation |
Hexagonal, P63/m | µ = 2.03 mm−1 |
a = 10.2148 (14) Å | T = 293 K |
c = 7.1740 (14) Å | 0.30 × 0.10 × 0.08 mm |
V = 648.26 (18) Å3 |
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 = 0.855 | Rint = 0.160 |
3024 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 1 restraint |
wR(F2) = 0.168 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.81 e Å−3 |
506 reflections | Δρmin = −0.69 e Å−3 |
43 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ag1 | 1.0000 | 1.0000 | 0.0000 | 0.0510 (5) | |
S1 | 0.7928 (2) | 0.7865 (2) | 0.2500 | 0.0352 (6) | |
N2 | 0.3333 | 0.6667 | 0.0774 (9) | 0.0213 (14) | |
C2 | 0.1800 (5) | 0.6260 (6) | 0.1463 (7) | 0.0256 (11) | |
N1 | 0.8424 (8) | 0.5408 (8) | 0.2500 | 0.0379 (16) | |
C1 | 0.8227 (8) | 0.6425 (8) | 0.2500 | 0.0268 (15) | |
H1 | 0.115 (5) | 0.538 (6) | 0.104 (7) | 0.009 (11)* | |
H2 | 0.163 (6) | 0.690 (7) | 0.092 (8) | 0.022 (13)* | |
H3 | 0.3333 | 0.6667 | −0.050 (3) | 0.03 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0514 (6) | 0.0514 (6) | 0.0503 (8) | 0.0257 (3) | 0.000 | 0.000 |
S1 | 0.0249 (10) | 0.0292 (10) | 0.0530 (12) | 0.0145 (8) | 0.000 | 0.000 |
N2 | 0.019 (2) | 0.019 (2) | 0.025 (3) | 0.0097 (10) | 0.000 | 0.000 |
C2 | 0.016 (2) | 0.027 (2) | 0.033 (3) | 0.010 (2) | −0.0035 (19) | 0.001 (2) |
N1 | 0.040 (4) | 0.031 (4) | 0.040 (3) | 0.015 (3) | 0.000 | 0.000 |
C1 | 0.022 (3) | 0.028 (4) | 0.027 (3) | 0.011 (3) | 0.000 | 0.000 |
Ag1—S1i | 2.7993 (15) | N2—C2 | 1.490 (5) |
Ag1—S1ii | 2.7993 (15) | N2—C2vii | 1.490 (5) |
Ag1—S1iii | 2.7993 (15) | N2—C2viii | 1.490 (5) |
Ag1—S1iv | 2.7993 (15) | N2—H3 | 0.91 (2) |
Ag1—S1v | 2.7993 (15) | C2—C2ix | 1.489 (10) |
Ag1—S1 | 2.7993 (15) | C2—H1 | 0.86 (5) |
S1—C1 | 1.645 (8) | C2—H2 | 0.86 (6) |
S1—Ag1vi | 2.7993 (15) | N1—C1 | 1.152 (10) |
S1i—Ag1—S1ii | 96.65 (4) | C1—S1—Ag1 | 106.89 (19) |
S1i—Ag1—S1iii | 83.35 (4) | Ag1vi—S1—Ag1 | 79.69 (5) |
S1ii—Ag1—S1iii | 180.0 | C2—N2—C2vii | 109.6 (3) |
S1i—Ag1—S1iv | 96.65 (4) | C2—N2—C2viii | 109.6 (3) |
S1ii—Ag1—S1iv | 83.35 (4) | C2vii—N2—C2viii | 109.6 (3) |
S1iii—Ag1—S1iv | 96.65 (4) | C2—N2—H3 | 109.4 (3) |
S1i—Ag1—S1v | 180.0 | C2vii—N2—H3 | 109.4 (3) |
S1ii—Ag1—S1v | 83.35 (4) | C2viii—N2—H3 | 109.4 (3) |
S1iii—Ag1—S1v | 96.65 (4) | C2ix—C2—N2 | 109.4 (3) |
S1iv—Ag1—S1v | 83.35 (4) | C2ix—C2—H1 | 111 (3) |
S1i—Ag1—S1 | 83.35 (4) | N2—C2—H1 | 109 (3) |
S1ii—Ag1—S1 | 96.65 (4) | C2ix—C2—H2 | 117 (4) |
S1iii—Ag1—S1 | 83.35 (4) | N2—C2—H2 | 103 (4) |
S1iv—Ag1—S1 | 180.0 | H1—C2—H2 | 107 (5) |
S1v—Ag1—S1 | 96.65 (4) | N1—C1—S1 | 179.5 (7) |
C1—S1—Ag1vi | 106.89 (19) | ||
S1i—Ag1—S1—C1 | −62.66 (19) | S1iii—Ag1—S1—Ag1vi | −42.023 (15) |
S1ii—Ag1—S1—C1 | 33.30 (18) | S1iv—Ag1—S1—Ag1vi | −99.40 (12) |
S1iii—Ag1—S1—C1 | −146.70 (18) | S1v—Ag1—S1—Ag1vi | −137.977 (15) |
S1iv—Ag1—S1—C1 | 156 (46) | C2vii—N2—C2—C2ix | −60.1 (4) |
S1v—Ag1—S1—C1 | 117.34 (19) | C2viii—N2—C2—C2ix | 60.1 (4) |
S1i—Ag1—S1—Ag1vi | 42.023 (15) | Ag1vi—S1—C1—N1 | 137.96 (6) |
S1ii—Ag1—S1—Ag1vi | 137.977 (15) | Ag1—S1—C1—N1 | −137.96 (6) |
Symmetry codes: (i) −y+2, x−y+1, z; (ii) x−y+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, x−y+1, z; (ix) x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H3···N1x | 0.91 (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] |
Mr | 396.30 |
Crystal system, space group | Hexagonal, P63/m |
Temperature (K) | 293 |
a, c (Å) | 10.2148 (14), 7.1740 (14) |
V (Å3) | 648.26 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.03 |
Crystal size (mm) | 0.30 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.582, 0.855 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3024, 506, 489 |
Rint | 0.160 |
(sin θ/λ)max (Å−1) | 0.638 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.168, 1.06 |
No. of reflections | 506 |
No. of parameters | 43 |
No. of restraints | 1 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.81, −0.69 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H3···N1i | 0.91 (2) | 2.443 (14) | 3.070 (7) | 125.9 (4) |
Symmetry code: (i) −x+1, −y+1, −z. |
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)