Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026360/bt2378sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026360/bt2378Isup2.hkl |
CCDC reference: 654697
Silver trifluoromethylsulfonate (0.1 mmol, 26 mg) dissolved in water (2 ml) was mixed with 4-amino-3,5-dimethyl-1,2,4-triazole (0.1 mmol, 12 mg) dissolved in ethanol (2 ml) of ethanol). Ether was then diffused into the solution to yield prisms in about 50% yield.
The two trifluoromethylsulfonate ions are not hydrogen bonded to the tetranuclear cluster. The six sulfur–oxygen bond distances were restrained to within 0.01 Å of each other, as were the six sulfur-oxygen and carbon-fluorine bond distances. The fluroine···fluorine distances were similarly restrained in each ion.
The anisotropic displacement parameters of the solvate acetonitrile molecule were restrained so that the atoms were nearly isotropic.
The carbon-bound H atoms were placed in calculated positions [C—H 0.93 to 0.96 Å; U(H) = 1.2 to 1.5 times Ueq(C)]. The nitrogen- and oxygen-bound H atoms were similarly treated. These were included in the refinement in the riding model approximation. The amino –NH2 groups were assumed to be planar whereas the methyl groups were rotated to fit the electron density. The amino groups are probably not planar as there are short intermolecular H···H interactions; they are probably disordered as there are no strong N···O hydrogen bonds in the crystal structure.
The final difference Fourier map had a large peak at about 1 Å from Ag1 as well as a deep hole at a similar distance from this atom, and is probably a consequence of inadequate absorption. This is supported by the large difference between the expected and calculated transmission factors.
Silver perchlorate reacts with 4-amino-3,5-dimethyl-1,2,4-triazole in acetonitrile to form [µ2-(C4H8N4)6Ag4] [µ2-(C4H8N4)6(C2H3N)2Ag4] 8[ClO4].2H2O, which features two tetranuclear cluster ions. The N-heterocycles in both each bridges two silver atoms. In acetonitrile-coordinated cluster, there are three-coordinate trigonal planar and four-coordinate tetrahedral silver atoms, with the higher coordination arising from coordination by the water molecules. The solvent-free cluster has only trigonal-planar silver atoms (Wang et al., 2006).
The synthesis when with silver trifluoromethylsulfonate in acetonitrile led to the isolation of the acetonitrile-coordinated tetranuclear cluster [µ2-(C4H8N4)6(C2H3N)2Ag4]4+, whose charge is balanced by four trifluoromethylsulfonate ions. The N-heterocycles bridge two silver atoms, and two of the silver atoms are also coordinated by acetonitrile. The salt crystallizes as an acetonitrile disolvate. The N-heterocycle each bridges to two silver atoms, and two of the silver atoms are also coordinated by acetonitrile.
For a study of the complex [µ2-(C4H8N4)6Ag4][µ2-(C4H8N4)6(C2H3N)2Ag4](ClO4)8.2H2O, see Wang et al. (2006).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: publCIF (Westrip, 2007).
Fig. 1. Thermal ellipsoid plot of the tetranuclear [(C7H8N4)6(C2H3N)2Ag4]4+ cation; ellipsoids are drawn at the 30% probability level. Symmetry code (i): 2 - x, 1 - y, 1 - z. |
[Ag4(C4H8N4)6(C2H3N)2](CF3O3S)4·2C2H3N | Z = 1 |
Mr = 1864.84 | F(000) = 928 |
Triclinic, P1 | Dx = 1.751 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 12.110 (3) Å | Cell parameters from 12901 reflections |
b = 12.695 (3) Å | θ = 3.2–27.5° |
c = 13.001 (3) Å | µ = 1.31 mm−1 |
α = 108.59 (2)° | T = 295 K |
β = 92.84 (2)° | Prism, colourless |
γ = 108.68 (2)° | 0.38 × 0.24 × 0.18 mm |
V = 1768.9 (7) Å3 |
Rigaku R-AXIS RAPID IP diffractometer | 8026 independent reflections |
Radiation source: fine-focus sealed tube | 5532 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −15→15 |
Tmin = 0.294, Tmax = 0.790 | k = −16→16 |
17453 measured reflections | l = −16→16 |
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)] = 0.074 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.239 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1356P)2 + 1.8203P] where P = (Fo2 + 2Fc2)/3 |
8026 reflections | (Δ/σ)max = 0.001 |
440 parameters | Δρmax = 2.27 e Å−3 |
150 restraints | Δρmin = −1.07 e Å−3 |
[Ag4(C4H8N4)6(C2H3N)2](CF3O3S)4·2C2H3N | γ = 108.68 (2)° |
Mr = 1864.84 | V = 1768.9 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 12.110 (3) Å | Mo Kα radiation |
b = 12.695 (3) Å | µ = 1.31 mm−1 |
c = 13.001 (3) Å | T = 295 K |
α = 108.59 (2)° | 0.38 × 0.24 × 0.18 mm |
β = 92.84 (2)° |
Rigaku R-AXIS RAPID IP diffractometer | 8026 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 5532 reflections with I > 2σ(I) |
Tmin = 0.294, Tmax = 0.790 | Rint = 0.046 |
17453 measured reflections |
R[F2 > 2σ(F2)] = 0.074 | 150 restraints |
wR(F2) = 0.239 | H-atom parameters constrained |
S = 1.07 | Δρmax = 2.27 e Å−3 |
8026 reflections | Δρmin = −1.07 e Å−3 |
440 parameters |
x | y | z | Uiso*/Ueq | ||
Ag1 | 0.88000 (5) | 0.37448 (5) | 0.53930 (4) | 0.0621 (2) | |
Ag2 | 0.88609 (5) | 0.34115 (5) | 0.27393 (5) | 0.0638 (2) | |
S1 | 0.7324 (2) | −0.2778 (2) | 0.18838 (19) | 0.0805 (6) | |
S2 | 0.35409 (18) | 0.13112 (19) | 0.22789 (16) | 0.0712 (5) | |
F1 | 0.9445 (7) | −0.1622 (9) | 0.2985 (8) | 0.170 (4) | |
F2 | 0.8266 (7) | −0.0761 (8) | 0.3487 (7) | 0.160 (3) | |
F3 | 0.8888 (11) | −0.0812 (11) | 0.2008 (9) | 0.217 (5) | |
F4 | 0.1809 (7) | −0.0452 (7) | 0.2334 (7) | 0.158 (3) | |
F5 | 0.1678 (7) | −0.0141 (7) | 0.0858 (6) | 0.160 (3) | |
F6 | 0.2856 (7) | −0.0934 (6) | 0.1161 (7) | 0.149 (3) | |
O1 | 0.6474 (7) | −0.2360 (8) | 0.1530 (7) | 0.132 (3) | |
O2 | 0.7789 (8) | −0.3403 (8) | 0.0991 (6) | 0.131 (3) | |
O3 | 0.7050 (9) | −0.3320 (9) | 0.2672 (7) | 0.159 (4) | |
O4 | 0.4239 (6) | 0.1125 (7) | 0.3072 (6) | 0.110 (2) | |
O5 | 0.4112 (6) | 0.1538 (7) | 0.1402 (5) | 0.111 (2) | |
O6 | 0.2899 (6) | 0.2062 (6) | 0.2726 (5) | 0.0957 (19) | |
N1 | 0.7678 (5) | 0.1969 (5) | 0.4177 (4) | 0.0578 (13) | |
N2 | 0.7624 (5) | 0.1844 (5) | 0.3087 (5) | 0.0579 (13) | |
N3 | 0.6319 (5) | 0.0297 (5) | 0.3212 (5) | 0.0582 (13) | |
N4 | 0.5376 (6) | −0.0794 (6) | 0.2984 (6) | 0.0746 (18) | |
H41 | 0.5009 | −0.1217 | 0.2303 | 0.090* | |
H42 | 0.5155 | −0.1049 | 0.3523 | 0.090* | |
N5 | 0.8361 (5) | 0.5079 (5) | 0.6744 (4) | 0.0562 (13) | |
N6 | 0.7571 (5) | 0.5996 (5) | 0.8023 (5) | 0.0561 (13) | |
N7 | 0.9223 (5) | 0.6100 (5) | 0.7420 (5) | 0.0561 (13) | |
N8 | 0.6722 (5) | 0.6246 (6) | 0.8662 (6) | 0.0739 (18) | |
H81 | 0.5984 | 0.5749 | 0.8477 | 0.089* | |
H82 | 0.6928 | 0.6899 | 0.9246 | 0.089* | |
N9 | 0.8379 (5) | 0.4932 (5) | 0.4025 (5) | 0.0561 (13) | |
N10 | 0.9244 (4) | 0.6030 (5) | 0.4585 (5) | 0.0541 (13) | |
N11 | 0.7536 (4) | 0.6201 (5) | 0.4680 (4) | 0.0517 (12) | |
N12 | 0.6623 (5) | 0.6652 (6) | 0.4855 (5) | 0.0665 (16) | |
H121 | 0.5886 | 0.6184 | 0.4565 | 0.080* | |
H112 | 0.6784 | 0.7404 | 0.5254 | 0.080* | |
N13 | 0.7755 (9) | 0.3396 (10) | 0.1152 (8) | 0.114 (3) | |
N14 | 0.250 (3) | −0.308 (3) | 0.189 (2) | 0.264 (11) | |
C1 | 0.6685 (9) | 0.0784 (10) | 0.5277 (8) | 0.097 (3) | |
H1A | 0.7029 | 0.0213 | 0.5322 | 0.145* | |
H1B | 0.5851 | 0.0474 | 0.5278 | 0.145* | |
H1C | 0.7045 | 0.1508 | 0.5897 | 0.145* | |
C2 | 0.6887 (6) | 0.1028 (7) | 0.4236 (6) | 0.0623 (17) | |
C3 | 0.6779 (6) | 0.0828 (6) | 0.2511 (6) | 0.0569 (15) | |
C4 | 0.6397 (8) | 0.0329 (8) | 0.1312 (6) | 0.075 (2) | |
H4A | 0.6872 | 0.0858 | 0.0985 | 0.113* | |
H4B | 0.5582 | 0.0233 | 0.1144 | 0.113* | |
H4C | 0.6487 | −0.0429 | 0.1022 | 0.113* | |
C5 | 0.6178 (7) | 0.4084 (9) | 0.6657 (9) | 0.084 (3) | |
H5A | 0.6170 | 0.3615 | 0.5911 | 0.126* | |
H5B | 0.5589 | 0.4444 | 0.6671 | 0.126* | |
H5C | 0.6010 | 0.3585 | 0.7092 | 0.126* | |
C6 | 0.7363 (6) | 0.5028 (7) | 0.7115 (6) | 0.0579 (16) | |
C7 | 0.8760 (6) | 0.6652 (7) | 0.8194 (6) | 0.0579 (16) | |
C8 | 0.9362 (8) | 0.7778 (9) | 0.9108 (8) | 0.091 (3) | |
H8A | 1.0201 | 0.8008 | 0.9125 | 0.136* | |
H8B | 0.9178 | 0.7680 | 0.9789 | 0.136* | |
H8C | 0.9100 | 0.8382 | 0.9008 | 0.136* | |
C9 | 0.9304 (7) | 0.8075 (7) | 0.5646 (8) | 0.077 (2) | |
H9A | 0.9333 | 0.8188 | 0.6415 | 0.116* | |
H9B | 0.8855 | 0.8506 | 0.5454 | 0.116* | |
H9C | 1.0093 | 0.8363 | 0.5499 | 0.116* | |
C10 | 0.8730 (5) | 0.6783 (6) | 0.4979 (5) | 0.0538 (15) | |
C11 | 0.7364 (6) | 0.5056 (6) | 0.4077 (5) | 0.0559 (15) | |
C12 | 0.6179 (6) | 0.4146 (7) | 0.3571 (7) | 0.069 (2) | |
H12C | 0.6038 | 0.4019 | 0.2800 | 0.104* | |
H12D | 0.5589 | 0.4413 | 0.3922 | 0.104* | |
H12E | 0.6141 | 0.3414 | 0.3662 | 0.104* | |
C13 | 0.6966 (9) | 0.3471 (10) | 0.0752 (8) | 0.089 (3) | |
C14 | 0.5926 (9) | 0.3532 (13) | 0.0198 (10) | 0.115 (4) | |
H14A | 0.5555 | 0.2814 | −0.0426 | 0.172* | |
H14B | 0.6158 | 0.4199 | −0.0045 | 0.172* | |
H14C | 0.5379 | 0.3625 | 0.0699 | 0.172* | |
C15 | 0.8526 (9) | −0.1444 (10) | 0.2621 (8) | 0.116 (4) | |
C16 | 0.2423 (8) | −0.0117 (9) | 0.1627 (7) | 0.104 (3) | |
C17 | 0.148 (2) | −0.3490 (19) | 0.1723 (19) | 0.167 (7) | |
C18 | 0.021 (3) | −0.403 (3) | 0.146 (3) | 0.265 (13) | |
H18A | −0.0037 | −0.4790 | 0.1551 | 0.398* | |
H18B | −0.0053 | −0.4133 | 0.0717 | 0.398* | |
H18C | −0.0137 | −0.3526 | 0.1952 | 0.398* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0531 (3) | 0.0673 (4) | 0.0490 (3) | 0.0140 (2) | 0.0020 (2) | 0.0068 (2) |
Ag2 | 0.0540 (3) | 0.0680 (4) | 0.0571 (3) | 0.0103 (3) | 0.0154 (2) | 0.0165 (3) |
S1 | 0.0831 (14) | 0.0877 (14) | 0.0694 (13) | 0.0274 (12) | 0.0081 (10) | 0.0298 (11) |
S2 | 0.0701 (11) | 0.0772 (12) | 0.0525 (10) | 0.0166 (9) | 0.0108 (8) | 0.0146 (9) |
F1 | 0.111 (5) | 0.201 (7) | 0.171 (7) | 0.060 (5) | −0.003 (5) | 0.032 (6) |
F2 | 0.139 (5) | 0.150 (6) | 0.147 (6) | 0.057 (5) | 0.001 (5) | −0.007 (5) |
F3 | 0.220 (8) | 0.199 (8) | 0.194 (8) | 0.006 (6) | 0.045 (7) | 0.088 (7) |
F4 | 0.138 (5) | 0.147 (6) | 0.165 (7) | 0.002 (4) | 0.055 (5) | 0.067 (5) |
F5 | 0.136 (5) | 0.156 (6) | 0.127 (6) | 0.009 (5) | −0.038 (5) | 0.023 (5) |
F6 | 0.173 (6) | 0.091 (4) | 0.146 (6) | 0.029 (4) | 0.037 (5) | 0.009 (4) |
O1 | 0.126 (5) | 0.131 (6) | 0.123 (6) | 0.054 (5) | −0.029 (4) | 0.022 (5) |
O2 | 0.137 (6) | 0.129 (6) | 0.112 (6) | 0.050 (5) | 0.019 (5) | 0.022 (5) |
O3 | 0.195 (8) | 0.164 (7) | 0.108 (6) | 0.024 (6) | 0.033 (6) | 0.071 (6) |
O4 | 0.095 (4) | 0.120 (5) | 0.113 (5) | 0.039 (4) | −0.005 (4) | 0.041 (4) |
O5 | 0.113 (5) | 0.122 (5) | 0.089 (5) | 0.023 (4) | 0.036 (4) | 0.039 (4) |
O6 | 0.107 (4) | 0.099 (4) | 0.075 (4) | 0.046 (4) | 0.015 (3) | 0.013 (3) |
N1 | 0.052 (3) | 0.064 (3) | 0.042 (3) | 0.007 (3) | 0.010 (2) | 0.012 (2) |
N2 | 0.060 (3) | 0.060 (3) | 0.042 (3) | 0.011 (3) | 0.015 (2) | 0.012 (2) |
N3 | 0.049 (3) | 0.062 (3) | 0.050 (3) | 0.008 (2) | 0.011 (2) | 0.012 (3) |
N4 | 0.071 (4) | 0.066 (4) | 0.057 (4) | −0.010 (3) | 0.007 (3) | 0.018 (3) |
N5 | 0.050 (3) | 0.067 (3) | 0.041 (3) | 0.016 (3) | 0.009 (2) | 0.010 (2) |
N6 | 0.051 (3) | 0.070 (3) | 0.054 (3) | 0.026 (3) | 0.017 (2) | 0.025 (3) |
N7 | 0.050 (3) | 0.063 (3) | 0.044 (3) | 0.013 (2) | 0.010 (2) | 0.012 (2) |
N8 | 0.058 (3) | 0.086 (4) | 0.073 (4) | 0.023 (3) | 0.028 (3) | 0.023 (4) |
N9 | 0.046 (3) | 0.060 (3) | 0.048 (3) | 0.012 (2) | 0.003 (2) | 0.006 (2) |
N10 | 0.044 (3) | 0.060 (3) | 0.049 (3) | 0.014 (2) | 0.004 (2) | 0.014 (2) |
N11 | 0.049 (3) | 0.061 (3) | 0.042 (3) | 0.020 (2) | 0.008 (2) | 0.013 (2) |
N12 | 0.046 (3) | 0.073 (4) | 0.065 (4) | 0.023 (3) | 0.008 (3) | 0.003 (3) |
N13 | 0.110 (7) | 0.126 (8) | 0.094 (6) | 0.028 (6) | −0.019 (5) | 0.043 (6) |
N14 | 0.259 (14) | 0.272 (14) | 0.261 (15) | 0.092 (10) | 0.042 (10) | 0.099 (10) |
C1 | 0.088 (6) | 0.121 (8) | 0.057 (5) | 0.001 (5) | 0.013 (4) | 0.036 (5) |
C2 | 0.056 (4) | 0.072 (4) | 0.051 (4) | 0.015 (3) | 0.015 (3) | 0.018 (3) |
C3 | 0.056 (4) | 0.050 (3) | 0.048 (3) | 0.008 (3) | 0.004 (3) | 0.006 (3) |
C4 | 0.090 (6) | 0.079 (5) | 0.035 (3) | 0.013 (4) | 0.005 (3) | 0.009 (3) |
C5 | 0.045 (4) | 0.091 (6) | 0.092 (6) | 0.007 (4) | 0.005 (4) | 0.021 (5) |
C6 | 0.050 (3) | 0.069 (4) | 0.051 (4) | 0.017 (3) | 0.005 (3) | 0.021 (3) |
C7 | 0.054 (4) | 0.068 (4) | 0.048 (3) | 0.019 (3) | 0.013 (3) | 0.018 (3) |
C8 | 0.081 (6) | 0.089 (6) | 0.071 (5) | 0.023 (5) | 0.019 (4) | −0.006 (5) |
C9 | 0.055 (4) | 0.066 (4) | 0.083 (6) | 0.012 (3) | −0.003 (4) | 0.002 (4) |
C10 | 0.048 (3) | 0.065 (4) | 0.042 (3) | 0.017 (3) | 0.006 (2) | 0.013 (3) |
C11 | 0.053 (4) | 0.065 (4) | 0.041 (3) | 0.013 (3) | 0.005 (3) | 0.017 (3) |
C12 | 0.051 (4) | 0.064 (4) | 0.069 (5) | 0.010 (3) | 0.000 (3) | 0.004 (4) |
C13 | 0.088 (6) | 0.103 (7) | 0.060 (5) | 0.019 (5) | −0.003 (4) | 0.025 (5) |
C14 | 0.081 (6) | 0.158 (11) | 0.099 (8) | 0.037 (7) | −0.001 (6) | 0.044 (8) |
C15 | 0.095 (8) | 0.135 (10) | 0.098 (9) | 0.035 (7) | −0.001 (6) | 0.025 (8) |
C16 | 0.110 (8) | 0.090 (7) | 0.095 (8) | 0.017 (6) | 0.024 (7) | 0.030 (6) |
C17 | 0.171 (10) | 0.171 (10) | 0.182 (11) | 0.066 (8) | 0.025 (8) | 0.088 (8) |
C18 | 0.256 (16) | 0.269 (16) | 0.278 (16) | 0.092 (10) | 0.023 (10) | 0.109 (10) |
Ag1—N1 | 2.232 (5) | N10—C10 | 1.291 (9) |
Ag1—N5 | 2.238 (5) | N10—Ag1i | 2.290 (5) |
Ag1—N10i | 2.290 (5) | N11—C11 | 1.354 (9) |
Ag1—Ag2 | 3.3469 (11) | N11—C10 | 1.366 (8) |
Ag2—N2 | 2.267 (6) | N11—N12 | 1.396 (7) |
Ag2—N7i | 2.241 (5) | N12—H121 | 0.8800 |
Ag2—N9 | 2.371 (6) | N12—H112 | 0.8800 |
Ag2—N13 | 2.395 (9) | N13—C13 | 1.110 (13) |
S1—O3 | 1.404 (6) | N14—C17 | 1.15 (3) |
S1—O1 | 1.419 (6) | C1—C2 | 1.496 (11) |
S1—O2 | 1.434 (6) | C1—H1A | 0.9600 |
S1—C15 | 1.776 (12) | C1—H1B | 0.9600 |
S2—O6 | 1.420 (5) | C1—H1C | 0.9600 |
S2—O4 | 1.425 (5) | C3—C4 | 1.469 (9) |
S2—O5 | 1.422 (5) | C4—H4A | 0.9600 |
S2—C16 | 1.781 (11) | C4—H4B | 0.9600 |
F1—C15 | 1.301 (7) | C4—H4C | 0.9600 |
F2—C15 | 1.306 (8) | C5—C6 | 1.486 (10) |
F3—C15 | 1.299 (8) | C5—H5A | 0.9600 |
F4—C16 | 1.301 (7) | C5—H5B | 0.9600 |
F5—C16 | 1.298 (7) | C5—H5C | 0.9600 |
F6—C16 | 1.302 (7) | C7—C8 | 1.466 (11) |
N1—C2 | 1.298 (9) | C8—H8A | 0.9600 |
N1—N2 | 1.370 (8) | C8—H8B | 0.9600 |
N2—C3 | 1.318 (8) | C8—H8C | 0.9600 |
N3—C3 | 1.341 (9) | C9—C10 | 1.493 (10) |
N3—C2 | 1.349 (9) | C9—H9A | 0.9600 |
N3—N4 | 1.415 (8) | C9—H9B | 0.9600 |
N4—H41 | 0.8800 | C9—H9C | 0.9600 |
N4—H42 | 0.8800 | C11—C12 | 1.479 (9) |
N5—C6 | 1.313 (9) | C12—H12C | 0.9600 |
N5—N7 | 1.363 (8) | C12—H12D | 0.9600 |
N6—C6 | 1.347 (9) | C12—H12E | 0.9600 |
N6—C7 | 1.379 (9) | C13—C14 | 1.456 (14) |
N6—N8 | 1.404 (8) | C14—H14A | 0.9600 |
N7—C7 | 1.294 (9) | C14—H14B | 0.9600 |
N7—Ag2i | 2.241 (5) | C14—H14C | 0.9600 |
N8—H81 | 0.8800 | C17—C18 | 1.44 (3) |
N8—H82 | 0.8800 | C18—H18A | 0.9600 |
N9—C11 | 1.291 (9) | C18—H18B | 0.9600 |
N9—N10 | 1.383 (7) | C18—H18C | 0.9600 |
N1—Ag1—N5 | 131.8 (2) | N3—C2—C1 | 126.1 (7) |
N1—Ag1—N10i | 109.7 (2) | N2—C3—N3 | 108.0 (6) |
N5—Ag1—N10i | 117.2 (2) | N2—C3—C4 | 127.2 (7) |
N1—Ag1—Ag2 | 64.14 (15) | N3—C3—C4 | 124.8 (6) |
N5—Ag1—Ag2 | 131.10 (16) | C3—C4—H4A | 109.5 |
N10i—Ag1—Ag2 | 82.56 (14) | C3—C4—H4B | 109.5 |
N2—Ag2—N9 | 97.9 (2) | H4A—C4—H4B | 109.5 |
N2—Ag2—N7i | 130.8 (2) | C3—C4—H4C | 109.5 |
N2—Ag2—N13 | 102.6 (3) | H4A—C4—H4C | 109.5 |
N7i—Ag2—N9 | 114.7 (2) | H4B—C4—H4C | 109.5 |
N7i—Ag2—N13 | 109.4 (3) | C6—C5—H5A | 109.5 |
N9—Ag2—N13 | 95.6 (3) | C6—C5—H5B | 109.5 |
N7i—Ag2—Ag1 | 105.28 (15) | H5A—C5—H5B | 109.5 |
N2—Ag2—Ag1 | 63.63 (14) | C6—C5—H5C | 109.5 |
N9—Ag2—Ag1 | 55.38 (15) | H5A—C5—H5C | 109.5 |
N13—Ag2—Ag1 | 142.1 (3) | H5B—C5—H5C | 109.5 |
O3—S1—O1 | 116.7 (5) | N5—C6—N6 | 108.7 (6) |
O3—S1—O2 | 114.5 (5) | N5—C6—C5 | 128.0 (7) |
O1—S1—O2 | 112.9 (4) | N6—C6—C5 | 123.3 (7) |
O3—S1—C15 | 103.2 (6) | N7—C7—N6 | 108.2 (6) |
O1—S1—C15 | 102.8 (5) | N7—C7—C8 | 127.5 (7) |
O2—S1—C15 | 104.7 (5) | N6—C7—C8 | 124.3 (6) |
O6—S2—O4 | 115.0 (4) | C7—C8—H8A | 109.5 |
O6—S2—O5 | 114.5 (4) | C7—C8—H8B | 109.5 |
O4—S2—O5 | 114.9 (4) | H8A—C8—H8B | 109.5 |
O6—S2—C16 | 103.9 (4) | C7—C8—H8C | 109.5 |
O4—S2—C16 | 102.9 (4) | H8A—C8—H8C | 109.5 |
O5—S2—C16 | 103.6 (4) | H8B—C8—H8C | 109.5 |
C2—N1—N2 | 107.5 (5) | C10—C9—H9A | 109.5 |
C2—N1—Ag1 | 134.9 (5) | C10—C9—H9B | 109.5 |
N2—N1—Ag1 | 116.6 (4) | H9A—C9—H9B | 109.5 |
C3—N2—N1 | 108.0 (6) | C10—C9—H9C | 109.5 |
C3—N2—Ag2 | 136.6 (5) | H9A—C9—H9C | 109.5 |
N1—N2—Ag2 | 115.2 (4) | H9B—C9—H9C | 109.5 |
C3—N3—C2 | 107.4 (6) | N10—C10—N11 | 108.3 (6) |
C3—N3—N4 | 128.8 (6) | N10—C10—C9 | 127.4 (6) |
C2—N3—N4 | 123.8 (6) | N11—C10—C9 | 124.2 (6) |
N3—N4—H41 | 120.0 | N9—C11—N11 | 108.8 (6) |
N3—N4—H42 | 120.0 | N9—C11—C12 | 128.1 (7) |
H41—N4—H42 | 120.0 | N11—C11—C12 | 123.0 (6) |
C6—N5—N7 | 107.9 (5) | C11—C12—H12C | 109.5 |
C6—N5—Ag1 | 130.7 (5) | C11—C12—H12D | 109.5 |
N7—N5—Ag1 | 121.0 (4) | H12C—C12—H12D | 109.5 |
C6—N6—C7 | 106.5 (5) | C11—C12—H12E | 109.5 |
C6—N6—N8 | 125.4 (6) | H12C—C12—H12E | 109.5 |
C7—N6—N8 | 128.1 (6) | H12D—C12—H12E | 109.5 |
C7—N7—N5 | 108.8 (5) | N13—C13—C14 | 178.1 (13) |
C7—N7—Ag2i | 127.3 (5) | C13—C14—H14A | 109.5 |
N5—N7—Ag2i | 123.7 (4) | C13—C14—H14B | 109.5 |
N6—N8—H81 | 120.0 | H14A—C14—H14B | 109.5 |
N6—N8—H82 | 120.0 | C13—C14—H14C | 109.5 |
H81—N8—H82 | 120.0 | H14A—C14—H14C | 109.5 |
C11—N9—N10 | 107.9 (6) | H14B—C14—H14C | 109.5 |
C11—N9—Ag2 | 128.4 (4) | F3—C15—F1 | 106.1 (8) |
N10—N9—Ag2 | 120.3 (4) | F3—C15—F2 | 106.6 (8) |
C10—N10—N9 | 108.2 (5) | F1—C15—F2 | 105.3 (7) |
C10—N10—Ag1i | 131.8 (4) | F3—C15—S1 | 111.5 (8) |
N9—N10—Ag1i | 119.9 (4) | F1—C15—S1 | 113.4 (8) |
C11—N11—C10 | 106.7 (5) | F2—C15—S1 | 113.3 (8) |
C11—N11—N12 | 123.7 (5) | F5—C16—F4 | 106.8 (7) |
C10—N11—N12 | 129.4 (6) | F5—C16—F6 | 106.1 (7) |
N11—N12—H121 | 120.0 | F4—C16—F6 | 107.4 (7) |
N11—N12—H112 | 120.0 | F5—C16—S2 | 112.8 (7) |
H121—N12—H112 | 120.0 | F4—C16—S2 | 111.0 (7) |
C13—N13—Ag2 | 150.4 (10) | F6—C16—S2 | 112.5 (7) |
C2—C1—H1A | 109.5 | N14—C17—C18 | 178 (3) |
C2—C1—H1B | 109.5 | C17—C18—H18A | 109.5 |
H1A—C1—H1B | 109.5 | C17—C18—H18B | 109.5 |
C2—C1—H1C | 109.5 | H18A—C18—H18B | 109.5 |
H1A—C1—H1C | 109.5 | C17—C18—H18C | 109.5 |
H1B—C1—H1C | 109.5 | H18A—C18—H18C | 109.5 |
N1—C2—N3 | 109.1 (6) | H18B—C18—H18C | 109.5 |
N1—C2—C1 | 124.8 (7) | ||
N1—Ag1—Ag2—N7i | −125.5 (2) | N4—N3—C2—N1 | −177.8 (7) |
N5—Ag1—Ag2—N7i | 110.5 (2) | C3—N3—C2—C1 | −178.3 (9) |
N10i—Ag1—Ag2—N7i | −9.4 (2) | N4—N3—C2—C1 | 4.5 (13) |
N1—Ag1—Ag2—N2 | 2.8 (2) | N1—N2—C3—N3 | −1.5 (8) |
N5—Ag1—Ag2—N2 | −121.2 (3) | Ag2—N2—C3—N3 | −176.5 (5) |
N10i—Ag1—Ag2—N2 | 119.0 (2) | N1—N2—C3—C4 | 179.3 (8) |
N1—Ag1—Ag2—N9 | 124.7 (2) | Ag2—N2—C3—C4 | 4.3 (13) |
N5—Ag1—Ag2—N9 | 0.7 (2) | C2—N3—C3—N2 | 1.4 (8) |
N10i—Ag1—Ag2—N9 | −119.1 (2) | N4—N3—C3—N2 | 178.3 (7) |
N1—Ag1—Ag2—N13 | 78.8 (5) | C2—N3—C3—C4 | −179.4 (8) |
N5—Ag1—Ag2—N13 | −45.2 (5) | N4—N3—C3—C4 | −2.5 (13) |
N10i—Ag1—Ag2—N13 | −165.0 (4) | N7—N5—C6—N6 | −0.4 (8) |
N5—Ag1—N1—C2 | −48.6 (8) | Ag1—N5—C6—N6 | 172.8 (5) |
N10i—Ag1—N1—C2 | 117.3 (7) | N7—N5—C6—C5 | −179.8 (8) |
Ag2—Ag1—N1—C2 | −171.7 (8) | Ag1—N5—C6—C5 | −6.6 (12) |
N5—Ag1—N1—N2 | 118.5 (5) | C7—N6—C6—N5 | 0.1 (8) |
N10i—Ag1—N1—N2 | −75.6 (5) | N8—N6—C6—N5 | −179.0 (6) |
Ag2—Ag1—N1—N2 | −4.6 (4) | C7—N6—C6—C5 | 179.5 (8) |
C2—N1—N2—C3 | 1.0 (8) | N8—N6—C6—C5 | 0.5 (12) |
Ag1—N1—N2—C3 | −169.4 (5) | N5—N7—C7—N6 | −0.6 (8) |
C2—N1—N2—Ag2 | 177.3 (5) | Ag2i—N7—C7—N6 | −174.9 (4) |
Ag1—N1—N2—Ag2 | 6.8 (6) | N5—N7—C7—C8 | 179.2 (9) |
N7i—Ag2—N2—C3 | −101.9 (7) | Ag2i—N7—C7—C8 | 4.9 (12) |
N9—Ag2—N2—C3 | 125.4 (7) | C6—N6—C7—N7 | 0.3 (8) |
N13—Ag2—N2—C3 | 27.9 (8) | N8—N6—C7—N7 | 179.3 (7) |
Ag1—Ag2—N2—C3 | 170.3 (8) | C6—N6—C7—C8 | −179.5 (9) |
N7i—Ag2—N2—N1 | 83.2 (5) | N8—N6—C7—C8 | −0.5 (12) |
N9—Ag2—N2—N1 | −49.4 (5) | N9—N10—C10—N11 | −0.5 (7) |
N13—Ag2—N2—N1 | −146.9 (5) | Ag1i—N10—C10—N11 | 176.2 (4) |
Ag1—Ag2—N2—N1 | −4.5 (4) | N9—N10—C10—C9 | 179.7 (8) |
N1—Ag1—N5—C6 | 4.8 (8) | Ag1i—N10—C10—C9 | −3.5 (12) |
N10i—Ag1—N5—C6 | −160.3 (6) | C11—N11—C10—N10 | −0.4 (7) |
Ag2—Ag1—N5—C6 | 94.9 (6) | N12—N11—C10—N10 | −175.7 (6) |
N1—Ag1—N5—N7 | 177.3 (4) | C11—N11—C10—C9 | 179.4 (8) |
N10i—Ag1—N5—N7 | 12.2 (6) | N12—N11—C10—C9 | 4.1 (11) |
Ag2—Ag1—N5—N7 | −92.6 (5) | N10—N9—C11—N11 | −1.5 (8) |
C6—N5—N7—C7 | 0.6 (8) | Ag2—N9—C11—N11 | −160.3 (5) |
Ag1—N5—N7—C7 | −173.4 (5) | N10—N9—C11—C12 | 177.7 (7) |
C6—N5—N7—Ag2i | 175.2 (5) | Ag2—N9—C11—C12 | 18.8 (11) |
Ag1—N5—N7—Ag2i | 1.2 (7) | C10—N11—C11—N9 | 1.2 (7) |
N7i—Ag2—N9—C11 | 158.4 (6) | N12—N11—C11—N9 | 176.9 (6) |
N2—Ag2—N9—C11 | −59.5 (6) | C10—N11—C11—C12 | −178.0 (7) |
N13—Ag2—N9—C11 | 44.1 (7) | N12—N11—C11—C12 | −2.4 (11) |
Ag1—Ag2—N9—C11 | −109.6 (6) | O3—S1—C15—F3 | −179.1 (8) |
N7i—Ag2—N9—N10 | 1.8 (6) | O1—S1—C15—F3 | −57.3 (8) |
N2—Ag2—N9—N10 | 144.0 (5) | O2—S1—C15—F3 | 60.8 (8) |
N13—Ag2—N9—N10 | −112.5 (5) | O3—S1—C15—F1 | 61.2 (8) |
Ag1—Ag2—N9—N10 | 93.8 (5) | O1—S1—C15—F1 | −177.0 (7) |
C11—N9—N10—C10 | 1.2 (8) | O2—S1—C15—F1 | −58.9 (8) |
Ag2—N9—N10—C10 | 162.1 (5) | O3—S1—C15—F2 | −58.8 (8) |
C11—N9—N10—Ag1i | −175.9 (4) | O1—S1—C15—F2 | 63.0 (8) |
Ag2—N9—N10—Ag1i | −15.0 (6) | O2—S1—C15—F2 | −178.9 (7) |
N7i—Ag2—N13—C13 | −156 (2) | O6—S2—C16—F5 | 60.0 (7) |
N2—Ag2—N13—C13 | 62 (2) | O4—S2—C16—F5 | −179.9 (6) |
N9—Ag2—N13—C13 | −37 (2) | O5—S2—C16—F5 | −59.9 (7) |
Ag1—Ag2—N13—C13 | 0 (2) | O6—S2—C16—F4 | −59.8 (7) |
N2—N1—C2—N3 | −0.2 (8) | O4—S2—C16—F4 | 60.4 (7) |
Ag1—N1—C2—N3 | 167.7 (5) | O5—S2—C16—F4 | −179.7 (6) |
N2—N1—C2—C1 | 177.5 (8) | O6—S2—C16—F6 | 179.9 (6) |
Ag1—N1—C2—C1 | −14.6 (13) | O4—S2—C16—F6 | −60.0 (7) |
C3—N3—C2—N1 | −0.7 (8) | O5—S2—C16—F6 | 60.0 (7) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ag4(C4H8N4)6(C2H3N)2](CF3O3S)4·2C2H3N |
Mr | 1864.84 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 12.110 (3), 12.695 (3), 13.001 (3) |
α, β, γ (°) | 108.59 (2), 92.84 (2), 108.68 (2) |
V (Å3) | 1768.9 (7) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.31 |
Crystal size (mm) | 0.38 × 0.24 × 0.18 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID IP |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.294, 0.790 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17453, 8026, 5532 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.239, 1.07 |
No. of reflections | 8026 |
No. of parameters | 440 |
No. of restraints | 150 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.27, −1.07 |
Computer programs: RAPID-AUTO (Rigaku, 1998), RAPID-AUTO, CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), publCIF (Westrip, 2007).
Ag1—N1 | 2.232 (5) | Ag2—N7i | 2.241 (5) |
Ag1—N5 | 2.238 (5) | Ag2—N9 | 2.371 (6) |
Ag1—N10i | 2.290 (5) | Ag2—N13 | 2.395 (9) |
Ag2—N2 | 2.267 (6) | ||
N1—Ag1—N5 | 131.8 (2) | N2—Ag2—N13 | 102.6 (3) |
N1—Ag1—N10i | 109.7 (2) | N7i—Ag2—N9 | 114.7 (2) |
N5—Ag1—N10i | 117.2 (2) | N7i—Ag2—N13 | 109.4 (3) |
N2—Ag2—N9 | 97.9 (2) | N9—Ag2—N13 | 95.6 (3) |
N2—Ag2—N7i | 130.8 (2) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Silver perchlorate reacts with 4-amino-3,5-dimethyl-1,2,4-triazole in acetonitrile to form [µ2-(C4H8N4)6Ag4] [µ2-(C4H8N4)6(C2H3N)2Ag4] 8[ClO4].2H2O, which features two tetranuclear cluster ions. The N-heterocycles in both each bridges two silver atoms. In acetonitrile-coordinated cluster, there are three-coordinate trigonal planar and four-coordinate tetrahedral silver atoms, with the higher coordination arising from coordination by the water molecules. The solvent-free cluster has only trigonal-planar silver atoms (Wang et al., 2006).
The synthesis when with silver trifluoromethylsulfonate in acetonitrile led to the isolation of the acetonitrile-coordinated tetranuclear cluster [µ2-(C4H8N4)6(C2H3N)2Ag4]4+, whose charge is balanced by four trifluoromethylsulfonate ions. The N-heterocycles bridge two silver atoms, and two of the silver atoms are also coordinated by acetonitrile. The salt crystallizes as an acetonitrile disolvate. The N-heterocycle each bridges to two silver atoms, and two of the silver atoms are also coordinated by acetonitrile.