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Acta Cryst. (2007). E63, m1987-m1988    [ doi:10.1107/S1600536807027389 ]

A new configuration of the one-dimensional anionic Mo/S/Ag polymer, {[Ce(dmac)7MeOH][Mo3S12Ag3]}n (dmac is N,N-dimethylacetamide)

Y. Cao, J.-F. Zhang and C. Zhang

Abstract top

The self-assembly of tetrathiomolybdate, silver iodide and cerium nitrate in N,N-dimethylacetamide (dmac) and methanol resulted in a one-dimensional anionic Mo/S/Ag polymer, catena-poly[heptakis(N,N-dimethylacetamide-[kappa]O)(methanol-[kappa]O)cerium(III) [di-[mu]3-sulfido-octa-[mu]2-sulfido-disulfidotrisilver(I)trimolybdenum(VI)]], {[Ce(C4H9NO)7(CH4O)][Mo3S12Ag3]}n. The polymeric anion {[Mo3S12Ag3]n}3n- assumes a new configuration of a saw-tooth chain with the lengths of the sides in a 1:2 ratio. Such a configuration is intermediate between the polymeric anions in two reported compounds, viz. {[Ca(DMF)6][Mo2S8Ag2]}n and {[Ca(DMSO)6]2[W4S16Ag4]}n (DMF is dimethylformamide and DMSO is dimethyl sulfoxide). The metal atoms in the chain are nearly coplanar. The central Ce in the solvent-coordinated cation has distorted square-antiprismatic coordination. Of the seven N,N-dimethylacetamide (dmac) molecules present, one is found to be disordered over two sites, with occupancy factors of 0.63 and 0.37. The overall structure can be viewed as consisting of staggered layers parallel to (010), which are formed by anionic chains propagating along the a axis and cations distributed in the spaces between the anionic chains. No notable interactions are found between cations and polymeric anions except for electrostatic attractions.

Comment top

Heterothiometallic Mo(W)/S/Cu(Ag) polymers are of considerable interests for their structural richness (Niu et al., 2004) and promising applications as third-order nonlinear optic (NLO) materials (Zhang et al., 2007). The title compound represents a new configuration of 1-D Mo(W)/S/Ag polymers.

The asymmetric unit of the title compound comprises one solvent-coordinated cation [Ce(dmac)7MeOH]3+ (dmac = N,N'-dimethylacetamide) and a repeat unit of the polymeric anion [Mo3S12Ag3]3− (Fig. 1). The central Ce in the solvent-coordinated cation has distorted square antiprismatic coordination. Of the seven dmac molecules present, one is found to be disordered. The two components of the disordered dmac have occupancies of 0.63 and 0.37 (3). The Ce—O bond lengths between Ce and seven O atoms from dmac are similar but much shorter than that between Ce and O from methanol. The repeat unit in the anionic chains consists of two butterfly-shaped and one linear [MoS4Ag2] sub-units joined together by shared silver atoms. The geometry of the sub-units is very similar to those in previous reported 1-D Mo(W)/S/Ag polymers, {[Ca(dmso)6]2[W4S16Ag4]}n (Yu et al., 1998) and {[Ca(dmf)6][Mo2S8Ag2]}n (Huang et al., 1996) but they are differently arranged leading to different chain configurations(Fig. 2). The anionic chains in the title compound are saw-tooth-shaped with the lengths of the sides in the ratio 1:2, as against the ratios of 1:1 and 1:3 observed in the aforementioned reported compounds. All metals in the anionic chain of the title compound are nearly coplanar. The overall structure can be viewed as consisting of staggered layers parallel to (010), which are formed by anionic chains propagating along the a axis and cations distributed in the spaces of the anionic chains (Fig. 3).

Related literature top

The two most relevant known analogs of the title compound are {[Ca(DMF)6][Mo2S8Ag2]}n (Yu et al., 1998) and {[Ca(DMSO)6]2[W4S16Ag4]}n (Huang et al., 1996) (DMF is dimethylformamide and DMSO is dimethyl sulfoxide), both also having saw-tooth-shaped polymeric anions but of different configurations, with the lengths of the sides in the ratio 1:1 and 1:3, respectively.

For related literature, see: Niu et al. (2004); Zhang et al. (2007).

Experimental top

1 mmol AgI was added to a solution of [NH4]2MoS4 (1 mmol in 10 mL dmac) with thorough stir for 10 minutes. The solution underwent an additional stir for one minute after 0.5 mmol Ce(NO3)36H2O was added. After filtration the black-red filtrate was carefully laid on the surface with 10 ml CH3OH. Black-red prism crystals were obtained after two weeks. Yield: 0.377 g in pure form, 63.6% (based on Mo). Analysis calculated for C29H67Ag3CeMo3N7O8S12: C 19.57, H 4.07, N 5.51%; found: C 19.32, H 3.86, N 5.72%. IR: ν, cm−1 1604vs (C═O), 495m, 482s h (Mo—St), 451 s (Mo-µ2-S) and 420s h (Mo-µ3-S).

Refinement top

One coordinated dmac molecule is disordered, with two distinct positions with partial occupancies except for the O atoms. The occupancy for the disordered parts was refined to be 0.63:0.37 (3). The minor component was restrained to obtain reasonable geometry. These disordered atoms were refined with anisotropic displacement parameters. H atoms were positioned geometrically and refined with a riding model, with Uiso = 1.5Ueq for methyl H atoms. The –OH H atom of methanol cannot be located in difference Fourier maps so it is not included in the crystallographic data.

Computing details top

Data collection: CAD-4-PC Software (Enraf–Nonius, 1992); cell refinement: SET4 and CELDIM in CAD-4-PC Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids. All H atoms have been omitted.
[Figure 2] Fig. 2. Different configurations of 1-D saw-tooth-shaped Mo(W)/S/Ag polymers.
[Figure 3] Fig. 3. The packing of the title compound, viewed down the b axis, only one layer of molecules shown for clarity. All H atoms have been omitted.
catena-poly[heptakis(N,N'-dimethylacetamide-κO)(methanol-κO)cerium(III) [di-µ3-sulfido-octa-µ2-sulfido-disulfidotrisilver(I)trimolybdenum(IV)]] top
Crystal data top
[Ce(C4H9NO)7(CH4O)][Mo3Ag3S12]Z = 2
Mr = 1777.28F000 = 1740
Triclinic, P1Dx = 1.968 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 12.326 (3) ÅCell parameters from 12323 reflections
b = 15.089 (3) Åθ = 1.2–26.0º
c = 16.747 (3) ŵ = 2.77 mm−1
α = 96.10 (3)ºT = 293 (2) K
β = 98.01 (3)ºPrism, black-red
γ = 101.00 (3)º0.25 × 0.20 × 0.18 mm
V = 2999.3 (12) Å3
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.045
Radiation source: sealed tubeθmax = 26.0º
Monochromator: graphiteθmin = 1.2º
T = 293(2) Kh = 0→15
ω scansk = −18→18
Absorption correction: ψ scan
(XCAD4; Harms & Wocadlo, 1995)		l = −20→20
Tmin = 0.494, Tmax = 0.6103 standard reflections
12323 measured reflections every . reflections
11741 independent reflections intensity decay: none
8829 reflections with I > 2σ(I)
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)] = 0.054H-atom parameters constrained
wR(F2) = 0.142  w = 1/[σ2(Fo2) + (0.065P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
11741 reflectionsΔρmax = 1.30 e Å−3
616 parametersΔρmin = −0.87 e Å−3
9 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ce(C4H9NO)7(CH4O)][Mo3Ag3S12]γ = 101.00 (3)º
Mr = 1777.28V = 2999.3 (12) Å3
Triclinic, P1Z = 2
a = 12.326 (3) ÅMo Kα
b = 15.089 (3) ŵ = 2.77 mm−1
c = 16.747 (3) ÅT = 293 (2) K
α = 96.10 (3)º0.25 × 0.20 × 0.18 mm
β = 98.01 (3)º
Data collection top
Enraf–Nonius CAD-4
diffractometer		8829 reflections with I > 2σ(I)
Absorption correction: ψ scan
(XCAD4; Harms & Wocadlo, 1995)		Rint = 0.045
Tmin = 0.494, Tmax = 0.6103 standard reflections
12323 measured reflections every . reflections
11741 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.0549 restraints
wR(F2) = 0.142H-atom parameters constrained
S = 1.00Δρmax = 1.30 e Å−3
11741 reflectionsΔρmin = −0.87 e Å−3
616 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ce10.25569 (4)0.25542 (3)0.26384 (3)0.03690 (12)
Mo3−0.21526 (6)0.30112 (5)0.57263 (4)0.03952 (16)
Mo10.66703 (5)0.23209 (5)0.89485 (4)0.03867 (16)
Mo20.22670 (6)0.25434 (5)0.71991 (4)0.03925 (16)
Ag20.01230 (5)0.27838 (4)0.63464 (4)0.04257 (15)
Ag10.44028 (5)0.23634 (5)0.81193 (4)0.04697 (16)
Ag3−0.26820 (6)0.27206 (4)0.73640 (4)0.04776 (16)
S70.16012 (18)0.20197 (16)0.59142 (13)0.0483 (5)
S11−0.31129 (18)0.38494 (15)0.64026 (13)0.0456 (4)
S10−0.18108 (19)0.18235 (15)0.63386 (15)0.0521 (5)
S60.38461 (19)0.35212 (15)0.72524 (15)0.0542 (5)
S50.24748 (19)0.13581 (15)0.78314 (16)0.0533 (5)
S40.58495 (19)0.14711 (14)0.77510 (14)0.0503 (5)
S12−0.3167 (2)0.24885 (18)0.45738 (14)0.0579 (6)
S30.5513 (2)0.30032 (17)0.95274 (14)0.0543 (5)
S80.1154 (2)0.32516 (16)0.78014 (14)0.0532 (5)
S9−0.0618 (2)0.39019 (16)0.55104 (15)0.0543 (5)
S20.7228 (2)0.14308 (16)0.97578 (15)0.0552 (5)
S10.8153 (2)0.33502 (18)0.88300 (15)0.0600 (6)
O10.2916 (6)0.3164 (4)0.1362 (4)0.0565 (15)
N10.2963 (10)0.3762 (10)0.0245 (10)0.053 (4)0.63 (3)
C10.3137 (15)0.3835 (15)0.1020 (13)0.062 (5)0.63 (3)
C110.373 (2)0.4798 (16)0.1453 (11)0.042 (5)0.63 (3)
H11A0.38050.48020.20310.064*0.63 (3)
H11B0.32890.52310.12940.064*0.63 (3)
H11C0.44550.49580.13010.064*0.63 (3)
C120.244 (2)0.2814 (19)−0.0182 (19)0.055 (8)0.63 (3)
H12A0.22880.24120.02160.083*0.63 (3)
H12B0.29400.2601−0.05090.083*0.63 (3)
H12C0.17480.2825−0.05230.083*0.63 (3)
C130.323 (2)0.4524 (15)−0.0244 (16)0.051 (5)0.63 (3)
H13A0.34290.50940.01110.077*0.63 (3)
H13B0.25910.4525−0.06410.077*0.63 (3)
H13C0.38510.4444−0.05150.077*0.63 (3)
N1'0.3063 (19)0.4207 (14)0.0662 (14)0.051 (7)0.37 (3)
C1'0.282 (2)0.3342 (13)0.0651 (10)0.050 (8)0.37 (3)
C11'0.275 (4)0.275 (3)−0.016 (2)0.044 (10)0.37 (3)
H11D0.26800.3115−0.05920.066*0.37 (3)
H11E0.21070.2260−0.02340.066*0.37 (3)
H11F0.34150.2511−0.01560.066*0.37 (3)
C12'0.338 (4)0.478 (3)0.149 (2)0.072 (18)0.37 (3)
H12D0.32590.43970.19040.109*0.37 (3)
H12E0.29210.52280.15210.109*0.37 (3)
H12F0.41520.50810.15680.109*0.37 (3)
C13'0.303 (4)0.469 (3)−0.0072 (18)0.056 (12)0.37 (3)
H13D0.32560.53390.00960.084*0.37 (3)
H13E0.22850.4553−0.03740.084*0.37 (3)
H13F0.35360.4501−0.04100.084*0.37 (3)
O20.3846 (5)0.1674 (4)0.2114 (4)0.0525 (15)
N20.5164 (6)0.0950 (5)0.1864 (5)0.0509 (17)
C20.4278 (7)0.1245 (6)0.1617 (5)0.049 (2)
C210.3960 (7)0.1166 (7)0.0700 (6)0.055 (2)
H21A0.33230.14360.05720.083*
H21B0.37770.05350.04700.083*
H21C0.45780.14780.04770.083*
C220.5481 (9)0.1043 (7)0.2779 (6)0.069 (3)
H22A0.50200.13960.30320.104*
H22B0.62540.13430.29360.104*
H22C0.53710.04490.29490.104*
C230.5706 (8)0.0382 (7)0.1323 (6)0.063 (2)
H23A0.54220.04100.07640.094*
H23B0.5541−0.02390.14280.094*
H23C0.65020.06080.14270.094*
O30.1029 (5)0.3306 (5)0.2131 (4)0.0573 (16)
N3−0.0014 (7)0.4207 (5)0.1652 (4)0.0559 (19)
C30.0411 (8)0.3489 (6)0.1572 (6)0.056 (2)
C31−0.0048 (8)0.2886 (7)0.0780 (6)0.063 (3)
H31A0.03010.23690.07520.094*
H31B0.01030.32210.03370.094*
H31C−0.08430.26810.07420.094*
C320.0317 (10)0.4821 (7)0.2463 (6)0.067 (3)
H32A0.08390.45830.28170.101*
H32B−0.03380.48450.27080.101*
H32C0.06590.54230.23780.101*
C33−0.0857 (9)0.4431 (8)0.1035 (7)0.066 (3)
H33A−0.10280.39690.05700.099*
H33B−0.05660.50100.08730.099*
H33C−0.15260.44620.12610.099*
O50.1308 (6)0.1204 (4)0.1755 (4)0.0599 (17)
N50.0311 (7)−0.0145 (5)0.1339 (5)0.061 (2)
C50.1202 (10)0.0364 (8)0.1709 (6)0.069 (3)
C510.2056 (9)−0.0116 (6)0.2111 (6)0.067 (3)
H51A0.26970.03280.23930.101*
H51B0.2284−0.05070.17040.101*
H51C0.1731−0.04740.24920.101*
C52−0.0618 (9)0.0308 (6)0.1024 (7)0.060 (2)
H52A−0.03650.09580.11360.090*
H52B−0.12530.01260.12880.090*
H52C−0.08300.01300.04470.090*
C530.0090 (8)−0.1155 (7)0.1205 (6)0.060 (2)
H53A0.0732−0.13590.14520.090*
H53B−0.0057−0.13660.06310.090*
H53C−0.0549−0.13950.14440.090*
O60.3340 (5)0.1890 (4)0.3810 (4)0.0477 (14)
N60.3873 (6)0.1322 (5)0.4908 (4)0.0523 (18)
C60.3731 (8)0.1975 (6)0.4534 (6)0.053 (2)
C610.4061 (8)0.2932 (6)0.5061 (6)0.064 (3)
H61A0.39020.33880.47300.096*
H61B0.48460.30610.52780.096*
H61C0.36370.29360.55010.096*
C620.3572 (9)0.0382 (6)0.4430 (6)0.061 (3)
H62A0.32410.04150.38820.092*
H62B0.3048−0.00060.46800.092*
H62C0.42360.01390.44210.092*
C630.4383 (8)0.1383 (7)0.5773 (5)0.058 (2)
H63A0.45600.20080.60200.086*
H63B0.50560.11470.58040.086*
H63C0.38640.10320.60560.086*
O70.4431 (5)0.3621 (4)0.3000 (4)0.0526 (15)
N70.6201 (7)0.3994 (6)0.2894 (5)0.061 (2)
C70.5409 (8)0.4003 (7)0.3275 (6)0.059 (2)
C710.5676 (9)0.4684 (7)0.4077 (6)0.063 (3)
H71A0.49960.47080.42890.094*
H71B0.60050.52790.39670.094*
H71C0.61910.44850.44690.094*
C720.5890 (9)0.3481 (7)0.2047 (6)0.063 (3)
H72A0.51020.32210.19410.094*
H72B0.63030.30040.19990.094*
H72C0.60680.38910.16610.094*
C730.7404 (8)0.4434 (7)0.3211 (6)0.057 (2)
H73A0.74630.47670.37420.086*
H73B0.76780.48440.28480.086*
H73C0.78420.39720.32450.086*
O80.0996 (5)0.1932 (4)0.3294 (4)0.0537 (15)
N8−0.0321 (6)0.0976 (5)0.3725 (5)0.0524 (18)
C80.0026 (9)0.1720 (7)0.3435 (6)0.058 (2)
C81−0.0862 (8)0.2282 (6)0.3240 (5)0.052 (2)
H81A−0.05310.28230.30350.079*
H81B−0.11500.24490.37250.079*
H81C−0.14610.19280.28370.079*
C820.0511 (8)0.0383 (6)0.3886 (6)0.054 (2)
H82A0.11980.06410.37100.081*
H82B0.0215−0.02160.35920.081*
H82C0.06530.03450.44580.081*
C83−0.1457 (9)0.0642 (7)0.3895 (7)0.064 (3)
H83A−0.19230.10610.37490.096*
H83B−0.14210.05930.44650.096*
H83C−0.17660.00540.35840.096*
O40.2456 (5)0.3896 (4)0.3731 (4)0.0509 (14)
C40.1747 (8)0.3940 (7)0.4364 (6)0.060 (2)
H4A0.19500.45340.46790.089*
H4B0.18540.34880.47130.089*
H4C0.09760.38260.41140.089*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ce10.0382 (2)0.0364 (2)0.0348 (2)0.00785 (17)0.00085 (17)0.00563 (16)
Mo30.0361 (3)0.0395 (3)0.0415 (4)0.0063 (3)0.0031 (3)0.0064 (3)
Mo10.0342 (3)0.0453 (4)0.0355 (3)0.0067 (3)0.0006 (3)0.0104 (3)
Mo20.0373 (3)0.0391 (3)0.0422 (4)0.0133 (3)0.0006 (3)0.0072 (3)
Ag20.0357 (3)0.0480 (3)0.0421 (3)0.0071 (2)−0.0015 (2)0.0111 (3)
Ag10.0406 (3)0.0527 (4)0.0433 (3)0.0049 (3)−0.0012 (3)0.0067 (3)
Ag30.0602 (4)0.0394 (3)0.0421 (3)0.0030 (3)0.0119 (3)0.0071 (3)
S70.0436 (11)0.0579 (12)0.0402 (10)0.0112 (9)0.0006 (9)−0.0013 (9)
S110.0428 (11)0.0491 (11)0.0458 (11)0.0138 (9)0.0041 (9)0.0068 (9)
S100.0461 (12)0.0503 (12)0.0623 (13)0.0139 (10)0.0130 (10)0.0061 (10)
S60.0483 (12)0.0475 (11)0.0576 (13)0.0021 (9)−0.0120 (10)0.0082 (10)
S50.0481 (12)0.0448 (11)0.0677 (14)0.0115 (9)0.0109 (11)0.0062 (10)
S40.0487 (12)0.0408 (10)0.0573 (13)0.0034 (9)0.0056 (10)0.0033 (9)
S120.0554 (13)0.0649 (14)0.0452 (12)0.0118 (11)−0.0065 (10)−0.0078 (10)
S30.0498 (12)0.0637 (14)0.0489 (12)0.0083 (10)0.0146 (10)0.0035 (10)
S80.0546 (13)0.0562 (13)0.0496 (12)0.0159 (10)0.0071 (10)0.0053 (10)
S90.0486 (12)0.0553 (13)0.0605 (13)0.0117 (10)0.0138 (10)0.0072 (10)
S20.0637 (14)0.0487 (12)0.0533 (12)0.0141 (11)0.0026 (11)0.0116 (10)
S10.0501 (13)0.0661 (14)0.0557 (13)−0.0089 (11)0.0026 (10)0.0181 (11)
O10.062 (4)0.051 (4)0.053 (4)0.007 (3)0.006 (3)0.005 (3)
N10.042 (7)0.052 (9)0.059 (9)0.003 (6)−0.005 (6)0.009 (7)
C10.047 (9)0.069 (14)0.069 (13)0.019 (9)−0.001 (9)0.009 (11)
C110.036 (14)0.050 (10)0.036 (8)0.004 (8)−0.008 (6)0.009 (7)
C120.032 (16)0.048 (10)0.076 (14)0.011 (9)−0.018 (10)−0.005 (8)
C130.053 (12)0.047 (9)0.052 (13)0.011 (8)0.005 (9)0.000 (10)
N1'0.043 (12)0.050 (15)0.044 (15)−0.012 (10)−0.006 (10)−0.014 (12)
C1'0.054 (15)0.051 (15)0.028 (13)−0.014 (12)−0.009 (10)−0.011 (12)
C11'0.02 (2)0.06 (2)0.044 (17)0.012 (14)0.009 (14)0.000 (14)
C12'0.04 (3)0.06 (2)0.10 (3)−0.025 (19)−0.004 (18)0.001 (18)
C13'0.06 (2)0.08 (3)0.026 (14)0.029 (17)0.002 (12)−0.023 (14)
O20.051 (3)0.049 (3)0.059 (4)0.012 (3)0.023 (3)−0.005 (3)
N20.053 (4)0.046 (4)0.056 (4)0.013 (3)0.005 (3)0.017 (3)
C20.045 (5)0.048 (5)0.049 (5)−0.002 (4)0.006 (4)0.009 (4)
C210.041 (5)0.061 (5)0.062 (6)0.011 (4)−0.007 (4)0.017 (4)
C220.077 (7)0.055 (5)0.063 (6)0.023 (5)−0.031 (5)−0.008 (5)
C230.056 (6)0.064 (6)0.067 (6)0.004 (5)0.020 (5)0.004 (5)
O30.051 (4)0.066 (4)0.049 (3)0.011 (3)−0.001 (3)−0.003 (3)
N30.061 (5)0.058 (4)0.044 (4)0.014 (4)−0.015 (3)0.012 (3)
C30.059 (5)0.056 (5)0.045 (5)0.013 (4)−0.006 (4)−0.007 (4)
C310.047 (5)0.061 (6)0.071 (6)0.005 (4)0.003 (5)−0.013 (5)
C320.080 (7)0.049 (5)0.067 (6)0.011 (5)−0.005 (5)0.007 (5)
C330.058 (6)0.075 (7)0.068 (6)0.023 (5)0.001 (5)0.021 (5)
O50.060 (4)0.052 (4)0.058 (4)0.007 (3)−0.002 (3)−0.015 (3)
N50.073 (5)0.040 (4)0.064 (5)0.000 (4)0.012 (4)−0.004 (3)
C50.070 (7)0.068 (7)0.055 (6)−0.011 (5)−0.006 (5)0.010 (5)
C510.079 (7)0.048 (5)0.065 (6)−0.006 (5)−0.010 (5)0.027 (5)
C520.073 (6)0.040 (4)0.078 (7)0.024 (4)0.030 (5)0.016 (4)
C530.040 (5)0.064 (6)0.066 (6)−0.010 (4)0.015 (4)−0.009 (5)
O60.041 (3)0.045 (3)0.051 (3)0.008 (2)−0.017 (3)0.011 (3)
N60.057 (4)0.058 (4)0.038 (4)0.024 (4)−0.014 (3)−0.003 (3)
C60.049 (5)0.043 (4)0.064 (6)0.012 (4)−0.006 (4)0.010 (4)
C610.057 (6)0.046 (5)0.079 (7)0.005 (4)−0.027 (5)0.027 (5)
C620.074 (6)0.043 (5)0.056 (5)0.001 (4)−0.020 (5)0.021 (4)
C630.050 (5)0.069 (6)0.049 (5)0.010 (4)−0.004 (4)0.010 (4)
O70.048 (3)0.051 (3)0.047 (3)−0.013 (3)0.009 (3)−0.007 (3)
N70.053 (5)0.062 (5)0.062 (5)0.005 (4)0.003 (4)0.007 (4)
C70.048 (5)0.054 (5)0.066 (6)−0.003 (4)0.003 (5)0.007 (5)
C710.058 (6)0.053 (5)0.068 (6)−0.001 (4)0.003 (5)−0.007 (5)
C720.064 (6)0.056 (5)0.055 (5)−0.006 (5)0.000 (5)−0.004 (4)
C730.057 (5)0.061 (5)0.045 (5)−0.003 (4)0.002 (4)0.001 (4)
O80.050 (4)0.062 (4)0.051 (3)0.010 (3)0.018 (3)0.010 (3)
N80.046 (4)0.065 (5)0.049 (4)0.019 (4)0.010 (3)0.008 (4)
C80.063 (6)0.054 (5)0.058 (5)0.013 (5)0.003 (5)0.012 (4)
C810.061 (5)0.044 (5)0.049 (5)0.002 (4)0.007 (4)0.014 (4)
C820.048 (5)0.051 (5)0.060 (5)0.004 (4)0.013 (4)0.008 (4)
C830.066 (6)0.053 (5)0.068 (6)0.011 (5)−0.003 (5)0.014 (5)
O40.062 (4)0.039 (3)0.048 (3)0.012 (3)0.002 (3)−0.002 (2)
C40.066 (6)0.066 (6)0.045 (5)0.024 (5)−0.008 (4)0.003 (4)
Geometric parameters (Å, °) top
Ce1—O82.430 (6)O1—C11.22 (2)
Ce1—O22.450 (6)O1—C1'1.242 (15)
Ce1—O62.458 (5)N1—C11.28 (3)
Ce1—O32.476 (7)N1—C131.49 (2)
Ce1—O12.478 (6)N1—C121.51 (3)
Ce1—O52.497 (6)C1—C111.55 (3)
Ce1—O72.506 (6)N1'—C1'1.28 (2)
Ce1—O42.615 (6)N1'—C13'1.50 (2)
Mo3—S122.131 (2)N1'—C12'1.51 (2)
Mo3—S92.199 (3)C1'—C11'1.52 (2)
Mo3—S112.219 (2)O2—C21.240 (10)
Mo3—S102.236 (2)N2—C21.288 (11)
Mo3—Ag22.9487 (12)N2—C231.491 (12)
Mo3—Ag32.9641 (11)N2—C221.512 (12)
Mo1—S22.143 (2)C2—C211.518 (12)
Mo1—S32.183 (3)O3—C31.213 (11)
Mo1—S12.208 (2)N3—C31.291 (12)
Mo1—S42.254 (3)N3—C331.474 (11)
Mo1—Ag12.9579 (12)N3—C321.518 (12)
Mo1—Ag3i2.9646 (11)C3—C311.500 (12)
Mo2—S82.181 (2)O5—C51.243 (13)
Mo2—S62.191 (3)N5—C51.252 (13)
Mo2—S72.197 (2)N5—C531.483 (12)
Mo2—S52.211 (2)N5—C521.505 (13)
Mo2—Ag22.9290 (12)C5—C511.511 (15)
Mo2—Ag12.9343 (12)O6—C61.225 (11)
Ag2—S72.483 (2)N6—C61.248 (11)
Ag2—S92.525 (3)N6—C631.484 (10)
Ag2—S102.540 (3)N6—C621.505 (11)
Ag2—S82.545 (3)C6—C611.561 (13)
Ag1—S52.516 (3)O7—C71.234 (11)
Ag1—S62.520 (2)N7—C71.239 (13)
Ag1—S42.534 (3)N7—C731.500 (12)
Ag1—S32.545 (3)N7—C721.503 (12)
Ag3—S1ii2.533 (3)C7—C711.557 (14)
Ag3—S112.543 (2)O8—C81.239 (12)
Ag3—S102.551 (2)N8—C81.291 (12)
Ag3—S4ii2.556 (2)N8—C831.473 (13)
Ag3—Mo1ii2.9646 (11)N8—C821.500 (12)
S4—Ag3i2.556 (2)C8—C811.530 (13)
S1—Ag3i2.533 (3)O4—C41.467 (12)
O8—Ce1—O2124.7 (2)S8—Mo2—S6107.53 (10)
O8—Ce1—O673.1 (2)S8—Mo2—S7113.29 (9)
O2—Ce1—O675.0 (2)S6—Mo2—S7108.06 (10)
O8—Ce1—O375.1 (2)S8—Mo2—S5107.83 (10)
O2—Ce1—O3139.8 (2)S6—Mo2—S5113.00 (9)
O6—Ce1—O3143.4 (2)S7—Mo2—S5107.24 (10)
O8—Ce1—O1139.9 (2)Ag2—Mo2—Ag1177.26 (3)
O2—Ce1—O175.7 (2)S7—Ag2—S9120.29 (8)
O6—Ce1—O1145.6 (2)S7—Ag2—S10118.75 (8)
O3—Ce1—O170.1 (2)S9—Ag2—S1093.70 (8)
O8—Ce1—O569.2 (2)S7—Ag2—S893.32 (8)
O2—Ce1—O575.6 (2)S9—Ag2—S8122.38 (8)
O6—Ce1—O5103.0 (2)S10—Ag2—S8110.11 (9)
O3—Ce1—O581.9 (2)Mo2—Ag2—Mo3171.36 (3)
O1—Ce1—O586.6 (2)S5—Ag1—S693.59 (8)
O8—Ce1—O7139.1 (2)S5—Ag1—S4110.62 (8)
O2—Ce1—O776.0 (2)S6—Ag1—S4120.53 (9)
O6—Ce1—O781.0 (2)S5—Ag1—S3125.48 (9)
O3—Ce1—O7113.3 (2)S6—Ag1—S3115.81 (8)
O1—Ce1—O774.8 (2)S4—Ag1—S393.18 (8)
O5—Ce1—O7149.2 (2)Mo2—Ag1—Mo1174.07 (3)
O8—Ce1—O476.1 (2)S1ii—Ag3—S11117.64 (8)
O2—Ce1—O4142.9 (2)S1ii—Ag3—S10127.35 (9)
O6—Ce1—O484.62 (19)S11—Ag3—S1093.57 (8)
O3—Ce1—O470.5 (2)S1ii—Ag3—S4ii93.65 (8)
O1—Ce1—O4109.1 (2)S11—Ag3—S4ii124.63 (8)
O5—Ce1—O4140.1 (2)S10—Ag3—S4ii102.10 (8)
O7—Ce1—O470.3 (2)Mo2—S7—Ag277.22 (7)
S12—Mo3—S9107.79 (11)Mo3—S11—Ag376.66 (7)
S12—Mo3—S11106.54 (9)Mo3—S10—Ag275.96 (8)
S9—Mo3—S11108.80 (9)Mo3—S10—Ag376.20 (7)
S12—Mo3—S10107.68 (10)Ag2—S10—Ag3105.48 (9)
S9—Mo3—S10112.83 (9)Mo2—S6—Ag176.70 (8)
S11—Mo3—S10112.89 (9)Mo2—S5—Ag176.44 (8)
Ag2—Mo3—Ag386.51 (4)Mo1—S4—Ag176.06 (8)
S2—Mo1—S3107.19 (10)Mo1—S4—Ag3i75.79 (7)
S2—Mo1—S1107.36 (10)Ag1—S4—Ag3i101.22 (8)
S3—Mo1—S1108.89 (11)Mo1—S3—Ag177.02 (8)
S2—Mo1—S4108.10 (9)Mo2—S8—Ag276.15 (8)
S3—Mo1—S4112.48 (9)Mo3—S9—Ag276.90 (8)
S1—Mo1—S4112.55 (10)Mo1—S1—Ag3i77.08 (8)
Ag1—Mo1—Ag3i83.24 (3)
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.
Acknowledgements top

Financial support from the National Natural Science Foundation of China (No. 50472048) and the Program for New Century Excellent Talents in Universities (NCET-05–0499, NCET-04–0333) is acknowledged.

references
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