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

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-κO)(methanol-κO)cerium(III) [di-μ₃-sulfido-octa-μ₂-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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.014 Å
• Disorder in main residue
• R factor = 0.054
• wR factor = 0.142
• Data-to-parameter ratio = 19.1

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT761_ALERT_1_A CIF Contains no X-H Bonds ......................          ?
PLAT762_ALERT_1_A CIF Contains no X-Y-H or H-Y-H Angles ..........          ?

Alert level C
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        300 Ang.
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Ce1
PLAT301_ALERT_3_C Main Residue  Disorder .........................       5.00 Perc.
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         14

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

   2 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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—S_t), 451 s (Mo-µ₂-S) and 420s h (Mo-µ₃-S).

S3. Refinement

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 U_iso = 1.5U_eq 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

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

	Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids. All H atoms have been omitted.
	Fig. 2. Different configurations of 1-D saw-tooth-shaped Mo(W)/S/Ag polymers.
	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)]]

Crystal data

[Ce(C4H9NO)7(CH4O)][Mo3Ag3S12]	Z = 2
Mr = 1777.28	F(000) = 1740
Triclinic, P1	Dx = 1.968 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.326 (3) Å	Cell parameters from 12323 reflections
b = 15.089 (3) Å	θ = 1.2–26.0°
c = 16.747 (3) Å	µ = 2.77 mm^−1
α = 96.10 (3)°	T = 293 K
β = 98.01 (3)°	Prism, black-red
γ = 101.00 (3)°	0.25 × 0.20 × 0.18 mm
V = 2999.3 (12) Å^3

Data collection

Enraf–Nonius CAD-4 diffractometer	8829 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.045
Graphite monochromator	θmax = 26.0°, θmin = 1.2°
ω scans	h = 0→15
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995)	k = −18→18
Tmin = 0.494, Tmax = 0.610	l = −20→20
12323 measured reflections	3 standard reflections every 120 min
11741 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.065P)^2] where P = (Fo^2 + 2Fc^2)/3
11741 reflections	(Δ/σ)max = 0.001
616 parameters	Δρmax = 1.30 e Å^−3
9 restraints	Δρmin = −0.87 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ce1	0.25569 (4)	0.25542 (3)	0.26384 (3)	0.03690 (12)
Mo3	−0.21526 (6)	0.30112 (5)	0.57263 (4)	0.03952 (16)
Mo1	0.66703 (5)	0.23209 (5)	0.89485 (4)	0.03867 (16)
Mo2	0.22670 (6)	0.25434 (5)	0.71991 (4)	0.03925 (16)
Ag2	0.01230 (5)	0.27838 (4)	0.63464 (4)	0.04257 (15)
Ag1	0.44028 (5)	0.23634 (5)	0.81193 (4)	0.04697 (16)
Ag3	−0.26820 (6)	0.27206 (4)	0.73640 (4)	0.04776 (16)
S7	0.16012 (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)
S6	0.38461 (19)	0.35212 (15)	0.72524 (15)	0.0542 (5)
S5	0.24748 (19)	0.13581 (15)	0.78314 (16)	0.0533 (5)
S4	0.58495 (19)	0.14711 (14)	0.77510 (14)	0.0503 (5)
S12	−0.3167 (2)	0.24885 (18)	0.45738 (14)	0.0579 (6)
S3	0.5513 (2)	0.30032 (17)	0.95274 (14)	0.0543 (5)
S8	0.1154 (2)	0.32516 (16)	0.78014 (14)	0.0532 (5)
S9	−0.0618 (2)	0.39019 (16)	0.55104 (15)	0.0543 (5)
S2	0.7228 (2)	0.14308 (16)	0.97578 (15)	0.0552 (5)
S1	0.8153 (2)	0.33502 (18)	0.88300 (15)	0.0600 (6)
O1	0.2916 (6)	0.3164 (4)	0.1362 (4)	0.0565 (15)
N1	0.2963 (10)	0.3762 (10)	0.0245 (10)	0.053 (4)	0.63 (3)
C1	0.3137 (15)	0.3835 (15)	0.1020 (13)	0.062 (5)	0.63 (3)
C11	0.373 (2)	0.4798 (16)	0.1453 (11)	0.042 (5)	0.63 (3)
H11A	0.3805	0.4802	0.2031	0.064*	0.63 (3)
H11B	0.3289	0.5231	0.1294	0.064*	0.63 (3)
H11C	0.4455	0.4958	0.1301	0.064*	0.63 (3)
C12	0.244 (2)	0.2814 (19)	−0.0182 (19)	0.055 (8)	0.63 (3)
H12A	0.2288	0.2412	0.0216	0.083*	0.63 (3)
H12B	0.2940	0.2601	−0.0509	0.083*	0.63 (3)
H12C	0.1748	0.2825	−0.0523	0.083*	0.63 (3)
C13	0.323 (2)	0.4524 (15)	−0.0244 (16)	0.051 (5)	0.63 (3)
H13A	0.3429	0.5094	0.0111	0.077*	0.63 (3)
H13B	0.2591	0.4525	−0.0641	0.077*	0.63 (3)
H13C	0.3851	0.4444	−0.0515	0.077*	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)
H11D	0.2680	0.3115	−0.0592	0.066*	0.37 (3)
H11E	0.2107	0.2260	−0.0234	0.066*	0.37 (3)
H11F	0.3415	0.2511	−0.0156	0.066*	0.37 (3)
C12'	0.338 (4)	0.478 (3)	0.149 (2)	0.072 (18)	0.37 (3)
H12D	0.3259	0.4397	0.1904	0.109*	0.37 (3)
H12E	0.2921	0.5228	0.1521	0.109*	0.37 (3)
H12F	0.4152	0.5081	0.1568	0.109*	0.37 (3)
C13'	0.303 (4)	0.469 (3)	−0.0072 (18)	0.056 (12)	0.37 (3)
H13D	0.3256	0.5339	0.0096	0.084*	0.37 (3)
H13E	0.2285	0.4553	−0.0374	0.084*	0.37 (3)
H13F	0.3536	0.4501	−0.0410	0.084*	0.37 (3)
O2	0.3846 (5)	0.1674 (4)	0.2114 (4)	0.0525 (15)
N2	0.5164 (6)	0.0950 (5)	0.1864 (5)	0.0509 (17)
C2	0.4278 (7)	0.1245 (6)	0.1617 (5)	0.049 (2)
C21	0.3960 (7)	0.1166 (7)	0.0700 (6)	0.055 (2)
H21A	0.3323	0.1436	0.0572	0.083*
H21B	0.3777	0.0535	0.0470	0.083*
H21C	0.4578	0.1478	0.0477	0.083*
C22	0.5481 (9)	0.1043 (7)	0.2779 (6)	0.069 (3)
H22A	0.5020	0.1396	0.3032	0.104*
H22B	0.6254	0.1343	0.2936	0.104*
H22C	0.5371	0.0449	0.2949	0.104*
C23	0.5706 (8)	0.0382 (7)	0.1323 (6)	0.063 (2)
H23A	0.5422	0.0410	0.0764	0.094*
H23B	0.5541	−0.0239	0.1428	0.094*
H23C	0.6502	0.0608	0.1427	0.094*
O3	0.1029 (5)	0.3306 (5)	0.2131 (4)	0.0573 (16)
N3	−0.0014 (7)	0.4207 (5)	0.1652 (4)	0.0559 (19)
C3	0.0411 (8)	0.3489 (6)	0.1572 (6)	0.056 (2)
C31	−0.0048 (8)	0.2886 (7)	0.0780 (6)	0.063 (3)
H31A	0.0301	0.2369	0.0752	0.094*
H31B	0.0103	0.3221	0.0337	0.094*
H31C	−0.0843	0.2681	0.0742	0.094*
C32	0.0317 (10)	0.4821 (7)	0.2463 (6)	0.067 (3)
H32A	0.0839	0.4583	0.2817	0.101*
H32B	−0.0338	0.4845	0.2708	0.101*
H32C	0.0659	0.5423	0.2378	0.101*
C33	−0.0857 (9)	0.4431 (8)	0.1035 (7)	0.066 (3)
H33A	−0.1028	0.3969	0.0570	0.099*
H33B	−0.0566	0.5010	0.0873	0.099*
H33C	−0.1526	0.4462	0.1261	0.099*
O5	0.1308 (6)	0.1204 (4)	0.1755 (4)	0.0599 (17)
N5	0.0311 (7)	−0.0145 (5)	0.1339 (5)	0.061 (2)
C5	0.1202 (10)	0.0364 (8)	0.1709 (6)	0.069 (3)
C51	0.2056 (9)	−0.0116 (6)	0.2111 (6)	0.067 (3)
H51A	0.2697	0.0328	0.2393	0.101*
H51B	0.2284	−0.0507	0.1704	0.101*
H51C	0.1731	−0.0474	0.2492	0.101*
C52	−0.0618 (9)	0.0308 (6)	0.1024 (7)	0.060 (2)
H52A	−0.0365	0.0958	0.1136	0.090*
H52B	−0.1253	0.0126	0.1288	0.090*
H52C	−0.0830	0.0130	0.0447	0.090*
C53	0.0090 (8)	−0.1155 (7)	0.1205 (6)	0.060 (2)
H53A	0.0732	−0.1359	0.1452	0.090*
H53B	−0.0057	−0.1366	0.0631	0.090*
H53C	−0.0549	−0.1395	0.1444	0.090*
O6	0.3340 (5)	0.1890 (4)	0.3810 (4)	0.0477 (14)
N6	0.3873 (6)	0.1322 (5)	0.4908 (4)	0.0523 (18)
C6	0.3731 (8)	0.1975 (6)	0.4534 (6)	0.053 (2)
C61	0.4061 (8)	0.2932 (6)	0.5061 (6)	0.064 (3)
H61A	0.3902	0.3388	0.4730	0.096*
H61B	0.4846	0.3061	0.5278	0.096*
H61C	0.3637	0.2936	0.5501	0.096*
C62	0.3572 (9)	0.0382 (6)	0.4430 (6)	0.061 (3)
H62A	0.3241	0.0415	0.3882	0.092*
H62B	0.3048	−0.0006	0.4680	0.092*
H62C	0.4236	0.0139	0.4421	0.092*
C63	0.4383 (8)	0.1383 (7)	0.5773 (5)	0.058 (2)
H63A	0.4560	0.2008	0.6020	0.086*
H63B	0.5056	0.1147	0.5804	0.086*
H63C	0.3864	0.1032	0.6056	0.086*
O7	0.4431 (5)	0.3621 (4)	0.3000 (4)	0.0526 (15)
N7	0.6201 (7)	0.3994 (6)	0.2894 (5)	0.061 (2)
C7	0.5409 (8)	0.4003 (7)	0.3275 (6)	0.059 (2)
C71	0.5676 (9)	0.4684 (7)	0.4077 (6)	0.063 (3)
H71A	0.4996	0.4708	0.4289	0.094*
H71B	0.6005	0.5279	0.3967	0.094*
H71C	0.6191	0.4485	0.4469	0.094*
C72	0.5890 (9)	0.3481 (7)	0.2047 (6)	0.063 (3)
H72A	0.5102	0.3221	0.1941	0.094*
H72B	0.6303	0.3004	0.1999	0.094*
H72C	0.6068	0.3891	0.1661	0.094*
C73	0.7404 (8)	0.4434 (7)	0.3211 (6)	0.057 (2)
H73A	0.7463	0.4767	0.3742	0.086*
H73B	0.7678	0.4844	0.2848	0.086*
H73C	0.7842	0.3972	0.3245	0.086*
O8	0.0996 (5)	0.1932 (4)	0.3294 (4)	0.0537 (15)
N8	−0.0321 (6)	0.0976 (5)	0.3725 (5)	0.0524 (18)
C8	0.0026 (9)	0.1720 (7)	0.3435 (6)	0.058 (2)
C81	−0.0862 (8)	0.2282 (6)	0.3240 (5)	0.052 (2)
H81A	−0.0531	0.2823	0.3035	0.079*
H81B	−0.1150	0.2449	0.3725	0.079*
H81C	−0.1461	0.1928	0.2837	0.079*
C82	0.0511 (8)	0.0383 (6)	0.3886 (6)	0.054 (2)
H82A	0.1198	0.0641	0.3710	0.081*
H82B	0.0215	−0.0216	0.3592	0.081*
H82C	0.0653	0.0345	0.4458	0.081*
C83	−0.1457 (9)	0.0642 (7)	0.3895 (7)	0.064 (3)
H83A	−0.1923	0.1061	0.3749	0.096*
H83B	−0.1421	0.0593	0.4465	0.096*
H83C	−0.1766	0.0054	0.3584	0.096*
O4	0.2456 (5)	0.3896 (4)	0.3731 (4)	0.0509 (14)
C4	0.1747 (8)	0.3940 (7)	0.4364 (6)	0.060 (2)
H4A	0.1950	0.4534	0.4679	0.089*
H4B	0.1854	0.3488	0.4713	0.089*
H4C	0.0976	0.3826	0.4114	0.089*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ce1	0.0382 (2)	0.0364 (2)	0.0348 (2)	0.00785 (17)	0.00085 (17)	0.00563 (16)
Mo3	0.0361 (3)	0.0395 (3)	0.0415 (4)	0.0063 (3)	0.0031 (3)	0.0064 (3)
Mo1	0.0342 (3)	0.0453 (4)	0.0355 (3)	0.0067 (3)	0.0006 (3)	0.0104 (3)
Mo2	0.0373 (3)	0.0391 (3)	0.0422 (4)	0.0133 (3)	0.0006 (3)	0.0072 (3)
Ag2	0.0357 (3)	0.0480 (3)	0.0421 (3)	0.0071 (2)	−0.0015 (2)	0.0111 (3)
Ag1	0.0406 (3)	0.0527 (4)	0.0433 (3)	0.0049 (3)	−0.0012 (3)	0.0067 (3)
Ag3	0.0602 (4)	0.0394 (3)	0.0421 (3)	0.0030 (3)	0.0119 (3)	0.0071 (3)
S7	0.0436 (11)	0.0579 (12)	0.0402 (10)	0.0112 (9)	0.0006 (9)	−0.0013 (9)
S11	0.0428 (11)	0.0491 (11)	0.0458 (11)	0.0138 (9)	0.0041 (9)	0.0068 (9)
S10	0.0461 (12)	0.0503 (12)	0.0623 (13)	0.0139 (10)	0.0130 (10)	0.0061 (10)
S6	0.0483 (12)	0.0475 (11)	0.0576 (13)	0.0021 (9)	−0.0120 (10)	0.0082 (10)
S5	0.0481 (12)	0.0448 (11)	0.0677 (14)	0.0115 (9)	0.0109 (11)	0.0062 (10)
S4	0.0487 (12)	0.0408 (10)	0.0573 (13)	0.0034 (9)	0.0056 (10)	0.0033 (9)
S12	0.0554 (13)	0.0649 (14)	0.0452 (12)	0.0118 (11)	−0.0065 (10)	−0.0078 (10)
S3	0.0498 (12)	0.0637 (14)	0.0489 (12)	0.0083 (10)	0.0146 (10)	0.0035 (10)
S8	0.0546 (13)	0.0562 (13)	0.0496 (12)	0.0159 (10)	0.0071 (10)	0.0053 (10)
S9	0.0486 (12)	0.0553 (13)	0.0605 (13)	0.0117 (10)	0.0138 (10)	0.0072 (10)
S2	0.0637 (14)	0.0487 (12)	0.0533 (12)	0.0141 (11)	0.0026 (11)	0.0116 (10)
S1	0.0501 (13)	0.0661 (14)	0.0557 (13)	−0.0089 (11)	0.0026 (10)	0.0181 (11)
O1	0.062 (4)	0.051 (4)	0.053 (4)	0.007 (3)	0.006 (3)	0.005 (3)
N1	0.042 (7)	0.052 (9)	0.059 (9)	0.003 (6)	−0.005 (6)	0.009 (7)
C1	0.047 (9)	0.069 (14)	0.069 (13)	0.019 (9)	−0.001 (9)	0.009 (11)
C11	0.036 (14)	0.050 (10)	0.036 (8)	0.004 (8)	−0.008 (6)	0.009 (7)
C12	0.032 (16)	0.048 (10)	0.076 (14)	0.011 (9)	−0.018 (10)	−0.005 (8)
C13	0.053 (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)
O2	0.051 (3)	0.049 (3)	0.059 (4)	0.012 (3)	0.023 (3)	−0.005 (3)
N2	0.053 (4)	0.046 (4)	0.056 (4)	0.013 (3)	0.005 (3)	0.017 (3)
C2	0.045 (5)	0.048 (5)	0.049 (5)	−0.002 (4)	0.006 (4)	0.009 (4)
C21	0.041 (5)	0.061 (5)	0.062 (6)	0.011 (4)	−0.007 (4)	0.017 (4)
C22	0.077 (7)	0.055 (5)	0.063 (6)	0.023 (5)	−0.031 (5)	−0.008 (5)
C23	0.056 (6)	0.064 (6)	0.067 (6)	0.004 (5)	0.020 (5)	0.004 (5)
O3	0.051 (4)	0.066 (4)	0.049 (3)	0.011 (3)	−0.001 (3)	−0.003 (3)
N3	0.061 (5)	0.058 (4)	0.044 (4)	0.014 (4)	−0.015 (3)	0.012 (3)
C3	0.059 (5)	0.056 (5)	0.045 (5)	0.013 (4)	−0.006 (4)	−0.007 (4)
C31	0.047 (5)	0.061 (6)	0.071 (6)	0.005 (4)	0.003 (5)	−0.013 (5)
C32	0.080 (7)	0.049 (5)	0.067 (6)	0.011 (5)	−0.005 (5)	0.007 (5)
C33	0.058 (6)	0.075 (7)	0.068 (6)	0.023 (5)	0.001 (5)	0.021 (5)
O5	0.060 (4)	0.052 (4)	0.058 (4)	0.007 (3)	−0.002 (3)	−0.015 (3)
N5	0.073 (5)	0.040 (4)	0.064 (5)	0.000 (4)	0.012 (4)	−0.004 (3)
C5	0.070 (7)	0.068 (7)	0.055 (6)	−0.011 (5)	−0.006 (5)	0.010 (5)
C51	0.079 (7)	0.048 (5)	0.065 (6)	−0.006 (5)	−0.010 (5)	0.027 (5)
C52	0.073 (6)	0.040 (4)	0.078 (7)	0.024 (4)	0.030 (5)	0.016 (4)
C53	0.040 (5)	0.064 (6)	0.066 (6)	−0.010 (4)	0.015 (4)	−0.009 (5)
O6	0.041 (3)	0.045 (3)	0.051 (3)	0.008 (2)	−0.017 (3)	0.011 (3)
N6	0.057 (4)	0.058 (4)	0.038 (4)	0.024 (4)	−0.014 (3)	−0.003 (3)
C6	0.049 (5)	0.043 (4)	0.064 (6)	0.012 (4)	−0.006 (4)	0.010 (4)
C61	0.057 (6)	0.046 (5)	0.079 (7)	0.005 (4)	−0.027 (5)	0.027 (5)
C62	0.074 (6)	0.043 (5)	0.056 (5)	0.001 (4)	−0.020 (5)	0.021 (4)
C63	0.050 (5)	0.069 (6)	0.049 (5)	0.010 (4)	−0.004 (4)	0.010 (4)
O7	0.048 (3)	0.051 (3)	0.047 (3)	−0.013 (3)	0.009 (3)	−0.007 (3)
N7	0.053 (5)	0.062 (5)	0.062 (5)	0.005 (4)	0.003 (4)	0.007 (4)
C7	0.048 (5)	0.054 (5)	0.066 (6)	−0.003 (4)	0.003 (5)	0.007 (5)
C71	0.058 (6)	0.053 (5)	0.068 (6)	−0.001 (4)	0.003 (5)	−0.007 (5)
C72	0.064 (6)	0.056 (5)	0.055 (5)	−0.006 (5)	0.000 (5)	−0.004 (4)
C73	0.057 (5)	0.061 (5)	0.045 (5)	−0.003 (4)	0.002 (4)	0.001 (4)
O8	0.050 (4)	0.062 (4)	0.051 (3)	0.010 (3)	0.018 (3)	0.010 (3)
N8	0.046 (4)	0.065 (5)	0.049 (4)	0.019 (4)	0.010 (3)	0.008 (4)
C8	0.063 (6)	0.054 (5)	0.058 (5)	0.013 (5)	0.003 (5)	0.012 (4)
C81	0.061 (5)	0.044 (5)	0.049 (5)	0.002 (4)	0.007 (4)	0.014 (4)
C82	0.048 (5)	0.051 (5)	0.060 (5)	0.004 (4)	0.013 (4)	0.008 (4)
C83	0.066 (6)	0.053 (5)	0.068 (6)	0.011 (5)	−0.003 (5)	0.014 (5)
O4	0.062 (4)	0.039 (3)	0.048 (3)	0.012 (3)	0.002 (3)	−0.002 (2)
C4	0.066 (6)	0.066 (6)	0.045 (5)	0.024 (5)	−0.008 (4)	0.003 (4)

Geometric parameters (Å, º)

Ce1—O8	2.430 (6)	O1—C1	1.22 (2)
Ce1—O2	2.450 (6)	O1—C1'	1.242 (15)
Ce1—O6	2.458 (5)	N1—C1	1.28 (3)
Ce1—O3	2.476 (7)	N1—C13	1.49 (2)
Ce1—O1	2.478 (6)	N1—C12	1.51 (3)
Ce1—O5	2.497 (6)	C1—C11	1.55 (3)
Ce1—O7	2.506 (6)	N1'—C1'	1.28 (2)
Ce1—O4	2.615 (6)	N1'—C13'	1.50 (2)
Mo3—S12	2.131 (2)	N1'—C12'	1.51 (2)
Mo3—S9	2.199 (3)	C1'—C11'	1.52 (2)
Mo3—S11	2.219 (2)	O2—C2	1.240 (10)
Mo3—S10	2.236 (2)	N2—C2	1.288 (11)
Mo3—Ag2	2.9487 (12)	N2—C23	1.491 (12)
Mo3—Ag3	2.9641 (11)	N2—C22	1.512 (12)
Mo1—S2	2.143 (2)	C2—C21	1.518 (12)
Mo1—S3	2.183 (3)	O3—C3	1.213 (11)
Mo1—S1	2.208 (2)	N3—C3	1.291 (12)
Mo1—S4	2.254 (3)	N3—C33	1.474 (11)
Mo1—Ag1	2.9579 (12)	N3—C32	1.518 (12)
Mo1—Ag3^i	2.9646 (11)	C3—C31	1.500 (12)
Mo2—S8	2.181 (2)	O5—C5	1.243 (13)
Mo2—S6	2.191 (3)	N5—C5	1.252 (13)
Mo2—S7	2.197 (2)	N5—C53	1.483 (12)
Mo2—S5	2.211 (2)	N5—C52	1.505 (13)
Mo2—Ag2	2.9290 (12)	C5—C51	1.511 (15)
Mo2—Ag1	2.9343 (12)	O6—C6	1.225 (11)
Ag2—S7	2.483 (2)	N6—C6	1.248 (11)
Ag2—S9	2.525 (3)	N6—C63	1.484 (10)
Ag2—S10	2.540 (3)	N6—C62	1.505 (11)
Ag2—S8	2.545 (3)	C6—C61	1.561 (13)
Ag1—S5	2.516 (3)	O7—C7	1.234 (11)
Ag1—S6	2.520 (2)	N7—C7	1.239 (13)
Ag1—S4	2.534 (3)	N7—C73	1.500 (12)
Ag1—S3	2.545 (3)	N7—C72	1.503 (12)
Ag3—S1^ii	2.533 (3)	C7—C71	1.557 (14)
Ag3—S11	2.543 (2)	O8—C8	1.239 (12)
Ag3—S10	2.551 (2)	N8—C8	1.291 (12)
Ag3—S4^ii	2.556 (2)	N8—C83	1.473 (13)
Ag3—Mo1^ii	2.9646 (11)	N8—C82	1.500 (12)
S4—Ag3^i	2.556 (2)	C8—C81	1.530 (13)
S1—Ag3^i	2.533 (3)	O4—C4	1.467 (12)
O8—Ce1—O2	124.7 (2)	S8—Mo2—S6	107.53 (10)
O8—Ce1—O6	73.1 (2)	S8—Mo2—S7	113.29 (9)
O2—Ce1—O6	75.0 (2)	S6—Mo2—S7	108.06 (10)
O8—Ce1—O3	75.1 (2)	S8—Mo2—S5	107.83 (10)
O2—Ce1—O3	139.8 (2)	S6—Mo2—S5	113.00 (9)
O6—Ce1—O3	143.4 (2)	S7—Mo2—S5	107.24 (10)
O8—Ce1—O1	139.9 (2)	Ag2—Mo2—Ag1	177.26 (3)
O2—Ce1—O1	75.7 (2)	S7—Ag2—S9	120.29 (8)
O6—Ce1—O1	145.6 (2)	S7—Ag2—S10	118.75 (8)
O3—Ce1—O1	70.1 (2)	S9—Ag2—S10	93.70 (8)
O8—Ce1—O5	69.2 (2)	S7—Ag2—S8	93.32 (8)
O2—Ce1—O5	75.6 (2)	S9—Ag2—S8	122.38 (8)
O6—Ce1—O5	103.0 (2)	S10—Ag2—S8	110.11 (9)
O3—Ce1—O5	81.9 (2)	Mo2—Ag2—Mo3	171.36 (3)
O1—Ce1—O5	86.6 (2)	S5—Ag1—S6	93.59 (8)
O8—Ce1—O7	139.1 (2)	S5—Ag1—S4	110.62 (8)
O2—Ce1—O7	76.0 (2)	S6—Ag1—S4	120.53 (9)
O6—Ce1—O7	81.0 (2)	S5—Ag1—S3	125.48 (9)
O3—Ce1—O7	113.3 (2)	S6—Ag1—S3	115.81 (8)
O1—Ce1—O7	74.8 (2)	S4—Ag1—S3	93.18 (8)
O5—Ce1—O7	149.2 (2)	Mo2—Ag1—Mo1	174.07 (3)
O8—Ce1—O4	76.1 (2)	S1^ii—Ag3—S11	117.64 (8)
O2—Ce1—O4	142.9 (2)	S1^ii—Ag3—S10	127.35 (9)
O6—Ce1—O4	84.62 (19)	S11—Ag3—S10	93.57 (8)
O3—Ce1—O4	70.5 (2)	S1^ii—Ag3—S4^ii	93.65 (8)
O1—Ce1—O4	109.1 (2)	S11—Ag3—S4^ii	124.63 (8)
O5—Ce1—O4	140.1 (2)	S10—Ag3—S4^ii	102.10 (8)
O7—Ce1—O4	70.3 (2)	Mo2—S7—Ag2	77.22 (7)
S12—Mo3—S9	107.79 (11)	Mo3—S11—Ag3	76.66 (7)
S12—Mo3—S11	106.54 (9)	Mo3—S10—Ag2	75.96 (8)
S9—Mo3—S11	108.80 (9)	Mo3—S10—Ag3	76.20 (7)
S12—Mo3—S10	107.68 (10)	Ag2—S10—Ag3	105.48 (9)
S9—Mo3—S10	112.83 (9)	Mo2—S6—Ag1	76.70 (8)
S11—Mo3—S10	112.89 (9)	Mo2—S5—Ag1	76.44 (8)
Ag2—Mo3—Ag3	86.51 (4)	Mo1—S4—Ag1	76.06 (8)
S2—Mo1—S3	107.19 (10)	Mo1—S4—Ag3^i	75.79 (7)
S2—Mo1—S1	107.36 (10)	Ag1—S4—Ag3^i	101.22 (8)
S3—Mo1—S1	108.89 (11)	Mo1—S3—Ag1	77.02 (8)
S2—Mo1—S4	108.10 (9)	Mo2—S8—Ag2	76.15 (8)
S3—Mo1—S4	112.48 (9)	Mo3—S9—Ag2	76.90 (8)
S1—Mo1—S4	112.55 (10)	Mo1—S1—Ag3^i	77.08 (8)
Ag1—Mo1—Ag3^i	83.24 (3)

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.