catena-Poly[[tetra­kis­(hexa­methyl­phospho­ramide-κO)bis­(nitrato-κ2O,O′)terbium(III)] [silver(I)-di-μ-sulfido-tungstate(VI)-di-μ-sulfido]]

Zhang, J.

doi:10.1107/S1600536812023823

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages m843-m844

doi:10.1107/S1600536812023823

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catena-Poly[[tetrakis(hexamethylphosphoramide-κO)bis(nitrato-κ²O,O′)terbium(III)] [silver(I)-di-μ-sulfido-tungstate(VI)-di-μ-sulfido]]

Jinfang Zhang ^a ^*

^aMolecular Materials Research Center, Scientific Research Academy, School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
^*Correspondence e-mail: zjf260@ujs.edu.cn

(Received 17 May 2012; accepted 25 May 2012; online 31 May 2012)

In the title compound, {[Tb(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]}_n, the polymeric anionic chain {[AgWS₄]⁻}_n extends along [001]. The Tb^III atom in the cation is coordinated by eight O atoms from two nitrate and four hexamethylphosphate ligands in a distorted square-antiprismatic geometry. Together with the two nitrate ligands, the cation is univalent, which leads to the anionic chain having a [WS₄Ag] repeat unit. The polymeric anionic chain has a distorted linear configuration with W—Ag—W and Ag—W—Ag angles of 161.49 (2) and 153.743 (13) °, respectively. The title complex is isotypic with the Y, Yb, Eu, Nd, La, Dy, Sm and Lu analogues.

Related literature

For one-dimensional Mo(W)/S/Ag anionic polymers, see: Niu et al. (2004 ); Zhang, Meng et al. (2010 ). For the structures of isotypic Y, Yb, Eu, Nd, La, Dy and Sm complexes, see: Zhang, Cao et al. (2007 ); Zhang (2010 , 2011a ,b , 2012 ); Cao et al. (2007 ); Zhang, Qian et al. (2007 ); Tang, Zhang & Zhang (2008 ); Tang, Zhang, Zhang & Lu (2008 ).

Experimental

Crystal data

[Tb(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]
M_r = 1419.76
Monoclinic, P 2₁ /c
a = 15.786 (3) Å
b = 29.654 (6) Å
c = 11.369 (2) Å
β = 90.89 (3)°
V = 5321.4 (17) Å³
Z = 4
Mo Kα radiation
μ = 4.17 mm⁻¹
T = 293 K
0.23 × 0.17 × 0.13 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.432, T_max = 0.582
24824 measured reflections
9675 independent reflections
8650 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.095
S = 1.09
9675 reflections
532 parameters
H-atom parameters constrained
Δρ_max = 0.91 e Å⁻³
Δρ_min = −1.10 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812023823/rz2763sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023823/rz2763Isup2.hkl

checkCIF report

Comment top

One-dimensional Mo(W)/S/Ag anionic polymers have attracted much attention for their intriguing structures (Niu et al., 2004 and Zhang, Meng et al. 2010). Different solvent-coordinated rare-earth cations proved effective to obtain various configurations of anionic chains (Niu et al., 2004). The title compound {[Tb(hmp)₄(NO₃)₂][WS₄Ag]}_n (hmp = hexamethylphosphoramide) with a wave-like anionic chain was prepared by following such route using Tb(III)-hmp complex as counterion.

The title complex is isostructural with the Y (Zhang, Cao et al., 2007 and Zhang, 2011a), Yb (Cao et al., 2007), Eu (Zhang, Qian et al., 2007), Nd (Tang, Zhang & Zhang, 2008), La (Tang, Zhang, Zhang & Lu, 2008), Dy(Zhang, 2010), Sm (Zhang, 2011b) and Lu (Zhang, 2012) isomorphs. Tb³⁺ in the cation is coordinated by eight O atoms from two nitrate and four hmp ligands. In possession of two nitrate ligands, the cation in the title compound is univalent (Fig. 1), which leads to an anionic chain with a univalent repeat unit. As illustrated in Fig. 2, the anionic chain in the title compound has a distorted linear configuration with W—Ag—W and Ag—W—Ag angles of 161.49 (2) and 153.743 (13) ° respectively.

Related literature top

For one-dimensional Mo(W)/S/Ag anionic polymers, see: Niu et al. (2004); Zhang, Meng et al. (2010). For the structures of isotypic Y, Yb, Eu, Nd, La, Dy and Sm complexes, see: Zhang, Cao et al. (2007); Zhang (2010, 2011a,b); Cao et al. (2007); Zhang, Qian et al. (2007); Tang, Zhang & Zhang (2008); Tang, Zhang, Zhang & Lu (2008); Zhang (2012).

Experimental top

0.5 mmol AgI was added to a solution of [NH₄]₂WS₄ (0.5 mmol in 6 ml hmp) with thorough stirring for 20 minutes. The solution underwent an additional stir for two minute after 0.25 mmol Tb(NO₃)₃.6H₂O was added. After filtration the orange filtrate was carefully laid on the surface with 8 ml i-PrOH. Orange block crystals were obtained after about one week.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the cation in the title compound, with probability displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted.
	Fig. 2. The molecular structure of a portion of the anionic chain in the title compound, with 30% probability displacement ellipsoids. Symmetry code: (i) x,-y + 1/2,z + 1/2.

catena-Poly[[tetrakis(hexamethylphosphoramide-κO)bis(nitrato-κ²O,O')terbium(III)] [silver(I)-di-µ-sulfido-tungstate(VI)-di-µ-sulfido]] top

Crystal data top

[Tb(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]	F(000) = 2816
M_r = 1419.76	D_x = 1.772 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 19930 reflections
a = 15.786 (3) Å	θ = 2.6–29.1°
b = 29.654 (6) Å	µ = 4.17 mm⁻¹
c = 11.369 (2) Å	T = 293 K
β = 90.89 (3)°	Block, orange
V = 5321.4 (17) Å³	0.23 × 0.17 × 0.13 mm
Z = 4

Data collection top

Rigaku Saturn724+ diffractometer	9675 independent reflections
Radiation source: fine-focus sealed tube	8650 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
dtprofit.ref scans	θ_max = 25.4°, θ_min = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	h = −19→12
T_min = 0.432, T_max = 0.582	k = −35→34
24824 measured reflections	l = −13→13

Refinement top

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0215P)² + 26.747P] where P = (F_o² + 2F_c²)/3
9675 reflections	(Δ/σ)_max = 0.001
532 parameters	Δρ_max = 0.91 e Å⁻³
0 restraints	Δρ_min = −1.10 e Å⁻³

Crystal data top

[Tb(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]	V = 5321.4 (17) Å³
M_r = 1419.76	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.786 (3) Å	µ = 4.17 mm⁻¹
b = 29.654 (6) Å	T = 293 K
c = 11.369 (2) Å	0.23 × 0.17 × 0.13 mm
β = 90.89 (3)°

Data collection top

Rigaku Saturn724+ diffractometer	9675 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	8650 reflections with I > 2σ(I)
T_min = 0.432, T_max = 0.582	R_int = 0.043
24824 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0215P)² + 26.747P] where P = (F_o² + 2F_c²)/3
9675 reflections	Δρ_max = 0.91 e Å⁻³
532 parameters	Δρ_min = −1.10 e Å⁻³

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

	x	y	z	U_iso*/U_eq
Tb1	0.26214 (2)	0.082647 (11)	0.67164 (3)	0.02568 (10)
P1	0.30295 (14)	−0.03046 (7)	0.80226 (19)	0.0357 (5)
P2	0.04075 (13)	0.09595 (7)	0.7685 (2)	0.0347 (5)
P3	0.20427 (17)	0.14674 (7)	0.4015 (2)	0.0467 (6)
P4	0.47851 (13)	0.13354 (7)	0.67633 (18)	0.0322 (5)
O1	0.2932 (3)	0.01770 (15)	0.7722 (4)	0.0345 (12)
O2	0.1237 (3)	0.08045 (17)	0.7198 (5)	0.0376 (13)
O3	0.2270 (3)	0.12714 (17)	0.5169 (4)	0.0363 (13)
O4	0.3977 (3)	0.10718 (16)	0.6762 (4)	0.0316 (12)
O5	0.1997 (3)	0.02638 (17)	0.5320 (5)	0.0373 (13)
O6	0.3321 (3)	0.04051 (17)	0.5097 (5)	0.0380 (13)
O7	0.2641 (4)	0.0011 (2)	0.3781 (6)	0.0614 (18)
O8	0.2481 (3)	0.15874 (16)	0.7626 (5)	0.0395 (13)
O9	0.2760 (4)	0.10391 (17)	0.8808 (5)	0.0421 (14)
O10	0.2749 (5)	0.1725 (2)	0.9471 (6)	0.074 (2)
N1	0.2645 (5)	0.0220 (2)	0.4699 (7)	0.0428 (17)
N2	0.2661 (4)	0.1459 (2)	0.8671 (7)	0.0429 (17)
N3	0.2809 (5)	−0.0366 (2)	0.9424 (6)	0.0436 (18)
N4	0.3961 (5)	−0.0479 (3)	0.7640 (7)	0.058 (2)
N5	0.2388 (5)	−0.0661 (2)	0.7356 (7)	0.055 (2)
N6	−0.0346 (4)	0.0705 (3)	0.6967 (7)	0.052 (2)
N7	0.0154 (4)	0.1487 (2)	0.7621 (7)	0.053 (2)
N8	0.0431 (5)	0.0858 (3)	0.9111 (6)	0.054 (2)
N9	0.2574 (8)	0.1240 (3)	0.2998 (8)	0.086 (3)
N10	0.1026 (6)	0.1383 (3)	0.3757 (9)	0.087 (3)
N11	0.2229 (6)	0.2000 (2)	0.4035 (7)	0.062 (2)
N12	0.5566 (4)	0.0986 (2)	0.6501 (6)	0.0349 (15)
N13	0.4765 (4)	0.1729 (2)	0.5769 (7)	0.0485 (19)
N14	0.4951 (4)	0.1578 (3)	0.8017 (6)	0.0494 (19)
C1	0.3023 (7)	−0.0015 (3)	1.0253 (8)	0.065 (3)
H1A	0.2849	−0.0104	1.1025	0.098*
H1B	0.2738	0.0258	1.0031	0.098*
H1C	0.3624	0.0033	1.0258	0.098*
C2	0.2764 (7)	−0.0821 (3)	0.9968 (8)	0.063 (3)
H2A	0.2632	−0.0792	1.0786	0.095*
H2B	0.3300	−0.0970	0.9892	0.095*
H2C	0.2331	−0.0995	0.9577	0.095*
C3	0.4656 (6)	−0.0162 (4)	0.7524 (10)	0.070 (3)
H3A	0.5159	−0.0322	0.7307	0.105*
H3B	0.4753	−0.0011	0.8260	0.105*
H3C	0.4516	0.0056	0.6927	0.105*
C4	0.4193 (8)	−0.0958 (4)	0.7809 (10)	0.094 (4)
H4A	0.4765	−0.1005	0.7560	0.141*
H4B	0.3817	−0.1145	0.7351	0.141*
H4C	0.4149	−0.1035	0.8626	0.141*
C5	0.2474 (9)	−0.0815 (4)	0.6174 (10)	0.096 (4)
H5A	0.2017	−0.1017	0.5980	0.144*
H5B	0.3004	−0.0969	0.6099	0.144*
H5C	0.2458	−0.0561	0.5650	0.144*
C6	0.1503 (7)	−0.0693 (4)	0.7687 (12)	0.101 (4)
H6A	0.1222	−0.0914	0.7204	0.152*
H6B	0.1234	−0.0405	0.7578	0.152*
H6C	0.1470	−0.0781	0.8498	0.152*
C7	−0.0210 (6)	0.0277 (3)	0.6392 (10)	0.071 (3)
H7A	−0.0727	0.0180	0.6016	0.107*
H7B	−0.0034	0.0057	0.6965	0.107*
H7C	0.0222	0.0310	0.5813	0.107*
C8	−0.1236 (6)	0.0803 (4)	0.7160 (11)	0.096 (5)
H8A	−0.1579	0.0617	0.6653	0.144*
H8B	−0.1345	0.1114	0.6989	0.144*
H8C	−0.1369	0.0742	0.7965	0.144*
C9	−0.0126 (8)	0.1685 (4)	0.6521 (10)	0.096 (5)
H9A	−0.0247	0.1999	0.6638	0.144*
H9B	−0.0629	0.1534	0.6245	0.144*
H9C	0.0311	0.1654	0.5949	0.144*
C10	0.0472 (7)	0.1820 (3)	0.8464 (12)	0.096 (5)
H10A	0.0247	0.2111	0.8266	0.143*
H10B	0.1079	0.1829	0.8440	0.143*
H10C	0.0298	0.1738	0.9241	0.143*
C11	0.0911 (7)	0.0476 (4)	0.9566 (9)	0.070 (3)
H11A	0.0859	0.0463	1.0406	0.105*
H11B	0.1497	0.0510	0.9370	0.105*
H11C	0.0695	0.0202	0.9224	0.105*
C12	−0.0310 (7)	0.0962 (5)	0.9829 (10)	0.098 (5)
H12A	−0.0193	0.0881	1.0632	0.147*
H12B	−0.0790	0.0795	0.9541	0.147*
H12C	−0.0429	0.1279	0.9781	0.147*
C13	0.2146 (12)	0.1066 (6)	0.1889 (10)	0.156 (8)
H13A	0.2564	0.0943	0.1377	0.234*
H13B	0.1856	0.1310	0.1498	0.234*
H13C	0.1745	0.0836	0.2088	0.234*
C14	0.3498 (9)	0.1215 (4)	0.3088 (11)	0.100 (5)
H14A	0.3714	0.1071	0.2399	0.150*
H14B	0.3658	0.1044	0.3773	0.150*
H14C	0.3727	0.1514	0.3150	0.150*
C15	0.0467 (9)	0.1716 (5)	0.3159 (12)	0.128 (6)
H15A	−0.0095	0.1595	0.3088	0.192*
H15B	0.0680	0.1779	0.2389	0.192*
H15C	0.0455	0.1989	0.3610	0.192*
C16	0.0639 (8)	0.0954 (4)	0.3877 (12)	0.101 (5)
H16A	0.0049	0.0976	0.3672	0.152*
H16B	0.0700	0.0853	0.4677	0.152*
H16C	0.0908	0.0742	0.3364	0.152*
C17	0.1951 (7)	0.2273 (3)	0.5032 (8)	0.059 (3)
H17A	0.2106	0.2582	0.4908	0.089*
H17B	0.2218	0.2165	0.5743	0.089*
H17C	0.1347	0.2250	0.5100	0.089*
C18	0.2483 (10)	0.2257 (4)	0.2962 (10)	0.113 (6)
H18A	0.2559	0.2569	0.3161	0.169*
H18B	0.2048	0.2230	0.2366	0.169*
H18C	0.3004	0.2138	0.2670	0.169*
C19	0.6443 (5)	0.1082 (3)	0.6860 (8)	0.051 (2)
H19A	0.6801	0.0837	0.6622	0.077*
H19B	0.6476	0.1114	0.7699	0.077*
H19C	0.6627	0.1356	0.6494	0.077*
C20	0.5459 (6)	0.0651 (3)	0.5564 (8)	0.050 (2)
H20A	0.5965	0.0472	0.5512	0.075*
H20B	0.5356	0.0801	0.4828	0.075*
H20C	0.4988	0.0459	0.5738	0.075*
C21	0.5452 (6)	0.1831 (3)	0.4980 (9)	0.063 (3)
H21A	0.5292	0.2079	0.4480	0.095*
H21B	0.5571	0.1572	0.4507	0.095*
H21C	0.5949	0.1912	0.5432	0.095*
C22	0.4103 (7)	0.2070 (3)	0.5774 (10)	0.070 (3)
H22A	0.4185	0.2276	0.5134	0.105*
H22B	0.4126	0.2232	0.6505	0.105*
H22C	0.3560	0.1927	0.5686	0.105*
C23	0.5369 (7)	0.2021 (4)	0.8159 (10)	0.080 (4)
H23A	0.5400	0.2098	0.8979	0.120*
H23B	0.5048	0.2246	0.7742	0.120*
H23C	0.5931	0.2007	0.7850	0.120*
C24	0.4828 (7)	0.1333 (4)	0.9095 (8)	0.083 (4)
H24A	0.4952	0.1526	0.9753	0.124*
H24B	0.5199	0.1076	0.9119	0.124*
H24C	0.4250	0.1233	0.9131	0.124*
W1	0.784283 (19)	0.272296 (9)	0.52525 (2)	0.02401 (9)
Ag1	0.78311 (4)	0.23447 (2)	0.28548 (5)	0.04097 (17)
S1	0.78623 (13)	0.31531 (6)	0.36704 (16)	0.0341 (5)
S2	0.78394 (15)	0.19939 (6)	0.48471 (17)	0.0389 (5)
S3	0.66994 (13)	0.28840 (7)	0.62533 (18)	0.0398 (5)
S4	0.89820 (13)	0.28726 (8)	0.63134 (18)	0.0407 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb1	0.02178 (19)	0.01952 (17)	0.0357 (2)	0.00038 (14)	0.00070 (15)	0.00066 (15)
P1	0.0397 (13)	0.0254 (10)	0.0422 (12)	0.0059 (9)	0.0092 (10)	0.0066 (9)
P2	0.0227 (11)	0.0330 (11)	0.0485 (13)	−0.0005 (8)	0.0032 (9)	−0.0085 (10)
P3	0.0647 (17)	0.0343 (12)	0.0405 (13)	0.0108 (11)	−0.0197 (12)	0.0002 (10)
P4	0.0239 (11)	0.0362 (11)	0.0363 (11)	−0.0060 (8)	−0.0007 (9)	−0.0045 (9)
O1	0.038 (3)	0.023 (3)	0.042 (3)	0.000 (2)	0.000 (2)	0.006 (2)
O2	0.023 (3)	0.035 (3)	0.055 (4)	0.001 (2)	0.007 (3)	−0.004 (3)
O3	0.037 (3)	0.034 (3)	0.038 (3)	0.003 (2)	−0.010 (2)	0.010 (2)
O4	0.019 (3)	0.038 (3)	0.038 (3)	−0.004 (2)	0.001 (2)	0.003 (2)
O5	0.025 (3)	0.035 (3)	0.052 (3)	−0.005 (2)	−0.008 (3)	−0.002 (3)
O6	0.029 (3)	0.037 (3)	0.048 (3)	−0.001 (2)	−0.001 (3)	−0.006 (3)
O7	0.064 (5)	0.067 (4)	0.054 (4)	0.008 (3)	−0.006 (3)	−0.030 (4)
O8	0.045 (4)	0.024 (3)	0.049 (4)	0.005 (2)	−0.006 (3)	−0.002 (3)
O9	0.058 (4)	0.028 (3)	0.041 (3)	0.002 (3)	0.006 (3)	0.004 (3)
O10	0.112 (6)	0.052 (4)	0.057 (4)	0.025 (4)	−0.018 (4)	−0.030 (4)
N1	0.039 (5)	0.036 (4)	0.053 (5)	0.006 (3)	0.002 (4)	0.001 (4)
N2	0.038 (4)	0.038 (4)	0.053 (5)	0.004 (3)	0.000 (3)	−0.008 (4)
N3	0.058 (5)	0.034 (4)	0.040 (4)	0.009 (3)	0.013 (3)	0.006 (3)
N4	0.049 (5)	0.051 (5)	0.075 (6)	0.020 (4)	0.022 (4)	0.025 (4)
N5	0.079 (6)	0.032 (4)	0.053 (5)	−0.014 (4)	0.016 (4)	−0.011 (4)
N6	0.026 (4)	0.064 (5)	0.065 (5)	0.000 (3)	0.003 (4)	−0.037 (4)
N7	0.036 (4)	0.039 (4)	0.083 (6)	0.004 (3)	0.006 (4)	−0.010 (4)
N8	0.040 (5)	0.073 (5)	0.049 (5)	0.010 (4)	0.006 (4)	−0.006 (4)
N9	0.140 (10)	0.065 (6)	0.054 (6)	0.028 (6)	−0.001 (6)	−0.009 (5)
N10	0.091 (7)	0.059 (6)	0.108 (8)	0.006 (5)	−0.074 (6)	0.005 (5)
N11	0.106 (7)	0.037 (4)	0.043 (4)	0.008 (4)	−0.003 (4)	0.010 (4)
N12	0.020 (3)	0.045 (4)	0.040 (4)	−0.001 (3)	0.000 (3)	−0.009 (3)
N13	0.038 (4)	0.039 (4)	0.069 (5)	−0.008 (3)	0.008 (4)	0.004 (4)
N14	0.034 (4)	0.067 (5)	0.047 (4)	−0.001 (4)	−0.006 (3)	−0.025 (4)
C1	0.082 (8)	0.062 (7)	0.051 (6)	0.006 (6)	0.004 (5)	0.004 (5)
C2	0.078 (8)	0.053 (6)	0.059 (6)	0.012 (5)	0.024 (6)	0.026 (5)
C3	0.043 (6)	0.077 (7)	0.091 (8)	0.004 (5)	−0.008 (6)	−0.015 (6)
C4	0.123 (11)	0.070 (8)	0.090 (9)	0.055 (7)	0.043 (8)	0.025 (7)
C5	0.129 (12)	0.071 (8)	0.088 (9)	−0.032 (8)	0.013 (8)	−0.030 (7)
C6	0.064 (9)	0.109 (11)	0.130 (12)	−0.021 (8)	0.001 (8)	−0.034 (9)
C7	0.038 (6)	0.062 (6)	0.114 (9)	−0.002 (5)	0.007 (6)	−0.033 (7)
C8	0.033 (6)	0.126 (11)	0.130 (11)	0.005 (6)	0.004 (6)	−0.083 (9)
C9	0.108 (11)	0.087 (9)	0.095 (9)	0.050 (8)	0.042 (8)	0.037 (8)
C10	0.057 (7)	0.053 (6)	0.178 (14)	−0.009 (5)	0.028 (8)	−0.056 (8)
C11	0.065 (8)	0.075 (7)	0.071 (7)	0.007 (6)	0.009 (6)	0.011 (6)
C12	0.079 (9)	0.152 (13)	0.064 (8)	0.045 (9)	0.025 (7)	−0.010 (8)
C13	0.28 (2)	0.146 (15)	0.044 (8)	−0.048 (15)	0.008 (11)	−0.041 (9)
C14	0.112 (12)	0.101 (10)	0.089 (9)	0.041 (9)	0.049 (8)	0.012 (8)
C15	0.137 (13)	0.119 (12)	0.126 (12)	0.067 (10)	−0.081 (10)	−0.007 (10)
C16	0.076 (9)	0.076 (8)	0.150 (13)	−0.006 (7)	−0.060 (9)	−0.017 (9)
C17	0.094 (8)	0.031 (5)	0.052 (6)	0.001 (5)	0.009 (5)	−0.012 (4)
C18	0.212 (17)	0.064 (8)	0.063 (8)	0.033 (9)	0.040 (9)	0.035 (7)
C19	0.035 (5)	0.067 (6)	0.052 (6)	0.006 (4)	0.000 (4)	−0.011 (5)
C20	0.042 (6)	0.054 (6)	0.054 (6)	0.002 (4)	0.000 (4)	−0.009 (5)
C21	0.062 (7)	0.054 (6)	0.075 (7)	−0.022 (5)	0.020 (6)	0.007 (5)
C22	0.064 (7)	0.046 (6)	0.100 (9)	0.007 (5)	0.008 (6)	0.023 (6)
C23	0.068 (8)	0.072 (7)	0.100 (9)	0.001 (6)	−0.013 (6)	−0.055 (7)
C24	0.059 (7)	0.148 (12)	0.041 (6)	0.008 (7)	−0.007 (5)	−0.008 (7)
W1	0.02862 (17)	0.02345 (15)	0.01991 (15)	−0.00267 (12)	−0.00162 (12)	0.00125 (12)
Ag1	0.0627 (5)	0.0387 (3)	0.0215 (3)	−0.0001 (3)	−0.0007 (3)	−0.0019 (3)
S1	0.0509 (13)	0.0252 (9)	0.0263 (10)	−0.0008 (9)	0.0025 (9)	0.0069 (8)
S2	0.0616 (15)	0.0244 (10)	0.0306 (10)	−0.0056 (9)	−0.0009 (10)	0.0023 (9)
S3	0.0324 (12)	0.0542 (13)	0.0328 (11)	0.0061 (10)	0.0027 (9)	0.0027 (10)
S4	0.0352 (12)	0.0539 (13)	0.0329 (11)	−0.0134 (10)	−0.0067 (9)	0.0044 (10)

Geometric parameters (Å, º) top

Tb1—O4	2.260 (5)	C6—H6A	0.9600
Tb1—O3	2.261 (5)	C6—H6B	0.9600
Tb1—O2	2.262 (5)	C6—H6C	0.9600
Tb1—O1	2.289 (5)	C7—H7A	0.9600
Tb1—O9	2.467 (5)	C7—H7B	0.9600
Tb1—O8	2.493 (5)	C7—H7C	0.9600
Tb1—O5	2.495 (5)	C8—H8A	0.9600
Tb1—O6	2.497 (5)	C8—H8B	0.9600
Tb1—N2	2.908 (7)	C8—H8C	0.9600
Tb1—N1	2.915 (8)	C9—H9A	0.9600
P1—O1	1.476 (5)	C9—H9B	0.9600
P1—N4	1.625 (7)	C9—H9C	0.9600
P1—N5	1.642 (8)	C10—H10A	0.9600
P1—N3	1.646 (7)	C10—H10B	0.9600
P2—O2	1.502 (5)	C10—H10C	0.9600
P2—N7	1.616 (7)	C11—H11A	0.9600
P2—N6	1.619 (7)	C11—H11B	0.9600
P2—N8	1.649 (8)	C11—H11C	0.9600
P3—O3	1.474 (5)	C12—H12A	0.9600
P3—N9	1.589 (10)	C12—H12B	0.9600
P3—N11	1.605 (8)	C12—H12C	0.9600
P3—N10	1.646 (9)	C13—H13A	0.9600
P4—O4	1.496 (5)	C13—H13B	0.9600
P4—N14	1.614 (7)	C13—H13C	0.9600
P4—N13	1.625 (7)	C14—H14A	0.9600
P4—N12	1.641 (6)	C14—H14B	0.9600
O5—N1	1.258 (8)	C14—H14C	0.9600
O6—N1	1.277 (8)	C15—H15A	0.9600
O7—N1	1.213 (8)	C15—H15B	0.9600
O8—N2	1.275 (8)	C15—H15C	0.9600
O9—N2	1.265 (8)	C16—H16A	0.9600
O10—N2	1.211 (8)	C16—H16B	0.9600
N3—C1	1.439 (11)	C16—H16C	0.9600
N3—C2	1.487 (10)	C17—H17A	0.9600
N4—C3	1.452 (12)	C17—H17B	0.9600
N4—C4	1.479 (11)	C17—H17C	0.9600
N5—C5	1.426 (12)	C18—H18A	0.9600
N5—C6	1.454 (13)	C18—H18B	0.9600
N6—C7	1.444 (11)	C18—H18C	0.9600
N6—C8	1.454 (11)	C19—H19A	0.9600
N7—C9	1.445 (13)	C19—H19B	0.9600
N7—C10	1.459 (12)	C19—H19C	0.9600
N8—C11	1.453 (11)	C20—H20A	0.9600
N8—C12	1.468 (11)	C20—H20B	0.9600
N9—C14	1.462 (15)	C20—H20C	0.9600
N9—C13	1.512 (15)	C21—H21A	0.9600
N10—C16	1.420 (13)	C21—H21B	0.9600
N10—C15	1.481 (12)	C21—H21C	0.9600
N11—C17	1.467 (11)	C22—H22A	0.9600
N11—C18	1.499 (12)	C22—H22B	0.9600
N12—C19	1.464 (10)	C22—H22C	0.9600
N12—C20	1.466 (10)	C23—H23A	0.9600
N13—C21	1.451 (10)	C23—H23B	0.9600
N13—C22	1.453 (11)	C23—H23C	0.9600
N14—C24	1.440 (12)	C24—H24A	0.9600
N14—C23	1.479 (12)	C24—H24B	0.9600
C1—H1A	0.9600	C24—H24C	0.9600
C1—H1B	0.9600	W1—S4	2.195 (2)
C1—H1C	0.9600	W1—S3	2.201 (2)
C2—H2A	0.9600	W1—S1	2.2057 (18)
C2—H2B	0.9600	W1—S2	2.211 (2)
C2—H2C	0.9600	W1—Ag1	2.9476 (8)
C3—H3A	0.9600	W1—Ag1ⁱ	2.9656 (8)
C3—H3B	0.9600	Ag1—S2	2.492 (2)
C3—H3C	0.9600	Ag1—S1	2.571 (2)
C4—H4A	0.9600	Ag1—S3ⁱⁱ	2.620 (2)
C4—H4B	0.9600	Ag1—S4ⁱⁱ	2.624 (2)
C4—H4C	0.9600	Ag1—W1ⁱⁱ	2.9656 (8)
C5—H5A	0.9600	S3—Ag1ⁱ	2.620 (2)
C5—H5B	0.9600	S4—Ag1ⁱ	2.624 (2)
C5—H5C	0.9600

O4—Tb1—O3	92.90 (18)	N5—C5—H5C	109.5
O4—Tb1—O2	157.15 (18)	H5A—C5—H5C	109.5
O3—Tb1—O2	88.80 (19)	H5B—C5—H5C	109.5
O4—Tb1—O1	93.66 (18)	N5—C6—H6A	109.5
O3—Tb1—O1	158.07 (18)	N5—C6—H6B	109.5
O2—Tb1—O1	93.17 (18)	H6A—C6—H6B	109.5
O4—Tb1—O9	79.95 (18)	N5—C6—H6C	109.5
O3—Tb1—O9	128.16 (18)	H6A—C6—H6C	109.5
O2—Tb1—O9	81.11 (19)	H6B—C6—H6C	109.5
O1—Tb1—O9	73.65 (17)	N6—C7—H7A	109.5
O4—Tb1—O8	77.82 (18)	N6—C7—H7B	109.5
O3—Tb1—O8	76.83 (18)	H7A—C7—H7B	109.5
O2—Tb1—O8	80.41 (18)	N6—C7—H7C	109.5
O1—Tb1—O8	125.03 (18)	H7A—C7—H7C	109.5
O9—Tb1—O8	51.39 (17)	H7B—C7—H7C	109.5
O4—Tb1—O5	126.46 (18)	N6—C8—H8A	109.5
O3—Tb1—O5	78.80 (18)	N6—C8—H8B	109.5
O2—Tb1—O5	76.21 (18)	H8A—C8—H8B	109.5
O1—Tb1—O5	80.48 (18)	N6—C8—H8C	109.5
O9—Tb1—O5	144.35 (18)	H8A—C8—H8C	109.5
O8—Tb1—O5	146.34 (17)	H8B—C8—H8C	109.5
O4—Tb1—O6	75.44 (18)	N7—C9—H9A	109.5
O3—Tb1—O6	79.88 (18)	N7—C9—H9B	109.5
O2—Tb1—O6	127.18 (18)	H9A—C9—H9B	109.5
O1—Tb1—O6	81.57 (18)	N7—C9—H9C	109.5
O9—Tb1—O6	143.62 (18)	H9A—C9—H9C	109.5
O8—Tb1—O6	143.30 (18)	H9B—C9—H9C	109.5
O5—Tb1—O6	51.02 (17)	N7—C10—H10A	109.5
O4—Tb1—N2	76.43 (19)	N7—C10—H10B	109.5
O3—Tb1—N2	102.7 (2)	H10A—C10—H10B	109.5
O2—Tb1—N2	80.97 (19)	N7—C10—H10C	109.5
O1—Tb1—N2	99.18 (19)	H10A—C10—H10C	109.5
O9—Tb1—N2	25.58 (17)	H10B—C10—H10C	109.5
O8—Tb1—N2	25.87 (17)	N8—C11—H11A	109.5
O5—Tb1—N2	157.11 (19)	N8—C11—H11B	109.5
O6—Tb1—N2	151.84 (18)	H11A—C11—H11B	109.5
O4—Tb1—N1	101.13 (19)	N8—C11—H11C	109.5
O3—Tb1—N1	75.76 (19)	H11A—C11—H11C	109.5
O2—Tb1—N1	101.4 (2)	H11B—C11—H11C	109.5
O1—Tb1—N1	82.45 (18)	N8—C12—H12A	109.5
O9—Tb1—N1	156.08 (18)	N8—C12—H12B	109.5
O8—Tb1—N1	152.48 (19)	H12A—C12—H12B	109.5
O5—Tb1—N1	25.40 (17)	N8—C12—H12C	109.5
O6—Tb1—N1	25.83 (17)	H12A—C12—H12C	109.5
N2—Tb1—N1	177.1 (2)	H12B—C12—H12C	109.5
O1—P1—N4	109.7 (3)	N9—C13—H13A	109.5
O1—P1—N5	117.1 (4)	N9—C13—H13B	109.5
N4—P1—N5	103.1 (4)	H13A—C13—H13B	109.5
O1—P1—N3	107.9 (3)	N9—C13—H13C	109.5
N4—P1—N3	115.5 (4)	H13A—C13—H13C	109.5
N5—P1—N3	103.8 (4)	H13B—C13—H13C	109.5
O2—P2—N7	119.8 (3)	N9—C14—H14A	109.5
O2—P2—N6	108.0 (3)	N9—C14—H14B	109.5
N7—P2—N6	104.4 (4)	H14A—C14—H14B	109.5
O2—P2—N8	107.5 (4)	N9—C14—H14C	109.5
N7—P2—N8	102.9 (4)	H14A—C14—H14C	109.5
N6—P2—N8	114.5 (4)	H14B—C14—H14C	109.5
O3—P3—N9	110.9 (4)	N10—C15—H15A	109.5
O3—P3—N11	109.5 (4)	N10—C15—H15B	109.5
N9—P3—N11	109.1 (5)	H15A—C15—H15B	109.5
O3—P3—N10	108.8 (4)	N10—C15—H15C	109.5
N9—P3—N10	109.3 (6)	H15A—C15—H15C	109.5
N11—P3—N10	109.2 (5)	H15B—C15—H15C	109.5
O4—P4—N14	111.1 (3)	N10—C16—H16A	109.5
O4—P4—N13	111.5 (3)	N10—C16—H16B	109.5
N14—P4—N13	107.2 (4)	H16A—C16—H16B	109.5
O4—P4—N12	108.3 (3)	N10—C16—H16C	109.5
N14—P4—N12	109.2 (4)	H16A—C16—H16C	109.5
N13—P4—N12	109.5 (4)	H16B—C16—H16C	109.5
P1—O1—Tb1	161.9 (3)	N11—C17—H17A	109.5
P2—O2—Tb1	158.7 (3)	N11—C17—H17B	109.5
P3—O3—Tb1	167.4 (3)	H17A—C17—H17B	109.5
P4—O4—Tb1	167.2 (3)	N11—C17—H17C	109.5
N1—O5—Tb1	96.3 (4)	H17A—C17—H17C	109.5
N1—O6—Tb1	95.7 (4)	H17B—C17—H17C	109.5
N2—O8—Tb1	95.6 (4)	N11—C18—H18A	109.5
N2—O9—Tb1	97.1 (5)	N11—C18—H18B	109.5
O7—N1—O5	122.8 (7)	H18A—C18—H18B	109.5
O7—N1—O6	121.2 (7)	N11—C18—H18C	109.5
O5—N1—O6	116.0 (7)	H18A—C18—H18C	109.5
O7—N1—Tb1	172.5 (6)	H18B—C18—H18C	109.5
O5—N1—Tb1	58.3 (4)	N12—C19—H19A	109.5
O6—N1—Tb1	58.4 (4)	N12—C19—H19B	109.5
O10—N2—O9	122.4 (8)	H19A—C19—H19B	109.5
O10—N2—O8	121.9 (7)	N12—C19—H19C	109.5
O9—N2—O8	115.7 (7)	H19A—C19—H19C	109.5
O10—N2—Tb1	174.6 (6)	H19B—C19—H19C	109.5
O9—N2—Tb1	57.3 (4)	N12—C20—H20A	109.5
O8—N2—Tb1	58.6 (4)	N12—C20—H20B	109.5
C1—N3—C2	113.3 (7)	H20A—C20—H20B	109.5
C1—N3—P1	120.3 (6)	N12—C20—H20C	109.5
C2—N3—P1	120.9 (6)	H20A—C20—H20C	109.5
C3—N4—C4	116.6 (8)	H20B—C20—H20C	109.5
C3—N4—P1	120.5 (7)	N13—C21—H21A	109.5
C4—N4—P1	119.6 (7)	N13—C21—H21B	109.5
C5—N5—C6	109.2 (9)	H21A—C21—H21B	109.5
C5—N5—P1	125.0 (7)	N13—C21—H21C	109.5
C6—N5—P1	120.7 (7)	H21A—C21—H21C	109.5
C7—N6—C8	113.2 (7)	H21B—C21—H21C	109.5
C7—N6—P2	121.6 (6)	N13—C22—H22A	109.5
C8—N6—P2	122.3 (6)	N13—C22—H22B	109.5
C9—N7—C10	113.0 (9)	H22A—C22—H22B	109.5
C9—N7—P2	120.4 (7)	N13—C22—H22C	109.5
C10—N7—P2	122.8 (7)	H22A—C22—H22C	109.5
C11—N8—C12	112.5 (8)	H22B—C22—H22C	109.5
C11—N8—P2	119.8 (6)	N14—C23—H23A	109.5
C12—N8—P2	120.1 (7)	N14—C23—H23B	109.5
C14—N9—C13	118.3 (11)	H23A—C23—H23B	109.5
C14—N9—P3	120.5 (8)	N14—C23—H23C	109.5
C13—N9—P3	121.1 (11)	H23A—C23—H23C	109.5
C16—N10—C15	112.8 (10)	H23B—C23—H23C	109.5
C16—N10—P3	122.5 (7)	N14—C24—H24A	109.5
C15—N10—P3	123.6 (9)	N14—C24—H24B	109.5
C17—N11—C18	115.8 (7)	H24A—C24—H24B	109.5
C17—N11—P3	119.8 (6)	N14—C24—H24C	109.5
C18—N11—P3	122.8 (7)	H24A—C24—H24C	109.5
C19—N12—C20	115.5 (6)	H24B—C24—H24C	109.5
C19—N12—P4	122.5 (5)	S4—W1—S3	110.09 (8)
C20—N12—P4	118.8 (5)	S4—W1—S1	108.03 (8)
C21—N13—C22	113.7 (8)	S3—W1—S1	108.55 (8)
C21—N13—P4	125.0 (6)	S4—W1—S2	108.15 (8)
C22—N13—P4	120.2 (6)	S3—W1—S2	108.70 (8)
C24—N14—C23	114.9 (8)	S1—W1—S2	113.30 (7)
C24—N14—P4	120.3 (7)	S4—W1—Ag1	125.34 (6)
C23—N14—P4	123.9 (7)	S3—W1—Ag1	124.56 (6)
N3—C1—H1A	109.5	S1—W1—Ag1	57.71 (5)
N3—C1—H1B	109.5	S2—W1—Ag1	55.60 (5)
H1A—C1—H1B	109.5	S4—W1—Ag1ⁱ	58.89 (6)
N3—C1—H1C	109.5	S3—W1—Ag1ⁱ	58.74 (6)
H1A—C1—H1C	109.5	S1—W1—Ag1ⁱ	148.54 (5)
H1B—C1—H1C	109.5	S2—W1—Ag1ⁱ	98.15 (5)
N3—C2—H2A	109.5	Ag1—W1—Ag1ⁱ	153.743 (13)
N3—C2—H2B	109.5	S2—Ag1—S1	93.53 (6)
H2A—C2—H2B	109.5	S2—Ag1—S3ⁱⁱ	121.16 (7)
N3—C2—H2C	109.5	S1—Ag1—S3ⁱⁱ	120.07 (7)
H2A—C2—H2C	109.5	S2—Ag1—S4ⁱⁱ	120.70 (7)
H2B—C2—H2C	109.5	S1—Ag1—S4ⁱⁱ	117.40 (7)
N4—C3—H3A	109.5	S3ⁱⁱ—Ag1—S4ⁱⁱ	86.80 (7)
N4—C3—H3B	109.5	S2—Ag1—W1	47.04 (5)
H3A—C3—H3B	109.5	S1—Ag1—W1	46.50 (4)
N4—C3—H3C	109.5	S3ⁱⁱ—Ag1—W1	137.35 (5)
H3A—C3—H3C	109.5	S4ⁱⁱ—Ag1—W1	135.77 (5)
H3B—C3—H3C	109.5	S2—Ag1—W1ⁱⁱ	151.45 (5)
N4—C4—H4A	109.5	S1—Ag1—W1ⁱⁱ	115.00 (5)
N4—C4—H4B	109.5	S3ⁱⁱ—Ag1—W1ⁱⁱ	45.90 (5)
H4A—C4—H4B	109.5	S4ⁱⁱ—Ag1—W1ⁱⁱ	45.74 (5)
N4—C4—H4C	109.5	W1—Ag1—W1ⁱⁱ	161.49 (2)
H4A—C4—H4C	109.5	W1—S1—Ag1	75.78 (6)
H4B—C4—H4C	109.5	W1—S2—Ag1	77.36 (6)
N5—C5—H5A	109.5	W1—S3—Ag1ⁱ	75.36 (6)
N5—C5—H5B	109.5	W1—S4—Ag1ⁱ	75.38 (6)
H5A—C5—H5B	109.5

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Tb(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]
M_r	1419.76
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	15.786 (3), 29.654 (6), 11.369 (2)
β (°)	90.89 (3)
V (Å³)	5321.4 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.17
Crystal size (mm)	0.23 × 0.17 × 0.13

Data collection
Diffractometer	Rigaku Saturn724+ diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.432, 0.582
No. of measured, independent and observed [I > 2σ(I)] reflections	24824, 9675, 8650
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.095, 1.09
No. of reflections	9675
No. of parameters	532
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0215P)² + 26.747P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.91, −1.10

Computer programs: CrystalClear (Rigaku, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Natural Science Foundation of Jiangsu High School (10KJB430005) and the Foundation of Jiangsu University (08JDG036).

References

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