Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039293/br2053sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039293/br2053Isup2.hkl |
CCDC reference: 660142
1 mmol A g2S was added to a solution of [NH4]2WS4 (2 mmol in 30 mL h mp) with thorough stir for 12 h. The solution underwent an additional stir for one minute after 1 mmol Eu(NO3)3.6H2O was added. After filtration the orange-red filtrate was carefully laid on the surface with 30 ml i-PrOH. Red block crystals were obtained after ten days. Yield: 1.291 g in pure form, 45.7% (based on W). Analysis calculated for C24H72AgEuN14O10P4S4W: C 20.40, H 5.14, N 13.88%; found: C 20.37, H 5.12, N 13.91%. IR: ν, cm-1, 482.7 m, 446.6 s (W-µ2-S).
H atoms were positioned geometrically and refined with riding model, with Uiso = 1.5Ueq for methyl H atoms and 0.98 Å for C—H bonds.
One-dimensional Mo(W)/S/Ag anionic polymers have attracted much attention for their configurational isomerism (Niu et al., 2004) and unique properties as functional materials, such as third-order nonlinear optical (NLO) materials (Zhang, Song et al., 2007, and references therein). Different solvent-coordinated rare-earth cations proved effective to obtain various configurations of anionic chains (Niu et al., 2004). The title compound, {[Eu(hmp)4(NO3)2][WS4Ag]}n (hmp = hexamethylphosphoramide), with a wave-like anionic chain was prepared by following such route using EuIII–hmp complex as counterion.
The cation in the title compound, where Eu3- is coordinated by eight O atoms from two nitrate and four hmp ligands, has the same structure as those in the isostructural {[Yb(hmp)4(NO3)2][WS4Ag]}n (Cao et al., 2007) and {[Y(hmp)4(NO3)2][WS4Ag]}n (Zhang, Cao et al., 2007). Parts of dimethylamine groups from hmp ligands have large librations. In possession of two nitrate ligands, the cation in the title compound is monovalent (Fig. 1), which leads to an anionic chain with a monovalent repeat unit, unlike other solvent-coordinated rare-earth cations (Niu et al., 2004), which are trivalent and induce trivalent repeat units. For example, [Nd(dmf)8]3+ induces an anionic chain with a trivalent repeat unit [W4S16Ag5]3- (Huang et al., 1996).
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 162.93 (2) and 154.250 (9)°, respectively, unlike those in {(γ-MePyH)[WS4Ag]}n (MePyH is protonated picoline; Lang et al., 1993) and {[NH3C(CH2OH)3][WS4Ag](2DMF)}n (Huang et al., 1997), showing an ideal linear chain and a nearly linear chain with W—Ag—W and Ag—W—Ag angles of 176.4 (5) and 176.4 (3)°, respectively. This fact suggests that cations with bigger bulk lead to more distorted anionic chains.
Similar angles of 160.81 (7) and 153.41 (7)° for W—Ag—W and Ag—W—Ag, respectively, are found in another two distorted linear chains in {[Yb(hmp)4(NO3)2][WS4Ag]}n (Cao et al., 2007) and {[Y(hmp)4(NO3)2][WS4Ag]}n (Zhang, Cao et al., 2007), implying that different rare earth cations with the same coordination environments will result in the same anionic structures.
Examples of one-dimensional [WS4Ag] anionic polymers with ideal and nearly linear configurations are {(γ-MePyH)[WS4Ag]}n (Lang et al., 1993) and {[NH3C(CH2OH)3][WS4Ag](2DMF)}n (DMF is dimethylformamide; Huang et al., 1997), respectively. Two more relevant analogs of the title compound are {[Yb(hmp)4(NO3)2][WS4Ag]}n (Cao et al., 2007) and {[Y(hmp)4(NO3)2][WS4Ag]}n (Zhang, Song et al., 2007 and/or Zhang, Cao et al., 2007?) (hmp is hexamethylphosphoramide), which have similar wave-like chains. {[Nd(DMF)8][W4S16Ag5]}n (Huang et al., 1996) contains solvent-coordinated rare-earth cations leading to an anionic chain with a trivalent repeat unit. Polymeric Mo(W)/S/Ag(Cu) clusters have been reviewed by Niu et al. (2004, and references therein). The third-order nonlinear optical properties of Mo(W)/S/Ag(Cu) clusters are reviewed by Zhang, Song et al. (2007) and/or Zhang, Cao et al. (2007).
Data collection: CrystalClear (Rigaku Corporation, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; 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.
[Eu(NO3)2(C6H18N3OP)4][WAgS4] | F(000) = 2808.0 |
Mr = 1412.79 | Dx = 1.744 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2ybc | Cell parameters from 20108 reflections |
a = 15.8182 (13) Å | θ = 3.0–25.4° |
b = 29.778 (2) Å | µ = 3.97 mm−1 |
c = 11.4267 (9) Å | T = 153 K |
β = 90.934 (2)° | Block, red |
V = 5381.7 (7) Å3 | 0.55 × 0.45 × 0.30 mm |
Z = 4 |
Rigaku Mercury CCD (2 × 2 bin mode) diffractometer | 9849 independent reflections |
Radiation source: fine-focus sealed tube | 9106 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: 14.6306 pixels mm-1 | θmax = 25.4°, θmin = 3.0° |
ω scans | h = −18→18 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −31→35 |
Tmin = 0.139, Tmax = 0.304 | l = −13→13 |
50038 measured reflections |
Refinement on F2 | Primary atom site location: isomorphous structure methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0282P)2 + 18.912P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max = 0.001 |
9849 reflections | Δρmax = 1.02 e Å−3 |
535 parameters | Δρmin = −0.99 e Å−3 |
0 restraints |
[Eu(NO3)2(C6H18N3OP)4][WAgS4] | V = 5381.7 (7) Å3 |
Mr = 1412.79 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.8182 (13) Å | µ = 3.97 mm−1 |
b = 29.778 (2) Å | T = 153 K |
c = 11.4267 (9) Å | 0.55 × 0.45 × 0.30 mm |
β = 90.934 (2)° |
Rigaku Mercury CCD (2 × 2 bin mode) diffractometer | 9849 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 9106 reflections with I > 2σ(I) |
Tmin = 0.139, Tmax = 0.304 | Rint = 0.047 |
50038 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0282P)2 + 18.912P] where P = (Fo2 + 2Fc2)/3 |
9849 reflections | Δρmax = 1.02 e Å−3 |
535 parameters | Δρmin = −0.99 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Eu1 | 0.237957 (17) | 0.082979 (9) | 0.83020 (2) | 0.02536 (8) | |
P1 | 0.19588 (11) | −0.03010 (6) | 0.69528 (15) | 0.0405 (4) | |
P2 | 0.46094 (10) | 0.09534 (6) | 0.73359 (16) | 0.0380 (4) | |
P3 | 0.29492 (13) | 0.14797 (6) | 1.10044 (16) | 0.0499 (5) | |
P4 | 0.02042 (9) | 0.13444 (6) | 0.82420 (14) | 0.0345 (4) | |
O1 | 0.3782 (2) | 0.08073 (14) | 0.7818 (4) | 0.0410 (10) | |
O4 | 0.2074 (3) | 0.01747 (13) | 0.7293 (4) | 0.0399 (10) | |
O8 | 0.1010 (2) | 0.10817 (14) | 0.8261 (4) | 0.0344 (9) | |
O11 | 0.2732 (3) | 0.12778 (14) | 0.9851 (4) | 0.0395 (10) | |
O12 | 0.2252 (5) | 0.1724 (2) | 0.5537 (5) | 0.095 (2) | |
O13 | 0.2522 (3) | 0.15902 (14) | 0.7367 (4) | 0.0436 (11) | |
O15 | 0.3007 (3) | 0.02648 (15) | 0.9710 (4) | 0.0444 (11) | |
O16 | 0.2350 (4) | 0.0010 (2) | 1.1235 (5) | 0.0717 (17) | |
O17 | 0.1680 (3) | 0.04047 (15) | 0.9930 (4) | 0.0410 (10) | |
O19 | 0.2235 (3) | 0.10444 (15) | 0.6198 (4) | 0.0454 (11) | |
N1 | 0.2603 (5) | −0.0660 (2) | 0.7601 (6) | 0.068 (2) | |
N2 | 0.2174 (4) | −0.0358 (2) | 0.5567 (5) | 0.0523 (15) | |
N3 | 0.1027 (5) | −0.0471 (3) | 0.7327 (7) | 0.081 (2) | |
N4 | 0.5348 (3) | 0.0699 (2) | 0.8040 (6) | 0.067 (2) | |
N5 | 0.4855 (4) | 0.1483 (2) | 0.7383 (7) | 0.071 (2) | |
N6 | 0.4597 (4) | 0.0858 (3) | 0.5925 (6) | 0.071 (2) | |
N7 | 0.2770 (6) | 0.2001 (2) | 1.0988 (6) | 0.083 (2) | |
N8 | 0.2390 (7) | 0.1250 (3) | 1.2012 (7) | 0.103 (3) | |
N9 | 0.3937 (6) | 0.1383 (3) | 1.1331 (9) | 0.115 (4) | |
N10 | 0.0224 (4) | 0.1743 (2) | 0.9212 (6) | 0.0548 (16) | |
N11 | 0.0042 (4) | 0.1578 (2) | 0.6986 (5) | 0.0588 (17) | |
N12 | −0.0574 (3) | 0.1001 (2) | 0.8512 (5) | 0.0414 (13) | |
N13 | 0.2340 (4) | 0.1463 (2) | 0.6344 (6) | 0.0509 (15) | |
N14 | 0.2353 (4) | 0.02194 (18) | 1.0309 (5) | 0.0451 (14) | |
C1 | 0.5132 (9) | 0.1681 (4) | 0.8488 (11) | 0.147 (6) | |
H1A | 0.5255 | 0.2001 | 0.8371 | 0.220* | |
H1B | 0.5644 | 0.1528 | 0.8771 | 0.220* | |
H1C | 0.4685 | 0.1649 | 0.9065 | 0.220* | |
C2 | 0.4540 (6) | 0.1805 (4) | 0.6513 (13) | 0.137 (6) | |
H2A | 0.4764 | 0.2105 | 0.6696 | 0.206* | |
H2B | 0.3921 | 0.1813 | 0.6527 | 0.206* | |
H2C | 0.4725 | 0.1715 | 0.5733 | 0.206* | |
C3 | 0.5320 (7) | 0.0960 (6) | 0.5201 (10) | 0.140 (6) | |
H3A | 0.5735 | 0.0717 | 0.5268 | 0.210* | |
H3B | 0.5579 | 0.1242 | 0.5465 | 0.210* | |
H3C | 0.5133 | 0.0990 | 0.4383 | 0.210* | |
C4 | 0.3065 (7) | 0.2278 (3) | 0.9985 (7) | 0.074 (3) | |
H4A | 0.2906 | 0.2592 | 1.0109 | 0.110* | |
H4B | 0.2802 | 0.2168 | 0.9258 | 0.110* | |
H4C | 0.3681 | 0.2255 | 0.9932 | 0.110* | |
C5 | 0.4336 (7) | 0.0961 (4) | 1.1182 (12) | 0.120 (5) | |
H5A | 0.4924 | 0.0979 | 1.1461 | 0.180* | |
H5B | 0.4323 | 0.0880 | 1.0351 | 0.180* | |
H5C | 0.4035 | 0.0732 | 1.1630 | 0.180* | |
C6 | 0.1481 (8) | 0.1232 (5) | 1.1876 (10) | 0.115 (4) | |
H6A | 0.1238 | 0.1088 | 1.2564 | 0.173* | |
H6B | 0.1332 | 0.1058 | 1.1174 | 0.173* | |
H6C | 0.1256 | 0.1537 | 1.1799 | 0.173* | |
C7 | 0.0897 (6) | 0.2079 (3) | 0.9205 (9) | 0.080 (3) | |
H7A | 0.0812 | 0.2293 | 0.9843 | 0.119* | |
H7B | 0.0884 | 0.2239 | 0.8455 | 0.119* | |
H7C | 0.1445 | 0.1931 | 0.9310 | 0.119* | |
C8 | −0.0453 (5) | 0.1845 (3) | 1.0028 (8) | 0.073 (2) | |
H8A | −0.0286 | 0.2100 | 1.0522 | 0.109* | |
H8B | −0.0556 | 0.1582 | 1.0523 | 0.109* | |
H8C | −0.0970 | 0.1920 | 0.9587 | 0.109* | |
C9 | −0.0484 (4) | 0.0666 (3) | 0.9441 (7) | 0.057 (2) | |
H9A | −0.1006 | 0.0490 | 0.9489 | 0.085* | |
H9B | −0.0376 | 0.0818 | 1.0190 | 0.085* | |
H9C | −0.0010 | 0.0466 | 0.9268 | 0.085* | |
C10 | 0.4501 (10) | 0.1727 (6) | 1.1869 (14) | 0.185 (8) | |
H10A | 0.5063 | 0.1598 | 1.2010 | 0.277* | |
H10B | 0.4265 | 0.1827 | 1.2613 | 0.277* | |
H10C | 0.4546 | 0.1985 | 1.1338 | 0.277* | |
C11 | −0.1443 (4) | 0.1096 (3) | 0.8152 (7) | 0.064 (2) | |
H11A | −0.1810 | 0.0850 | 0.8399 | 0.095* | |
H11B | −0.1476 | 0.1126 | 0.7298 | 0.095* | |
H11C | −0.1629 | 0.1377 | 0.8516 | 0.095* | |
C12 | −0.0357 (6) | 0.2023 (3) | 0.6820 (10) | 0.099 (4) | |
H12A | −0.0379 | 0.2096 | 0.5984 | 0.148* | |
H12B | −0.0024 | 0.2251 | 0.7240 | 0.148* | |
H12C | −0.0932 | 0.2016 | 0.7126 | 0.148* | |
C13 | 0.0173 (6) | 0.1324 (4) | 0.5934 (7) | 0.097 (4) | |
H13A | 0.0054 | 0.1514 | 0.5251 | 0.146* | |
H13B | −0.0207 | 0.1064 | 0.5921 | 0.146* | |
H13C | 0.0761 | 0.1221 | 0.5915 | 0.146* | |
C14 | 0.0347 (5) | −0.0153 (3) | 0.7535 (9) | 0.082 (3) | |
H14A | −0.0162 | −0.0317 | 0.7763 | 0.123* | |
H14B | 0.0229 | 0.0018 | 0.6818 | 0.123* | |
H14C | 0.0517 | 0.0053 | 0.8164 | 0.123* | |
C15 | 0.1975 (7) | −0.0008 (3) | 0.4747 (7) | 0.080 (3) | |
H15A | 0.2153 | −0.0098 | 0.3964 | 0.120* | |
H15B | 0.2273 | 0.0268 | 0.4979 | 0.120* | |
H15C | 0.1365 | 0.0047 | 0.4738 | 0.120* | |
C16 | 0.2237 (7) | −0.0813 (3) | 0.5035 (8) | 0.083 (3) | |
H16A | 0.2376 | −0.0784 | 0.4206 | 0.124* | |
H16B | 0.1695 | −0.0969 | 0.5107 | 0.124* | |
H16C | 0.2681 | −0.0984 | 0.5441 | 0.124* | |
C17 | 0.5220 (5) | 0.0281 (3) | 0.8643 (9) | 0.085 (3) | |
H17A | 0.5751 | 0.0187 | 0.9022 | 0.127* | |
H17B | 0.5035 | 0.0051 | 0.8082 | 0.127* | |
H17C | 0.4786 | 0.0321 | 0.9237 | 0.127* | |
C18 | 0.6243 (5) | 0.0806 (5) | 0.7837 (12) | 0.144 (7) | |
H18A | 0.6539 | 0.0844 | 0.8590 | 0.216* | |
H18B | 0.6281 | 0.1085 | 0.7385 | 0.216* | |
H18C | 0.6504 | 0.0560 | 0.7400 | 0.216* | |
C19 | 0.4087 (6) | 0.0490 (4) | 0.5441 (9) | 0.087 (3) | |
H19A | 0.4154 | 0.0479 | 0.4590 | 0.131* | |
H19B | 0.3491 | 0.0540 | 0.5620 | 0.131* | |
H19C | 0.4275 | 0.0205 | 0.5788 | 0.131* | |
C20 | 0.2500 (10) | 0.2257 (4) | 1.2042 (10) | 0.136 (6) | |
H20A | 0.2424 | 0.2574 | 1.1836 | 0.203* | |
H20B | 0.2934 | 0.2231 | 1.2660 | 0.203* | |
H20C | 0.1965 | 0.2135 | 1.2322 | 0.203* | |
C21 | 0.0789 (9) | −0.0953 (4) | 0.7149 (11) | 0.142 (6) | |
H21A | 0.0215 | −0.1002 | 0.7428 | 0.213* | |
H21B | 0.1185 | −0.1145 | 0.7587 | 0.213* | |
H21C | 0.0813 | −0.1026 | 0.6314 | 0.213* | |
C22 | 0.2524 (9) | −0.0824 (4) | 0.8744 (11) | 0.132 (5) | |
H22A | 0.2995 | −0.1028 | 0.8925 | 0.198* | |
H22B | 0.1988 | −0.0987 | 0.8810 | 0.198* | |
H22C | 0.2535 | −0.0573 | 0.9297 | 0.198* | |
C23 | 0.3489 (7) | −0.0687 (5) | 0.7285 (13) | 0.136 (5) | |
H23A | 0.3820 | −0.0477 | 0.7770 | 0.204* | |
H23B | 0.3547 | −0.0607 | 0.6458 | 0.204* | |
H23C | 0.3695 | −0.0993 | 0.7415 | 0.204* | |
C24 | 0.2820 (13) | 0.1085 (6) | 1.3115 (10) | 0.200 (9) | |
H24A | 0.2396 | 0.0960 | 1.3640 | 0.300* | |
H24B | 0.3111 | 0.1336 | 1.3503 | 0.300* | |
H24C | 0.3231 | 0.0852 | 1.2919 | 0.300* | |
W1 | 0.715479 (15) | 0.228140 (8) | 0.474607 (19) | 0.02705 (7) | |
Ag1 | 0.71643 (4) | 0.235706 (19) | 0.21504 (4) | 0.04964 (15) | |
S1 | 0.82933 (11) | 0.21256 (7) | 0.37402 (14) | 0.0474 (4) | |
S2 | 0.60182 (11) | 0.21406 (7) | 0.36870 (14) | 0.0475 (4) | |
S3 | 0.71359 (11) | 0.18439 (5) | 0.62998 (13) | 0.0401 (4) | |
S4 | 0.71643 (13) | 0.30024 (5) | 0.51802 (14) | 0.0461 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Eu1 | 0.02305 (15) | 0.01944 (14) | 0.03358 (16) | 0.00003 (11) | 0.00043 (11) | −0.00040 (11) |
P1 | 0.0537 (10) | 0.0286 (9) | 0.0396 (9) | −0.0101 (8) | 0.0113 (8) | −0.0095 (7) |
P2 | 0.0238 (8) | 0.0393 (9) | 0.0510 (10) | −0.0004 (7) | 0.0053 (7) | 0.0072 (8) |
P3 | 0.0700 (13) | 0.0395 (10) | 0.0395 (10) | −0.0077 (9) | −0.0207 (9) | −0.0011 (8) |
P4 | 0.0258 (8) | 0.0404 (9) | 0.0371 (9) | 0.0061 (7) | −0.0010 (6) | 0.0072 (7) |
O1 | 0.027 (2) | 0.040 (3) | 0.056 (3) | −0.0019 (19) | 0.0067 (19) | 0.008 (2) |
O4 | 0.046 (3) | 0.021 (2) | 0.053 (3) | −0.0020 (19) | −0.003 (2) | −0.0099 (19) |
O8 | 0.025 (2) | 0.037 (2) | 0.041 (2) | 0.0064 (18) | −0.0011 (17) | −0.0017 (19) |
O11 | 0.042 (2) | 0.038 (2) | 0.039 (2) | −0.0014 (19) | −0.0094 (19) | −0.0048 (19) |
O12 | 0.160 (7) | 0.057 (4) | 0.066 (4) | −0.029 (4) | −0.023 (4) | 0.037 (3) |
O13 | 0.053 (3) | 0.029 (2) | 0.049 (3) | −0.007 (2) | −0.002 (2) | 0.002 (2) |
O15 | 0.034 (2) | 0.039 (3) | 0.061 (3) | 0.001 (2) | −0.002 (2) | 0.009 (2) |
O16 | 0.076 (4) | 0.077 (4) | 0.062 (4) | −0.004 (3) | −0.007 (3) | 0.043 (3) |
O17 | 0.037 (2) | 0.042 (3) | 0.044 (3) | 0.001 (2) | −0.002 (2) | 0.011 (2) |
O19 | 0.059 (3) | 0.038 (3) | 0.039 (3) | −0.004 (2) | 0.005 (2) | −0.002 (2) |
N1 | 0.108 (6) | 0.028 (3) | 0.069 (5) | 0.014 (3) | 0.020 (4) | 0.004 (3) |
N2 | 0.075 (4) | 0.043 (3) | 0.039 (3) | −0.013 (3) | 0.009 (3) | −0.009 (3) |
N3 | 0.073 (5) | 0.080 (5) | 0.092 (6) | −0.041 (4) | 0.038 (4) | −0.045 (4) |
N4 | 0.026 (3) | 0.094 (5) | 0.080 (5) | 0.006 (3) | 0.008 (3) | 0.055 (4) |
N5 | 0.054 (4) | 0.051 (4) | 0.107 (6) | −0.011 (3) | 0.015 (4) | 0.015 (4) |
N6 | 0.046 (4) | 0.112 (6) | 0.055 (4) | −0.014 (4) | 0.011 (3) | 0.014 (4) |
N7 | 0.159 (8) | 0.040 (4) | 0.050 (4) | −0.009 (4) | −0.001 (4) | −0.007 (3) |
N8 | 0.178 (10) | 0.079 (6) | 0.050 (5) | −0.040 (6) | −0.009 (5) | 0.010 (4) |
N9 | 0.118 (7) | 0.075 (6) | 0.148 (9) | −0.004 (5) | −0.094 (7) | −0.024 (6) |
N10 | 0.046 (3) | 0.046 (4) | 0.072 (4) | 0.006 (3) | 0.010 (3) | −0.011 (3) |
N11 | 0.041 (3) | 0.086 (5) | 0.049 (4) | 0.003 (3) | −0.006 (3) | 0.029 (3) |
N12 | 0.026 (3) | 0.057 (4) | 0.042 (3) | −0.001 (2) | 0.001 (2) | 0.006 (3) |
N13 | 0.055 (4) | 0.040 (3) | 0.059 (4) | −0.005 (3) | 0.004 (3) | 0.015 (3) |
N14 | 0.048 (3) | 0.037 (3) | 0.049 (4) | −0.006 (3) | −0.012 (3) | 0.006 (3) |
C1 | 0.201 (15) | 0.121 (11) | 0.119 (11) | −0.100 (11) | 0.055 (10) | −0.052 (9) |
C2 | 0.066 (6) | 0.083 (8) | 0.263 (17) | 0.007 (6) | 0.025 (8) | 0.097 (10) |
C3 | 0.103 (9) | 0.246 (18) | 0.073 (7) | −0.061 (10) | 0.036 (7) | 0.003 (9) |
C4 | 0.130 (8) | 0.037 (4) | 0.053 (5) | −0.013 (5) | 0.000 (5) | −0.003 (4) |
C5 | 0.091 (8) | 0.084 (8) | 0.183 (13) | 0.008 (6) | −0.082 (8) | −0.003 (8) |
C6 | 0.110 (9) | 0.145 (12) | 0.093 (8) | −0.038 (9) | 0.043 (7) | −0.004 (8) |
C7 | 0.074 (6) | 0.051 (5) | 0.114 (8) | −0.009 (5) | 0.015 (5) | −0.022 (5) |
C8 | 0.066 (5) | 0.070 (6) | 0.082 (6) | 0.020 (5) | 0.021 (5) | −0.010 (5) |
C9 | 0.041 (4) | 0.069 (5) | 0.062 (5) | −0.001 (4) | 0.008 (3) | 0.017 (4) |
C10 | 0.164 (14) | 0.200 (17) | 0.187 (16) | −0.088 (13) | −0.102 (12) | −0.009 (13) |
C11 | 0.031 (4) | 0.095 (7) | 0.065 (5) | −0.007 (4) | −0.008 (3) | 0.011 (5) |
C12 | 0.081 (7) | 0.091 (8) | 0.124 (9) | 0.018 (6) | −0.021 (6) | 0.067 (7) |
C13 | 0.074 (6) | 0.174 (12) | 0.044 (5) | −0.018 (7) | −0.014 (4) | 0.000 (6) |
C14 | 0.042 (5) | 0.094 (7) | 0.110 (8) | −0.008 (5) | −0.011 (5) | 0.020 (6) |
C15 | 0.111 (8) | 0.081 (7) | 0.048 (5) | −0.006 (6) | 0.001 (5) | −0.002 (5) |
C16 | 0.113 (8) | 0.064 (6) | 0.071 (6) | −0.020 (5) | 0.033 (5) | −0.037 (5) |
C17 | 0.052 (5) | 0.068 (6) | 0.133 (9) | 0.006 (4) | 0.004 (5) | 0.047 (6) |
C18 | 0.028 (4) | 0.224 (15) | 0.180 (12) | 0.010 (6) | 0.011 (6) | 0.147 (12) |
C19 | 0.074 (6) | 0.108 (8) | 0.079 (7) | −0.007 (6) | 0.002 (5) | −0.029 (6) |
C20 | 0.260 (18) | 0.074 (8) | 0.074 (8) | −0.013 (9) | 0.031 (9) | −0.042 (6) |
C21 | 0.186 (13) | 0.098 (9) | 0.145 (11) | −0.102 (9) | 0.100 (10) | −0.067 (8) |
C22 | 0.169 (13) | 0.108 (10) | 0.121 (10) | 0.066 (9) | 0.030 (9) | 0.049 (8) |
C23 | 0.079 (8) | 0.158 (13) | 0.171 (14) | 0.041 (8) | 0.008 (8) | 0.042 (11) |
C24 | 0.36 (3) | 0.188 (17) | 0.049 (7) | −0.002 (17) | −0.003 (11) | 0.062 (9) |
W1 | 0.03451 (14) | 0.02849 (13) | 0.01806 (12) | −0.00325 (10) | −0.00220 (9) | 0.00184 (9) |
Ag1 | 0.0782 (4) | 0.0500 (3) | 0.0207 (2) | 0.0004 (3) | −0.0006 (2) | 0.0025 (2) |
S1 | 0.0401 (9) | 0.0705 (12) | 0.0317 (9) | 0.0070 (9) | 0.0016 (7) | 0.0033 (8) |
S2 | 0.0410 (9) | 0.0703 (12) | 0.0309 (9) | −0.0158 (9) | −0.0070 (7) | 0.0041 (8) |
S3 | 0.0620 (10) | 0.0313 (8) | 0.0270 (8) | 0.0004 (7) | 0.0005 (7) | 0.0069 (6) |
S4 | 0.0782 (12) | 0.0280 (8) | 0.0321 (8) | −0.0066 (8) | −0.0006 (8) | 0.0034 (7) |
Eu1—O11 | 2.279 (4) | N2—C15 | 1.434 (10) |
Eu1—O8 | 2.292 (4) | N2—C16 | 1.487 (9) |
Eu1—O1 | 2.296 (4) | N3—C14 | 1.455 (11) |
Eu1—O4 | 2.313 (4) | N3—C21 | 1.496 (11) |
Eu1—O19 | 2.494 (4) | N4—C17 | 1.439 (10) |
Eu1—O13 | 2.515 (4) | N4—C18 | 1.473 (10) |
Eu1—O15 | 2.520 (4) | N5—C1 | 1.455 (13) |
Eu1—O17 | 2.521 (4) | N5—C2 | 1.464 (12) |
P1—O4 | 1.479 (4) | N6—C3 | 1.454 (11) |
P1—N3 | 1.622 (7) | N6—C19 | 1.463 (11) |
P1—N2 | 1.634 (6) | N7—C4 | 1.492 (10) |
P1—N1 | 1.645 (7) | N7—C20 | 1.495 (11) |
P2—O1 | 1.493 (4) | N8—C6 | 1.444 (14) |
P2—N4 | 1.598 (6) | N8—C24 | 1.505 (14) |
P2—N5 | 1.625 (7) | N9—C5 | 1.418 (13) |
P2—N6 | 1.637 (7) | N9—C10 | 1.485 (13) |
P3—O11 | 1.484 (4) | N10—C7 | 1.460 (10) |
P3—N7 | 1.578 (7) | N10—C8 | 1.463 (9) |
P3—N8 | 1.615 (9) | N11—C13 | 1.439 (11) |
P3—N9 | 1.626 (9) | N11—C12 | 1.476 (11) |
P4—O8 | 1.496 (4) | N12—C11 | 1.457 (8) |
P4—N11 | 1.612 (6) | N12—C9 | 1.462 (9) |
P4—N10 | 1.625 (6) | W1—S2 | 2.1913 (16) |
P4—N12 | 1.633 (5) | W1—S1 | 2.2016 (17) |
O12—N13 | 1.212 (7) | W1—S3 | 2.2028 (15) |
O13—N13 | 1.258 (7) | W1—S4 | 2.2036 (16) |
O15—N14 | 1.257 (7) | W1—Ag1i | 2.9506 (6) |
O16—N14 | 1.227 (7) | W1—Ag1 | 2.9748 (6) |
O17—N14 | 1.268 (7) | Ag1—S4ii | 2.4929 (17) |
O19—N13 | 1.267 (7) | Ag1—S3ii | 2.5704 (17) |
N1—C22 | 1.402 (13) | Ag1—S1 | 2.6190 (18) |
N1—C23 | 1.455 (12) | Ag1—S2 | 2.6245 (18) |
O11—Eu1—O8 | 92.50 (15) | N13—O13—Eu1 | 95.9 (3) |
O11—Eu1—O1 | 88.80 (16) | N14—O15—Eu1 | 95.8 (3) |
O8—Eu1—O1 | 157.08 (15) | N14—O17—Eu1 | 95.5 (3) |
O11—Eu1—O4 | 158.04 (16) | N13—O19—Eu1 | 96.6 (4) |
O8—Eu1—O4 | 94.37 (15) | C22—N1—C23 | 108.2 (9) |
O1—Eu1—O4 | 92.88 (15) | C22—N1—P1 | 125.6 (7) |
O11—Eu1—O19 | 128.04 (15) | C23—N1—P1 | 121.0 (7) |
O8—Eu1—O19 | 79.91 (15) | C15—N2—C16 | 114.2 (7) |
O1—Eu1—O19 | 81.31 (15) | C15—N2—P1 | 120.7 (5) |
O4—Eu1—O19 | 73.78 (15) | C16—N2—P1 | 120.5 (5) |
O11—Eu1—O13 | 77.32 (15) | C14—N3—C21 | 117.4 (8) |
O8—Eu1—O13 | 77.74 (15) | C14—N3—P1 | 121.2 (6) |
O1—Eu1—O13 | 80.24 (15) | C21—N3—P1 | 119.4 (7) |
O4—Eu1—O13 | 124.54 (15) | C17—N4—C18 | 113.9 (7) |
O19—Eu1—O13 | 50.76 (15) | C17—N4—P2 | 122.9 (5) |
O11—Eu1—O15 | 78.82 (15) | C18—N4—P2 | 121.0 (5) |
O8—Eu1—O15 | 126.42 (14) | C1—N5—C2 | 114.7 (10) |
O1—Eu1—O15 | 76.26 (15) | C1—N5—P2 | 119.4 (7) |
O4—Eu1—O15 | 80.32 (15) | C2—N5—P2 | 122.4 (8) |
O19—Eu1—O15 | 144.60 (15) | C3—N6—C19 | 112.0 (8) |
O13—Eu1—O15 | 146.63 (15) | C3—N6—P2 | 121.8 (7) |
O11—Eu1—O17 | 79.94 (15) | C19—N6—P2 | 120.0 (6) |
O8—Eu1—O17 | 75.74 (14) | C4—N7—C20 | 115.7 (7) |
O1—Eu1—O17 | 126.90 (14) | C4—N7—P3 | 119.6 (6) |
O4—Eu1—O17 | 81.59 (15) | C20—N7—P3 | 123.1 (7) |
O19—Eu1—O17 | 143.68 (14) | C6—N8—C24 | 120.8 (11) |
O13—Eu1—O17 | 143.99 (15) | C6—N8—P3 | 119.7 (7) |
O15—Eu1—O17 | 50.69 (14) | C24—N8—P3 | 119.3 (10) |
O11—Eu1—N13 | 102.65 (17) | C5—N9—C10 | 113.4 (10) |
O8—Eu1—N13 | 76.40 (16) | C5—N9—P3 | 123.8 (6) |
O1—Eu1—N13 | 80.99 (16) | C10—N9—P3 | 122.7 (10) |
O4—Eu1—N13 | 99.23 (17) | C7—N10—C8 | 113.8 (7) |
O19—Eu1—N13 | 25.48 (16) | C7—N10—P4 | 120.2 (5) |
O13—Eu1—N13 | 25.34 (15) | C8—N10—P4 | 125.4 (6) |
O15—Eu1—N13 | 157.18 (16) | C13—N11—C12 | 115.6 (8) |
O17—Eu1—N13 | 152.10 (15) | C13—N11—P4 | 119.6 (7) |
O11—Eu1—N14 | 76.19 (15) | C12—N11—P4 | 124.3 (7) |
O8—Eu1—N14 | 101.16 (16) | C11—N12—C9 | 114.7 (5) |
O1—Eu1—N14 | 101.36 (16) | C11—N12—P4 | 122.4 (5) |
O4—Eu1—N14 | 82.03 (15) | C9—N12—P4 | 120.0 (4) |
O19—Eu1—N14 | 155.78 (15) | O12—N13—O13 | 122.3 (6) |
O13—Eu1—N14 | 153.41 (15) | O12—N13—O19 | 121.2 (7) |
O15—Eu1—N14 | 25.30 (14) | O13—N13—O19 | 116.5 (5) |
O17—Eu1—N14 | 25.55 (14) | O16—N14—O15 | 122.6 (6) |
N13—Eu1—N14 | 177.30 (17) | O16—N14—O17 | 120.0 (6) |
O4—P1—N3 | 109.8 (3) | O15—N14—O17 | 117.4 (5) |
O4—P1—N2 | 109.1 (3) | S2—W1—S1 | 110.00 (7) |
N3—P1—N2 | 115.3 (4) | S2—W1—S3 | 108.07 (7) |
O4—P1—N1 | 115.6 (3) | S1—W1—S3 | 108.55 (7) |
N3—P1—N1 | 103.7 (4) | S2—W1—S4 | 108.26 (7) |
N2—P1—N1 | 103.4 (3) | S1—W1—S4 | 108.68 (7) |
O1—P2—N4 | 108.3 (3) | S3—W1—S4 | 113.26 (6) |
O1—P2—N5 | 118.7 (3) | Ag1i—W1—Ag1 | 154.250 (9) |
N4—P2—N5 | 105.7 (4) | S4ii—Ag1—S3ii | 93.23 (5) |
O1—P2—N6 | 108.4 (3) | S4ii—Ag1—S1 | 120.22 (6) |
N4—P2—N6 | 114.2 (4) | S3ii—Ag1—S1 | 120.89 (6) |
N5—P2—N6 | 101.5 (4) | S4ii—Ag1—S2 | 120.59 (6) |
O11—P3—N7 | 110.4 (3) | S3ii—Ag1—S2 | 118.18 (6) |
O11—P3—N8 | 109.9 (4) | S1—Ag1—S2 | 86.67 (5) |
N7—P3—N8 | 108.9 (5) | S4ii—Ag1—W1ii | 46.83 (4) |
O11—P3—N9 | 109.9 (4) | S3ii—Ag1—W1ii | 46.40 (3) |
N7—P3—N9 | 110.4 (5) | S1—Ag1—W1ii | 137.30 (4) |
N8—P3—N9 | 107.3 (6) | S2—Ag1—W1ii | 136.01 (4) |
O8—P4—N11 | 111.2 (3) | S4ii—Ag1—W1 | 150.22 (4) |
O8—P4—N10 | 111.4 (3) | S3ii—Ag1—W1 | 116.54 (4) |
N11—P4—N10 | 107.0 (4) | S1—Ag1—W1 | 45.81 (4) |
O8—P4—N12 | 108.3 (3) | S2—Ag1—W1 | 45.55 (4) |
N11—P4—N12 | 109.2 (3) | W1ii—Ag1—W1 | 162.93 (2) |
N10—P4—N12 | 109.6 (3) | W1—S1—Ag1 | 75.66 (5) |
P2—O1—Eu1 | 159.5 (3) | W1—S2—Ag1 | 75.70 (5) |
P1—O4—Eu1 | 164.2 (3) | W1—S3—Ag1i | 75.93 (5) |
P4—O8—Eu1 | 167.6 (3) | W1—S4—Ag1i | 77.57 (5) |
P3—O11—Eu1 | 167.8 (3) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Eu(NO3)2(C6H18N3OP)4][WAgS4] |
Mr | 1412.79 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 153 |
a, b, c (Å) | 15.8182 (13), 29.778 (2), 11.4267 (9) |
β (°) | 90.934 (2) |
V (Å3) | 5381.7 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.97 |
Crystal size (mm) | 0.55 × 0.45 × 0.30 |
Data collection | |
Diffractometer | Rigaku Mercury CCD (2 × 2 bin mode) |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.139, 0.304 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 50038, 9849, 9106 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.090, 1.15 |
No. of reflections | 9849 |
No. of parameters | 535 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0282P)2 + 18.912P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.02, −0.99 |
Computer programs: CrystalClear (Rigaku Corporation, 2000), CrystalClear, SHELXTL (Sheldrick, 2000), SHELXTL.
One-dimensional Mo(W)/S/Ag anionic polymers have attracted much attention for their configurational isomerism (Niu et al., 2004) and unique properties as functional materials, such as third-order nonlinear optical (NLO) materials (Zhang, Song et al., 2007, and references therein). Different solvent-coordinated rare-earth cations proved effective to obtain various configurations of anionic chains (Niu et al., 2004). The title compound, {[Eu(hmp)4(NO3)2][WS4Ag]}n (hmp = hexamethylphosphoramide), with a wave-like anionic chain was prepared by following such route using EuIII–hmp complex as counterion.
The cation in the title compound, where Eu3- is coordinated by eight O atoms from two nitrate and four hmp ligands, has the same structure as those in the isostructural {[Yb(hmp)4(NO3)2][WS4Ag]}n (Cao et al., 2007) and {[Y(hmp)4(NO3)2][WS4Ag]}n (Zhang, Cao et al., 2007). Parts of dimethylamine groups from hmp ligands have large librations. In possession of two nitrate ligands, the cation in the title compound is monovalent (Fig. 1), which leads to an anionic chain with a monovalent repeat unit, unlike other solvent-coordinated rare-earth cations (Niu et al., 2004), which are trivalent and induce trivalent repeat units. For example, [Nd(dmf)8]3+ induces an anionic chain with a trivalent repeat unit [W4S16Ag5]3- (Huang et al., 1996).
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 162.93 (2) and 154.250 (9)°, respectively, unlike those in {(γ-MePyH)[WS4Ag]}n (MePyH is protonated picoline; Lang et al., 1993) and {[NH3C(CH2OH)3][WS4Ag](2DMF)}n (Huang et al., 1997), showing an ideal linear chain and a nearly linear chain with W—Ag—W and Ag—W—Ag angles of 176.4 (5) and 176.4 (3)°, respectively. This fact suggests that cations with bigger bulk lead to more distorted anionic chains.
Similar angles of 160.81 (7) and 153.41 (7)° for W—Ag—W and Ag—W—Ag, respectively, are found in another two distorted linear chains in {[Yb(hmp)4(NO3)2][WS4Ag]}n (Cao et al., 2007) and {[Y(hmp)4(NO3)2][WS4Ag]}n (Zhang, Cao et al., 2007), implying that different rare earth cations with the same coordination environments will result in the same anionic structures.