metal-organic compounds
Tris(thiocyanato-κN)tris(triphenylphosphine oxide-κO)europium(III)–(nitrato-κ2O,O′)bis(thiocyanato-κN)tris(triphenylphosphine oxide-κO)europium(III) (1/1)
aUniversity of South Alabama, Department of Chemistry, Mobile, AL 36688, USA
*Correspondence e-mail: rsykora@southalabama.edu
The title 3(C18H15OP)3][Eu(NCS)2(NO3)(C18H15OP)3], contains two distinct neutral complexes. Each complex has threefold symmetry about its central Eu3+ ion. As a result, the nitrate-containing molecule contains disorder of its bidentate nitrate and two N-bound thiocyanate anions, while the [Eu(NCS)3(OPPh3)3] complex is fully ordered. There is a weak π–π stacking interaction between the phenyl rings of the two molecules [centroid–centroid distance = 4.138 (4) Å].
[Eu(NCS)Related literature
For structural studies on related f-block triphenylphosphine oxide complexes, see: Feazell et al. (2004); Berthet et al. (2003); Long et al. (1999); Bowden et al. (2010). For syntheses and spectroscopic characterization of related compounds, see: Cousins & Hart (1967, 1968).
Experimental
Crystal data
|
Data collection: CrysAlis PRO (Agilent, 2012); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812047472/qm2089sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812047472/qm2089Isup2.hkl
Ethanol solutions of europium(III) nitrate hydrate (~1 mmol) and KSCN (~3 mmol) were combined. The resultant solution was decanted from the KNO3 precipitate. This solution was then mixed with an ethanol solution of triphenylphosphine oxide (~4 mmol). Within one hour, the colorless crystals suitable for the X-ray analysis were isolated.
H-atoms were placed in calculated positions and allowed to ride during subsequent
with Uiso(H) = 1.2Ueq(C) and C—H distances of 0.95 Å.Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The molecular structure of I, with the atom-numbering scheme. Displacement ellipsoids for non-hydrogen atoms are drawn at the 50% probability level. |
[Eu(NCS)3(C18H15OP)3][Eu(NCS)2(NO3)(C18H15OP)3] | Dx = 1.451 Mg m−3 |
Mr = 2325.95 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 5442 reflections |
a = 20.3249 (7) Å | θ = 3.2–25.0° |
c = 22.3186 (6) Å | µ = 1.42 mm−1 |
V = 7984.7 (4) Å3 | T = 180 K |
Z = 3 | Prism, colourless |
F(000) = 3534 | 0.12 × 0.07 × 0.05 mm |
Agilent Xcalibur Eos diffractometer | 6325 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 5614 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ω scans | θmax = 25.1°, θmin = 3.2° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −24→23 |
Tmin = 0.892, Tmax = 1.000 | k = −22→24 |
15970 measured reflections | l = −26→26 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.065 | w = 1/[σ2(Fo2) + (0.0112P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
6325 reflections | Δρmax = 1.30 e Å−3 |
439 parameters | Δρmin = −0.90 e Å−3 |
8 restraints | Absolute structure: Flack (1983), 3154 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.045 (9) |
[Eu(NCS)3(C18H15OP)3][Eu(NCS)2(NO3)(C18H15OP)3] | Z = 3 |
Mr = 2325.95 | Mo Kα radiation |
Trigonal, R3 | µ = 1.42 mm−1 |
a = 20.3249 (7) Å | T = 180 K |
c = 22.3186 (6) Å | 0.12 × 0.07 × 0.05 mm |
V = 7984.7 (4) Å3 |
Agilent Xcalibur Eos diffractometer | 6325 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 5614 reflections with I > 2σ(I) |
Tmin = 0.892, Tmax = 1.000 | Rint = 0.052 |
15970 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.065 | Δρmax = 1.30 e Å−3 |
S = 1.02 | Δρmin = −0.90 e Å−3 |
6325 reflections | Absolute structure: Flack (1983), 3154 Friedel pairs |
439 parameters | Absolute structure parameter: −0.045 (9) |
8 restraints |
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 > 2σ(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 | Occ. (<1) | |
Eu1 | 0.6667 | 0.3333 | 0.305072 (13) | 0.02675 (13) | |
Eu2 | 0.0000 | 0.0000 | 0.462118 (16) | 0.04265 (17) | |
P2 | 0.16058 (9) | 0.14280 (10) | 0.55807 (6) | 0.0392 (4) | |
C20 | 0.1572 (3) | 0.1238 (3) | 0.6370 (2) | 0.0325 (13) | |
C26 | 0.1639 (3) | 0.2324 (3) | 0.5478 (2) | 0.0422 (15) | |
C27 | 0.0969 (4) | 0.2320 (4) | 0.5345 (2) | 0.0556 (18) | |
H27 | 0.0511 | 0.1848 | 0.5302 | 0.067* | |
C25 | 0.1888 (3) | 0.1809 (3) | 0.6797 (2) | 0.0433 (15) | |
H25 | 0.2129 | 0.2327 | 0.6680 | 0.052* | |
C23 | 0.1489 (3) | 0.0872 (3) | 0.7568 (2) | 0.0476 (16) | |
H23 | 0.1458 | 0.0748 | 0.7981 | 0.057* | |
C21 | 0.1214 (3) | 0.0488 (3) | 0.6551 (2) | 0.0416 (15) | |
H21 | 0.0993 | 0.0096 | 0.6259 | 0.050* | |
C5 | 0.6419 (4) | 0.6382 (4) | 0.3299 (3) | 0.063 (2) | |
H5 | 0.6622 | 0.6894 | 0.3173 | 0.075* | |
C7 | 0.6563 (3) | 0.5304 (3) | 0.3457 (2) | 0.0447 (15) | |
H7 | 0.6869 | 0.5072 | 0.3435 | 0.054* | |
C22 | 0.1170 (3) | 0.0297 (3) | 0.7152 (2) | 0.0484 (16) | |
H22 | 0.0926 | −0.0220 | 0.7274 | 0.058* | |
C24 | 0.1848 (3) | 0.1616 (3) | 0.7400 (2) | 0.0538 (17) | |
H24 | 0.2071 | 0.2004 | 0.7694 | 0.065* | |
C3 | 0.5402 (3) | 0.5249 (4) | 0.3722 (2) | 0.0508 (16) | |
H3 | 0.4900 | 0.4981 | 0.3879 | 0.061* | |
C31 | 0.2310 (4) | 0.3011 (4) | 0.5537 (2) | 0.0543 (18) | |
H31 | 0.2775 | 0.3025 | 0.5619 | 0.065* | |
C4 | 0.5701 (4) | 0.5993 (4) | 0.3524 (3) | 0.069 (2) | |
H4 | 0.5402 | 0.6232 | 0.3545 | 0.083* | |
C32 | 0.2453 (3) | 0.1481 (3) | 0.5283 (3) | 0.0455 (15) | |
C28 | 0.0957 (6) | 0.2984 (5) | 0.5274 (3) | 0.076 (3) | |
H28 | 0.0494 | 0.2968 | 0.5175 | 0.091* | |
C6 | 0.6848 (4) | 0.6037 (4) | 0.3256 (2) | 0.0566 (19) | |
H6 | 0.7343 | 0.6304 | 0.3088 | 0.068* | |
C15 | 0.4249 (3) | 0.2996 (3) | 0.3298 (2) | 0.0411 (14) | |
H15 | 0.4606 | 0.2973 | 0.3037 | 0.049* | |
C14 | 0.4488 (3) | 0.3405 (3) | 0.3818 (2) | 0.0339 (13) | |
C19 | 0.3959 (3) | 0.3451 (3) | 0.4193 (2) | 0.0471 (16) | |
H19 | 0.4122 | 0.3741 | 0.4552 | 0.057* | |
C17 | 0.2956 (4) | 0.2656 (4) | 0.3514 (3) | 0.0572 (18) | |
H17 | 0.2434 | 0.2404 | 0.3405 | 0.069* | |
C18 | 0.3194 (3) | 0.3069 (4) | 0.4038 (3) | 0.0521 (17) | |
H18 | 0.2834 | 0.3093 | 0.4294 | 0.063* | |
C16 | 0.3476 (4) | 0.2612 (3) | 0.3151 (3) | 0.0507 (17) | |
H16 | 0.3309 | 0.2316 | 0.2796 | 0.061* | |
C2 | 0.5837 (3) | 0.4902 (3) | 0.3689 (2) | 0.0341 (13) | |
P1 | 0.54959 (10) | 0.39503 (10) | 0.39594 (7) | 0.0340 (4) | |
C33 | 0.2450 (4) | 0.1274 (4) | 0.4703 (3) | 0.069 (2) | |
H33 | 0.2013 | 0.1138 | 0.4464 | 0.083* | |
C35 | 0.3655 (6) | 0.1416 (6) | 0.4787 (4) | 0.106 (3) | |
H35 | 0.4063 | 0.1373 | 0.4622 | 0.127* | |
C34 | 0.3056 (5) | 0.1254 (5) | 0.4453 (4) | 0.096 (3) | |
H34 | 0.3046 | 0.1126 | 0.4042 | 0.115* | |
C36 | 0.3692 (5) | 0.1647 (6) | 0.5374 (4) | 0.128 (4) | |
H36 | 0.4139 | 0.1800 | 0.5603 | 0.153* | |
C8 | 0.5630 (3) | 0.3996 (3) | 0.4755 (2) | 0.0345 (13) | |
C9 | 0.5823 (3) | 0.4644 (3) | 0.5082 (2) | 0.0465 (16) | |
H9 | 0.5902 | 0.5090 | 0.4882 | 0.056* | |
C13 | 0.5536 (4) | 0.3365 (4) | 0.5059 (3) | 0.083 (3) | |
H13 | 0.5412 | 0.2913 | 0.4846 | 0.100* | |
C12 | 0.5624 (5) | 0.3390 (4) | 0.5682 (3) | 0.089 (3) | |
H12 | 0.5555 | 0.2952 | 0.5889 | 0.107* | |
C37 | 0.3063 (4) | 0.1655 (5) | 0.5630 (3) | 0.093 (3) | |
H37 | 0.3068 | 0.1781 | 0.6040 | 0.112* | |
C11 | 0.5805 (4) | 0.4029 (4) | 0.5991 (3) | 0.060 (2) | |
H11 | 0.5862 | 0.4040 | 0.6414 | 0.072* | |
C10 | 0.5904 (4) | 0.4652 (4) | 0.5695 (2) | 0.0555 (17) | |
H10 | 0.6031 | 0.5102 | 0.5912 | 0.067* | |
C29 | 0.1603 (7) | 0.3662 (5) | 0.5344 (3) | 0.089 (3) | |
H29 | 0.1592 | 0.4122 | 0.5304 | 0.107* | |
C30 | 0.2286 (5) | 0.3681 (4) | 0.5475 (3) | 0.072 (2) | |
H30 | 0.2739 | 0.4157 | 0.5522 | 0.086* | |
O1 | 0.5906 (3) | 0.3592 (3) | 0.36468 (18) | 0.0356 (12) | |
O2 | 0.0922 (3) | 0.0804 (3) | 0.52650 (18) | 0.0436 (13) | |
N1 | 0.5587 (3) | 0.2656 (4) | 0.2408 (2) | 0.0473 (17) | |
C1 | 0.5031 (4) | 0.2346 (4) | 0.2139 (2) | 0.0405 (16) | |
S1 | 0.42411 (10) | 0.18996 (11) | 0.17744 (7) | 0.0675 (6) | |
N2 | 0.0419 (7) | 0.1088 (7) | 0.4014 (5) | 0.059 (4) | 0.667 |
C38 | 0.0671 (12) | 0.1696 (9) | 0.3841 (9) | 0.065 (3) | 0.667 |
S2 | 0.0997 (3) | 0.25559 (18) | 0.36159 (19) | 0.0701 (11) | 0.667 |
O3 | 0.0028 (11) | 0.1221 (9) | 0.4189 (6) | 0.086 (5) | 0.333 |
O4 | 0.0805 (12) | 0.1092 (11) | 0.3900 (8) | 0.086 (5) | 0.333 |
O5 | 0.0886 (13) | 0.2223 (11) | 0.3588 (10) | 0.065 (3) | 0.333 |
N3 | 0.0614 (15) | 0.1602 (12) | 0.3857 (12) | 0.065 (3) | 0.333 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Eu1 | 0.02793 (16) | 0.02793 (16) | 0.0244 (3) | 0.01396 (8) | 0.000 | 0.000 |
Eu2 | 0.0534 (2) | 0.0534 (2) | 0.0211 (3) | 0.02671 (11) | 0.000 | 0.000 |
P2 | 0.0414 (10) | 0.0455 (11) | 0.0281 (8) | 0.0197 (9) | 0.0038 (7) | 0.0029 (7) |
C20 | 0.026 (3) | 0.038 (3) | 0.026 (3) | 0.010 (3) | 0.000 (2) | 0.005 (2) |
C26 | 0.052 (4) | 0.050 (4) | 0.025 (3) | 0.026 (4) | 0.005 (3) | 0.007 (3) |
C27 | 0.076 (5) | 0.079 (5) | 0.034 (3) | 0.055 (4) | 0.009 (3) | 0.002 (3) |
C25 | 0.057 (4) | 0.032 (3) | 0.031 (3) | 0.015 (3) | 0.004 (3) | 0.006 (3) |
C23 | 0.052 (4) | 0.052 (4) | 0.034 (3) | 0.023 (4) | 0.002 (3) | 0.013 (3) |
C21 | 0.048 (4) | 0.037 (4) | 0.034 (3) | 0.017 (3) | 0.002 (3) | 0.000 (3) |
C5 | 0.090 (6) | 0.043 (4) | 0.057 (4) | 0.034 (5) | −0.002 (4) | 0.009 (3) |
C7 | 0.048 (4) | 0.046 (4) | 0.036 (3) | 0.020 (3) | 0.003 (3) | −0.010 (3) |
C22 | 0.053 (4) | 0.040 (4) | 0.050 (4) | 0.021 (3) | 0.006 (3) | 0.014 (3) |
C24 | 0.059 (4) | 0.047 (4) | 0.038 (3) | 0.014 (4) | −0.009 (3) | −0.005 (3) |
C3 | 0.050 (4) | 0.053 (4) | 0.056 (4) | 0.031 (4) | 0.018 (3) | 0.015 (3) |
C31 | 0.069 (5) | 0.056 (5) | 0.035 (3) | 0.029 (4) | 0.004 (3) | 0.003 (3) |
C4 | 0.082 (6) | 0.059 (5) | 0.081 (5) | 0.047 (5) | 0.013 (4) | 0.015 (4) |
C32 | 0.042 (4) | 0.057 (4) | 0.042 (3) | 0.028 (4) | 0.009 (3) | 0.014 (3) |
C28 | 0.120 (8) | 0.097 (7) | 0.053 (5) | 0.087 (7) | 0.004 (5) | 0.004 (5) |
C6 | 0.052 (4) | 0.040 (4) | 0.048 (4) | 0.000 (4) | 0.013 (3) | 0.000 (3) |
C15 | 0.037 (4) | 0.042 (4) | 0.042 (3) | 0.018 (3) | 0.002 (3) | −0.008 (3) |
C14 | 0.033 (3) | 0.033 (3) | 0.036 (3) | 0.017 (3) | 0.008 (2) | 0.005 (2) |
C19 | 0.045 (4) | 0.058 (4) | 0.040 (3) | 0.027 (4) | 0.010 (3) | −0.001 (3) |
C17 | 0.036 (4) | 0.060 (5) | 0.078 (5) | 0.026 (4) | −0.010 (3) | −0.010 (4) |
C18 | 0.037 (4) | 0.060 (5) | 0.069 (5) | 0.031 (4) | 0.015 (3) | 0.005 (4) |
C16 | 0.055 (5) | 0.045 (4) | 0.052 (4) | 0.025 (4) | −0.014 (3) | −0.020 (3) |
C2 | 0.042 (4) | 0.041 (4) | 0.025 (3) | 0.025 (3) | −0.003 (2) | −0.008 (2) |
P1 | 0.0356 (10) | 0.0403 (10) | 0.0302 (9) | 0.0221 (9) | −0.0010 (7) | −0.0040 (7) |
C33 | 0.076 (6) | 0.105 (6) | 0.054 (4) | 0.066 (5) | 0.014 (4) | 0.007 (4) |
C35 | 0.121 (9) | 0.176 (10) | 0.073 (6) | 0.114 (8) | 0.057 (6) | 0.039 (6) |
C34 | 0.119 (8) | 0.148 (9) | 0.062 (5) | 0.099 (8) | 0.035 (5) | 0.024 (5) |
C36 | 0.064 (6) | 0.236 (12) | 0.101 (7) | 0.089 (8) | 0.013 (5) | 0.030 (7) |
C8 | 0.036 (3) | 0.043 (4) | 0.033 (3) | 0.026 (3) | 0.002 (2) | −0.003 (3) |
C9 | 0.060 (4) | 0.057 (4) | 0.032 (3) | 0.037 (4) | −0.003 (3) | −0.002 (3) |
C13 | 0.161 (9) | 0.067 (5) | 0.044 (4) | 0.074 (6) | −0.008 (4) | 0.001 (4) |
C12 | 0.160 (9) | 0.090 (7) | 0.049 (4) | 0.086 (7) | −0.003 (5) | 0.015 (4) |
C37 | 0.066 (6) | 0.156 (9) | 0.060 (5) | 0.058 (6) | 0.026 (4) | 0.015 (5) |
C11 | 0.065 (5) | 0.104 (6) | 0.030 (3) | 0.057 (5) | 0.001 (3) | −0.004 (4) |
C10 | 0.063 (5) | 0.065 (5) | 0.040 (3) | 0.032 (4) | −0.001 (3) | −0.009 (3) |
C29 | 0.176 (11) | 0.087 (7) | 0.037 (4) | 0.090 (8) | 0.018 (6) | 0.011 (5) |
C30 | 0.111 (7) | 0.046 (5) | 0.036 (4) | 0.022 (5) | 0.010 (4) | 0.002 (3) |
O1 | 0.036 (3) | 0.043 (3) | 0.035 (3) | 0.026 (2) | −0.002 (2) | −0.009 (2) |
O2 | 0.039 (3) | 0.053 (3) | 0.030 (2) | 0.016 (3) | −0.0020 (19) | −0.003 (2) |
N1 | 0.034 (4) | 0.064 (4) | 0.034 (3) | 0.018 (3) | −0.013 (3) | −0.006 (3) |
C1 | 0.054 (5) | 0.057 (5) | 0.028 (3) | 0.041 (4) | 0.009 (3) | 0.002 (3) |
S1 | 0.0499 (12) | 0.0825 (15) | 0.0536 (10) | 0.0207 (11) | −0.0238 (8) | −0.0100 (9) |
N2 | 0.063 (10) | 0.086 (11) | 0.038 (7) | 0.045 (9) | 0.017 (6) | 0.001 (6) |
C38 | 0.065 (6) | 0.085 (8) | 0.047 (5) | 0.040 (7) | 0.013 (4) | 0.004 (5) |
S2 | 0.096 (3) | 0.049 (2) | 0.067 (2) | 0.038 (2) | 0.0164 (17) | 0.0274 (19) |
O3 | 0.137 (15) | 0.069 (8) | 0.054 (8) | 0.053 (10) | 0.013 (8) | 0.027 (6) |
O4 | 0.137 (15) | 0.069 (8) | 0.054 (8) | 0.053 (10) | 0.013 (8) | 0.027 (6) |
O5 | 0.065 (6) | 0.085 (8) | 0.047 (5) | 0.040 (7) | 0.013 (4) | 0.004 (5) |
N3 | 0.065 (6) | 0.085 (8) | 0.047 (5) | 0.040 (7) | 0.013 (4) | 0.004 (5) |
Eu1—O1i | 2.292 (4) | C32—C37 | 1.350 (8) |
Eu1—O1ii | 2.292 (4) | C28—H28 | 0.9500 |
Eu1—O1 | 2.292 (4) | C28—C29 | 1.356 (11) |
Eu1—N1i | 2.397 (6) | C6—H6 | 0.9500 |
Eu1—N1 | 2.397 (6) | C15—H15 | 0.9500 |
Eu1—N1ii | 2.397 (6) | C15—C14 | 1.368 (7) |
Eu2—O2 | 2.277 (4) | C15—C16 | 1.400 (7) |
Eu2—O2iii | 2.277 (4) | C14—C19 | 1.403 (7) |
Eu2—O2iv | 2.277 (4) | C14—P1 | 1.804 (5) |
Eu2—N2iii | 2.359 (12) | C19—H19 | 0.9500 |
Eu2—N2 | 2.359 (12) | C19—C18 | 1.390 (7) |
Eu2—N2iv | 2.359 (12) | C17—H17 | 0.9500 |
Eu2—O3iv | 2.637 (16) | C17—C18 | 1.379 (7) |
Eu2—O3 | 2.637 (16) | C17—C16 | 1.369 (7) |
Eu2—O3iii | 2.637 (16) | C18—H18 | 0.9500 |
Eu2—O4iv | 2.562 (17) | C16—H16 | 0.9500 |
Eu2—O4 | 2.562 (18) | C2—P1 | 1.800 (6) |
Eu2—O4iii | 2.562 (17) | P1—C8 | 1.791 (5) |
P2—C20 | 1.799 (5) | P1—O1 | 1.522 (4) |
P2—C26 | 1.803 (6) | C33—H33 | 0.9500 |
P2—C32 | 1.799 (6) | C33—C34 | 1.372 (8) |
P2—O2 | 1.508 (5) | C35—H35 | 0.9500 |
C20—C25 | 1.387 (7) | C35—C34 | 1.321 (10) |
C20—C21 | 1.381 (7) | C35—C36 | 1.381 (10) |
C26—C27 | 1.390 (8) | C34—H34 | 0.9500 |
C26—C31 | 1.387 (8) | C36—H36 | 0.9500 |
C27—H27 | 0.9500 | C36—C37 | 1.407 (9) |
C27—C28 | 1.371 (9) | C8—C9 | 1.381 (7) |
C25—H25 | 0.9500 | C8—C13 | 1.377 (7) |
C25—C24 | 1.391 (6) | C9—H9 | 0.9500 |
C23—H23 | 0.9500 | C9—C10 | 1.376 (6) |
C23—C22 | 1.375 (7) | C13—H13 | 0.9500 |
C23—C24 | 1.363 (7) | C13—C12 | 1.399 (7) |
C21—H21 | 0.9500 | C12—H12 | 0.9500 |
C21—C22 | 1.387 (6) | C12—C11 | 1.348 (8) |
C5—H5 | 0.9500 | C37—H37 | 0.9500 |
C5—C4 | 1.361 (8) | C11—H11 | 0.9500 |
C5—C6 | 1.369 (8) | C11—C10 | 1.353 (8) |
C7—H7 | 0.9500 | C10—H10 | 0.9500 |
C7—C6 | 1.376 (7) | C29—H29 | 0.9500 |
C7—C2 | 1.381 (7) | C29—C30 | 1.401 (11) |
C22—H22 | 0.9500 | C30—H30 | 0.9500 |
C24—H24 | 0.9500 | N1—C1 | 1.150 (8) |
C3—H3 | 0.9500 | C1—S1 | 1.615 (7) |
C3—C4 | 1.390 (8) | N2—C38 | 1.144 (14) |
C3—C2 | 1.384 (7) | C38—S2 | 1.608 (13) |
C31—H31 | 0.9500 | O3—N3 | 1.283 (19) |
C31—C30 | 1.393 (9) | O4—N3 | 1.280 (19) |
C4—H4 | 0.9500 | O5—N3 | 1.249 (16) |
C32—C33 | 1.360 (7) | ||
O1i—Eu1—O1ii | 89.68 (16) | C4—C5—C6 | 120.0 (6) |
O1i—Eu1—O1 | 89.68 (16) | C6—C5—H5 | 120.0 |
O1ii—Eu1—O1 | 89.68 (16) | C6—C7—H7 | 119.7 |
O1ii—Eu1—N1i | 95.6 (2) | C6—C7—C2 | 120.6 (6) |
O1i—Eu1—N1i | 87.14 (19) | C2—C7—H7 | 119.7 |
O1—Eu1—N1i | 173.8 (2) | C23—C22—C21 | 118.5 (5) |
O1i—Eu1—N1 | 95.6 (2) | C23—C22—H22 | 120.7 |
O1ii—Eu1—N1 | 173.8 (2) | C21—C22—H22 | 120.7 |
O1i—Eu1—N1ii | 173.8 (2) | C25—C24—H24 | 119.9 |
O1—Eu1—N1 | 87.14 (19) | C23—C24—C25 | 120.2 (5) |
O1—Eu1—N1ii | 95.6 (2) | C23—C24—H24 | 119.9 |
O1ii—Eu1—N1ii | 87.14 (19) | C4—C3—H3 | 120.2 |
N1i—Eu1—N1 | 87.9 (2) | C2—C3—H3 | 120.2 |
N1i—Eu1—N1ii | 87.9 (2) | C2—C3—C4 | 119.7 (6) |
N1—Eu1—N1ii | 87.9 (2) | C26—C31—H31 | 120.7 |
O2—Eu2—O2iii | 84.41 (16) | C26—C31—C30 | 118.6 (7) |
O2—Eu2—O2iv | 84.41 (16) | C30—C31—H31 | 120.7 |
O2iii—Eu2—O2iv | 84.41 (16) | C5—C4—C3 | 120.6 (7) |
O2iii—Eu2—N2iii | 84.7 (3) | C5—C4—H4 | 119.7 |
O2—Eu2—N2iii | 166.8 (3) | C3—C4—H4 | 119.7 |
O2iv—Eu2—N2iii | 101.9 (3) | C33—C32—P2 | 118.4 (5) |
O2—Eu2—N2 | 84.7 (3) | C37—C32—P2 | 122.1 (5) |
O2iii—Eu2—N2 | 101.9 (3) | C37—C32—C33 | 119.3 (6) |
O2—Eu2—N2iv | 101.9 (3) | C27—C28—H28 | 119.9 |
O2iv—Eu2—N2 | 166.8 (3) | C29—C28—C27 | 120.1 (9) |
O2iv—Eu2—N2iv | 84.7 (3) | C29—C28—H28 | 119.9 |
O2iii—Eu2—N2iv | 166.8 (3) | C5—C6—C7 | 120.1 (6) |
O2iii—Eu2—O3iv | 161.7 (4) | C5—C6—H6 | 119.9 |
O2iv—Eu2—O3iv | 86.1 (4) | C7—C6—H6 | 119.9 |
O2—Eu2—O3iv | 79.1 (4) | C14—C15—H15 | 120.1 |
O2iv—Eu2—O3 | 161.7 (3) | C14—C15—C16 | 119.7 (5) |
O2iii—Eu2—O3 | 79.1 (4) | C16—C15—H15 | 120.1 |
O2—Eu2—O3 | 86.1 (4) | C15—C14—C19 | 119.7 (5) |
O2iv—Eu2—O3iii | 79.1 (4) | C15—C14—P1 | 118.1 (4) |
O2—Eu2—O3iii | 161.7 (3) | C19—C14—P1 | 121.8 (4) |
O2iii—Eu2—O3iii | 86.1 (4) | C14—C19—H19 | 120.2 |
O2iii—Eu2—O4 | 119.1 (4) | C18—C19—C14 | 119.6 (5) |
O2—Eu2—O4 | 80.5 (5) | C18—C19—H19 | 120.2 |
O2iv—Eu2—O4 | 150.2 (5) | C18—C17—H17 | 120.2 |
O2iv—Eu2—O4iii | 119.1 (4) | C16—C17—H17 | 120.2 |
O2iii—Eu2—O4iii | 80.5 (5) | C16—C17—C18 | 119.6 (6) |
O2iv—Eu2—O4iv | 80.5 (5) | C19—C18—H18 | 119.8 |
O2—Eu2—O4iii | 150.2 (5) | C17—C18—C19 | 120.4 (5) |
O2iii—Eu2—O4iv | 150.2 (5) | C17—C18—H18 | 119.8 |
O2—Eu2—O4iv | 119.1 (4) | C15—C16—H16 | 119.6 |
N2—Eu2—N2iv | 90.3 (4) | C17—C16—C15 | 120.9 (5) |
N2iii—Eu2—N2iv | 90.3 (4) | C17—C16—H16 | 119.6 |
N2iii—Eu2—N2 | 90.3 (4) | C7—C2—C3 | 119.0 (5) |
N2—Eu2—O3iv | 84.5 (5) | C7—C2—P1 | 119.1 (4) |
N2iii—Eu2—O3iv | 112.6 (5) | C3—C2—P1 | 121.9 (4) |
N2—Eu2—O3 | 23.1 (4) | C2—P1—C14 | 108.1 (3) |
N2iv—Eu2—O3 | 112.6 (5) | C8—P1—C14 | 107.6 (2) |
N2iv—Eu2—O3iv | 23.1 (4) | C8—P1—C2 | 108.0 (3) |
N2iii—Eu2—O3 | 84.5 (5) | O1—P1—C14 | 110.5 (3) |
N2iii—Eu2—O3iii | 23.1 (4) | O1—P1—C2 | 110.5 (3) |
N2iv—Eu2—O3iii | 84.5 (5) | O1—P1—C8 | 111.9 (3) |
N2—Eu2—O3iii | 112.6 (5) | C32—C33—H33 | 119.0 |
N2iii—Eu2—O4iii | 18.6 (5) | C32—C33—C34 | 122.0 (7) |
N2iv—Eu2—O4iv | 18.6 (5) | C34—C33—H33 | 119.0 |
N2iv—Eu2—O4 | 73.6 (5) | C34—C35—H35 | 119.8 |
N2—Eu2—O4 | 18.6 (5) | C34—C35—C36 | 120.4 (8) |
N2iv—Eu2—O4iii | 98.4 (5) | C36—C35—H35 | 119.8 |
N2—Eu2—O4iv | 98.4 (5) | C33—C34—H34 | 120.3 |
N2iii—Eu2—O4iv | 73.6 (5) | C35—C34—C33 | 119.5 (8) |
N2—Eu2—O4iii | 73.6 (5) | C35—C34—H34 | 120.3 |
N2iii—Eu2—O4 | 98.4 (5) | C35—C36—H36 | 120.2 |
O3iii—Eu2—O3iv | 107.4 (4) | C35—C36—C37 | 119.6 (8) |
O3—Eu2—O3iv | 107.4 (4) | C37—C36—H36 | 120.2 |
O3iii—Eu2—O3 | 107.4 (4) | C9—C8—P1 | 122.5 (4) |
O4iv—Eu2—O3 | 117.8 (5) | C13—C8—P1 | 119.6 (4) |
O4—Eu2—O3iii | 117.8 (5) | C13—C8—C9 | 117.9 (5) |
O4—Eu2—O3 | 41.5 (5) | C8—C9—H9 | 119.6 |
O4iii—Eu2—O3 | 66.0 (6) | C10—C9—C8 | 120.9 (5) |
O4iv—Eu2—O3iii | 66.0 (6) | C10—C9—H9 | 119.6 |
O4iv—Eu2—O3iv | 41.5 (5) | C8—C13—H13 | 120.0 |
O4—Eu2—O3iv | 66.0 (6) | C8—C13—C12 | 120.0 (6) |
O4iii—Eu2—O3iii | 41.5 (5) | C12—C13—H13 | 120.0 |
O4iii—Eu2—O3iv | 117.8 (5) | C13—C12—H12 | 119.6 |
O4iii—Eu2—O4 | 84.7 (7) | C11—C12—C13 | 120.9 (6) |
O4—Eu2—O4iv | 84.7 (7) | C11—C12—H12 | 119.6 |
O4iii—Eu2—O4iv | 84.7 (7) | C32—C37—C36 | 118.9 (7) |
C20—P2—C26 | 108.7 (2) | C32—C37—H37 | 120.5 |
C20—P2—C32 | 107.9 (3) | C36—C37—H37 | 120.5 |
C32—P2—C26 | 110.0 (3) | C12—C11—H11 | 120.3 |
O2—P2—C20 | 110.9 (3) | C12—C11—C10 | 119.5 (6) |
O2—P2—C26 | 110.1 (3) | C10—C11—H11 | 120.3 |
O2—P2—C32 | 109.3 (3) | C9—C10—H10 | 119.5 |
C25—C20—P2 | 122.8 (4) | C11—C10—C9 | 120.9 (6) |
C21—C20—P2 | 117.8 (4) | C11—C10—H10 | 119.5 |
C21—C20—C25 | 119.4 (4) | C28—C29—H29 | 120.2 |
C27—C26—P2 | 118.7 (5) | C28—C29—C30 | 119.7 (8) |
C31—C26—P2 | 121.8 (5) | C30—C29—H29 | 120.2 |
C31—C26—C27 | 119.5 (6) | C31—C30—C29 | 120.8 (8) |
C26—C27—H27 | 119.4 | C31—C30—H30 | 119.6 |
C28—C27—C26 | 121.3 (7) | C29—C30—H30 | 119.6 |
C28—C27—H27 | 119.4 | P1—O1—Eu1 | 165.8 (3) |
C20—C25—H25 | 120.3 | P2—O2—Eu2 | 168.6 (3) |
C20—C25—C24 | 119.3 (5) | C1—N1—Eu1 | 173.5 (6) |
C24—C25—H25 | 120.3 | N1—C1—S1 | 178.8 (7) |
C22—C23—H23 | 119.3 | C38—N2—Eu2 | 164.6 (14) |
C24—C23—H23 | 119.3 | N2—C38—S2 | 177 (2) |
C24—C23—C22 | 121.4 (5) | N3—O3—Eu2 | 110.8 (14) |
C20—C21—H21 | 119.4 | N3—O4—Eu2 | 115.3 (14) |
C20—C21—C22 | 121.1 (5) | O4—N3—O3 | 92.0 (17) |
C22—C21—H21 | 119.4 | O5—N3—O3 | 134 (2) |
C4—C5—H5 | 120.0 | O5—N3—O4 | 134 (2) |
Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z; (iii) −y, x−y, z; (iv) −x+y, −x, z. |
Experimental details
Crystal data | |
Chemical formula | [Eu(NCS)3(C18H15OP)3][Eu(NCS)2(NO3)(C18H15OP)3] |
Mr | 2325.95 |
Crystal system, space group | Trigonal, R3 |
Temperature (K) | 180 |
a, c (Å) | 20.3249 (7), 22.3186 (6) |
V (Å3) | 7984.7 (4) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 1.42 |
Crystal size (mm) | 0.12 × 0.07 × 0.05 |
Data collection | |
Diffractometer | Agilent Xcalibur Eos diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.892, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15970, 6325, 5614 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.065, 1.02 |
No. of reflections | 6325 |
No. of parameters | 439 |
No. of restraints | 8 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.30, −0.90 |
Absolute structure | Flack (1983), 3154 Friedel pairs |
Absolute structure parameter | −0.045 (9) |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009), publCIF (Westrip, 2010).
Acknowledgements
The authors acknowledge the National Science Foundation for their generous support (NSF-CAREER grant to RES, CHE-0846680).
References
Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Berthet, J.-C., Nierlich, M. & Ephritikhine, M. (2003). Polyhedron, 22, 3475–3482. Web of Science CSD CrossRef CAS Google Scholar
Bowden, A., Platt, A. W. G., Singh, K. & Townsend, R. (2010). Inorg. Chim. Acta, 363, 243–249. Web of Science CSD CrossRef CAS Google Scholar
Cousins, D. R. & Hart, F. A. (1967). J. Inorg. Nucl. Chem. 29, 1745–1757. CrossRef CAS Web of Science Google Scholar
Cousins, D. R. & Hart, F. A. (1968). J. Inorg. Nucl. Chem. 30, 3009–3015. CrossRef CAS Web of Science Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Feazell, R. P., Gary, J. B., Kautz, J. A., Klausmeyer, K. K., Wong, C. W. & Zancanella, M. (2004). Acta Cryst. E60, m532–m534. Web of Science CSD CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Long, D.-L., Hu, H.-M., Chen, J.-T. & Huang, J.-S. (1999). Acta Cryst. C55, 1662–1664. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
From previous studies, it has been known that lanthanide triphenylphosphine oxide complexes can be prepared with a number of anions including nitrate (Cousins & Hart, 1967; Long et al., 1999), thiocyanate (Cousins & Hart, 1968; Feazell et al., 2004), bromide (Bowden et al., 2010), trifluoromethanesulfonate (Berthet et al., 2003), and iodide (Berthet et al., 2003). The title compound, [Eu(OPPh3)3(SCN)3][Eu(OPPh3)3(SCN)2NO3], is of particular interest because of the anion disorder in one of the two neutral molecules in this co-crystal. There are two crystallographically unique europium(III) sites in the structure, one at the center of each neutral complex, [Eu(OPPh3)3(SCN)3] and [Eu(OPPh3)3(SCN)2NO3], as shown in Fig. 1. Each complex has threefold symmetry and therefore the two thiocyanato and one bidentate nitrate anions are disordered over the three positions in the latter. In [Eu(OPPh3)3(SCN)3], the three triphenylphosphine oxide ligands and three thiocyanto anions are found in a fac arrangement. The isolation of the mixed-anion system is interesting from a coordinating viewpoint, as the thiocyanato displays a monodentate (kN) coordination while the nitrato is bidentate (κ2O,O'). The thiocyanato-kN coordination is also observed in previous lanthanide complexes, such as [Nd(OPPh3)4(SCN)3] (Feazell et al., 2004), likely due to the hard nature of the Ln(III) ions. Also of note is the fact that the title compound contains a 1:3 ratio of Eu(III) to phosphine oxide in both of its complexes, whereas with the larger Nd(III) ion, four triphenylphosphine ligands coordinate. Regarding intermolecular interactions, the title compound contains one weak π-stacking interaction, with plane-to-centroid distances of 3.529 (8) and 3.841 (5) Å, between adjacent rings of the two complexes as illustrated in Fig. 1.
It should be noted that the stoichiometry of the reaction conditions to prepare the title compound were not rigorously controlled and it is likely that the introduced nitrate is a result of a slightly less than 1:3 ratio of Eu(III) to KSCN.