Tris(thio­cyanato-κN)tris­(triphenyl­phosphine oxide-κO)europium(III)–(nitrato-κ2O,O′)bis­(thio­cyanato-κN)tris­(triphenyl­phosphine oxide-κO)europium(III) (1/1)

Thames, A.T.; White, F.D.; Pham, L.N.; Xiang, K.R.; Sykora, R.E.

doi:10.1107/S1600536812047472

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page m1530

doi:10.1107/S1600536812047472

Open

access

Tris(thiocyanato-κN)tris(triphenylphosphine oxide-κO)europium(III)–(nitrato-κ²O,O′)bis(thiocyanato-κN)tris(triphenylphosphine oxide-κO)europium(III) (1/1)

Anthony T. Thames,^a Frankie D. White,^a Lam N. Pham,^a Kang Rui Xiang ^a and Richard E. Sykora ^a ^*

^aUniversity of South Alabama, Department of Chemistry, Mobile, AL 36688, USA
^*Correspondence e-mail: rsykora@southalabama.edu

(Received 12 November 2012; accepted 19 November 2012; online 24 November 2012)

The title co-crystal, [Eu(NCS)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].

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

[Eu(NCS)₃(C₁₈H₁₅OP)₃][Eu(NCS)₂(NO₃)(C₁₈H₁₅OP)₃]
M_r = 2325.95
Trigonal, R 3
a = 20.3249 (7) Å
c = 22.3186 (6) Å
V = 7984.7 (4) Å³
Z = 3
Mo Kα radiation
μ = 1.42 mm⁻¹
T = 180 K
0.12 × 0.07 × 0.05 mm

Data collection

Agilent Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.892, T_max = 1.000
15970 measured reflections
6325 independent reflections
5614 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.065
S = 1.02
6325 reflections
439 parameters
8 restraints
H-atom parameters constrained
Δρ_max = 1.30 e Å⁻³
Δρ_min = −0.90 e Å⁻³
Absolute structure: Flack (1983 ), 3154 Friedel pairs
Flack parameter: −0.045 (9)

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812047472/qm2089sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047472/qm2089Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: 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).

Figures top

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.

Tris(thiocyanato-κN)tris(triphenylphosphine oxide-κO)europium(III)– (nitrato-κ²O,O')bis(thiocyanato- κN)tris(triphenylphosphine oxide-κO)europium(III) (1/1) top

Crystal data top

[Eu(NCS)₃(C₁₈H₁₅OP)₃][Eu(NCS)₂(NO₃)(C₁₈H₁₅OP)₃]	D_x = 1.451 Mg m⁻³
M_r = 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

Data collection top

Agilent Xcalibur Eos diffractometer	6325 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5614 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ω scans	θ_max = 25.1°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −24→23
T_min = 0.892, T_max = 1.000	k = −22→24
15970 measured reflections	l = −26→26

Refinement top

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(F_o²) + (0.0112P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
6325 reflections	Δρ_max = 1.30 e Å⁻³
439 parameters	Δρ_min = −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)

Crystal data top

[Eu(NCS)₃(C₁₈H₁₅OP)₃][Eu(NCS)₂(NO₃)(C₁₈H₁₅OP)₃]	Z = 3
M_r = 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

Data collection top

Agilent Xcalibur Eos diffractometer	6325 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	5614 reflections with I > 2σ(I)
T_min = 0.892, T_max = 1.000	R_int = 0.052
15970 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.065	Δρ_max = 1.30 e Å⁻³
S = 1.02	Δρ_min = −0.90 e Å⁻³
6325 reflections	Absolute structure: Flack (1983), 3154 Friedel pairs
439 parameters	Absolute structure parameter: −0.045 (9)
8 restraints

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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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—O2^iv	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—N2^iv	2.359 (12)	C17—H17	0.9500
Eu2—O3^iv	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—O4^iv	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—O2^iv	84.41 (16)	C30—C31—H31	120.7
O2ⁱⁱⁱ—Eu2—O2^iv	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
O2^iv—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—N2^iv	101.9 (3)	C27—C28—H28	119.9
O2^iv—Eu2—N2	166.8 (3)	C29—C28—C27	120.1 (9)
O2^iv—Eu2—N2^iv	84.7 (3)	C29—C28—H28	119.9
O2ⁱⁱⁱ—Eu2—N2^iv	166.8 (3)	C5—C6—C7	120.1 (6)
O2ⁱⁱⁱ—Eu2—O3^iv	161.7 (4)	C5—C6—H6	119.9
O2^iv—Eu2—O3^iv	86.1 (4)	C7—C6—H6	119.9
O2—Eu2—O3^iv	79.1 (4)	C14—C15—H15	120.1
O2^iv—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)
O2^iv—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
O2^iv—Eu2—O4	150.2 (5)	C18—C17—H17	120.2
O2^iv—Eu2—O4ⁱⁱⁱ	119.1 (4)	C16—C17—H17	120.2
O2ⁱⁱⁱ—Eu2—O4ⁱⁱⁱ	80.5 (5)	C16—C17—C18	119.6 (6)
O2^iv—Eu2—O4^iv	80.5 (5)	C19—C18—H18	119.8
O2—Eu2—O4ⁱⁱⁱ	150.2 (5)	C17—C18—C19	120.4 (5)
O2ⁱⁱⁱ—Eu2—O4^iv	150.2 (5)	C17—C18—H18	119.8
O2—Eu2—O4^iv	119.1 (4)	C15—C16—H16	119.6
N2—Eu2—N2^iv	90.3 (4)	C17—C16—C15	120.9 (5)
N2ⁱⁱⁱ—Eu2—N2^iv	90.3 (4)	C17—C16—H16	119.6
N2ⁱⁱⁱ—Eu2—N2	90.3 (4)	C7—C2—C3	119.0 (5)
N2—Eu2—O3^iv	84.5 (5)	C7—C2—P1	119.1 (4)
N2ⁱⁱⁱ—Eu2—O3^iv	112.6 (5)	C3—C2—P1	121.9 (4)
N2—Eu2—O3	23.1 (4)	C2—P1—C14	108.1 (3)
N2^iv—Eu2—O3	112.6 (5)	C8—P1—C14	107.6 (2)
N2^iv—Eu2—O3^iv	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)
N2^iv—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)
N2^iv—Eu2—O4^iv	18.6 (5)	C34—C33—H33	119.0
N2^iv—Eu2—O4	73.6 (5)	C34—C35—H35	119.8
N2—Eu2—O4	18.6 (5)	C34—C35—C36	120.4 (8)
N2^iv—Eu2—O4ⁱⁱⁱ	98.4 (5)	C36—C35—H35	119.8
N2—Eu2—O4^iv	98.4 (5)	C33—C34—H34	120.3
N2ⁱⁱⁱ—Eu2—O4^iv	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—O3^iv	107.4 (4)	C35—C36—C37	119.6 (8)
O3—Eu2—O3^iv	107.4 (4)	C37—C36—H36	120.2
O3ⁱⁱⁱ—Eu2—O3	107.4 (4)	C9—C8—P1	122.5 (4)
O4^iv—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)
O4^iv—Eu2—O3ⁱⁱⁱ	66.0 (6)	C10—C9—H9	119.6
O4^iv—Eu2—O3^iv	41.5 (5)	C8—C13—H13	120.0
O4—Eu2—O3^iv	66.0 (6)	C8—C13—C12	120.0 (6)
O4ⁱⁱⁱ—Eu2—O3ⁱⁱⁱ	41.5 (5)	C12—C13—H13	120.0
O4ⁱⁱⁱ—Eu2—O3^iv	117.8 (5)	C13—C12—H12	119.6
O4ⁱⁱⁱ—Eu2—O4	84.7 (7)	C11—C12—C13	120.9 (6)
O4—Eu2—O4^iv	84.7 (7)	C11—C12—H12	119.6
O4ⁱⁱⁱ—Eu2—O4^iv	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]
M_r	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)
T_min, T_max	0.892, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15970, 6325, 5614
R_int	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
Δρ_max, Δρ_min (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.