The dinuclear scandium(III) cyclo­octa­tetra­enyl chloride complex di-μ-chlorido-bis­[(η⁸-cyclo­octa­tetra­ene)(tetra­hydro­furan-κO)scandium(III)]

Only a few cyclo­octa­tetra­ene dianion (COT) π-complexes of lanthanides have been crystallographically characterized. This first single-crystal X-ray diffraction characterization of a scandium(III) COT chloride complex, namely di-μ-chlorido-bis­[(η⁸-cyclo­octa­tetra­ene)(tetra­hydro­furan-κO)scandium(III)], [Sc₂(C₈H₈)₂Cl₂(C₄H₈O)₂] or [Sc(COT)Cl(THF)]₂ (THF is tetrahydrofuran), (1), reveals a dimeric mol­ecular structure with symmetric chloride bridges [average Sc—Cl = 2.5972 (7) Å] and a η⁸-bound COT ligand. The COT ring is planar, with an average C—C bond length of 1.399 (3) Å. The Sc—C bond lengths range from 2.417 (2) to 2.438 (2) Å [average 2.427 (2) Å]. Direct comparison of (1) with the known lanthanide (Ln) analogues (La, Ce, Pr, Nd, and Sm) illustrates the effect of metal-ion (M) size on mol­ecular structure. Overall, the M—Cl, M—O, and M—C bond lengths in (1) are the shortest in the series. In addition, only one THF mol­ecule completes the coordination environment of the small Sc^III ion, in contrast to the previously reported dinuclear Ln–COT–Cl complexes, which all have two bound THF mol­ecules per metal atom.

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: XSHELL (Bruker, 2016); software used to prepare material for publication: APEX3 (Bruker, 2016), XPREP (Bruker, 2016) and XCIF (Bruker, 2016).

Di-µ-chlorido-bis[(η⁸-cyclooctatetraene)(tetrahydrofuran-κO)scandium(III)]

Crystal data

[Sc2(C8H8)2Cl2(C4H8O)2]	F(000) = 536
Mr = 513.31	Dx = 1.484 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.3324 (5) Å	Cell parameters from 3993 reflections
b = 10.7540 (7) Å	θ = 3.0–29.2°
c = 12.2892 (7) Å	µ = 0.84 mm^−1
β = 111.349 (2)°	T = 100 K
V = 1148.72 (12) Å^3	Rod, yellow
Z = 2	0.18 × 0.05 × 0.04 mm

Data collection

Bruker D8 Venture PHOTON 100 CMOS diffractometer	3102 independent reflections
Radiation source: fine-focus sealed tube	2298 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ω and phi scans	θmax = 29.2°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −12→12
Tmin = 0.896, Tmax = 1	k = −14→14
11306 measured reflections	l = −16→13

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0197P)^2 + 1.0743P] where P = (Fo^2 + 2Fc^2)/3
3102 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.42 e Å^−3
104 restraints	Δρmin = −0.41 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Sc1	0.59247 (5)	0.46855 (4)	0.38141 (4)	0.00863 (11)
Cl1	0.67613 (6)	0.49376 (5)	0.60615 (5)	0.01179 (13)
O1	0.59829 (18)	0.67545 (14)	0.39236 (14)	0.0126 (3)
C1	0.4578 (3)	0.3109 (2)	0.2380 (2)	0.0167 (5)
H1	0.358902	0.274099	0.203718	0.020*
C2	0.5510 (3)	0.2478 (2)	0.3384 (2)	0.0180 (5)
H2	0.499983	0.179536	0.357549	0.022*
C3	0.7030 (3)	0.2624 (2)	0.4174 (2)	0.0183 (5)
H3	0.730051	0.202659	0.478451	0.022*
C4	0.8234 (3)	0.3436 (2)	0.4274 (2)	0.0202 (6)
H4	0.913891	0.325140	0.492605	0.024*
C5	0.8420 (3)	0.4461 (2)	0.3637 (2)	0.0211 (6)
H5	0.942482	0.480455	0.395618	0.025*
C6	0.7481 (3)	0.5101 (2)	0.2643 (2)	0.0216 (5)
H6	0.799882	0.577457	0.244563	0.026*
C7	0.5955 (3)	0.4981 (2)	0.1868 (2)	0.0209 (5)
H7	0.567058	0.560470	0.128098	0.025*
C8	0.4755 (3)	0.4155 (2)	0.1761 (2)	0.0190 (5)
H8	0.384449	0.434810	0.111621	0.023*
C9	0.4927 (3)	0.7582 (2)	0.3077 (2)	0.0158 (5)
H9A	0.386467	0.724964	0.280368	0.019*
H9B	0.523581	0.770304	0.239432	0.019*
C10	0.7328 (3)	0.7508 (2)	0.4516 (2)	0.0187 (5)
H10A	0.798595	0.757442	0.404293	0.022*
H10B	0.794087	0.714732	0.528628	0.022*
C11	0.6686 (3)	0.8778 (2)	0.4658 (2)	0.0183 (5)
H11A	0.730984	0.945532	0.450909	0.022*
H11B	0.667290	0.887686	0.545493	0.022*
C12	0.5041 (3)	0.8791 (2)	0.3741 (2)	0.0199 (5)
H12A	0.427067	0.881876	0.412075	0.024*
H12B	0.488370	0.951608	0.321347	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sc1	0.0100 (2)	0.0083 (2)	0.0087 (2)	0.00018 (17)	0.00469 (16)	−0.00100 (17)
Cl1	0.0098 (2)	0.0161 (3)	0.0096 (3)	0.0007 (2)	0.0036 (2)	−0.0012 (2)
O1	0.0116 (8)	0.0091 (8)	0.0152 (9)	−0.0013 (6)	0.0027 (7)	−0.0010 (6)
C1	0.0114 (11)	0.0180 (12)	0.0216 (14)	−0.0043 (9)	0.0072 (10)	−0.0111 (10)
C2	0.0269 (13)	0.0091 (11)	0.0252 (14)	−0.0024 (10)	0.0181 (11)	−0.0049 (10)
C3	0.0292 (13)	0.0133 (12)	0.0148 (13)	0.0114 (10)	0.0109 (10)	0.0025 (10)
C4	0.0135 (12)	0.0299 (14)	0.0145 (13)	0.0105 (10)	0.0017 (10)	−0.0066 (10)
C5	0.0104 (11)	0.0305 (15)	0.0256 (14)	−0.0074 (10)	0.0104 (10)	−0.0169 (11)
C6	0.0348 (13)	0.0176 (13)	0.0258 (14)	−0.0106 (11)	0.0270 (11)	−0.0076 (10)
C7	0.0410 (15)	0.0147 (12)	0.0119 (12)	0.0054 (11)	0.0154 (11)	0.0029 (10)
C8	0.0208 (13)	0.0232 (13)	0.0083 (12)	0.0086 (10)	−0.0004 (10)	−0.0048 (10)
C9	0.0150 (12)	0.0132 (12)	0.0185 (13)	0.0018 (10)	0.0052 (10)	0.0037 (9)
C10	0.0152 (12)	0.0142 (12)	0.0238 (14)	−0.0063 (10)	0.0037 (10)	−0.0024 (10)
C11	0.0268 (14)	0.0131 (12)	0.0197 (14)	−0.0068 (10)	0.0140 (11)	−0.0050 (10)
C12	0.0250 (13)	0.0121 (12)	0.0275 (15)	0.0024 (10)	0.0154 (11)	0.0006 (10)

Geometric parameters (Å, º)

Sc1—C1	2.438 (2)	C4—C5	1.398 (4)
Sc1—C2	2.432 (2)	C4—H4	0.9500
Sc1—C3	2.417 (2)	C5—C6	1.398 (4)
Sc1—C4	2.425 (2)	C5—H5	0.9500
Sc1—C5	2.428 (2)	C6—C7	1.401 (4)
Sc1—C6	2.430 (2)	C6—H6	0.9500
Sc1—C7	2.422 (2)	C7—C8	1.398 (4)
Sc1—C8	2.424 (2)	C7—H7	0.9500
Sc1—O1	2.2285 (15)	C8—H8	0.9500
Sc1—Cl1	2.5963 (7)	C9—C12	1.519 (3)
Sc1—Cl1^i	2.5980 (7)	C9—H9A	0.9900
O1—C10	1.448 (3)	C9—H9B	0.9900
O1—C9	1.449 (3)	C10—C11	1.527 (3)
C1—C2	1.399 (3)	C10—H10A	0.9900
C1—C8	1.401 (3)	C10—H10B	0.9900
C1—H1	0.9500	C11—C12	1.538 (3)
C2—C3	1.406 (3)	C11—H11A	0.9900
C2—H2	0.9500	C11—H11B	0.9900
C3—C4	1.393 (4)	C12—H12A	0.9900
C3—H3	0.9500	C12—H12B	0.9900
O1—Sc1—C3	154.86 (8)	C1—C2—Sc1	73.55 (14)
O1—Sc1—C7	85.41 (7)	C3—C2—Sc1	72.55 (14)
C3—Sc1—C7	98.22 (8)	C1—C2—H2	112.7
O1—Sc1—C8	106.84 (7)	C3—C2—H2	112.7
C3—Sc1—C8	88.56 (8)	Sc1—C2—H2	139.0
C7—Sc1—C8	33.52 (8)	C4—C3—C2	135.2 (2)
O1—Sc1—C4	122.61 (8)	C4—C3—Sc1	73.62 (14)
C3—Sc1—C4	33.43 (9)	C2—C3—Sc1	73.75 (14)
C7—Sc1—C4	88.50 (9)	C4—C3—H3	112.4
C8—Sc1—C4	97.89 (8)	C2—C3—H3	112.4
O1—Sc1—C5	95.83 (8)	Sc1—C3—H3	137.6
C3—Sc1—C5	64.26 (9)	C3—C4—C5	134.8 (2)
C7—Sc1—C5	64.42 (9)	C3—C4—Sc1	72.95 (14)
C8—Sc1—C5	88.08 (8)	C5—C4—Sc1	73.38 (14)
C4—Sc1—C5	33.49 (9)	C3—C4—H4	112.6
O1—Sc1—C6	81.12 (7)	C5—C4—H4	112.6
C3—Sc1—C6	88.25 (9)	Sc1—C4—H4	138.9
C7—Sc1—C6	33.57 (9)	C6—C5—C4	135.3 (2)
C8—Sc1—C6	64.31 (9)	C6—C5—Sc1	73.33 (14)
C4—Sc1—C6	64.38 (9)	C4—C5—Sc1	73.13 (14)
C5—Sc1—C6	33.45 (9)	C6—C5—H5	112.3
O1—Sc1—C2	170.42 (8)	C4—C5—H5	112.3
C3—Sc1—C2	33.70 (8)	Sc1—C5—H5	139.4
C7—Sc1—C2	88.37 (8)	C5—C6—C7	135.0 (2)
C8—Sc1—C2	64.43 (9)	C5—C6—Sc1	73.22 (14)
C4—Sc1—C2	64.38 (9)	C7—C6—Sc1	72.92 (14)
C5—Sc1—C2	88.01 (8)	C5—C6—H6	112.5
C6—Sc1—C2	97.63 (8)	C7—C6—H6	112.5
O1—Sc1—C1	137.10 (7)	Sc1—C6—H6	139.5
C3—Sc1—C1	64.40 (8)	C8—C7—C6	134.8 (2)
C7—Sc1—C1	64.28 (9)	C8—C7—Sc1	73.32 (14)
C8—Sc1—C1	33.49 (8)	C6—C7—Sc1	73.51 (14)
C4—Sc1—C1	87.93 (8)	C8—C7—H7	112.6
C5—Sc1—C1	97.18 (8)	C6—C7—H7	112.6
C6—Sc1—C1	87.80 (8)	Sc1—C7—H7	137.9
C2—Sc1—C1	33.39 (8)	C7—C8—C1	135.0 (2)
O1—Sc1—Cl1	80.81 (4)	C7—C8—Sc1	73.16 (14)
C3—Sc1—Cl1	87.61 (6)	C1—C8—Sc1	73.80 (14)
C7—Sc1—Cl1	158.32 (7)	C7—C8—H8	112.5
C8—Sc1—Cl1	168.15 (7)	C1—C8—H8	112.5
C4—Sc1—Cl1	84.98 (6)	Sc1—C8—H8	138.1
C5—Sc1—Cl1	100.32 (6)	O1—C9—C12	104.09 (18)
C6—Sc1—Cl1	126.73 (7)	O1—C9—H9A	110.9
C2—Sc1—Cl1	107.19 (6)	C12—C9—H9A	110.9
C1—Sc1—Cl1	135.85 (6)	O1—C9—H9B	110.9
O1—Sc1—Cl1^i	81.00 (4)	C12—C9—H9B	110.9
C3—Sc1—Cl1^i	119.28 (6)	H9A—C9—H9B	109.0
C7—Sc1—Cl1^i	113.32 (7)	O1—C10—C11	104.70 (19)
C8—Sc1—Cl1^i	91.11 (6)	O1—C10—H10A	110.8
C4—Sc1—Cl1^i	150.14 (7)	C11—C10—H10A	110.8
C5—Sc1—Cl1^i	176.35 (7)	O1—C10—H10B	110.8
C6—Sc1—Cl1^i	143.50 (7)	C11—C10—H10B	110.8
C2—Sc1—Cl1^i	94.84 (6)	H10A—C10—H10B	108.9
C1—Sc1—Cl1^i	84.05 (6)	C10—C11—C12	104.65 (19)
Cl1—Sc1—Cl1^i	81.03 (2)	C10—C11—H11A	110.8
Sc1—Cl1—Sc1^i	98.97 (2)	C12—C11—H11A	110.8
C10—O1—C9	104.84 (16)	C10—C11—H11B	110.8
C10—O1—Sc1	125.92 (13)	C12—C11—H11B	110.8
C9—O1—Sc1	125.06 (13)	H11A—C11—H11B	108.9
C2—C1—C8	135.2 (2)	C9—C12—C11	104.01 (19)
C2—C1—Sc1	73.06 (14)	C9—C12—H12A	111.0
C8—C1—Sc1	72.71 (14)	C11—C12—H12A	111.0
C2—C1—H1	112.4	C9—C12—H12B	111.0
C8—C1—H1	112.4	C11—C12—H12B	111.0
Sc1—C1—H1	140.6	H12A—C12—H12B	109.0
C1—C2—C3	134.6 (2)
C8—C1—C2—C3	−1.6 (5)	Sc1—C6—C7—C8	−44.3 (3)
Sc1—C1—C2—C3	−43.1 (3)	C5—C6—C7—Sc1	42.8 (3)
C8—C1—C2—Sc1	41.6 (3)	C6—C7—C8—C1	0.1 (5)
C1—C2—C3—C4	−1.2 (5)	Sc1—C7—C8—C1	−44.3 (3)
Sc1—C2—C3—C4	−44.7 (3)	C6—C7—C8—Sc1	44.4 (3)
C1—C2—C3—Sc1	43.4 (3)	C2—C1—C8—C7	2.4 (5)
C2—C3—C4—C5	1.3 (5)	Sc1—C1—C8—C7	44.1 (3)
Sc1—C3—C4—C5	−43.4 (3)	C2—C1—C8—Sc1	−41.7 (3)
C2—C3—C4—Sc1	44.7 (3)	C10—O1—C9—C12	−42.6 (2)
C3—C4—C5—C6	0.4 (5)	Sc1—O1—C9—C12	159.41 (14)
Sc1—C4—C5—C6	−42.9 (3)	C9—O1—C10—C11	39.2 (2)
C3—C4—C5—Sc1	43.3 (3)	Sc1—O1—C10—C11	−163.06 (14)
C4—C5—C6—C7	0.1 (5)	O1—C10—C11—C12	−20.2 (3)
Sc1—C5—C6—C7	−42.7 (3)	O1—C9—C12—C11	28.5 (2)
C4—C5—C6—Sc1	42.8 (3)	C10—C11—C12—C9	−5.0 (3)
C5—C6—C7—C8	−1.5 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.