Mol­ecular structures of tris­(1-tert-butyl-2-mercapto­imidazol­yl)hydro­borate complexes of titanium, zirconium and hafnium

Rong, Y.; Sambade, D.; Parkin, G.

doi:10.1107/S2053229616008925

Molecular structures of tris(1-tert-butyl-2-mercaptoimidazolyl)hydroborate complexes of titanium, zirconium and hafnium

Cyclopentadienyl and tris(pyrazolyl)hydroborate have found much use as supporting ligands in the chemistry of titanium, zirconium and hafnium, especially with respect to applications involving olefin polymerization catalysis. In contrast, closely related tris(1-alkyl-2-mercaptoimidazolyl)hydroborate, [Tm^R], ligands have so far found little application to the chemistry of these elements, despite the fact that such ligands are currently used extensively in coordination chemistry. In view of the fact that a substituent in the 2-position exerts a direct influence on the steric environment of the metal center, we report here the application of the sterically demanding tris(1-tert-butyl-2-mercaptoimidazolyl)hydroborate [Tm $^{{\rm Bu}^{\rm t}}$ ] ligand to these metals. Dichlorido(η⁵-cyclopentadienyl)[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ³S,S′,H]zirconium(IV) benzene hemisolvate, [Zr(C₂₁H₃₄BN₆S₃)(C₅H₅)Cl₂]·0.5C₆H₆, (I), dichlorido(η⁵-cyclopentadienyl)[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ³S,S′,H]titanium(IV) benzene hemisolvate, [Ti(C₂₁H₃₄BN₆S₃)(C₅H₅)Cl₂]·0.5C₆H₆, (II), [bis(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ³S,S′,H]dichlorido(η⁵-cyclopentadienyl)zirconium(IV), [Zr(C₁₄H₂₄BN₄S₂)(C₅H₅)Cl₂], (III), (1-tert-butyl-2,3-dihydro-1H-imidazole-2-thione-κS)(1-tert-butyl-2-sulfanylidene-1H-imidazol-3-ido-κ²N³,S)dichlorido(η⁵-cyclopentadienyl)zirconium(IV) benzene monosolvate, [Zr(C₇H₁₁N₂S)(C₇H₁₂N₂S)(C₅H₅)Cl₂]·C₆H₆, (IV), and tribenzyl[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ³S,S′,S′′]hafnium(IV) benzene tetrasolvate, [Hf(C₇H₇)₃(C₂₁H₃₄BN₆S₃)]·4C₆H₆, (V), have been structurally characterized by X-ray diffraction. The [Tm $^{{\rm Bu}^{\rm t}}$ $^{{\rm Bu}^{\rm t}}$ ] ligand coordinates to Ti and Zr in Cp[κ³S₂,H-Tm $^{{\rm Bu}^{\rm t}}$ ]MCl₂ [M = Zr, (I), and Ti, (II)] in a κ³S₂,H mode, while the benzyl compounds [Tm $^{{\rm Bu}^{\rm t}}$ ]M(CH₂Ph)₃ [M = Zr and Hf, (V)] exhibit κ³S₃ coordination.

Keywords: scorpionates; coordination compounds; tris(1-tert-butyl-2-mercaptoimidazolyl)hydroborate; titanium; zirconium; hafnium; crystal structure; olefin polymerization; precatalyst.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616008925/yp3125sup1.cif Contains datablocks I, II, III, IV, V, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616008925/yp3125cptmzr_dssup2.hkl Contains datablock cptmzr_ds
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616008925/yp3125cptmticl2_dssup3.hkl Contains datablock cptmticl2_ds
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616008925/yp3125bmcpzr_dssup4.hkl Contains datablock bmcpzr_ds
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616008925/yp3125cpzrtm_dssup5.hkl Contains datablock cpzrtm_ds
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616008925/yp3125tmhf_dssup6.hkl Contains datablock tmhf_ds

CCDC references: 1478870; 1478869; 1478871; 1478872; 1478868

Computing details top

For all compounds, data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(I) Dichlorido(η⁵-cyclopentadienyl)[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ³S,S',H]zirconium(IV) benzene hemisolvate top

Crystal data top

[Zr(C₂₁H₃₄BN₆S₃)Cl₂(C₅H₅)]·0.5C₆H₆	F(000) = 1540
M_r = 743.79	D_x = 1.454 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.761 (3) Å	Cell parameters from 6566 reflections
b = 11.358 (2) Å	θ = 2.3–27.6°
c = 20.730 (4) Å	µ = 0.70 mm⁻¹
β = 102.130 (3)°	T = 125 K
V = 3397.8 (12) Å³	Block, colorless
Z = 4	0.11 × 0.06 × 0.04 mm

Data collection top

Bruker APEXII CCD diffractometer	5386 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.171
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2014)	θ_max = 30.5°, θ_min = 1.6°
T_min = 0.658, T_max = 0.746	h = −21→21
53472 measured reflections	k = −16→16
10340 independent reflections	l = −29→29

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0225P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
10340 reflections	Δρ_max = 0.65 e Å⁻³
370 parameters	Δρ_min = −0.58 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.

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

	x	y	z	U_iso*/U_eq
Zr1	0.34991 (2)	0.21501 (3)	0.18040 (2)	0.01777 (9)
B1	0.2630 (3)	0.2102 (4)	0.02067 (19)	0.0184 (8)
H1	0.300 (2)	0.246 (3)	0.0677 (11)	0.022*
Cl1	0.48691 (6)	0.15797 (9)	0.13854 (5)	0.0274 (2)
Cl2	0.39131 (7)	0.42515 (8)	0.17071 (5)	0.0280 (2)
N11	0.30328 (19)	0.0873 (2)	0.01085 (13)	0.0176 (6)
N12	0.3659 (2)	−0.0863 (3)	0.03806 (14)	0.0196 (7)
N21	0.15970 (19)	0.2018 (2)	0.02495 (13)	0.0176 (6)
N22	0.0316 (2)	0.1922 (3)	0.06368 (14)	0.0224 (7)
N31	0.28352 (19)	0.3034 (2)	−0.02982 (13)	0.0145 (6)
N32	0.2914 (2)	0.4168 (3)	−0.11388 (15)	0.0252 (7)
S1	0.27644 (7)	0.01207 (8)	0.13004 (4)	0.0210 (2)
S2	0.17756 (6)	0.28178 (9)	0.15313 (4)	0.0248 (2)
S3	0.19898 (7)	0.20851 (10)	−0.14854 (5)	0.0300 (2)
C11	0.3165 (2)	0.0025 (3)	0.05762 (17)	0.0198 (8)
C12	0.3474 (2)	0.0513 (3)	−0.03861 (17)	0.0222 (9)
H12A	0.3507	0.0942	−0.0774	0.027*
C13	0.3844 (3)	−0.0546 (3)	−0.02185 (18)	0.0229 (9)
H13A	0.4180	−0.1004	−0.0472	0.028*
C14	0.3961 (3)	−0.2006 (3)	0.07400 (18)	0.0259 (9)
C15	0.4534 (3)	−0.1747 (4)	0.1431 (2)	0.0428 (12)
H15A	0.4726	−0.2490	0.1659	0.064*
H15B	0.5085	−0.1290	0.1394	0.064*
H15C	0.4159	−0.1295	0.1681	0.064*
C16	0.4572 (3)	−0.2684 (3)	0.0357 (2)	0.0345 (10)
H16A	0.4771	−0.3425	0.0584	0.052*
H16B	0.4218	−0.2852	−0.0089	0.052*
H16C	0.5116	−0.2209	0.0329	0.052*
C17	0.3099 (3)	−0.2729 (3)	0.07580 (19)	0.0299 (9)
H17A	0.3280	−0.3472	0.0989	0.045*
H17B	0.2695	−0.2286	0.0991	0.045*
H17C	0.2766	−0.2893	0.0306	0.045*
C21	0.1224 (2)	0.2234 (3)	0.07871 (17)	0.0195 (8)
C22	0.0898 (3)	0.1568 (3)	−0.02380 (18)	0.0227 (8)
H22A	0.0963	0.1335	−0.0666	0.027*
C23	0.0119 (3)	0.1512 (3)	−0.00102 (18)	0.0240 (9)
H23A	−0.0466	0.1242	−0.0247	0.029*
C24	−0.0333 (3)	0.1781 (3)	0.11105 (18)	0.0237 (9)
C25	0.0045 (3)	0.0768 (3)	0.15775 (19)	0.0323 (10)
H25A	−0.0357	0.0649	0.1893	0.048*
H25B	0.0062	0.0046	0.1321	0.048*
H25C	0.0673	0.0961	0.1817	0.048*
C26	−0.0412 (3)	0.2917 (4)	0.1484 (2)	0.0345 (10)
H26A	−0.0835	0.2797	0.1784	0.052*
H26B	0.0200	0.3142	0.1738	0.052*
H26C	−0.0653	0.3543	0.1169	0.052*
C27	−0.1295 (3)	0.1476 (4)	0.0711 (2)	0.0341 (10)
H27A	−0.1724	0.1382	0.1010	0.051*
H27B	−0.1515	0.2112	0.0397	0.051*
H27C	−0.1265	0.0740	0.0470	0.051*
C31	0.2579 (3)	0.3115 (3)	−0.09648 (18)	0.0235 (9)
C32	0.3345 (3)	0.4021 (3)	−0.00570 (19)	0.0246 (9)
H32A	0.3611	0.4180	0.0393	0.030*
C33	0.3396 (3)	0.4710 (3)	−0.05703 (18)	0.0265 (9)
H33A	0.3708	0.5445	−0.0549	0.032*
C34	0.2813 (3)	0.4690 (4)	−0.18276 (18)	0.0294 (10)
C35	0.3219 (3)	0.5922 (4)	−0.1761 (2)	0.0450 (12)
H35A	0.3876	0.5883	−0.1547	0.068*
H35B	0.3154	0.6276	−0.2200	0.068*
H35C	0.2888	0.6405	−0.1493	0.068*
C36	0.3343 (3)	0.3921 (4)	−0.2221 (2)	0.0396 (12)
H36A	0.3996	0.3889	−0.1997	0.059*
H36B	0.3082	0.3125	−0.2257	0.059*
H36C	0.3291	0.4255	−0.2663	0.059*
C37	0.1796 (3)	0.4763 (4)	−0.2159 (2)	0.0366 (11)
H37A	0.1471	0.5262	−0.1895	0.055*
H37B	0.1734	0.5102	−0.2601	0.055*
H37C	0.1525	0.3972	−0.2195	0.055*
C41	0.3205 (4)	0.0991 (5)	0.2759 (2)	0.0553 (16)
H41A	0.2784	0.0294	0.2731	0.066*
C42	0.4138 (4)	0.0946 (5)	0.2790 (2)	0.0532 (16)
H42A	0.4515	0.0213	0.2796	0.064*
C43	0.4488 (3)	0.2079 (6)	0.29191 (19)	0.0507 (14)
H43A	0.5157	0.2303	0.3043	0.061*
C44	0.3742 (4)	0.2779 (4)	0.29776 (19)	0.0469 (13)
H44A	0.3782	0.3612	0.3137	0.056*
C45	0.2979 (3)	0.2106 (6)	0.28765 (19)	0.0535 (15)
H45A	0.2357	0.2368	0.2940	0.064*
C51	−0.0352 (3)	0.5611 (3)	0.04659 (19)	0.0327 (6)
H51A	−0.0594	0.6025	0.0790	0.039*
C52	−0.0948 (3)	0.5028 (3)	−0.00384 (19)	0.0327 (6)
H52A	−0.1598	0.5056	−0.0066	0.039*
C53	−0.0594 (3)	0.4408 (3)	−0.0499 (2)	0.0327 (6)
H53A	−0.0999	0.3993	−0.0841	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.02181 (19)	0.01842 (18)	0.01399 (17)	0.00101 (17)	0.00584 (14)	−0.00053 (16)
B1	0.022 (2)	0.018 (2)	0.016 (2)	0.000 (2)	0.0070 (17)	−0.0038 (18)
Cl1	0.0238 (5)	0.0366 (6)	0.0240 (5)	0.0029 (4)	0.0098 (4)	−0.0036 (4)
Cl2	0.0395 (6)	0.0208 (5)	0.0231 (5)	−0.0053 (4)	0.0054 (4)	−0.0013 (4)
N11	0.0191 (17)	0.0190 (16)	0.0158 (16)	−0.0027 (13)	0.0063 (13)	−0.0037 (13)
N12	0.0223 (17)	0.0170 (16)	0.0216 (17)	0.0006 (13)	0.0094 (14)	−0.0025 (13)
N21	0.0219 (16)	0.0164 (16)	0.0148 (15)	−0.0006 (13)	0.0046 (12)	0.0009 (12)
N22	0.0214 (17)	0.0251 (19)	0.0225 (17)	−0.0001 (14)	0.0083 (14)	−0.0016 (14)
N31	0.0201 (16)	0.0124 (15)	0.0126 (14)	−0.0019 (12)	0.0074 (12)	−0.0019 (12)
N32	0.0308 (19)	0.0237 (18)	0.0211 (18)	−0.0004 (15)	0.0058 (15)	0.0033 (14)
S1	0.0306 (6)	0.0176 (5)	0.0177 (5)	0.0013 (4)	0.0113 (4)	0.0006 (4)
S2	0.0234 (5)	0.0304 (5)	0.0209 (5)	0.0055 (5)	0.0053 (4)	−0.0085 (4)
S3	0.0353 (6)	0.0348 (6)	0.0195 (5)	−0.0073 (5)	0.0047 (4)	−0.0047 (5)
C11	0.021 (2)	0.0172 (19)	0.022 (2)	−0.0013 (16)	0.0066 (16)	−0.0022 (16)
C12	0.027 (2)	0.025 (2)	0.018 (2)	−0.0050 (17)	0.0143 (17)	−0.0045 (16)
C13	0.024 (2)	0.023 (2)	0.025 (2)	−0.0036 (17)	0.0120 (17)	−0.0099 (17)
C14	0.032 (2)	0.018 (2)	0.028 (2)	0.0056 (17)	0.0076 (18)	−0.0013 (16)
C15	0.047 (3)	0.038 (3)	0.037 (3)	0.022 (2)	−0.005 (2)	−0.002 (2)
C16	0.035 (3)	0.023 (2)	0.049 (3)	0.0032 (19)	0.018 (2)	−0.005 (2)
C17	0.040 (3)	0.019 (2)	0.034 (2)	0.0066 (19)	0.0153 (19)	0.0070 (18)
C21	0.022 (2)	0.0167 (19)	0.0207 (18)	0.0024 (17)	0.0064 (15)	0.0016 (16)
C22	0.027 (2)	0.022 (2)	0.0183 (19)	−0.0033 (17)	0.0042 (17)	−0.0027 (16)
C23	0.020 (2)	0.028 (2)	0.023 (2)	−0.0013 (17)	0.0027 (17)	−0.0010 (17)
C24	0.028 (2)	0.023 (2)	0.025 (2)	0.0025 (16)	0.0168 (18)	0.0017 (16)
C25	0.037 (3)	0.029 (2)	0.037 (3)	0.005 (2)	0.022 (2)	0.0077 (19)
C26	0.034 (2)	0.033 (2)	0.042 (3)	0.003 (2)	0.020 (2)	−0.003 (2)
C27	0.022 (2)	0.043 (3)	0.040 (3)	−0.001 (2)	0.0105 (19)	0.000 (2)
C31	0.023 (2)	0.028 (2)	0.021 (2)	0.0001 (17)	0.0092 (16)	0.0015 (16)
C32	0.028 (2)	0.023 (2)	0.021 (2)	0.0021 (17)	0.0016 (17)	0.0016 (16)
C33	0.034 (2)	0.022 (2)	0.024 (2)	−0.0052 (18)	0.0072 (18)	−0.0019 (17)
C34	0.036 (3)	0.033 (2)	0.020 (2)	0.0032 (19)	0.0088 (18)	0.0104 (18)
C35	0.066 (3)	0.040 (3)	0.030 (3)	−0.006 (2)	0.012 (2)	0.014 (2)
C36	0.040 (3)	0.055 (3)	0.028 (2)	0.018 (2)	0.017 (2)	0.010 (2)
C37	0.037 (3)	0.041 (3)	0.031 (2)	0.013 (2)	0.006 (2)	0.011 (2)
C41	0.084 (4)	0.062 (4)	0.017 (2)	−0.043 (3)	0.005 (3)	0.007 (2)
C42	0.090 (5)	0.049 (3)	0.019 (2)	0.048 (3)	0.009 (3)	0.011 (2)
C43	0.027 (3)	0.110 (5)	0.012 (2)	−0.019 (3)	−0.0032 (18)	0.010 (3)
C44	0.099 (4)	0.026 (2)	0.015 (2)	0.003 (3)	0.009 (2)	−0.0029 (19)
C45	0.038 (3)	0.109 (5)	0.016 (2)	0.023 (3)	0.011 (2)	0.010 (3)
C51	0.0423 (15)	0.0280 (14)	0.0276 (13)	0.0039 (12)	0.0070 (11)	0.0015 (10)
C52	0.0423 (15)	0.0280 (14)	0.0276 (13)	0.0039 (12)	0.0070 (11)	0.0015 (10)
C53	0.0423 (15)	0.0280 (14)	0.0276 (13)	0.0039 (12)	0.0070 (11)	0.0015 (10)

Geometric parameters (Å, º) top

Zr1—H1	2.32 (2)	N32—C31	1.371 (4)
Zr1—Cl1	2.4495 (10)	N32—C33	1.386 (5)
Zr1—C43	2.462 (4)	N32—C34	1.524 (5)
Zr1—C42	2.476 (4)	S1—C11	1.729 (4)
Zr1—Cl2	2.4824 (11)	S2—C21	1.719 (4)
Zr1—C44	2.488 (4)	S3—C31	1.701 (4)
Zr1—C41	2.491 (4)	C12—C13	1.337 (5)
Zr1—C45	2.501 (4)	C14—C17	1.522 (5)
Zr1—S2	2.6005 (11)	C14—C16	1.529 (5)
Zr1—S1	2.6650 (11)	C14—C15	1.531 (5)
Zr1—B1	3.290 (4)	C22—C23	1.334 (5)
B1—H1	1.090 (17)	C24—C26	1.521 (5)
B1—N11	1.547 (5)	C24—C27	1.526 (5)
B1—N21	1.549 (5)	C24—C25	1.531 (5)
B1—N31	1.563 (5)	C32—C33	1.336 (5)
N11—C11	1.352 (4)	C34—C37	1.516 (5)
N11—C12	1.387 (4)	C34—C36	1.518 (5)
N12—C11	1.355 (4)	C34—C35	1.518 (6)
N12—C13	1.374 (4)	C41—C45	1.345 (7)
N12—C14	1.516 (5)	C41—C42	1.366 (7)
N21—C21	1.365 (4)	C42—C43	1.391 (7)
N21—C22	1.381 (4)	C43—C44	1.384 (6)
N22—C21	1.357 (4)	C44—C45	1.341 (7)
N22—C23	1.391 (4)	C51—C53ⁱ	1.385 (5)
N22—C24	1.518 (4)	C51—C52	1.385 (5)
N31—C31	1.357 (4)	C52—C53	1.375 (5)
N31—C32	1.384 (4)	C53—C51ⁱ	1.385 (5)

H1—Zr1—Cl1	78.1 (8)	C11—N12—C13	107.3 (3)
H1—Zr1—C43	161.6 (7)	C11—N12—C14	127.6 (3)
Cl1—Zr1—C43	87.33 (12)	C13—N12—C14	125.1 (3)
H1—Zr1—C42	153.9 (7)	C21—N21—C22	107.2 (3)
Cl1—Zr1—C42	86.96 (13)	C21—N21—B1	127.4 (3)
C43—Zr1—C42	32.73 (16)	C22—N21—B1	125.0 (3)
H1—Zr1—Cl2	78.8 (7)	C21—N22—C23	107.8 (3)
Cl1—Zr1—Cl2	89.42 (4)	C21—N22—C24	127.3 (3)
C43—Zr1—Cl2	90.01 (14)	C23—N22—C24	123.7 (3)
C42—Zr1—Cl2	122.71 (15)	C31—N31—C32	109.1 (3)
H1—Zr1—C44	152.9 (7)	C31—N31—B1	132.6 (3)
Cl1—Zr1—C44	117.53 (14)	C32—N31—B1	118.3 (3)
C43—Zr1—C44	32.45 (15)	C31—N32—C33	108.2 (3)
C42—Zr1—C44	53.09 (15)	C31—N32—C34	128.0 (3)
Cl2—Zr1—C44	79.39 (11)	C33—N32—C34	123.8 (3)
H1—Zr1—C41	143.8 (7)	C11—S1—Zr1	102.09 (12)
Cl1—Zr1—C41	115.90 (17)	C21—S2—Zr1	109.88 (12)
C43—Zr1—C41	53.43 (15)	N11—C11—N12	108.7 (3)
C42—Zr1—C41	31.93 (16)	N11—C11—S1	123.6 (3)
Cl2—Zr1—C41	131.26 (13)	N12—C11—S1	127.6 (3)
C44—Zr1—C41	52.24 (15)	C13—C12—N11	107.6 (3)
H1—Zr1—C45	143.7 (8)	C12—C13—N12	108.8 (3)
Cl1—Zr1—C45	137.76 (11)	N12—C14—C17	108.2 (3)
C43—Zr1—C45	52.90 (14)	N12—C14—C16	108.7 (3)
C42—Zr1—C45	52.37 (16)	C17—C14—C16	109.2 (3)
Cl2—Zr1—C45	102.60 (16)	N12—C14—C15	110.1 (3)
C44—Zr1—C45	31.18 (15)	C17—C14—C15	112.4 (3)
C41—Zr1—C45	31.25 (16)	C16—C14—C15	108.2 (3)
H1—Zr1—S2	69.5 (8)	N22—C21—N21	108.3 (3)
Cl1—Zr1—S2	147.45 (3)	N22—C21—S2	124.5 (3)
C43—Zr1—S2	124.99 (12)	N21—C21—S2	127.2 (3)
C42—Zr1—S2	121.74 (14)	C23—C22—N21	109.0 (3)
Cl2—Zr1—S2	87.04 (4)	C22—C23—N22	107.7 (3)
C44—Zr1—S2	93.57 (14)	N22—C24—C26	111.5 (3)
C41—Zr1—S2	90.05 (16)	N22—C24—C27	108.4 (3)
C45—Zr1—S2	74.33 (11)	C26—C24—C27	107.8 (3)
H1—Zr1—S1	73.7 (7)	N22—C24—C25	107.0 (3)
Cl1—Zr1—S1	86.03 (3)	C26—C24—C25	111.9 (3)
C43—Zr1—S1	116.84 (15)	C27—C24—C25	110.3 (3)
C42—Zr1—S1	84.19 (14)	N31—C31—N32	106.7 (3)
Cl2—Zr1—S1	152.46 (3)	N31—C31—S3	126.5 (3)
C44—Zr1—S1	126.47 (12)	N32—C31—S3	126.7 (3)
C41—Zr1—S1	74.32 (12)	C33—C32—N31	107.7 (3)
C45—Zr1—S1	98.93 (16)	C32—C33—N32	108.2 (3)
S2—Zr1—S1	82.42 (3)	C37—C34—C36	111.2 (3)
H1—Zr1—B1	10.4 (7)	C37—C34—C35	109.0 (3)
Cl1—Zr1—B1	79.36 (7)	C36—C34—C35	109.9 (3)
C43—Zr1—B1	166.67 (13)	C37—C34—N32	109.8 (3)
C42—Zr1—B1	145.30 (14)	C36—C34—N32	108.7 (3)
Cl2—Zr1—B1	89.15 (8)	C35—C34—N32	108.3 (3)
C44—Zr1—B1	159.12 (14)	C45—C41—C42	108.2 (5)
C41—Zr1—B1	134.03 (13)	C45—C41—Zr1	74.8 (3)
C45—Zr1—B1	140.07 (13)	C42—C41—Zr1	73.4 (3)
S2—Zr1—B1	68.25 (7)	C41—C42—C43	107.7 (4)
S1—Zr1—B1	63.32 (8)	C41—C42—Zr1	74.7 (3)
H1—B1—N11	108.4 (17)	C43—C42—Zr1	73.1 (2)
H1—B1—N21	106.7 (17)	C44—C43—C42	106.2 (4)
N11—B1—N21	111.2 (3)	C44—C43—Zr1	74.8 (2)
H1—B1—N31	102.6 (17)	C42—C43—Zr1	74.2 (2)
N11—B1—N31	112.9 (3)	C45—C44—C43	108.4 (4)
N21—B1—N31	114.3 (3)	C45—C44—Zr1	74.9 (2)
H1—B1—Zr1	22.7 (17)	C43—C44—Zr1	72.7 (2)
N11—B1—Zr1	93.9 (2)	C44—C45—C41	109.4 (5)
N21—B1—Zr1	97.10 (19)	C44—C45—Zr1	73.9 (2)
N31—B1—Zr1	125.0 (2)	C41—C45—Zr1	74.0 (3)
C11—N11—C12	107.5 (3)	C53ⁱ—C51—C52	120.3 (4)
C11—N11—B1	123.4 (3)	C53—C52—C51	119.7 (4)
C12—N11—B1	128.0 (3)	C52—C53—C51ⁱ	120.0 (4)

Symmetry code: (i) −x, −y+1, −z.

(II) Dichlorido(η⁵-cyclopentadienyl)[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ³S,S',H]titanium(IV) benzene hemisolvate top

Crystal data top

[Ti(C₂₁H₃₄BN₆S₃)Cl₂(C₅H₅)]·0.5C₆H₆	F(000) = 1468
M_r = 700.47	D_x = 1.400 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.720 (7) Å	Cell parameters from 2949 reflections
b = 11.327 (5) Å	θ = 2.3–19.5°
c = 20.422 (10) Å	µ = 0.64 mm⁻¹
β = 102.593 (7)°	T = 150 K
V = 3323 (3) Å³	Block, black
Z = 4	0.28 × 0.10 × 0.02 mm

Data collection top

Bruker APEXII CCD diffractometer	2173 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.230
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2014)	θ_max = 25.0°, θ_min = 1.6°
T_min = 0.664, T_max = 0.746	h = −17→17
34971 measured reflections	k = −13→13
5853 independent reflections	l = −24→24

Refinement top

Refinement on F²	194 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0209P)²] where P = (F_o² + 2F_c²)/3
S = 0.68	(Δ/σ)_max < 0.001
5853 reflections	Δρ_max = 0.36 e Å⁻³
434 parameters	Δρ_min = −0.32 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ti1	0.34802 (6)	0.28961 (9)	0.18194 (4)	0.0340 (3)
B1	0.2641 (4)	0.2894 (5)	0.0204 (3)	0.0267 (15)
H1	0.2998	0.2618	0.0682	0.032*
Cl1	0.38382 (10)	0.08661 (12)	0.17163 (7)	0.0468 (4)
Cl2	0.47882 (9)	0.33781 (12)	0.13980 (7)	0.0426 (4)
S1	0.28001 (10)	0.48546 (12)	0.13111 (7)	0.0367 (4)
S2	0.18251 (9)	0.22789 (13)	0.15579 (7)	0.0413 (4)
S3	0.19699 (10)	0.28492 (14)	−0.15091 (7)	0.0459 (4)
N11	0.3041 (3)	0.4126 (4)	0.0094 (2)	0.0288 (11)
N12	0.3678 (3)	0.5859 (4)	0.0379 (2)	0.0332 (11)
N21	0.1607 (3)	0.3006 (4)	0.0244 (2)	0.0313 (11)
N22	0.0332 (3)	0.3109 (4)	0.0648 (2)	0.0366 (12)
N31	0.2847 (3)	0.1967 (4)	−0.0287 (2)	0.0292 (11)
N32	0.2928 (3)	0.0800 (4)	−0.1135 (2)	0.0334 (11)
C11	0.3177 (3)	0.4966 (5)	0.0573 (2)	0.0297 (13)
C12	0.3456 (3)	0.4489 (5)	−0.0413 (3)	0.0299 (14)
H12A	0.3471	0.4066	−0.0812	0.036*
C13	0.3839 (3)	0.5554 (5)	−0.0240 (3)	0.0363 (15)
H13A	0.4165	0.6018	−0.0500	0.044*
C14	0.3998 (4)	0.6980 (5)	0.0751 (3)	0.0392 (15)
C15	0.4589 (3)	0.7672 (4)	0.0363 (3)	0.0503 (17)
H15A	0.4246	0.7771	−0.0103	0.075*
H15B	0.5169	0.7243	0.0370	0.075*
H15C	0.4733	0.8449	0.0570	0.075*
C16	0.3137 (3)	0.7727 (4)	0.0783 (3)	0.0478 (16)
H16A	0.2816	0.7951	0.0328	0.072*
H16B	0.3332	0.8439	0.1049	0.072*
H16C	0.2715	0.7265	0.0993	0.072*
C17	0.4585 (4)	0.6697 (5)	0.1448 (3)	0.0579 (18)
H17A	0.4208	0.6255	0.1704	0.087*
H17B	0.4799	0.7434	0.1683	0.087*
H17C	0.5124	0.6221	0.1403	0.087*
C21	0.1251 (3)	0.2807 (5)	0.0794 (2)	0.0346 (14)
C22	0.0898 (4)	0.3442 (4)	−0.0258 (3)	0.0400 (15)
H22A	0.0951	0.3666	−0.0696	0.048*
C23	0.0116 (4)	0.3491 (5)	−0.0013 (3)	0.0462 (16)
H23A	−0.0479	0.3743	−0.0252	0.055*
C24	−0.0311 (4)	0.3249 (5)	0.1128 (3)	0.0373 (15)
C25	0.0070 (3)	0.4256 (5)	0.1602 (3)	0.0483 (17)
H25A	0.0692	0.4047	0.1860	0.072*
H25B	−0.0345	0.4394	0.1910	0.072*
H25C	0.0108	0.4973	0.1341	0.072*
C26	−0.1283 (3)	0.3524 (5)	0.0722 (3)	0.0580 (19)
H26A	−0.1485	0.2895	0.0393	0.087*
H26B	−0.1274	0.4278	0.0488	0.087*
H26C	−0.1716	0.3577	0.1023	0.087*
C27	−0.0370 (3)	0.2120 (5)	0.1495 (3)	0.0528 (17)
H27A	−0.0556	0.1480	0.1171	0.079*
H27B	−0.0831	0.2201	0.1773	0.079*
H27C	0.0240	0.1940	0.1782	0.079*
C31	0.2574 (3)	0.1844 (5)	−0.0975 (3)	0.0311 (14)
C32	0.3362 (4)	0.0989 (5)	−0.0040 (3)	0.0354 (15)
H32A	0.3633	0.0839	0.0419	0.043*
C33	0.3418 (4)	0.0287 (5)	−0.0553 (3)	0.0437 (16)
H33A	0.3741	−0.0444	−0.0522	0.052*
C34	0.2835 (4)	0.0253 (5)	−0.1811 (3)	0.0454 (16)
C35	0.1816 (4)	0.0159 (5)	−0.2159 (3)	0.0600 (19)
H35A	0.1556	0.0952	−0.2256	0.090*
H35B	0.1475	−0.0256	−0.1867	0.090*
H35C	0.1759	−0.0281	−0.2579	0.090*
C36	0.3346 (4)	0.0998 (5)	−0.2220 (3)	0.0596 (19)
H36A	0.3099	0.1804	−0.2249	0.089*
H36B	0.3263	0.0665	−0.2672	0.089*
H36C	0.4010	0.1011	−0.2006	0.089*
C37	0.3252 (4)	−0.0958 (5)	−0.1741 (3)	0.067 (2)
H37A	0.2958	−0.1431	−0.1443	0.101*
H37B	0.3922	−0.0901	−0.1551	0.101*
H37C	0.3149	−0.1335	−0.2183	0.101*
C41	0.2961 (13)	0.353 (2)	0.2803 (7)	0.0369 (11)	0.431 (10)
H41A	0.2310	0.3765	0.2818	0.044*	0.431 (10)
C42	0.3672 (17)	0.4309 (18)	0.2729 (7)	0.0371 (11)	0.431 (10)
H42A	0.3618	0.5186	0.2681	0.044*	0.431 (10)
C43	0.4486 (14)	0.365 (2)	0.2797 (7)	0.0372 (11)	0.431 (10)
H43A	0.5118	0.3995	0.2813	0.045*	0.431 (10)
C44	0.4307 (17)	0.2469 (18)	0.2913 (7)	0.0372 (11)	0.431 (10)
H44A	0.4787	0.1836	0.3039	0.045*	0.431 (10)
C45	0.3347 (15)	0.235 (2)	0.2902 (7)	0.0371 (11)	0.431 (10)
H45A	0.3029	0.1628	0.3027	0.045*	0.431 (10)
C51	0.2958 (10)	0.2890 (17)	0.2849 (5)	0.0371 (11)	0.569 (10)
H51A	0.2337	0.2612	0.2911	0.044*	0.569 (10)
C52	0.3763 (12)	0.2226 (14)	0.2945 (5)	0.0371 (11)	0.569 (10)
H52A	0.3822	0.1381	0.3091	0.045*	0.569 (10)
C53	0.4502 (10)	0.2960 (17)	0.2865 (6)	0.0372 (11)	0.569 (10)
H53A	0.5176	0.2739	0.2962	0.045*	0.569 (10)
C54	0.4140 (11)	0.4106 (15)	0.2731 (5)	0.0370 (11)	0.569 (10)
H54A	0.4508	0.4842	0.2712	0.044*	0.569 (10)
C55	0.3192 (13)	0.4044 (13)	0.2728 (5)	0.0370 (11)	0.569 (10)
H55A	0.2761	0.4736	0.2684	0.044*	0.569 (10)
C61	0.0951 (4)	0.0035 (6)	0.0038 (3)	0.0580 (19)
H61A	0.1602	0.0068	0.0060	0.070*
C62	0.0330 (5)	0.0609 (5)	−0.0477 (3)	0.0560 (19)
H62A	0.0558	0.1031	−0.0809	0.067*
C63	−0.0616 (5)	0.0567 (6)	−0.0506 (3)	0.0591 (19)
H63A	−0.1033	0.0965	−0.0857	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ti1	0.0333 (6)	0.0414 (7)	0.0279 (6)	−0.0025 (5)	0.0079 (5)	0.0036 (5)
B1	0.028 (4)	0.031 (4)	0.022 (3)	0.006 (3)	0.008 (3)	0.003 (3)
Cl1	0.0554 (10)	0.0465 (10)	0.0369 (9)	0.0053 (9)	0.0070 (8)	0.0039 (8)
Cl2	0.0340 (9)	0.0557 (10)	0.0401 (9)	−0.0015 (8)	0.0127 (7)	0.0058 (8)
S1	0.0457 (10)	0.0364 (9)	0.0323 (8)	−0.0010 (8)	0.0178 (8)	0.0005 (7)
S2	0.0353 (9)	0.0534 (11)	0.0355 (9)	−0.0071 (8)	0.0083 (7)	0.0110 (8)
S3	0.0476 (10)	0.0595 (11)	0.0292 (8)	0.0096 (9)	0.0055 (8)	0.0076 (8)
N11	0.034 (3)	0.029 (3)	0.024 (3)	0.003 (2)	0.010 (2)	0.005 (2)
N12	0.033 (3)	0.034 (3)	0.036 (3)	0.000 (2)	0.015 (2)	0.003 (3)
N21	0.030 (3)	0.037 (3)	0.028 (3)	0.004 (2)	0.010 (2)	0.005 (2)
N22	0.028 (3)	0.047 (3)	0.035 (3)	0.001 (3)	0.008 (2)	−0.003 (3)
N31	0.027 (3)	0.032 (3)	0.028 (3)	0.002 (2)	0.005 (2)	0.004 (2)
N32	0.036 (3)	0.034 (3)	0.031 (3)	0.000 (2)	0.009 (2)	−0.002 (3)
C11	0.023 (3)	0.033 (4)	0.035 (3)	0.002 (3)	0.010 (3)	0.005 (3)
C12	0.028 (3)	0.038 (4)	0.027 (3)	0.006 (3)	0.014 (3)	0.007 (3)
C13	0.027 (3)	0.046 (4)	0.040 (4)	0.007 (3)	0.016 (3)	0.015 (3)
C14	0.042 (4)	0.034 (4)	0.043 (4)	−0.003 (3)	0.012 (3)	0.000 (3)
C15	0.038 (4)	0.040 (4)	0.073 (4)	0.000 (3)	0.012 (3)	0.015 (3)
C16	0.051 (4)	0.036 (4)	0.063 (4)	−0.005 (3)	0.025 (3)	−0.004 (3)
C17	0.064 (5)	0.055 (4)	0.048 (4)	−0.023 (4)	−0.001 (4)	0.005 (4)
C21	0.027 (3)	0.043 (4)	0.034 (3)	−0.010 (3)	0.006 (3)	−0.004 (3)
C22	0.040 (4)	0.047 (4)	0.031 (3)	0.015 (3)	0.005 (3)	0.012 (3)
C23	0.040 (4)	0.059 (4)	0.039 (4)	0.012 (3)	0.006 (3)	0.008 (3)
C24	0.033 (4)	0.032 (4)	0.051 (4)	−0.003 (3)	0.019 (3)	−0.004 (3)
C25	0.049 (4)	0.049 (4)	0.053 (4)	0.006 (3)	0.023 (3)	0.000 (4)
C26	0.026 (4)	0.082 (5)	0.069 (4)	0.003 (4)	0.016 (3)	−0.011 (4)
C27	0.043 (4)	0.056 (4)	0.069 (4)	−0.005 (4)	0.031 (3)	0.005 (4)
C31	0.034 (3)	0.030 (4)	0.033 (3)	−0.003 (3)	0.014 (3)	0.004 (3)
C32	0.041 (4)	0.037 (4)	0.027 (3)	0.005 (3)	0.004 (3)	0.007 (3)
C33	0.056 (4)	0.034 (4)	0.039 (4)	0.006 (3)	0.006 (3)	0.009 (3)
C34	0.050 (4)	0.053 (4)	0.037 (4)	−0.014 (4)	0.015 (3)	−0.020 (3)
C35	0.057 (5)	0.074 (5)	0.046 (4)	−0.021 (4)	0.006 (4)	−0.014 (4)
C36	0.052 (4)	0.093 (5)	0.041 (4)	−0.014 (4)	0.025 (3)	−0.016 (4)
C37	0.096 (6)	0.051 (5)	0.051 (4)	0.011 (4)	0.008 (4)	−0.028 (4)
C41	0.035 (3)	0.050 (4)	0.0254 (16)	−0.005 (3)	0.006 (2)	−0.001 (2)
C42	0.035 (3)	0.050 (4)	0.0256 (16)	−0.005 (3)	0.005 (2)	−0.001 (2)
C43	0.035 (3)	0.050 (4)	0.0258 (16)	−0.005 (3)	0.005 (2)	0.000 (2)
C44	0.035 (3)	0.050 (4)	0.0257 (17)	−0.005 (3)	0.005 (2)	0.000 (2)
C45	0.035 (3)	0.050 (4)	0.0255 (16)	−0.005 (3)	0.005 (2)	0.000 (2)
C51	0.035 (3)	0.050 (4)	0.0254 (17)	−0.005 (3)	0.006 (2)	0.000 (2)
C52	0.035 (3)	0.050 (3)	0.0255 (16)	−0.005 (3)	0.005 (2)	0.000 (2)
C53	0.035 (3)	0.050 (4)	0.0259 (16)	−0.005 (3)	0.004 (2)	0.000 (2)
C54	0.035 (3)	0.049 (4)	0.0256 (16)	−0.005 (3)	0.005 (2)	−0.001 (2)
C55	0.035 (3)	0.050 (4)	0.0255 (16)	−0.005 (3)	0.006 (2)	−0.001 (2)
C61	0.051 (5)	0.067 (5)	0.058 (5)	−0.010 (4)	0.016 (4)	−0.002 (4)
C62	0.084 (6)	0.050 (4)	0.040 (4)	−0.010 (4)	0.027 (4)	0.007 (4)
C63	0.055 (5)	0.069 (5)	0.048 (5)	0.001 (4)	0.000 (4)	0.006 (4)

Geometric parameters (Å, º) top

Ti1—H1	2.2981	N31—C32	1.375 (6)
Ti1—C53	2.330 (12)	N31—C31	1.380 (5)
Ti1—Cl2	2.3386 (18)	N32—C31	1.362 (6)
Ti1—C45	2.345 (16)	N32—C33	1.378 (6)
Ti1—C54	2.344 (12)	N32—C34	1.491 (6)
Ti1—C44	2.350 (16)	C12—C13	1.345 (6)
Ti1—C43	2.372 (16)	C14—C15	1.516 (6)
Ti1—C52	2.371 (12)	C14—C17	1.530 (6)
Ti1—Cl1	2.379 (2)	C14—C16	1.537 (6)
Ti1—C55	2.379 (12)	C22—C23	1.352 (6)
Ti1—C51	2.392 (11)	C24—C27	1.494 (6)
Ti1—C41	2.410 (16)	C24—C25	1.520 (6)
Ti1—C42	2.421 (16)	C24—C26	1.521 (6)
Ti1—S2	2.4783 (19)	C32—C33	1.331 (6)
Ti1—S1	2.5589 (19)	C34—C37	1.497 (7)
B1—H1	1.0500	C34—C36	1.499 (7)
B1—N31	1.528 (6)	C34—C35	1.517 (7)
B1—N21	1.546 (6)	C41—C42	1.40 (2)
B1—N11	1.550 (6)	C41—C45	1.46 (2)
S1—C11	1.721 (5)	C42—C43	1.39 (2)
S2—C21	1.713 (5)	C43—C44	1.40 (2)
S3—C31	1.689 (5)	C44—C45	1.41 (2)
N11—C11	1.347 (6)	C51—C52	1.381 (16)
N11—C12	1.375 (5)	C51—C55	1.388 (16)
N12—C11	1.360 (6)	C52—C53	1.408 (17)
N12—C13	1.380 (6)	C53—C54	1.407 (18)
N12—C14	1.501 (6)	C54—C55	1.395 (16)
N21—C21	1.357 (5)	C61—C63ⁱ	1.351 (7)
N21—C22	1.385 (5)	C61—C62	1.395 (7)
N22—C21	1.364 (6)	C62—C63	1.381 (7)
N22—C23	1.387 (6)	C63—C61ⁱ	1.351 (7)
N22—C24	1.513 (6)

H1—Ti1—C53	157.9	C11—S1—Ti1	104.29 (17)
H1—Ti1—Cl2	76.0	C21—S2—Ti1	111.35 (18)
C53—Ti1—Cl2	84.9 (3)	C11—N11—C12	108.4 (4)
H1—Ti1—C45	147.7	C11—N11—B1	122.1 (4)
Cl2—Ti1—C45	130.8 (5)	C12—N11—B1	128.6 (4)
H1—Ti1—C54	150.0	C11—N12—C13	107.0 (4)
C53—Ti1—C54	35.0 (4)	C11—N12—C14	127.8 (4)
Cl2—Ti1—C54	85.6 (4)	C13—N12—C14	125.2 (4)
H1—Ti1—C44	156.2	C21—N21—C22	107.9 (4)
Cl2—Ti1—C44	95.8 (6)	C21—N21—B1	126.3 (4)
C45—Ti1—C44	35.1 (5)	C22—N21—B1	125.6 (4)
H1—Ti1—C43	154.0	C21—N22—C23	107.2 (4)
Cl2—Ti1—C43	79.2 (4)	C21—N22—C24	128.1 (4)
C45—Ti1—C43	57.9 (7)	C23—N22—C24	123.7 (5)
C44—Ti1—C43	34.5 (5)	C32—N31—C31	107.9 (4)
H1—Ti1—C52	152.5	C32—N31—B1	119.0 (4)
C53—Ti1—C52	34.9 (4)	C31—N31—B1	133.0 (4)
Cl2—Ti1—C52	116.6 (4)	C31—N32—C33	108.3 (4)
C54—Ti1—C52	57.5 (5)	C31—N32—C34	128.4 (5)
H1—Ti1—Cl1	78.7	C33—N32—C34	123.3 (5)
C53—Ti1—Cl1	90.0 (5)	N11—C11—N12	108.6 (4)
Cl2—Ti1—Cl1	88.68 (6)	N11—C11—S1	123.9 (4)
C45—Ti1—Cl1	83.8 (6)	N12—C11—S1	127.4 (4)
C54—Ti1—Cl1	125.0 (5)	C13—C12—N11	107.4 (5)
C44—Ti1—Cl1	78.8 (5)	C12—C13—N12	108.7 (5)
C43—Ti1—Cl1	108.4 (6)	N12—C14—C15	109.0 (4)
C52—Ti1—Cl1	77.3 (3)	N12—C14—C17	110.1 (4)
H1—Ti1—C55	142.7	C15—C14—C17	108.8 (4)
C53—Ti1—C55	57.1 (5)	N12—C14—C16	108.4 (4)
Cl2—Ti1—C55	117.4 (5)	C15—C14—C16	108.1 (4)
C54—Ti1—C55	34.4 (4)	C17—C14—C16	112.2 (5)
C52—Ti1—C55	56.1 (5)	N21—C21—N22	108.8 (4)
Cl1—Ti1—C55	132.7 (3)	N21—C21—S2	127.5 (4)
H1—Ti1—C51	143.2	N22—C21—S2	123.7 (4)
C53—Ti1—C51	57.4 (5)	C23—C22—N21	107.8 (5)
Cl2—Ti1—C51	140.6 (3)	C22—C23—N22	108.3 (5)
C54—Ti1—C51	57.3 (5)	C27—C24—N22	110.3 (4)
C52—Ti1—C51	33.7 (4)	C27—C24—C25	112.1 (5)
Cl1—Ti1—C51	101.2 (5)	N22—C24—C25	107.1 (4)
C55—Ti1—C51	33.8 (3)	C27—C24—C26	107.4 (5)
H1—Ti1—C41	143.0	N22—C24—C26	108.4 (4)
Cl2—Ti1—C41	132.3 (5)	C25—C24—C26	111.5 (4)
C45—Ti1—C41	35.7 (5)	N32—C31—N31	106.9 (4)
C44—Ti1—C41	57.5 (7)	N32—C31—S3	127.2 (4)
C43—Ti1—C41	56.2 (6)	N31—C31—S3	125.8 (4)
Cl1—Ti1—C41	118.7 (6)	C33—C32—N31	108.4 (5)
H1—Ti1—C42	145.6	C32—C33—N32	108.5 (5)
Cl2—Ti1—C42	99.2 (6)	N32—C34—C37	109.8 (5)
C45—Ti1—C42	58.1 (7)	N32—C34—C36	109.0 (4)
C44—Ti1—C42	57.1 (6)	C37—C34—C36	108.9 (5)
C43—Ti1—C42	33.7 (5)	N32—C34—C35	110.2 (5)
Cl1—Ti1—C42	135.7 (4)	C37—C34—C35	108.9 (5)
C41—Ti1—C42	33.7 (5)	C36—C34—C35	110.1 (5)
H1—Ti1—S2	70.8	C42—C41—C45	108.4 (14)
C53—Ti1—S2	127.9 (4)	C42—C41—Ti1	73.6 (8)
Cl2—Ti1—S2	146.73 (6)	C45—C41—Ti1	69.7 (8)
C45—Ti1—S2	81.3 (5)	C43—C42—C41	107.7 (15)
C54—Ti1—S2	123.6 (4)	C43—C42—Ti1	71.2 (8)
C44—Ti1—S2	115.3 (6)	C41—C42—Ti1	72.7 (8)
C43—Ti1—S2	133.4 (4)	C42—C43—C44	109.8 (16)
C52—Ti1—S2	94.3 (4)	C42—C43—Ti1	75.1 (8)
Cl1—Ti1—S2	86.25 (6)	C44—C43—Ti1	71.9 (9)
C55—Ti1—S2	89.3 (5)	C43—C44—C45	108.4 (16)
C51—Ti1—S2	72.5 (3)	C43—C44—Ti1	73.6 (8)
C41—Ti1—S2	77.8 (4)	C45—C44—Ti1	72.3 (8)
C42—Ti1—S2	107.3 (6)	C44—C45—C41	105.7 (15)
H1—Ti1—S1	72.6	C44—C45—Ti1	72.6 (8)
C53—Ti1—S1	117.5 (5)	C41—C45—Ti1	74.6 (9)
Cl2—Ti1—S1	85.93 (6)	C52—C51—C55	107.5 (11)
C45—Ti1—S1	120.4 (6)	C52—C51—Ti1	72.3 (6)
C54—Ti1—S1	82.7 (4)	C55—C51—Ti1	72.6 (6)
C44—Ti1—S1	129.8 (5)	C51—C52—C53	108.8 (12)
C43—Ti1—S1	98.3 (6)	C51—C52—Ti1	74.0 (6)
C52—Ti1—S1	129.9 (3)	C53—C52—Ti1	71.0 (6)
Cl1—Ti1—S1	151.26 (6)	C54—C53—C52	107.3 (11)
C55—Ti1—S1	73.9 (3)	C54—C53—Ti1	73.0 (6)
C51—Ti1—S1	100.8 (5)	C52—C53—Ti1	74.2 (6)
C41—Ti1—S1	84.9 (6)	C55—C54—C53	106.9 (11)
C42—Ti1—S1	73.0 (4)	C55—C54—Ti1	74.2 (6)
S2—Ti1—S1	82.99 (6)	C53—C54—Ti1	71.9 (6)
H1—B1—N31	105.9	C51—C55—C54	109.5 (11)
H1—B1—N21	105.9	C51—C55—Ti1	73.6 (6)
N31—B1—N21	115.4 (4)	C54—C55—Ti1	71.5 (6)
H1—B1—N11	105.9	C63ⁱ—C61—C62	119.2 (6)
N31—B1—N11	112.8 (4)	C63—C62—C61	120.3 (6)
N21—B1—N11	110.1 (4)	C61ⁱ—C63—C62	120.5 (6)

Symmetry code: (i) −x, −y, −z.

(III) [Bis(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ³S,S',H]dichlorido(η⁵-cyclopentadienyl)zirconium(IV) top

Crystal data top

[Zr(C₁₄H₂₄BN₄S₂)Cl₂(C₅H₅)]	F(000) = 1128
M_r = 550.51	D_x = 1.474 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 10.202 (3) Å	Cell parameters from 9905 reflections
b = 18.210 (6) Å	θ = 2.2–28.1°
c = 13.356 (4) Å	µ = 0.84 mm⁻¹
β = 90.814 (5)°	T = 150 K
V = 2481.1 (14) Å³	Plate, yellow
Z = 4	0.17 × 0.10 × 0.06 mm

Data collection top

Bruker APEXII CCD diffractometer	10542 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.072
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2014)	θ_max = 30.6°, θ_min = 1.5°
T_min = 0.650, T_max = 0.746	h = −14→14
40175 measured reflections	k = −26→26
15132 independent reflections	l = −19→19

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.056	w = 1/[σ²(F_o²) + (0.0535P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.129	(Δ/σ)_max = 0.001
S = 1.00	Δρ_max = 2.42 e Å⁻³
15132 reflections	Δρ_min = −0.57 e Å⁻³
542 parameters	Absolute structure: Refined as an inversion twin
2 restraints	Absolute structure parameter: −0.06 (6)

Special details top

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq
Zr1	−0.08463 (6)	0.03014 (3)	0.68589 (5)	0.02395 (15)
Zr2	0.61061 (7)	0.00823 (4)	0.19824 (5)	0.02781 (16)
B1	0.2225 (7)	0.0416 (4)	0.7126 (6)	0.0274 (17)
H11	0.2738	−0.0077	0.7245	0.033*
H12	0.131 (4)	0.003 (3)	0.723 (5)	0.033*
B2	0.2986 (8)	0.0107 (5)	0.1980 (6)	0.0284 (16)
H21	0.2526	0.0619	0.2062	0.034*
H22	0.408 (4)	0.033 (4)	0.204 (5)	0.034*
Cl1	−0.0641 (2)	−0.09353 (10)	0.76340 (14)	0.0393 (5)
Cl2	−0.0122 (2)	−0.02022 (11)	0.52511 (14)	0.0402 (4)
Cl11	0.5698 (2)	0.06303 (12)	0.03324 (15)	0.0474 (5)
Cl12	0.5977 (2)	0.13123 (10)	0.27860 (15)	0.0399 (5)
S1	−0.02925 (17)	0.09099 (10)	0.85954 (13)	0.0270 (4)
S2	0.01531 (16)	0.15579 (10)	0.61984 (13)	0.0265 (4)
S11	0.50360 (17)	−0.11164 (10)	0.11772 (13)	0.0283 (4)
S12	0.52529 (16)	−0.05079 (10)	0.36463 (13)	0.0286 (4)
N11	0.2272 (5)	0.0988 (3)	0.7983 (4)	0.0279 (13)
N12	0.1811 (6)	0.1774 (3)	0.9155 (4)	0.0343 (15)
N21	0.2432 (5)	0.0807 (3)	0.6116 (4)	0.0272 (13)
N22	0.2197 (5)	0.1552 (3)	0.4834 (4)	0.0245 (12)
N41	0.2841 (5)	−0.0285 (3)	0.0946 (4)	0.0246 (12)
N42	0.3061 (5)	−0.1071 (3)	−0.0280 (4)	0.0250 (12)
N51	0.2772 (5)	−0.0471 (3)	0.2808 (4)	0.0260 (13)
N52	0.2976 (6)	−0.1263 (3)	0.4035 (4)	0.0265 (13)
C11	0.1303 (7)	0.1232 (4)	0.8562 (5)	0.0264 (14)
C12	0.3392 (7)	0.1372 (5)	0.8216 (6)	0.043 (2)
H12A	0.4224	0.1301	0.7921	0.051*
C13	0.3120 (8)	0.1856 (6)	0.8921 (7)	0.051 (2)
H13A	0.3715	0.2197	0.9214	0.062*
C14	0.1081 (9)	0.2274 (4)	0.9856 (6)	0.041 (2)
C15	0.0061 (10)	0.2714 (5)	0.9248 (6)	0.050 (2)
H15A	−0.0391	0.3056	0.9692	0.075*
H15B	−0.0578	0.2376	0.8944	0.075*
H15C	0.0502	0.2990	0.8721	0.075*
C16	0.2058 (11)	0.2782 (5)	1.0371 (7)	0.060 (3)
H16A	0.1588	0.3130	1.0797	0.090*
H16B	0.2549	0.3054	0.9865	0.090*
H16C	0.2668	0.2492	1.0784	0.090*
C17	0.0426 (11)	0.1814 (5)	1.0685 (6)	0.053 (3)
H17A	0.0166	0.2137	1.1233	0.079*
H17B	0.1048	0.1446	1.0939	0.079*
H17C	−0.0351	0.1566	1.0407	0.079*
C21	0.1646 (6)	0.1307 (4)	0.5695 (5)	0.0227 (13)
C22	0.3522 (7)	0.0723 (4)	0.5496 (5)	0.0296 (15)
H22A	0.4240	0.0401	0.5616	0.035*
C23	0.3383 (6)	0.1173 (4)	0.4709 (5)	0.0285 (15)
H23A	0.3973	0.1226	0.4170	0.034*
C24	0.1667 (7)	0.2138 (4)	0.4138 (5)	0.0308 (16)
C25	0.2692 (8)	0.2278 (5)	0.3309 (6)	0.042 (2)
H25A	0.2352	0.2646	0.2838	0.063*
H25B	0.2860	0.1818	0.2950	0.063*
H25C	0.3510	0.2456	0.3616	0.063*
C26	0.0392 (7)	0.1869 (5)	0.3652 (6)	0.042 (2)
H26A	−0.0006	0.2267	0.3259	0.063*
H26B	−0.0214	0.1714	0.4174	0.063*
H26C	0.0578	0.1453	0.3212	0.063*
C27	0.1497 (8)	0.2842 (4)	0.4725 (6)	0.0378 (18)
H27A	0.1079	0.3213	0.4296	0.057*
H27B	0.2356	0.3020	0.4954	0.057*
H27C	0.0944	0.2748	0.5306	0.057*
C31	−0.3023 (8)	0.0546 (6)	0.7640 (7)	0.054 (3)
H31A	−0.3187	0.0588	0.8374	0.065*
C32	−0.2759 (7)	0.1137 (5)	0.6988 (7)	0.046 (2)
H32A	−0.2725	0.1668	0.7179	0.055*
C33	−0.2800 (7)	0.0860 (5)	0.6007 (6)	0.042 (2)
H33A	−0.2785	0.1162	0.5382	0.050*
C34	−0.3061 (7)	0.0108 (5)	0.6055 (6)	0.044 (2)
H34A	−0.3248	−0.0217	0.5467	0.053*
C35	−0.3198 (8)	−0.0091 (6)	0.7056 (8)	0.055 (3)
H35A	−0.3501	−0.0579	0.7305	0.066*
C41	0.3604 (7)	−0.0822 (4)	0.0588 (5)	0.0251 (14)
C42	0.1798 (7)	−0.0196 (4)	0.0288 (5)	0.0282 (15)
H42A	0.1103	0.0146	0.0360	0.034*
C43	0.1926 (7)	−0.0667 (4)	−0.0464 (5)	0.0291 (15)
H43A	0.1349	−0.0719	−0.1024	0.035*
C44	0.3573 (7)	−0.1671 (4)	−0.0948 (5)	0.0308 (16)
C45	0.4866 (8)	−0.1406 (5)	−0.1393 (6)	0.043 (2)
H45A	0.5205	−0.1782	−0.1847	0.065*
H45B	0.5506	−0.1317	−0.0853	0.065*
H45C	0.4714	−0.0950	−0.1766	0.065*
C46	0.2558 (8)	−0.1797 (5)	−0.1808 (5)	0.0369 (18)
H46A	0.2880	−0.2180	−0.2258	0.055*
H46B	0.2433	−0.1340	−0.2184	0.055*
H46C	0.1721	−0.1952	−0.1526	0.055*
C47	0.3710 (9)	−0.2378 (4)	−0.0355 (6)	0.043 (2)
H47A	0.3960	−0.2777	−0.0806	0.064*
H47B	0.2872	−0.2496	−0.0044	0.064*
H47C	0.4387	−0.2317	0.0166	0.064*
C51	0.3622 (6)	−0.0747 (4)	0.3495 (5)	0.0237 (14)
C52	0.1584 (6)	−0.0814 (4)	0.2922 (6)	0.0337 (17)
H52A	0.0816	−0.0723	0.2531	0.040*
C53	0.1685 (7)	−0.1291 (5)	0.3665 (6)	0.0372 (18)
H53A	0.1005	−0.1598	0.3905	0.045*
C54	0.3524 (7)	−0.1763 (4)	0.4836 (5)	0.0316 (16)
C55	0.4532 (9)	−0.2269 (4)	0.4342 (7)	0.043 (2)
H55A	0.4833	−0.2638	0.4827	0.065*
H55B	0.5280	−0.1977	0.4120	0.065*
H55C	0.4125	−0.2515	0.3764	0.065*
C56	0.4125 (9)	−0.1312 (4)	0.5684 (5)	0.040 (2)
H56A	0.4434	−0.1642	0.6217	0.060*
H56B	0.3463	−0.0978	0.5950	0.060*
H56C	0.4864	−0.1027	0.5431	0.060*
C57	0.2412 (9)	−0.2213 (5)	0.5280 (6)	0.044 (2)
H57A	0.2766	−0.2541	0.5799	0.066*
H57B	0.1990	−0.2506	0.4751	0.066*
H57C	0.1766	−0.1882	0.5575	0.066*
C61	0.8455 (9)	0.0234 (7)	0.1557 (13)	0.090 (5)
H61A	0.8828	0.0628	0.1124	0.108*
C62	0.8129 (8)	−0.0471 (6)	0.1254 (6)	0.048 (2)
H62A	0.8206	−0.0666	0.0558	0.057*
C63	0.7871 (7)	−0.0879 (5)	0.2082 (7)	0.042 (2)
H63A	0.7724	−0.1422	0.2092	0.050*
C64	0.8062 (9)	−0.0442 (9)	0.2909 (8)	0.082 (5)
H64A	0.8071	−0.0614	0.3620	0.098*
C65	0.8405 (9)	0.0243 (9)	0.2594 (14)	0.109 (7)
H65A	0.8728	0.0651	0.3035	0.130*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.0222 (3)	0.0271 (3)	0.0224 (3)	−0.0024 (3)	−0.0053 (2)	0.0024 (3)
Zr2	0.0257 (3)	0.0307 (4)	0.0271 (3)	−0.0065 (3)	0.0041 (3)	−0.0064 (3)
B1	0.021 (4)	0.024 (4)	0.037 (4)	0.007 (3)	0.000 (3)	0.000 (3)
B2	0.032 (4)	0.027 (4)	0.026 (4)	−0.003 (3)	−0.006 (3)	0.002 (3)
Cl1	0.0457 (11)	0.0295 (10)	0.0423 (11)	−0.0107 (8)	−0.0177 (9)	0.0065 (8)
Cl2	0.0489 (12)	0.0429 (11)	0.0286 (9)	0.0018 (9)	−0.0061 (8)	−0.0103 (8)
Cl11	0.0714 (15)	0.0394 (11)	0.0317 (10)	−0.0050 (10)	0.0129 (10)	0.0029 (8)
Cl12	0.0446 (11)	0.0338 (10)	0.0416 (11)	−0.0123 (8)	0.0134 (9)	−0.0126 (8)
S1	0.0254 (8)	0.0325 (10)	0.0232 (8)	−0.0027 (7)	0.0013 (7)	−0.0012 (7)
S2	0.0233 (8)	0.0287 (9)	0.0275 (9)	0.0051 (7)	0.0049 (7)	0.0042 (7)
S11	0.0254 (9)	0.0283 (9)	0.0310 (9)	0.0023 (7)	−0.0085 (7)	−0.0055 (7)
S12	0.0205 (8)	0.0394 (10)	0.0258 (9)	−0.0047 (7)	−0.0035 (6)	0.0002 (7)
N11	0.022 (3)	0.031 (3)	0.030 (3)	0.004 (2)	−0.005 (2)	0.000 (3)
N12	0.042 (4)	0.037 (4)	0.024 (3)	−0.011 (3)	0.002 (3)	−0.004 (3)
N21	0.024 (3)	0.028 (3)	0.030 (3)	0.005 (2)	0.003 (2)	−0.001 (2)
N22	0.024 (3)	0.025 (3)	0.025 (3)	0.000 (2)	0.003 (2)	0.001 (2)
N41	0.022 (3)	0.026 (3)	0.026 (3)	0.000 (2)	−0.002 (2)	−0.002 (2)
N42	0.027 (3)	0.027 (3)	0.021 (3)	0.002 (2)	−0.007 (2)	−0.004 (2)
N51	0.020 (3)	0.034 (3)	0.024 (3)	−0.002 (2)	0.002 (2)	0.000 (3)
N52	0.024 (3)	0.033 (3)	0.022 (3)	−0.003 (2)	−0.002 (2)	0.001 (2)
C11	0.031 (4)	0.026 (4)	0.022 (3)	0.001 (3)	−0.007 (3)	0.004 (3)
C12	0.023 (4)	0.066 (6)	0.039 (4)	−0.010 (4)	−0.006 (3)	−0.002 (4)
C13	0.034 (5)	0.071 (6)	0.049 (5)	−0.028 (4)	−0.006 (4)	−0.018 (5)
C14	0.063 (6)	0.031 (4)	0.030 (4)	−0.014 (4)	0.013 (4)	−0.006 (3)
C15	0.079 (7)	0.029 (4)	0.043 (5)	−0.001 (4)	0.017 (5)	0.002 (4)
C16	0.101 (8)	0.045 (5)	0.034 (5)	−0.029 (5)	0.003 (5)	−0.012 (4)
C17	0.091 (8)	0.037 (5)	0.031 (4)	−0.011 (5)	0.021 (5)	−0.006 (4)
C21	0.021 (3)	0.024 (3)	0.023 (3)	−0.004 (3)	0.004 (3)	−0.002 (3)
C22	0.019 (3)	0.031 (4)	0.038 (4)	0.004 (3)	0.007 (3)	−0.001 (3)
C23	0.021 (3)	0.029 (4)	0.036 (4)	−0.004 (3)	0.009 (3)	−0.002 (3)
C24	0.025 (4)	0.039 (4)	0.029 (4)	0.002 (3)	0.002 (3)	0.005 (3)
C25	0.034 (4)	0.050 (5)	0.041 (5)	0.003 (4)	0.005 (4)	0.018 (4)
C26	0.027 (4)	0.066 (6)	0.033 (4)	−0.003 (4)	0.001 (3)	0.006 (4)
C27	0.039 (5)	0.028 (4)	0.046 (5)	0.003 (3)	−0.003 (4)	0.009 (3)
C31	0.022 (4)	0.104 (9)	0.037 (5)	0.017 (4)	0.005 (3)	0.006 (5)
C32	0.021 (4)	0.055 (6)	0.062 (6)	0.012 (4)	−0.005 (4)	−0.010 (5)
C33	0.019 (4)	0.057 (6)	0.048 (5)	0.000 (4)	−0.007 (3)	0.015 (4)
C34	0.025 (4)	0.059 (6)	0.048 (5)	−0.011 (4)	−0.016 (3)	−0.007 (4)
C35	0.019 (4)	0.071 (7)	0.074 (7)	−0.011 (4)	−0.008 (4)	0.025 (5)
C41	0.027 (4)	0.026 (4)	0.022 (3)	−0.002 (3)	−0.003 (3)	0.001 (3)
C42	0.028 (4)	0.029 (4)	0.028 (3)	0.003 (3)	−0.006 (3)	0.000 (3)
C43	0.030 (4)	0.029 (4)	0.029 (4)	0.000 (3)	−0.005 (3)	0.005 (3)
C44	0.028 (4)	0.035 (4)	0.030 (4)	0.000 (3)	−0.007 (3)	−0.005 (3)
C45	0.044 (5)	0.056 (5)	0.031 (4)	0.006 (4)	0.005 (4)	−0.006 (4)
C46	0.043 (5)	0.040 (4)	0.027 (4)	−0.002 (4)	−0.009 (3)	−0.005 (3)
C47	0.049 (5)	0.027 (4)	0.052 (5)	0.005 (4)	−0.018 (4)	−0.002 (4)
C51	0.021 (3)	0.030 (4)	0.020 (3)	−0.001 (3)	−0.004 (3)	−0.005 (3)
C52	0.012 (3)	0.049 (5)	0.041 (4)	0.000 (3)	0.001 (3)	0.001 (4)
C53	0.022 (4)	0.054 (5)	0.036 (4)	−0.011 (3)	0.001 (3)	0.005 (4)
C54	0.032 (4)	0.031 (4)	0.032 (4)	−0.006 (3)	−0.008 (3)	0.003 (3)
C55	0.048 (5)	0.027 (4)	0.055 (5)	0.001 (4)	−0.013 (4)	−0.003 (4)
C56	0.059 (5)	0.039 (5)	0.022 (4)	−0.013 (4)	−0.005 (4)	0.005 (3)
C57	0.055 (6)	0.035 (5)	0.042 (5)	−0.015 (4)	−0.005 (4)	0.004 (4)
C61	0.038 (5)	0.051 (7)	0.183 (14)	−0.006 (5)	0.053 (7)	0.026 (8)
C62	0.040 (5)	0.073 (7)	0.030 (4)	0.012 (4)	0.008 (4)	−0.004 (4)
C63	0.024 (4)	0.046 (5)	0.055 (5)	−0.001 (3)	−0.003 (4)	0.012 (4)
C64	0.019 (4)	0.181 (15)	0.045 (6)	0.024 (7)	−0.013 (4)	−0.033 (8)
C65	0.016 (4)	0.106 (11)	0.203 (17)	−0.003 (6)	−0.002 (7)	−0.113 (12)

Geometric parameters (Å, º) top

Zr1—H12	2.30 (5)	N22—C23	1.406 (9)
Zr1—Cl2	2.458 (2)	N22—C24	1.511 (9)
Zr1—C32	2.483 (8)	N41—C41	1.342 (9)
Zr1—Cl1	2.486 (2)	N41—C42	1.380 (8)
Zr1—C33	2.498 (7)	N42—C41	1.356 (8)
Zr1—C31	2.507 (8)	N42—C43	1.391 (9)
Zr1—C34	2.513 (7)	N42—C44	1.508 (9)
Zr1—C35	2.521 (8)	N51—C51	1.350 (8)
Zr1—S1	2.6247 (19)	N51—C52	1.374 (9)
Zr1—S2	2.661 (2)	N52—C51	1.361 (9)
Zr1—B1	3.155 (8)	N52—C53	1.401 (9)
Zr2—H22	2.12 (4)	N52—C54	1.506 (9)
Zr2—Cl11	2.449 (2)	C12—C13	1.322 (12)
Zr2—C61	2.486 (9)	C14—C16	1.518 (12)
Zr2—Cl12	2.488 (2)	C14—C15	1.536 (13)
Zr2—C65	2.490 (9)	C14—C17	1.548 (11)
Zr2—C62	2.505 (8)	C22—C23	1.338 (10)
Zr2—C63	2.513 (8)	C24—C27	1.513 (11)
Zr2—C64	2.521 (10)	C24—C26	1.526 (10)
Zr2—S12	2.6281 (19)	C24—C25	1.555 (10)
Zr2—S11	2.6608 (19)	C31—C35	1.408 (14)
Zr2—B2	3.183 (8)	C31—C32	1.412 (13)
B1—N21	1.542 (10)	C32—C33	1.403 (12)
B1—N11	1.547 (10)	C33—C34	1.397 (13)
B2—N51	1.544 (10)	C34—C35	1.394 (12)
B2—N41	1.560 (10)	C42—C43	1.329 (10)
S1—C11	1.732 (7)	C44—C47	1.516 (11)
S2—C21	1.735 (6)	C44—C45	1.533 (11)
S11—C41	1.734 (7)	C44—C46	1.553 (10)
S12—C51	1.729 (7)	C52—C53	1.322 (11)
N11—C11	1.340 (9)	C54—C56	1.521 (10)
N11—C12	1.372 (9)	C54—C57	1.526 (11)
N12—C11	1.363 (9)	C54—C55	1.536 (11)
N12—C13	1.383 (10)	C61—C62	1.385 (16)
N12—C14	1.509 (10)	C61—C65	1.39 (2)
N21—C21	1.332 (8)	C62—C63	1.361 (12)
N21—C22	1.404 (8)	C63—C64	1.374 (14)
N22—C21	1.362 (8)	C64—C65	1.36 (2)

H12—Zr1—Cl2	78.9 (16)	S11—Zr2—B2	66.84 (16)
H12—Zr1—C32	150.2 (14)	N21—B1—N11	109.5 (6)
Cl2—Zr1—C32	122.4 (2)	N21—B1—Zr1	94.6 (4)
H12—Zr1—Cl1	68.9 (12)	N11—B1—Zr1	98.5 (4)
Cl2—Zr1—Cl1	90.07 (7)	N51—B2—N41	108.1 (6)
C32—Zr1—Cl1	126.0 (2)	N51—B2—Zr2	98.1 (4)
H12—Zr1—C33	160.0 (14)	N41—B2—Zr2	94.4 (4)
Cl2—Zr1—C33	90.1 (2)	C11—S1—Zr1	108.1 (2)
C32—Zr1—C33	32.7 (3)	C21—S2—Zr1	104.2 (2)
Cl1—Zr1—C33	128.4 (2)	C41—S11—Zr2	105.5 (2)
H12—Zr1—C31	143.0 (16)	C51—S12—Zr2	109.5 (2)
Cl2—Zr1—C31	135.1 (2)	C11—N11—C12	108.6 (6)
C32—Zr1—C31	32.9 (3)	C11—N11—B1	129.4 (6)
Cl1—Zr1—C31	93.3 (3)	C12—N11—B1	121.9 (6)
C33—Zr1—C31	53.9 (3)	C11—N12—C13	107.9 (6)
H12—Zr1—C34	155.8 (14)	C11—N12—C14	127.6 (6)
Cl2—Zr1—C34	81.6 (2)	C13—N12—C14	124.2 (6)
C32—Zr1—C34	54.0 (3)	C21—N21—C22	107.6 (6)
Cl1—Zr1—C34	96.9 (2)	C21—N21—B1	126.5 (5)
C33—Zr1—C34	32.4 (3)	C22—N21—B1	125.8 (6)
C31—Zr1—C34	53.5 (3)	C21—N22—C23	107.8 (5)
H12—Zr1—C35	145.5 (12)	C21—N22—C24	127.1 (6)
Cl2—Zr1—C35	106.5 (3)	C23—N22—C24	125.1 (5)
C32—Zr1—C35	54.3 (3)	C41—N41—C42	107.7 (6)
Cl1—Zr1—C35	76.9 (2)	C41—N41—B2	126.9 (6)
C33—Zr1—C35	53.7 (3)	C42—N41—B2	125.0 (6)
C31—Zr1—C35	32.5 (3)	C41—N42—C43	107.6 (6)
C34—Zr1—C35	32.2 (3)	C41—N42—C44	127.4 (6)
H12—Zr1—S1	73.1 (16)	C43—N42—C44	125.0 (5)
Cl2—Zr1—S1	149.97 (7)	C51—N51—C52	108.3 (6)
C32—Zr1—S1	80.8 (2)	C51—N51—B2	130.1 (6)
Cl1—Zr1—S1	89.93 (6)	C52—N51—B2	121.6 (6)
C33—Zr1—S1	113.0 (2)	C51—N52—C53	107.3 (6)
C31—Zr1—S1	74.8 (2)	C51—N52—C54	128.1 (6)
C34—Zr1—S1	128.1 (2)	C53—N52—C54	124.5 (6)
C35—Zr1—S1	102.7 (3)	N11—C11—N12	107.4 (6)
H12—Zr1—S2	83.5 (12)	N11—C11—S1	127.1 (5)
Cl2—Zr1—S2	84.83 (7)	N12—C11—S1	125.5 (5)
C32—Zr1—S2	78.5 (2)	C13—C12—N11	108.6 (7)
Cl1—Zr1—S2	152.47 (6)	C12—C13—N12	107.6 (7)
C33—Zr1—S2	78.8 (2)	N12—C14—C16	108.8 (7)
C31—Zr1—S2	109.3 (3)	N12—C14—C15	108.9 (6)
C34—Zr1—S2	109.0 (2)	C16—C14—C15	110.9 (7)
C35—Zr1—S2	130.4 (2)	N12—C14—C17	109.8 (6)
S1—Zr1—S2	81.44 (6)	C16—C14—C17	107.0 (7)
H12—Zr1—B1	17.4 (12)	C15—C14—C17	111.4 (8)
Cl2—Zr1—B1	79.23 (15)	N21—C21—N22	109.1 (5)
C32—Zr1—B1	137.0 (3)	N21—C21—S2	122.9 (5)
Cl1—Zr1—B1	86.31 (15)	N22—C21—S2	128.0 (5)
C33—Zr1—B1	144.0 (2)	C23—C22—N21	108.7 (6)
C31—Zr1—B1	145.6 (3)	C22—C23—N22	106.8 (6)
C34—Zr1—B1	160.6 (2)	N22—C24—C27	108.8 (6)
C35—Zr1—B1	162.2 (3)	N22—C24—C26	109.2 (6)
S1—Zr1—B1	70.81 (15)	C27—C24—C26	112.9 (7)
S2—Zr1—B1	66.16 (15)	N22—C24—C25	108.4 (6)
H22—Zr2—Cl11	78.1 (18)	C27—C24—C25	108.3 (6)
H22—Zr2—C61	158.4 (18)	C26—C24—C25	109.1 (6)
Cl11—Zr2—C61	84.3 (4)	C35—C31—C32	108.1 (8)
H22—Zr2—Cl12	74.8 (16)	C35—C31—Zr1	74.3 (5)
Cl11—Zr2—Cl12	90.69 (8)	C32—C31—Zr1	72.6 (4)
C61—Zr2—Cl12	93.2 (3)	C33—C32—C31	107.4 (8)
H22—Zr2—C65	151.5 (17)	C33—C32—Zr1	74.2 (5)
Cl11—Zr2—C65	113.2 (5)	C31—C32—Zr1	74.5 (5)
C61—Zr2—C65	32.4 (5)	C34—C33—C32	108.2 (8)
Cl12—Zr2—C65	78.9 (3)	C34—C33—Zr1	74.4 (5)
H22—Zr2—C62	155.4 (17)	C32—C33—Zr1	73.0 (4)
Cl11—Zr2—C62	86.8 (2)	C35—C34—C33	108.7 (8)
C61—Zr2—C62	32.2 (4)	C35—C34—Zr1	74.2 (4)
Cl12—Zr2—C62	125.3 (2)	C33—C34—Zr1	73.2 (4)
C65—Zr2—C62	52.9 (3)	C34—C35—C31	107.6 (8)
H22—Zr2—C63	147.6 (17)	C34—C35—Zr1	73.6 (4)
Cl11—Zr2—C63	116.3 (2)	C31—C35—Zr1	73.2 (5)
C61—Zr2—C63	52.9 (3)	N41—C41—N42	108.4 (6)
Cl12—Zr2—C63	130.3 (2)	N41—C41—S11	123.6 (5)
C65—Zr2—C63	52.7 (4)	N42—C41—S11	128.0 (5)
C62—Zr2—C63	31.5 (3)	C43—C42—N41	108.8 (6)
H22—Zr2—C64	146.0 (18)	C42—C43—N42	107.4 (6)
Cl11—Zr2—C64	136.0 (3)	N42—C44—C47	109.7 (6)
C61—Zr2—C64	52.8 (4)	N42—C44—C45	108.0 (6)
Cl12—Zr2—C64	100.1 (3)	C47—C44—C45	113.3 (7)
C65—Zr2—C64	31.6 (5)	N42—C44—C46	108.2 (6)
C62—Zr2—C64	52.2 (3)	C47—C44—C46	108.4 (6)
C63—Zr2—C64	31.7 (3)	C45—C44—C46	109.1 (6)
H22—Zr2—S12	73.8 (18)	N51—C51—N52	107.9 (6)
Cl11—Zr2—S12	150.85 (7)	N51—C51—S12	126.4 (5)
C61—Zr2—S12	124.8 (4)	N52—C51—S12	125.7 (5)
Cl12—Zr2—S12	89.04 (7)	C53—C52—N51	108.8 (6)
C65—Zr2—S12	95.3 (5)	C52—C53—N52	107.7 (6)
C62—Zr2—S12	116.6 (2)	N52—C54—C56	110.1 (6)
C63—Zr2—S12	85.19 (19)	N52—C54—C57	109.3 (6)
C64—Zr2—S12	72.5 (3)	C56—C54—C57	107.1 (6)
H22—Zr2—S11	78.0 (16)	N52—C54—C55	107.6 (6)
Cl11—Zr2—S11	84.67 (7)	C56—C54—C55	112.2 (7)
C61—Zr2—S11	113.0 (3)	C57—C54—C55	110.5 (7)
Cl12—Zr2—S11	152.76 (7)	C62—C61—C65	106.9 (10)
C65—Zr2—S11	127.5 (3)	C62—C61—Zr2	74.7 (5)
C62—Zr2—S11	81.3 (2)	C65—C61—Zr2	74.0 (5)
C63—Zr2—S11	74.9 (2)	C63—C62—C61	108.5 (9)
C64—Zr2—S11	101.8 (4)	C63—C62—Zr2	74.6 (5)
S12—Zr2—S11	82.38 (6)	C61—C62—Zr2	73.1 (5)
H22—Zr2—B2	11.6 (16)	C62—C63—C64	108.0 (10)
Cl11—Zr2—B2	80.57 (15)	C62—C63—Zr2	73.9 (5)
C61—Zr2—B2	164.8 (4)	C64—C63—Zr2	74.5 (6)
Cl12—Zr2—B2	85.92 (16)	C65—C64—C63	108.4 (11)
C65—Zr2—B2	159.4 (4)	C65—C64—Zr2	73.0 (7)
C62—Zr2—B2	146.6 (3)	C63—C64—Zr2	73.8 (5)
C63—Zr2—B2	136.5 (2)	C64—C65—C61	108.1 (10)
C64—Zr2—B2	142.2 (3)	C64—C65—Zr2	75.5 (6)
S12—Zr2—B2	70.34 (14)	C61—C65—Zr2	73.6 (6)

(IV) (1-tert-butyl-2,3-dihydro-1H-imidazole-2-thione-κS)(1-tert-butyl-2-sulfanylidene-1H-imidazol-3-ido-κ²N³,S)dichlorido(η⁵-cyclopentadienyl)zirconium(IV) benzene monosolvate top

Crystal data top

[Zr(C₇H₁₁N₂S)Cl₂(C₇H₁₂N₂S)(C₅H₅)]·C₆H₆	Z = 2
M_r = 616.80	F(000) = 636
Triclinic, P1	D_x = 1.448 Mg m⁻³
a = 10.5741 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.7222 (17) Å	Cell parameters from 6838 reflections
c = 14.246 (4) Å	θ = 2.2–30.5°
α = 93.930 (3)°	µ = 0.75 mm⁻¹
β = 92.094 (3)°	T = 125 K
γ = 118.274 (2)°	Block, yellow
V = 1414.7 (5) Å³	0.11 × 0.04 × 0.03 mm

Data collection top

Bruker APEXII CCD diffractometer	5590 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.071
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2014)	θ_max = 30.5°, θ_min = 1.4°
T_min = 0.656, T_max = 0.746	h = −15→15
22462 measured reflections	k = −15→15
8562 independent reflections	l = −20→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.033P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
8562 reflections	Δρ_max = 1.17 e Å⁻³
311 parameters	Δρ_min = −0.71 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Zr1	0.13605 (3)	1.02868 (3)	0.23071 (2)	0.01617 (8)
Cl1	0.13487 (8)	1.13751 (8)	0.39467 (5)	0.02213 (16)
Cl2	0.31344 (8)	0.96925 (9)	0.30943 (6)	0.02681 (18)
S1	−0.11218 (8)	1.03204 (8)	0.18949 (5)	0.02070 (17)
S2	0.05183 (8)	0.80308 (8)	0.11107 (5)	0.02182 (17)
N11	−0.2012 (3)	0.9872 (3)	0.36682 (18)	0.0229 (6)
H11	−0.118 (4)	1.048 (4)	0.386 (3)	0.043 (12)*
N12	−0.3750 (2)	0.8575 (3)	0.26191 (17)	0.0187 (5)
N21	−0.0258 (3)	0.8176 (3)	0.28178 (16)	0.0176 (5)
N22	−0.1150 (3)	0.5902 (3)	0.22980 (17)	0.0186 (5)
C11	−0.2329 (3)	0.9533 (3)	0.2732 (2)	0.0191 (6)
C12	−0.3205 (3)	0.9162 (4)	0.4151 (2)	0.0259 (7)
H12A	−0.3253	0.9223	0.4816	0.031*
C13	−0.4291 (3)	0.8364 (3)	0.3501 (2)	0.0225 (7)
H13A	−0.5263	0.7759	0.3622	0.027*
C14	−0.4618 (3)	0.7808 (3)	0.1701 (2)	0.0201 (6)
C15	−0.4678 (3)	0.8910 (3)	0.1087 (2)	0.0243 (7)
H15A	−0.5238	0.8425	0.0488	0.037*
H15B	−0.5135	0.9401	0.1420	0.037*
H15C	−0.3698	0.9604	0.0962	0.037*
C16	−0.3920 (3)	0.6983 (3)	0.1235 (2)	0.0269 (7)
H16A	−0.4468	0.6476	0.0636	0.040*
H16B	−0.2927	0.7648	0.1115	0.040*
H16C	−0.3917	0.6297	0.1654	0.040*
C17	−0.6145 (3)	0.6756 (3)	0.1905 (2)	0.0279 (7)
H17A	−0.6711	0.6255	0.1310	0.042*
H17B	−0.6117	0.6065	0.2310	0.042*
H17C	−0.6590	0.7270	0.2226	0.042*
C21	−0.0362 (3)	0.7269 (3)	0.2092 (2)	0.0173 (6)
C22	−0.1000 (3)	0.7373 (3)	0.3522 (2)	0.0206 (6)
H22A	−0.1105	0.7735	0.4124	0.025*
C23	−0.1556 (3)	0.5976 (3)	0.3208 (2)	0.0212 (6)
H23A	−0.2120	0.5190	0.3549	0.025*
C24	−0.1450 (3)	0.4570 (3)	0.1692 (2)	0.0202 (6)
C25	−0.0021 (3)	0.4647 (4)	0.1465 (3)	0.0300 (8)
H25A	−0.0202	0.3785	0.1071	0.045*
H25B	0.0527	0.5483	0.1126	0.045*
H25C	0.0532	0.4722	0.2054	0.045*
C26	−0.2344 (3)	0.4467 (4)	0.0793 (2)	0.0293 (8)
H26A	−0.2549	0.3604	0.0391	0.044*
H26B	−0.3252	0.4428	0.0961	0.044*
H26C	−0.1805	0.5303	0.0453	0.044*
C27	−0.2288 (3)	0.3289 (3)	0.2226 (2)	0.0286 (8)
H27A	−0.2485	0.2420	0.1833	0.043*
H27B	−0.1722	0.3367	0.2808	0.043*
H27C	−0.3200	0.3250	0.2383	0.043*
C31	0.2437 (4)	1.1237 (4)	0.0789 (2)	0.0374 (9)
H31A	0.2277	1.0651	0.0176	0.045*
C32	0.3595 (4)	1.1664 (4)	0.1453 (3)	0.0324 (8)
H32A	0.4412	1.1446	0.1397	0.039*
C33	0.3532 (3)	1.2647 (4)	0.2138 (2)	0.0318 (8)
H33A	0.4299	1.3248	0.2649	0.038*
C34	0.2326 (4)	1.2793 (4)	0.1881 (3)	0.0335 (8)
H34A	0.2088	1.3520	0.2179	0.040*
C35	0.1668 (4)	1.1941 (4)	0.1053 (2)	0.0360 (9)
H35A	0.0867	1.1943	0.0659	0.043*
C41	−0.1588 (4)	0.4036 (4)	0.5645 (3)	0.0376 (9)
H41A	−0.0714	0.4255	0.5996	0.045*
C42	−0.2317 (4)	0.2769 (4)	0.5098 (3)	0.0379 (9)
H42A	−0.1940	0.2121	0.5060	0.045*
C43	−0.3598 (4)	0.2431 (4)	0.4603 (2)	0.0362 (9)
H43A	−0.4112	0.1545	0.4228	0.043*
C44	−0.4131 (4)	0.3381 (4)	0.4652 (2)	0.0375 (9)
H44A	−0.5015	0.3153	0.4312	0.045*
C45	−0.3368 (4)	0.4678 (4)	0.5203 (3)	0.0366 (9)
H45A	−0.3727	0.5341	0.5237	0.044*
C46	−0.2101 (4)	0.4995 (4)	0.5694 (2)	0.0327 (8)
H46A	−0.1577	0.5879	0.6069	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.01380 (14)	0.01805 (15)	0.01473 (14)	0.00624 (12)	−0.00021 (10)	0.00083 (11)
Cl1	0.0210 (4)	0.0243 (4)	0.0188 (4)	0.0100 (3)	−0.0021 (3)	−0.0042 (3)
Cl2	0.0250 (4)	0.0340 (5)	0.0260 (4)	0.0181 (4)	−0.0024 (3)	0.0026 (3)
S1	0.0157 (4)	0.0259 (4)	0.0204 (4)	0.0096 (3)	0.0021 (3)	0.0051 (3)
S2	0.0262 (4)	0.0209 (4)	0.0155 (4)	0.0090 (3)	0.0037 (3)	0.0007 (3)
N11	0.0184 (14)	0.0291 (16)	0.0184 (13)	0.0095 (12)	0.0015 (11)	−0.0007 (12)
N12	0.0143 (12)	0.0235 (14)	0.0178 (12)	0.0085 (11)	0.0021 (10)	0.0018 (11)
N21	0.0201 (12)	0.0176 (13)	0.0137 (12)	0.0081 (11)	0.0005 (10)	0.0002 (10)
N22	0.0173 (12)	0.0178 (13)	0.0187 (13)	0.0073 (11)	−0.0003 (10)	−0.0013 (10)
C11	0.0155 (14)	0.0240 (16)	0.0188 (15)	0.0100 (13)	0.0007 (12)	0.0035 (13)
C12	0.0244 (17)	0.037 (2)	0.0191 (16)	0.0165 (15)	0.0042 (13)	0.0022 (14)
C13	0.0222 (16)	0.0295 (18)	0.0182 (15)	0.0137 (14)	0.0057 (12)	0.0055 (13)
C14	0.0153 (14)	0.0229 (16)	0.0183 (15)	0.0060 (13)	0.0018 (12)	0.0024 (13)
C15	0.0193 (15)	0.0306 (18)	0.0221 (16)	0.0111 (14)	0.0001 (13)	0.0040 (14)
C16	0.0269 (17)	0.0238 (17)	0.0278 (17)	0.0106 (14)	0.0042 (14)	−0.0016 (14)
C17	0.0201 (16)	0.0261 (18)	0.0280 (18)	0.0037 (14)	0.0008 (13)	0.0006 (14)
C21	0.0190 (14)	0.0173 (15)	0.0155 (14)	0.0090 (12)	−0.0012 (11)	−0.0005 (12)
C22	0.0214 (15)	0.0228 (16)	0.0176 (15)	0.0104 (13)	0.0049 (12)	0.0025 (13)
C23	0.0200 (15)	0.0233 (17)	0.0213 (16)	0.0109 (13)	0.0033 (12)	0.0031 (13)
C24	0.0173 (15)	0.0165 (15)	0.0242 (16)	0.0066 (12)	−0.0007 (12)	−0.0025 (12)
C25	0.0239 (17)	0.0243 (18)	0.042 (2)	0.0122 (15)	0.0035 (15)	−0.0023 (15)
C26	0.0258 (17)	0.0229 (17)	0.0332 (19)	0.0084 (14)	−0.0055 (14)	−0.0052 (14)
C27	0.0254 (17)	0.0183 (17)	0.039 (2)	0.0079 (14)	0.0034 (15)	0.0011 (15)
C31	0.038 (2)	0.031 (2)	0.0228 (18)	−0.0006 (17)	0.0118 (16)	0.0026 (15)
C32	0.0235 (17)	0.031 (2)	0.050 (2)	0.0161 (16)	0.0194 (16)	0.0178 (17)
C33	0.0227 (17)	0.0290 (19)	0.0274 (18)	−0.0008 (15)	−0.0063 (14)	0.0068 (15)
C34	0.037 (2)	0.0218 (18)	0.047 (2)	0.0156 (16)	0.0186 (17)	0.0164 (16)
C35	0.0199 (17)	0.048 (2)	0.031 (2)	0.0057 (16)	0.0027 (15)	0.0281 (18)
C41	0.034 (2)	0.044 (2)	0.038 (2)	0.0225 (18)	−0.0025 (17)	0.0006 (18)
C42	0.043 (2)	0.035 (2)	0.040 (2)	0.0221 (19)	0.0077 (18)	0.0014 (18)
C43	0.032 (2)	0.034 (2)	0.0253 (18)	0.0017 (17)	0.0071 (15)	−0.0002 (16)
C44	0.0228 (17)	0.060 (3)	0.0238 (18)	0.0135 (18)	0.0054 (14)	0.0175 (18)
C45	0.038 (2)	0.046 (2)	0.037 (2)	0.0268 (19)	0.0141 (17)	0.0178 (19)
C46	0.035 (2)	0.032 (2)	0.0284 (19)	0.0134 (17)	0.0051 (15)	0.0042 (15)

Geometric parameters (Å, º) top

Zr1—N21	2.287 (2)	N22—C21	1.360 (4)
Zr1—Cl2	2.5017 (8)	N22—C23	1.388 (4)
Zr1—C34	2.510 (3)	N22—C24	1.506 (4)
Zr1—C33	2.520 (3)	C12—C13	1.339 (4)
Zr1—C35	2.525 (3)	C14—C17	1.523 (4)
Zr1—C31	2.528 (3)	C14—C16	1.531 (4)
Zr1—C32	2.529 (3)	C14—C15	1.541 (4)
Zr1—Cl1	2.5417 (9)	C22—C23	1.358 (4)
Zr1—S2	2.6139 (9)	C24—C27	1.513 (4)
Zr1—S1	2.6862 (9)	C24—C25	1.522 (4)
Zr1—C21	2.849 (3)	C24—C26	1.528 (4)
Cl1—H11	2.37 (4)	C31—C32	1.389 (5)
Cl1—N11	3.125 (3)	C31—C35	1.392 (5)
S1—C11	1.731 (3)	C32—C33	1.414 (5)
S2—C21	1.738 (3)	C33—C34	1.396 (5)
N11—C11	1.344 (4)	C34—C35	1.378 (5)
N11—C12	1.367 (4)	C41—C42	1.366 (5)
N12—C11	1.355 (4)	C41—C46	1.371 (5)
N12—C13	1.387 (4)	C42—C43	1.376 (5)
N12—C14	1.509 (4)	C43—C44	1.378 (5)
N21—C21	1.333 (4)	C44—C45	1.394 (5)
N21—C22	1.378 (4)	C45—C46	1.366 (5)

N21—Zr1—Cl2	82.27 (6)	C21—S2—Zr1	79.01 (10)
N21—Zr1—C34	157.21 (10)	C11—N11—C12	111.0 (3)
Cl2—Zr1—C34	116.38 (9)	C11—N11—Cl1	105.25 (18)
N21—Zr1—C33	164.68 (9)	C12—N11—Cl1	141.0 (2)
Cl2—Zr1—C33	84.66 (8)	C11—N12—C13	108.7 (2)
C34—Zr1—C33	32.21 (11)	C11—N12—C14	126.8 (2)
N21—Zr1—C35	142.35 (10)	C13—N12—C14	124.5 (2)
Cl2—Zr1—C35	130.56 (8)	C21—N21—C22	107.1 (2)
C34—Zr1—C35	31.77 (12)	C21—N21—Zr1	100.52 (18)
C33—Zr1—C35	52.91 (11)	C22—N21—Zr1	151.3 (2)
N21—Zr1—C31	138.54 (10)	C21—N22—C23	106.2 (2)
Cl2—Zr1—C31	104.39 (10)	C21—N22—C24	127.3 (2)
C34—Zr1—C31	53.03 (12)	C23—N22—C24	126.4 (2)
C33—Zr1—C31	53.15 (11)	N11—C11—N12	105.9 (3)
C35—Zr1—C31	31.99 (12)	N11—C11—S1	124.1 (2)
N21—Zr1—C32	148.72 (10)	N12—C11—S1	129.9 (2)
Cl2—Zr1—C32	77.70 (8)	C13—C12—N11	106.4 (3)
C34—Zr1—C32	53.46 (11)	C12—C13—N12	108.0 (3)
C33—Zr1—C32	32.52 (11)	N12—C14—C17	109.3 (2)
C35—Zr1—C32	52.97 (11)	N12—C14—C16	108.2 (2)
C31—Zr1—C32	31.88 (11)	C17—C14—C16	108.8 (3)
N21—Zr1—Cl1	85.44 (6)	N12—C14—C15	108.6 (2)
Cl2—Zr1—Cl1	84.00 (3)	C17—C14—C15	108.8 (2)
C34—Zr1—Cl1	83.81 (9)	C16—C14—C15	113.1 (3)
C33—Zr1—Cl1	85.28 (8)	N21—C21—N22	110.6 (3)
C35—Zr1—Cl1	112.39 (10)	N21—C21—S2	116.0 (2)
C31—Zr1—Cl1	135.55 (9)	N22—C21—S2	133.4 (2)
C32—Zr1—Cl1	115.70 (9)	N21—C21—Zr1	52.09 (14)
N21—Zr1—S2	64.03 (6)	N22—C21—Zr1	161.5 (2)
Cl2—Zr1—S2	89.08 (3)	S2—C21—Zr1	64.22 (9)
C34—Zr1—S2	125.55 (9)	C23—C22—N21	108.4 (3)
C33—Zr1—S2	123.82 (9)	C22—C23—N22	107.7 (3)
C35—Zr1—S2	94.72 (10)	N22—C24—C27	109.3 (2)
C31—Zr1—S2	75.07 (9)	N22—C24—C25	108.7 (2)
C32—Zr1—S2	91.67 (9)	C27—C24—C25	109.4 (3)
Cl1—Zr1—S2	149.36 (3)	N22—C24—C26	108.5 (2)
N21—Zr1—S1	79.32 (6)	C27—C24—C26	109.6 (3)
Cl2—Zr1—S1	159.88 (3)	C25—C24—C26	111.3 (3)
C34—Zr1—S1	80.01 (8)	C32—C31—C35	108.3 (3)
C33—Zr1—S1	112.21 (8)	C32—C31—Zr1	74.08 (19)
C35—Zr1—S1	69.53 (8)	C35—C31—Zr1	73.87 (19)
C31—Zr1—S1	94.82 (9)	C31—C32—C33	107.4 (3)
C32—Zr1—S1	122.43 (8)	C31—C32—Zr1	74.04 (19)
Cl1—Zr1—S1	86.48 (3)	C33—C32—Zr1	73.41 (18)
S2—Zr1—S1	90.14 (3)	C34—C33—C32	107.5 (3)
N21—Zr1—C21	27.39 (8)	C34—C33—Zr1	73.51 (19)
Cl2—Zr1—C21	82.27 (6)	C32—C33—Zr1	74.07 (19)
C34—Zr1—C21	157.16 (11)	C35—C34—C33	108.2 (3)
C33—Zr1—C21	156.45 (11)	C35—C34—Zr1	74.7 (2)
C35—Zr1—C21	126.02 (11)	C33—C34—Zr1	74.28 (19)
C31—Zr1—C21	111.78 (10)	C34—C35—C31	108.6 (3)
C32—Zr1—C21	124.74 (10)	C34—C35—Zr1	73.54 (19)
Cl1—Zr1—C21	112.59 (6)	C31—C35—Zr1	74.1 (2)
S2—Zr1—C21	36.77 (6)	C42—C41—C46	120.8 (3)
S1—Zr1—C21	85.10 (6)	C41—C42—C43	120.0 (4)
H11—Cl1—Zr1	94.7 (9)	C42—C43—C44	119.8 (3)
H11—Cl1—N11	7.3 (9)	C43—C44—C45	119.7 (3)
Zr1—Cl1—N11	88.44 (5)	C46—C45—C44	119.8 (4)
C11—S1—Zr1	110.69 (10)	C45—C46—C41	120.0 (4)

(V) Tribenzyl[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ³S,S',S'']hafnium(IV) benzene tetrasolvate top

Crystal data top

[Hf(C₇H₇)₃(C₂₁H₃₄BN₆S₃)]·4C₆H₆	Mo Kα radiation, λ = 0.71073 Å
M_r = 1241.83	Cell parameters from 9951 reflections
Cubic, Pa3	θ = 2.2–22.1°
a = 23.1441 (13) Å	µ = 1.83 mm⁻¹
V = 12397 (2) Å³	T = 150 K
Z = 8	Block, yellow
F(000) = 5136	0.10 × 0.09 × 0.05 mm
D_x = 1.331 Mg m⁻³

Data collection top

Bruker APEXII CCD diffractometer	2164 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.240
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2014)	θ_max = 25.0°, θ_min = 1.5°
T_min = 0.657, T_max = 0.746	h = −27→27
128334 measured reflections	k = −27→27
3649 independent reflections	l = −27→27

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.198	w = 1/[σ²(F_o²) + (0.085P)² + 97.741P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3649 reflections	Δρ_max = 1.31 e Å⁻³
227 parameters	Δρ_min = −0.90 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Hf1	0.19081 (2)	0.19081 (2)	0.19081 (2)	0.0386 (3)
B1	0.2977 (5)	0.2977 (5)	0.2977 (5)	0.054 (5)
H1	0.3241 (8)	0.3241 (8)	0.3241 (8)	0.064*
S1	0.16643 (11)	0.29489 (11)	0.22949 (11)	0.0463 (6)
N11	0.2742 (3)	0.3384 (3)	0.2504 (4)	0.048 (2)
N12	0.2250 (4)	0.3879 (3)	0.1865 (4)	0.049 (2)
C11	0.2238 (4)	0.3419 (4)	0.2209 (4)	0.045 (2)
C12	0.3074 (5)	0.3841 (4)	0.2332 (5)	0.055 (3)
H12A	0.3450	0.3926	0.2471	0.066*
C13	0.2788 (5)	0.4148 (5)	0.1938 (5)	0.058 (3)
H13A	0.2922	0.4484	0.1744	0.069*
C14	0.1782 (5)	0.4119 (4)	0.1479 (5)	0.056 (3)
C15	0.1622 (5)	0.3680 (5)	0.1040 (5)	0.060 (3)
H15A	0.1318	0.3836	0.0790	0.090*
H15B	0.1962	0.3584	0.0807	0.090*
H15C	0.1481	0.3332	0.1234	0.090*
C16	0.2013 (6)	0.4651 (5)	0.1169 (5)	0.070 (3)
H16A	0.2120	0.4945	0.1454	0.105*
H16B	0.2353	0.4545	0.0941	0.105*
H16C	0.1713	0.4806	0.0912	0.105*
C17	0.1260 (5)	0.4284 (5)	0.1851 (5)	0.062 (3)
H17A	0.1377	0.4574	0.2137	0.092*
H17B	0.0956	0.4444	0.1605	0.092*
H17C	0.1115	0.3940	0.2051	0.092*
C21	0.1870 (4)	0.2066 (4)	0.0940 (4)	0.046 (2)
H21A	0.1486	0.2233	0.0853	0.055*
H21B	0.2161	0.2366	0.0848	0.055*
C22	0.1962 (5)	0.1583 (5)	0.0542 (4)	0.059 (3)
C23	0.2502 (6)	0.1374 (5)	0.0419 (5)	0.063 (3)
H23A	0.2821	0.1573	0.0584	0.076*
C24	0.2625 (9)	0.0910 (6)	0.0082 (6)	0.099 (5)
H24A	0.3010	0.0791	0.0005	0.118*
C25	0.2152 (11)	0.0623 (7)	−0.0140 (7)	0.116 (7)
H25A	0.2214	0.0286	−0.0366	0.139*
C26	0.1577 (11)	0.0813 (9)	−0.0044 (7)	0.121 (7)
H26A	0.1262	0.0618	−0.0220	0.146*
C27	0.1483 (7)	0.1285 (6)	0.0309 (5)	0.080 (4)
H27A	0.1101	0.1407	0.0393	0.096*
C31	0.422 (2)	0.101 (2)	−0.1181 (15)	0.184 (13)	0.3333
H31A	0.4084	0.1052	−0.1565	0.220*	0.3333
C32	0.473 (2)	0.070 (2)	−0.1080 (14)	0.184 (13)	0.3333
H32A	0.4933	0.0529	−0.1395	0.220*	0.3333
C33	0.4931 (16)	0.063 (2)	−0.0520 (17)	0.184 (13)	0.3333
H33A	0.5276	0.0416	−0.0451	0.220*	0.3333
C34	0.4631 (18)	0.087 (2)	−0.0060 (12)	0.184 (13)	0.3333
H34A	0.4770	0.0824	0.0324	0.220*	0.3333
C35	0.4127 (17)	0.118 (2)	−0.0161 (16)	0.184 (13)	0.3333
H35A	0.3921	0.1347	0.0154	0.220*	0.3333
C36	0.3923 (17)	0.125 (2)	−0.072 (2)	0.184 (13)	0.3333
H36A	0.3578	0.1460	−0.0790	0.220*	0.3333
C41	0.3419 (6)	0.3520 (6)	−0.0641 (6)	0.078 (4)
H41A	0.3502	0.3532	−0.1043	0.094*
C42	0.3433 (6)	0.4009 (6)	−0.0333 (6)	0.078 (4)
H42A	0.3521	0.4369	−0.0511	0.094*
C43	0.3316 (6)	0.3977 (7)	0.0245 (7)	0.088 (4)
H43A	0.3337	0.4317	0.0474	0.105*
C44	0.3171 (6)	0.3466 (7)	0.0497 (6)	0.082 (4)
H44A	0.3082	0.3453	0.0898	0.099*
C45	0.3155 (5)	0.2979 (7)	0.0180 (6)	0.078 (4)
H45A	0.3051	0.2621	0.0351	0.093*
C46	0.3288 (6)	0.3010 (6)	−0.0389 (6)	0.075 (4)
H46A	0.3290	0.2667	−0.0615	0.090*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hf1	0.0386 (3)	0.0386 (3)	0.0386 (3)	−0.00142 (18)	−0.00142 (18)	−0.00142 (18)
B1	0.054 (5)	0.054 (5)	0.054 (5)	−0.004 (6)	−0.004 (6)	−0.004 (6)
S1	0.0423 (13)	0.0473 (15)	0.0493 (15)	−0.0008 (11)	0.0000 (11)	−0.0044 (11)
N11	0.046 (5)	0.045 (5)	0.053 (5)	−0.005 (4)	−0.003 (4)	−0.008 (4)
N12	0.060 (5)	0.033 (4)	0.055 (5)	0.001 (4)	0.003 (4)	−0.008 (4)
C11	0.052 (6)	0.037 (6)	0.046 (6)	0.005 (5)	0.003 (5)	−0.010 (5)
C12	0.061 (7)	0.047 (6)	0.058 (7)	−0.007 (5)	−0.005 (6)	−0.004 (5)
C13	0.063 (7)	0.051 (6)	0.060 (7)	−0.006 (6)	0.008 (6)	−0.007 (6)
C14	0.079 (8)	0.035 (5)	0.054 (6)	−0.004 (5)	−0.003 (6)	−0.002 (5)
C15	0.074 (8)	0.052 (7)	0.055 (7)	0.004 (6)	0.004 (6)	0.008 (5)
C16	0.094 (10)	0.041 (6)	0.075 (8)	−0.003 (6)	0.001 (7)	0.005 (6)
C17	0.062 (7)	0.058 (7)	0.065 (7)	0.012 (6)	−0.001 (6)	−0.008 (6)
C21	0.036 (5)	0.055 (6)	0.047 (6)	−0.001 (5)	0.002 (4)	0.003 (5)
C22	0.076 (8)	0.060 (7)	0.040 (6)	−0.001 (6)	−0.009 (6)	0.011 (5)
C23	0.078 (8)	0.063 (7)	0.049 (7)	0.011 (6)	0.013 (6)	−0.007 (6)
C24	0.177 (18)	0.061 (9)	0.058 (8)	0.008 (10)	−0.005 (10)	−0.003 (7)
C25	0.22 (2)	0.056 (9)	0.067 (10)	−0.010 (13)	0.035 (13)	−0.007 (7)
C26	0.19 (2)	0.119 (15)	0.059 (9)	−0.073 (15)	0.002 (12)	0.000 (10)
C27	0.103 (11)	0.090 (10)	0.046 (7)	−0.041 (8)	−0.006 (7)	−0.008 (7)
C31	0.13 (2)	0.32 (4)	0.106 (19)	0.06 (2)	−0.026 (17)	−0.10 (2)
C32	0.13 (2)	0.32 (4)	0.106 (19)	0.06 (2)	−0.026 (17)	−0.10 (2)
C33	0.13 (2)	0.32 (4)	0.106 (19)	0.06 (2)	−0.026 (17)	−0.10 (2)
C34	0.13 (2)	0.32 (4)	0.106 (19)	0.06 (2)	−0.026 (17)	−0.10 (2)
C35	0.13 (2)	0.32 (4)	0.106 (19)	0.06 (2)	−0.026 (17)	−0.10 (2)
C36	0.13 (2)	0.32 (4)	0.106 (19)	0.06 (2)	−0.026 (17)	−0.10 (2)
C41	0.090 (10)	0.084 (10)	0.060 (8)	0.008 (8)	0.023 (7)	0.003 (7)
C42	0.081 (9)	0.075 (9)	0.078 (9)	0.006 (7)	0.015 (8)	−0.008 (8)
C43	0.072 (9)	0.102 (12)	0.091 (11)	−0.010 (8)	0.008 (8)	−0.026 (9)
C44	0.094 (11)	0.100 (11)	0.053 (8)	−0.010 (9)	−0.007 (7)	0.003 (8)
C45	0.063 (8)	0.104 (11)	0.066 (8)	0.013 (7)	−0.002 (7)	0.007 (8)
C46	0.069 (8)	0.077 (9)	0.079 (9)	0.002 (7)	0.003 (7)	−0.003 (7)

Geometric parameters (Å, º) top

Hf1—C21	2.271 (10)	C21—C22	1.464 (15)
Hf1—C21ⁱ	2.271 (10)	C22—C23	1.371 (16)
Hf1—C21ⁱⁱ	2.271 (10)	C22—C27	1.413 (16)
Hf1—S1	2.631 (3)	C23—C24	1.356 (17)
Hf1—S1ⁱ	2.631 (3)	C24—C25	1.38 (2)
Hf1—S1ⁱⁱ	2.631 (3)	C25—C26	1.42 (3)
B1—H1	1.05 (2)	C26—C27	1.38 (2)
B1—N11	1.544 (10)	C31—C32	1.3900
B1—N11ⁱ	1.544 (10)	C31—C36	1.3900
B1—N11ⁱⁱ	1.544 (10)	C32—C33	1.3900
S1—C11	1.728 (11)	C33—C34	1.3900
N11—C11	1.355 (12)	C34—C35	1.3900
N11—C12	1.365 (12)	C35—C36	1.3900
N12—C11	1.329 (12)	C41—C42	1.338 (17)
N12—C13	1.401 (14)	C41—C46	1.352 (17)
N12—C14	1.511 (14)	C42—C43	1.366 (18)
C12—C13	1.332 (15)	C43—C44	1.36 (2)
C14—C15	1.483 (14)	C44—C45	1.346 (19)
C14—C16	1.522 (15)	C45—C46	1.355 (18)
C14—C17	1.531 (15)

C21—Hf1—C21ⁱ	97.3 (3)	N11—C11—S1	124.5 (8)
C21—Hf1—C21ⁱⁱ	97.3 (3)	C13—C12—N11	109.5 (10)
C21ⁱ—Hf1—C21ⁱⁱ	97.3 (3)	C12—C13—N12	106.6 (10)
C21—Hf1—S1	100.3 (3)	C15—C14—N12	109.4 (9)
C21ⁱ—Hf1—S1	76.7 (2)	C15—C14—C16	108.5 (9)
C21ⁱⁱ—Hf1—S1	161.9 (2)	N12—C14—C16	109.0 (9)
C21—Hf1—S1ⁱ	161.9 (2)	C15—C14—C17	111.1 (10)
C21ⁱ—Hf1—S1ⁱ	100.4 (3)	N12—C14—C17	109.0 (9)
C21ⁱⁱ—Hf1—S1ⁱ	76.7 (2)	C16—C14—C17	109.9 (9)
S1—Hf1—S1ⁱ	87.59 (8)	C22—C21—Hf1	119.5 (7)
C21—Hf1—S1ⁱⁱ	76.7 (2)	C23—C22—C27	117.6 (12)
C21ⁱ—Hf1—S1ⁱⁱ	161.9 (2)	C23—C22—C21	122.2 (11)
C21ⁱⁱ—Hf1—S1ⁱⁱ	100.4 (3)	C27—C22—C21	120.0 (11)
S1—Hf1—S1ⁱⁱ	87.59 (8)	C24—C23—C22	126.1 (14)
S1ⁱ—Hf1—S1ⁱⁱ	87.59 (8)	C23—C24—C25	115.5 (17)
H1—B1—N11	105.1 (9)	C24—C25—C26	122.4 (16)
H1—B1—N11ⁱ	105.1 (8)	C27—C26—C25	119.1 (17)
N11—B1—N11ⁱ	113.4 (7)	C26—C27—C22	119.3 (16)
H1—B1—N11ⁱⁱ	105.1 (9)	C32—C31—C36	120.0
N11—B1—N11ⁱⁱ	113.4 (7)	C31—C32—C33	120.0
N11ⁱ—B1—N11ⁱⁱ	113.4 (7)	C32—C33—C34	120.0
C11—S1—Hf1	111.9 (3)	C35—C34—C33	120.0
C11—N11—C12	106.9 (9)	C34—C35—C36	120.0
C11—N11—B1	134.3 (10)	C35—C36—C31	120.0
C12—N11—B1	118.8 (10)	C42—C41—C46	121.0 (13)
C11—N12—C13	107.6 (9)	C41—C42—C43	118.0 (14)
C11—N12—C14	129.3 (9)	C42—C43—C44	121.1 (14)
C13—N12—C14	123.0 (9)	C45—C44—C43	120.0 (14)
N12—C11—N11	109.3 (9)	C44—C45—C46	118.7 (15)
N12—C11—S1	126.2 (8)	C41—C46—C45	121.1 (14)

Symmetry codes: (i) z, x, y; (ii) y, z, x.

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

Mol­ecular structures of tris­(1-tert-butyl-2-mercapto­imidazol­yl)hydro­borate complexes of titanium, zirconium and hafnium

Supporting information

Molecular structures of tris(1-tert-butyl-2-mercaptoimidazolyl)hydroborate complexes of titanium, zirconium and hafnium