Crystal structure and DFT calculations of Cp₂NbH(SiIMe₂)(SiFMe₂): an asymmetric bis­(sil­yl) niobocene hy­dride com­plex

An asymmetric bis­(sil­yl) niobocene hy­dride com­plex, namely, bis­(η⁵-cyclo­penta­dien­yl)(fluoro­dimethyl­sil­yl)hydrido(iodo­dimethyl­sil­yl)niobium, [Nb(C₅H₅)₂(C₂H₆FSi)(C₂H₆ISi)H] or Cp₂NbH(SiIMe₂)(SiFMe₂), has been studied to determine the effect of the silyl ligand on the position of the hy­dride attached to the Nb atom. It has been shown that when a Group 17 atom is substituted onto one of the silyl ligands, there is a greater inter­action between the hy­dride and this ligand, as demonstrated by a shorter Si...H distance. In the present work, we have investigated the effect when the silyl ligands are substituted by dif­ferent Group 17 atoms. We present here the structure and DFT calculations of Cp₂NbH(SiIMe₂)(SiFMe₂), showing that the position of the hy­dride is located between the two silyl ligands. The results from our investigation show that the hy­dride is closer to the silyl ligand that is substituted by fluorine.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Bis(η⁵-cyclopentadienyl)(fluorodimethylsilyl)hydrido(iododimethylsilyl)niobium

Crystal data

[Nb(C5H5)2(C2H6FSi)(C2H6ISi)H]	F(000) = 1904
Mr = 486.31	Dx = 1.845 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.1427 (10) Å	Cell parameters from 7099 reflections
b = 8.9369 (10) Å	θ = 2.7–27.5°
c = 26.143 (2) Å	µ = 2.58 mm^−1
β = 98.304 (2)°	T = 133 K
V = 3500.8 (5) Å^3	Prism, purple
Z = 8	0.15 × 0.10 × 0.05 mm

Data collection

Bruker SMART APEX CCD area detector diffractometer	3520 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.028
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θmax = 27.5°, θmin = 1.6°
Tmin = 0.649, Tmax = 0.984	h = −19→18
10487 measured reflections	k = −11→10
3966 independent reflections	l = −30→33

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.069	w = 1/[σ^2(Fo^2) + (0.0302P)^2 + 9.7861P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.002
3966 reflections	Δρmax = 1.56 e Å^−3
180 parameters	Δρmin = −0.47 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Data for the title compound, 1, were collected using a Bruker SMART APEX diffractometer with Mo-K_α radiation (λ = 0.71073 Å). The cell parameters were obtained from the least squares refinement of the reflections (collected from 60 frames) using SMART (Bruker AXS, 2000). Data collection was performed using SMART and data processing was performed using the SAINT (Bruker AXS, 2000) program. Initial atomic positions for 1 were located using direct methods. The structure was corrected for absorption effects using SADABS (Krause et al., 2015) and refined by least squares methods using SHELXL2018 (Sheldrick, 2015a; 2015b).

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

	x	y	z	Uiso*/Ueq
Nb1	0.31140 (2)	0.50211 (3)	0.61509 (2)	0.01973 (8)
I1	0.45368 (2)	0.16640 (3)	0.54217 (2)	0.03710 (8)
F1	0.24068 (14)	0.7889 (3)	0.69500 (8)	0.0431 (5)
Si1	0.46281 (5)	0.36884 (9)	0.61508 (3)	0.02300 (17)
Si2	0.33328 (6)	0.69613 (9)	0.69073 (3)	0.02609 (18)
C1	0.3622 (2)	0.5701 (4)	0.53535 (12)	0.0298 (7)
H1	0.408590	0.516302	0.522608	0.036*
C2	0.3731 (2)	0.6960 (4)	0.56844 (12)	0.0293 (7)
H2	0.428371	0.740172	0.582471	0.035*
C3	0.2881 (2)	0.7446 (4)	0.57706 (12)	0.0308 (7)
H3	0.275747	0.828220	0.597313	0.037*
C4	0.2250 (2)	0.6473 (4)	0.55032 (13)	0.0335 (7)
H4	0.162166	0.653000	0.549518	0.040*
C5	0.2709 (2)	0.5392 (4)	0.52479 (12)	0.0321 (7)
H5	0.244293	0.459411	0.504032	0.039*
C6	0.2857 (2)	0.2455 (3)	0.63630 (13)	0.0304 (7)
H6	0.326113	0.168634	0.630107	0.036*
C7	0.2890 (2)	0.3312 (3)	0.68197 (12)	0.0285 (7)
H7	0.333064	0.323510	0.711634	0.034*
C8	0.2155 (2)	0.4302 (4)	0.67600 (13)	0.0313 (7)
H8	0.200615	0.498845	0.701159	0.038*
C9	0.1683 (2)	0.4089 (4)	0.62609 (14)	0.0342 (7)
H9	0.116339	0.461912	0.611453	0.041*
C10	0.2113 (2)	0.2951 (4)	0.60154 (14)	0.0325 (7)
H10	0.193363	0.258247	0.567545	0.039*
C11	0.5091 (2)	0.2520 (4)	0.67259 (13)	0.0313 (7)
H11A	0.566414	0.208898	0.666914	0.047*
H11B	0.467155	0.171370	0.677216	0.047*
H11C	0.517937	0.314972	0.703606	0.047*
C12	0.5611 (2)	0.4817 (4)	0.60056 (13)	0.0330 (7)
H12A	0.577193	0.555595	0.628025	0.049*
H12B	0.545492	0.533282	0.567416	0.049*
H12C	0.611916	0.414945	0.598690	0.049*
C13	0.4146 (3)	0.8528 (4)	0.68581 (15)	0.0405 (9)
H13A	0.397704	0.906630	0.653199	0.061*
H13B	0.474792	0.811586	0.686841	0.061*
H13C	0.413656	0.921946	0.714836	0.061*
C14	0.3663 (2)	0.6178 (4)	0.75750 (12)	0.0311 (7)
H14A	0.371346	0.699497	0.782780	0.047*
H14B	0.423898	0.566657	0.759286	0.047*
H14C	0.320865	0.546566	0.765253	0.047*
H1A	0.407 (3)	0.544 (4)	0.6576 (15)	0.043 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Nb1	0.01890 (13)	0.02119 (13)	0.01944 (13)	−0.00022 (9)	0.00392 (10)	0.00287 (10)
I1	0.02859 (12)	0.04315 (14)	0.03831 (14)	0.00405 (9)	0.00056 (9)	−0.01994 (10)
F1	0.0341 (11)	0.0554 (13)	0.0392 (12)	0.0196 (10)	0.0038 (9)	−0.0108 (10)
Si1	0.0199 (4)	0.0253 (4)	0.0235 (4)	0.0000 (3)	0.0025 (3)	−0.0041 (3)
Si2	0.0290 (4)	0.0235 (4)	0.0255 (4)	0.0051 (3)	0.0032 (3)	−0.0004 (3)
C1	0.0323 (17)	0.0386 (18)	0.0199 (15)	−0.0005 (14)	0.0085 (12)	0.0085 (13)
C2	0.0322 (17)	0.0322 (16)	0.0241 (15)	−0.0031 (13)	0.0056 (12)	0.0095 (13)
C3	0.0335 (17)	0.0299 (17)	0.0288 (16)	0.0048 (13)	0.0038 (13)	0.0107 (13)
C4	0.0279 (17)	0.0406 (19)	0.0307 (17)	0.0024 (14)	0.0003 (13)	0.0149 (14)
C5	0.0334 (18)	0.0390 (18)	0.0220 (15)	−0.0050 (14)	−0.0028 (13)	0.0066 (14)
C6	0.0305 (17)	0.0217 (15)	0.0399 (18)	−0.0041 (12)	0.0080 (14)	0.0040 (13)
C7	0.0296 (16)	0.0301 (16)	0.0265 (16)	−0.0030 (13)	0.0066 (13)	0.0097 (13)
C8	0.0302 (17)	0.0330 (17)	0.0337 (17)	−0.0017 (13)	0.0153 (14)	0.0075 (14)
C9	0.0229 (16)	0.0382 (18)	0.0422 (19)	−0.0036 (13)	0.0076 (14)	0.0120 (15)
C10	0.0285 (17)	0.0328 (17)	0.0360 (18)	−0.0124 (13)	0.0037 (14)	0.0018 (14)
C11	0.0292 (17)	0.0289 (16)	0.0332 (17)	0.0026 (13)	−0.0038 (13)	−0.0019 (13)
C12	0.0237 (16)	0.0421 (19)	0.0346 (18)	−0.0065 (13)	0.0087 (13)	−0.0077 (15)
C13	0.054 (2)	0.0247 (17)	0.040 (2)	−0.0034 (15)	−0.0028 (17)	−0.0002 (14)
C14	0.0363 (18)	0.0330 (17)	0.0242 (16)	0.0051 (14)	0.0049 (13)	−0.0018 (13)

Geometric parameters (Å, º)

Nb1—C4	2.371 (3)	C4—C5	1.412 (5)
Nb1—C5	2.375 (3)	C4—H4	0.9500
Nb1—C9	2.378 (3)	C5—H5	0.9500
Nb1—C7	2.383 (3)	C6—C10	1.412 (5)
Nb1—C10	2.385 (3)	C6—C7	1.413 (5)
Nb1—C2	2.386 (3)	C6—H6	0.9500
Nb1—C3	2.389 (3)	C7—C8	1.412 (5)
Nb1—C8	2.393 (3)	C7—H7	0.9500
Nb1—C1	2.402 (3)	C8—C9	1.407 (5)
Nb1—C6	2.404 (3)	C8—H8	0.9500
Nb1—Si1	2.5837 (9)	C9—C10	1.411 (5)
Nb1—Si2	2.6148 (9)	C9—H9	0.9500
Nb1—H1A	1.74 (4)	C10—H10	0.9500
I1—Si1	2.6172 (9)	C11—H11A	0.9800
F1—Si2	1.647 (2)	C11—H11B	0.9800
Si1—C11	1.881 (3)	C11—H11C	0.9800
Si1—C12	1.882 (3)	C12—H12A	0.9800
Si2—C14	1.880 (3)	C12—H12B	0.9800
Si2—C13	1.881 (4)	C12—H12C	0.9800
C1—C5	1.398 (5)	C13—H13A	0.9800
C1—C2	1.414 (5)	C13—H13B	0.9800
C1—H1	0.9500	C13—H13C	0.9800
C2—C3	1.407 (5)	C14—H14A	0.9800
C2—H2	0.9500	C14—H14B	0.9800
C3—C4	1.402 (5)	C14—H14C	0.9800
C3—H3	0.9500
C4—Nb1—C5	34.62 (12)	F1—Si2—Nb1	111.66 (8)
C4—Nb1—C9	81.93 (12)	C14—Si2—Nb1	116.30 (11)
C5—Nb1—C9	93.44 (12)	C13—Si2—Nb1	117.05 (13)
C4—Nb1—C7	138.79 (12)	C5—C1—C2	107.6 (3)
C5—Nb1—C7	140.82 (12)	C5—C1—Nb1	71.91 (18)
C9—Nb1—C7	57.15 (11)	C2—C1—Nb1	72.17 (17)
C4—Nb1—C10	92.58 (12)	C5—C1—H1	126.2
C5—Nb1—C10	83.88 (12)	C2—C1—H1	126.2
C9—Nb1—C10	34.46 (12)	Nb1—C1—H1	121.5
C7—Nb1—C10	57.10 (11)	C3—C2—C1	108.4 (3)
C4—Nb1—C2	56.91 (12)	C3—C2—Nb1	73.01 (18)
C5—Nb1—C2	56.94 (11)	C1—C2—Nb1	73.47 (18)
C9—Nb1—C2	138.37 (11)	C3—C2—H2	125.8
C7—Nb1—C2	161.55 (12)	C1—C2—H2	125.8
C10—Nb1—C2	140.78 (12)	Nb1—C2—H2	119.5
C4—Nb1—C3	34.26 (12)	C4—C3—C2	107.6 (3)
C5—Nb1—C3	57.19 (12)	C4—C3—Nb1	72.16 (18)
C9—Nb1—C3	106.61 (12)	C2—C3—Nb1	72.72 (18)
C7—Nb1—C3	149.18 (11)	C4—C3—H3	126.2
C10—Nb1—C3	126.11 (12)	C2—C3—H3	126.2
C2—Nb1—C3	34.27 (11)	Nb1—C3—H3	120.7
C4—Nb1—C8	107.27 (12)	C3—C4—C5	108.3 (3)
C5—Nb1—C8	127.19 (12)	C3—C4—Nb1	73.58 (18)
C9—Nb1—C8	34.31 (12)	C5—C4—Nb1	72.85 (18)
C7—Nb1—C8	34.40 (11)	C3—C4—H4	125.9
C10—Nb1—C8	57.10 (12)	C5—C4—H4	125.9
C2—Nb1—C8	148.80 (11)	Nb1—C4—H4	119.5
C3—Nb1—C8	116.96 (11)	C1—C5—C4	108.2 (3)
C4—Nb1—C1	56.96 (12)	C1—C5—Nb1	74.05 (18)
C5—Nb1—C1	34.04 (11)	C4—C5—Nb1	72.53 (18)
C9—Nb1—C1	127.27 (12)	C1—C5—H5	125.9
C7—Nb1—C1	153.70 (11)	C4—C5—H5	125.9
C10—Nb1—C1	110.11 (12)	Nb1—C5—H5	119.4
C2—Nb1—C1	34.35 (11)	C10—C6—C7	107.5 (3)
C3—Nb1—C1	57.04 (12)	C10—C6—Nb1	72.14 (18)
C8—Nb1—C1	161.22 (12)	C7—C6—Nb1	72.01 (17)
C4—Nb1—C6	126.55 (12)	C10—C6—H6	126.2
C5—Nb1—C6	109.59 (12)	C7—C6—H6	126.2
C9—Nb1—C6	57.11 (12)	Nb1—C6—H6	121.4
C7—Nb1—C6	34.34 (11)	C8—C7—C6	108.4 (3)
C10—Nb1—C6	34.30 (11)	C8—C7—Nb1	73.20 (17)
C2—Nb1—C6	154.04 (12)	C6—C7—Nb1	73.65 (18)
C3—Nb1—C6	160.40 (11)	C8—C7—H7	125.8
C8—Nb1—C6	57.05 (12)	C6—C7—H7	125.8
C1—Nb1—C6	121.63 (12)	Nb1—C7—H7	119.2
C4—Nb1—Si1	130.56 (9)	C9—C8—C7	107.7 (3)
C5—Nb1—Si1	99.56 (9)	C9—C8—Nb1	72.27 (18)
C9—Nb1—Si1	131.51 (9)	C7—C8—Nb1	72.40 (17)
C7—Nb1—Si1	85.71 (8)	C9—C8—H8	126.1
C10—Nb1—Si1	100.80 (9)	C7—C8—H8	126.1
C2—Nb1—Si1	85.51 (8)	Nb1—C8—H8	121.0
C3—Nb1—Si1	119.71 (8)	C8—C9—C10	108.2 (3)
C8—Nb1—Si1	120.01 (8)	C8—C9—Nb1	73.42 (18)
C1—Nb1—Si1	73.80 (8)	C10—C9—Nb1	73.06 (18)
C6—Nb1—Si1	74.56 (8)	C8—C9—H9	125.9
C4—Nb1—Si2	100.01 (9)	C10—C9—H9	125.9
C5—Nb1—Si2	130.19 (9)	Nb1—C9—H9	119.5
C9—Nb1—Si2	99.16 (9)	C9—C10—C6	108.1 (3)
C7—Nb1—Si2	83.46 (8)	C9—C10—Nb1	72.48 (18)
C10—Nb1—Si2	129.42 (9)	C6—C10—Nb1	73.57 (18)
C2—Nb1—Si2	83.61 (8)	C9—C10—H10	125.9
C3—Nb1—Si2	73.03 (8)	C6—C10—H10	125.9
C8—Nb1—Si2	72.41 (9)	Nb1—C10—H10	119.8
C1—Nb1—Si2	117.83 (9)	Si1—C11—H11A	109.5
C6—Nb1—Si2	117.72 (8)	Si1—C11—H11B	109.5
Si1—Nb1—Si2	106.87 (3)	H11A—C11—H11B	109.5
C4—Nb1—H1A	131.4 (13)	Si1—C11—H11C	109.5
C5—Nb1—H1A	132.7 (13)	H11A—C11—H11C	109.5
C9—Nb1—H1A	133.6 (13)	H11B—C11—H11C	109.5
C7—Nb1—H1A	82.2 (13)	Si1—C12—H12A	109.5
C10—Nb1—H1A	135.9 (13)	Si1—C12—H12B	109.5
C2—Nb1—H1A	79.4 (13)	H12A—C12—H12B	109.5
C3—Nb1—H1A	97.4 (13)	Si1—C12—H12C	109.5
C8—Nb1—H1A	99.4 (13)	H12A—C12—H12C	109.5
C1—Nb1—H1A	99.1 (13)	H12B—C12—H12C	109.5
C6—Nb1—H1A	102.0 (13)	Si2—C13—H13A	109.5
Si1—Nb1—H1A	56.0 (13)	Si2—C13—H13B	109.5
Si2—Nb1—H1A	50.8 (13)	H13A—C13—H13B	109.5
C11—Si1—C12	104.13 (16)	Si2—C13—H13C	109.5
C11—Si1—Nb1	118.96 (11)	H13A—C13—H13C	109.5
C12—Si1—Nb1	118.75 (12)	H13B—C13—H13C	109.5
C11—Si1—I1	99.96 (11)	Si2—C14—H14A	109.5
C12—Si1—I1	100.58 (11)	Si2—C14—H14B	109.5
Nb1—Si1—I1	111.42 (3)	H14A—C14—H14B	109.5
F1—Si2—C14	103.85 (14)	Si2—C14—H14C	109.5
F1—Si2—C13	101.64 (16)	H14A—C14—H14C	109.5
C14—Si2—C13	104.57 (16)	H14B—C14—H14C	109.5