Preferential crystallization of (±)-pinenyllithium·TMEDA

(±)-Pinenyllithium·TMEDA or (tetra­methyl­ethylenedi­amine-κ²N,N′)(η³-6,6-di­methyl-2-methylenebi­cyclo­[3.1.1]hept­yl)lithium, [Li(C₁₀H₁₅)(C₆H₁₆N₂)], is readily pre­pared from β-pinene, butyl­lithium and TMEDA, and the racemic material pre­fer­entially crystallizes even from 96:4 (92% ee) mixtures of (−)- and (+)-β-pinene, respectively. The structure is monomeric, with the geminal-dimethyl bridge of the bicyclic structure shielding one face of the allyl system, restricting the lithium to the opposite face and preventing the Li–all­yl–Li aggregation observed with some other allyl­lithium systems. The symmetry of the allyl system, bond lengths, bond angles and out-of-plane deviations are com­pared to existing structures. In addition, a much older structure of this com­plex is compared to this very recent one.

Computing details

(Tetramethylethylenediamine-κ²N,N')(η³-2,6,6-\ trimethylbicyclo[3.1.1]heptyl)lithium

Crystal data

[Li(C10H15)(C6H16N2)]	Z = 2
Mr = 258.37	F(000) = 288
Triclinic, P1	Dx = 1.047 Mg m^−3
a = 6.3160 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.6925 (2) Å	Cell parameters from 17767 reflections
c = 13.7463 (2) Å	θ = 3.3–77.9°
α = 97.336 (1)°	µ = 0.44 mm^−1
β = 99.662 (2)°	T = 120 K
γ = 93.520 (2)°	Plate, translucent pale yellow
V = 819.83 (3) Å^3	0.35 × 0.11 × 0.04 mm

Data collection

Rigaku XtaLAB Synergy-S single source diffractometer	3373 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet-S (Cu) X-ray Source	3167 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.056
Detector resolution: 10.0000 pixels mm^-1	θmax = 77.9°, θmin = 3.3°
combination of ω and φ–scans	h = −7→6
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2021)	k = −12→12
Tmin = 0.675, Tmax = 1.000	l = −17→16
20391 measured reflections

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)] = 0.039	Hydrogen site location: difference Fourier map
wR(F^2) = 0.108	All H-atom parameters refined
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0589P)^2 + 0.1668P] where P = (Fo^2 + 2Fc^2)/3
3373 reflections	(Δ/σ)max < 0.001
296 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.22 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. All hydrogen atoms were found from difference Fourier maps and allowed to refine freely.

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

	x	y	z	Uiso*/Ueq
Li	0.7333 (3)	0.33286 (17)	0.29985 (12)	0.0238 (3)
C1	0.96126 (15)	0.54977 (10)	0.17707 (7)	0.0192 (2)
H1	1.093 (2)	0.5059 (13)	0.1561 (9)	0.025 (3)*
C2	0.92371 (15)	0.51687 (9)	0.27849 (7)	0.0188 (2)
C3	0.73585 (15)	0.56432 (10)	0.30578 (7)	0.0219 (2)
H3	0.710 (2)	0.5586 (14)	0.3725 (10)	0.032 (3)*
C4	0.60919 (16)	0.66118 (11)	0.24454 (8)	0.0248 (2)
H4A	0.451 (2)	0.6263 (14)	0.2234 (10)	0.034 (3)*
H4B	0.614 (2)	0.7578 (14)	0.2846 (9)	0.029 (3)*
C5	0.70154 (15)	0.67625 (10)	0.14985 (7)	0.0224 (2)
H5	0.617 (2)	0.7371 (14)	0.1054 (10)	0.030 (3)*
C6	0.95159 (14)	0.71071 (10)	0.17399 (7)	0.0186 (2)
C7	0.74359 (16)	0.52871 (11)	0.10259 (7)	0.0247 (2)
H7A	0.762 (2)	0.5245 (14)	0.0308 (10)	0.032 (3)*
H7B	0.636 (2)	0.4509 (14)	0.1098 (10)	0.032 (3)*
C8	1.04218 (16)	0.75584 (11)	0.08552 (7)	0.0242 (2)
H8A	0.990 (2)	0.6944 (15)	0.0226 (11)	0.036 (3)*
H8B	1.204 (2)	0.7590 (14)	0.0975 (10)	0.035 (3)*
H8C	1.000 (2)	0.8539 (15)	0.0756 (10)	0.034 (3)*
C9	1.04919 (16)	0.81089 (10)	0.26738 (7)	0.0220 (2)
H9A	1.030 (2)	0.9114 (15)	0.2559 (10)	0.037 (4)*
H9B	0.980 (2)	0.7952 (14)	0.3236 (10)	0.031 (3)*
H9C	1.209 (2)	0.8000 (14)	0.2866 (10)	0.031 (3)*
C10	1.06426 (16)	0.43194 (10)	0.32858 (7)	0.0223 (2)
H10A	1.200 (2)	0.4133 (13)	0.3047 (10)	0.029 (3)*
H10B	1.058 (2)	0.4284 (14)	0.3996 (10)	0.029 (3)*
N1	0.57757 (12)	0.16997 (8)	0.19027 (6)	0.01942 (19)
N2	0.64698 (13)	0.21831 (8)	0.40976 (6)	0.02063 (19)
C11	0.48749 (16)	0.11036 (10)	0.34912 (7)	0.0235 (2)
H11B	0.465 (2)	0.0293 (14)	0.3874 (10)	0.033 (3)*
H11A	0.345 (2)	0.1544 (14)	0.3348 (10)	0.033 (3)*
C12	0.55534 (17)	0.05691 (10)	0.25143 (7)	0.0237 (2)
H12A	0.703 (2)	0.0165 (14)	0.2645 (10)	0.032 (3)*
H12B	0.447 (2)	−0.0193 (14)	0.2145 (10)	0.031 (3)*
C13	0.54955 (19)	0.29174 (12)	0.48925 (8)	0.0300 (2)
H13A	0.659 (2)	0.3632 (16)	0.5323 (11)	0.041 (4)*
H13B	0.501 (2)	0.2253 (16)	0.5344 (11)	0.045 (4)*
H13C	0.423 (2)	0.3379 (15)	0.4594 (10)	0.036 (3)*
C14	0.83887 (18)	0.15574 (12)	0.45485 (8)	0.0297 (2)
H14A	0.937 (2)	0.2281 (14)	0.4958 (10)	0.032 (3)*
H14B	0.913 (2)	0.1087 (16)	0.4018 (11)	0.041 (4)*
H14C	0.800 (2)	0.0820 (15)	0.4964 (11)	0.041 (4)*
C15	0.36571 (16)	0.19779 (11)	0.13816 (8)	0.0261 (2)
H15A	0.379 (2)	0.2717 (16)	0.0963 (11)	0.040 (4)*
H15B	0.287 (2)	0.1110 (15)	0.0927 (11)	0.038 (4)*
H15C	0.273 (2)	0.2299 (15)	0.1865 (11)	0.037 (3)*
C16	0.71351 (18)	0.12824 (13)	0.11672 (8)	0.0306 (2)
H16A	0.863 (3)	0.1163 (16)	0.1501 (11)	0.044 (4)*
H16B	0.655 (2)	0.0380 (17)	0.0737 (12)	0.045 (4)*
H16C	0.721 (2)	0.2032 (16)	0.0746 (12)	0.044 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li	0.0257 (8)	0.0230 (8)	0.0214 (8)	−0.0040 (6)	0.0009 (6)	0.0053 (6)
C1	0.0184 (4)	0.0206 (4)	0.0188 (4)	0.0026 (3)	0.0036 (3)	0.0032 (3)
C2	0.0182 (4)	0.0172 (4)	0.0204 (4)	−0.0018 (3)	0.0028 (3)	0.0033 (3)
C3	0.0224 (5)	0.0220 (5)	0.0239 (5)	0.0024 (4)	0.0085 (4)	0.0075 (4)
C4	0.0184 (5)	0.0254 (5)	0.0340 (5)	0.0043 (4)	0.0090 (4)	0.0101 (4)
C5	0.0171 (4)	0.0245 (5)	0.0264 (5)	0.0031 (4)	0.0017 (4)	0.0092 (4)
C6	0.0169 (4)	0.0212 (4)	0.0187 (4)	0.0022 (3)	0.0036 (3)	0.0056 (3)
C7	0.0233 (5)	0.0260 (5)	0.0223 (5)	−0.0020 (4)	−0.0017 (4)	0.0041 (4)
C8	0.0235 (5)	0.0302 (5)	0.0211 (5)	0.0025 (4)	0.0058 (4)	0.0095 (4)
C9	0.0223 (5)	0.0209 (5)	0.0228 (5)	0.0002 (3)	0.0043 (4)	0.0032 (4)
C10	0.0195 (5)	0.0246 (5)	0.0229 (5)	0.0012 (4)	0.0017 (4)	0.0061 (4)
N1	0.0200 (4)	0.0219 (4)	0.0163 (4)	0.0000 (3)	0.0033 (3)	0.0035 (3)
N2	0.0233 (4)	0.0217 (4)	0.0163 (4)	−0.0001 (3)	0.0015 (3)	0.0039 (3)
C11	0.0257 (5)	0.0238 (5)	0.0208 (5)	−0.0046 (4)	0.0046 (4)	0.0050 (4)
C12	0.0301 (5)	0.0184 (4)	0.0221 (5)	−0.0012 (4)	0.0041 (4)	0.0035 (4)
C13	0.0384 (6)	0.0317 (5)	0.0207 (5)	0.0058 (5)	0.0072 (4)	0.0029 (4)
C14	0.0276 (5)	0.0362 (6)	0.0261 (5)	0.0045 (5)	0.0004 (4)	0.0126 (4)
C15	0.0224 (5)	0.0302 (5)	0.0237 (5)	0.0012 (4)	−0.0009 (4)	0.0034 (4)
C16	0.0296 (6)	0.0391 (6)	0.0247 (5)	0.0031 (5)	0.0112 (4)	0.0018 (4)

Geometric parameters (Å, º)

Li—N1	2.1057 (18)	C9—H9A	1.017 (15)
Li—N2	2.1078 (18)	C9—H9B	0.973 (14)
Li—C2	2.1684 (18)	C9—H9C	1.018 (13)
Li—C3	2.2334 (19)	C10—H10A	0.989 (13)
Li—C10	2.1971 (19)	C10—H10B	0.988 (13)
Li—H3	2.311 (13)	N1—C15	1.4657 (12)
Li—H10B	2.334 (13)	N1—C16	1.4673 (13)
C1—C2	1.5222 (12)	N1—C12	1.4775 (12)
C1—C7	1.5555 (13)	N2—C14	1.4680 (13)
C1—C6	1.5705 (13)	N2—C13	1.4698 (13)
C1—H1	1.024 (13)	N2—C11	1.4732 (12)
C2—C3	1.3902 (14)	C11—C12	1.5160 (14)
C2—C10	1.4032 (13)	C11—H11B	1.015 (14)
C3—C4	1.5159 (13)	C11—H11A	1.019 (14)
C3—H3	0.966 (14)	C12—H12A	1.029 (14)
C4—C5	1.5326 (14)	C12—H12B	1.000 (14)
C4—H4A	1.014 (14)	C13—H13A	1.004 (15)
C4—H4B	1.019 (13)	C13—H13B	1.017 (16)
C5—C7	1.5508 (14)	C13—H13C	0.993 (14)
C5—C6	1.5643 (13)	C14—H14A	0.961 (14)
C5—H5	1.014 (13)	C14—H14B	1.007 (15)
C6—C9	1.5210 (13)	C14—H14C	1.013 (15)
C6—C8	1.5286 (12)	C15—H15A	0.983 (15)
C7—H7A	1.009 (14)	C15—H15B	1.027 (14)
C7—H7B	1.008 (14)	C15—H15C	0.990 (15)
C8—H8A	0.980 (15)	C16—H16A	0.999 (16)
C8—H8B	1.006 (14)	C16—H16B	1.003 (16)
C8—H8C	1.021 (14)	C16—H16C	0.989 (16)
N1—Li—N2	88.76 (7)	H8A—C8—H8B	106.9 (11)
N1—Li—C2	127.71 (9)	C6—C8—H8C	109.4 (8)
N2—Li—C2	143.10 (9)	H8A—C8—H8C	107.7 (11)
N1—Li—C10	131.22 (9)	H8B—C8—H8C	107.6 (11)
N2—Li—C10	116.38 (8)	C6—C9—H9A	110.5 (8)
C2—Li—C10	37.49 (4)	C6—C9—H9B	111.8 (8)
N1—Li—C3	130.88 (8)	H9A—C9—H9B	106.9 (11)
N2—Li—C3	125.26 (9)	C6—C9—H9C	110.5 (7)
C2—Li—C3	36.78 (4)	H9A—C9—H9C	108.5 (11)
C10—Li—C3	68.75 (6)	H9B—C9—H9C	108.4 (11)
N1—Li—H3	144.2 (3)	C2—C10—Li	70.15 (7)
N2—Li—H3	101.0 (4)	C2—C10—H10A	118.8 (7)
C2—Li—H3	54.2 (3)	Li—C10—H10A	136.4 (8)
C10—Li—H3	74.7 (3)	C2—C10—H10B	117.1 (8)
C3—Li—H3	24.5 (3)	Li—C10—H10B	85.3 (7)
N1—Li—H10B	146.3 (3)	H10A—C10—H10B	118.6 (11)
N2—Li—H10B	93.3 (3)	C15—N1—C16	109.20 (8)
C2—Li—H10B	54.1 (3)	C15—N1—C12	110.40 (8)
C10—Li—H10B	24.9 (3)	C16—N1—C12	109.29 (8)
C3—Li—H10B	73.2 (3)	C15—N1—Li	115.05 (8)
H3—Li—H10B	68.1 (5)	C16—N1—Li	111.74 (8)
C2—C1—C7	109.50 (8)	C12—N1—Li	100.82 (7)
C2—C1—C6	109.22 (7)	C14—N2—C13	109.09 (8)
C7—C1—C6	87.13 (7)	C14—N2—C11	110.86 (8)
C2—C1—H1	112.5 (7)	C13—N2—C11	109.16 (8)
C7—C1—H1	119.1 (7)	C14—N2—Li	108.18 (8)
C6—C1—H1	116.8 (7)	C13—N2—Li	117.95 (8)
C3—C2—C10	127.17 (9)	C11—N2—Li	101.34 (7)
C3—C2—C1	114.19 (8)	N2—C11—C12	111.64 (8)
C10—C2—C1	118.27 (8)	N2—C11—H11B	110.5 (8)
C3—C2—Li	74.15 (7)	C12—C11—H11B	109.4 (8)
C10—C2—Li	72.36 (7)	N2—C11—H11A	107.5 (7)
C1—C2—Li	123.80 (7)	C12—C11—H11A	109.3 (8)
C2—C3—C4	119.68 (8)	H11B—C11—H11A	108.3 (11)
C2—C3—Li	69.07 (7)	N1—C12—C11	111.51 (8)
C4—C3—Li	134.63 (8)	N1—C12—H12A	107.2 (7)
C2—C3—H3	119.2 (8)	C11—C12—H12A	110.4 (7)
C4—C3—H3	118.7 (8)	N1—C12—H12B	110.6 (8)
Li—C3—H3	82.2 (8)	C11—C12—H12B	108.8 (7)
C3—C4—C5	110.65 (8)	H12A—C12—H12B	108.3 (10)
C3—C4—H4A	112.3 (8)	N2—C13—H13A	109.5 (8)
C5—C4—H4A	107.7 (8)	N2—C13—H13B	111.6 (9)
C3—C4—H4B	110.8 (7)	H13A—C13—H13B	107.0 (12)
C5—C4—H4B	108.5 (7)	N2—C13—H13C	109.7 (8)
H4A—C4—H4B	106.7 (10)	H13A—C13—H13C	110.0 (12)
C4—C5—C7	108.05 (8)	H13B—C13—H13C	109.0 (12)
C4—C5—C6	111.37 (8)	N2—C14—H14A	108.9 (8)
C7—C5—C6	87.51 (7)	N2—C14—H14B	110.7 (8)
C4—C5—H5	112.9 (7)	H14A—C14—H14B	108.9 (12)
C7—C5—H5	118.0 (7)	N2—C14—H14C	111.6 (8)
C6—C5—H5	116.4 (7)	H14A—C14—H14C	109.8 (11)
C9—C6—C8	108.90 (8)	H14B—C14—H14C	107.0 (12)
C9—C6—C5	118.81 (8)	N1—C15—H15A	111.1 (9)
C8—C6—C5	112.52 (8)	N1—C15—H15B	112.2 (8)
C9—C6—C1	118.35 (7)	H15A—C15—H15B	107.4 (12)
C8—C6—C1	111.55 (8)	N1—C15—H15C	110.6 (8)
C5—C6—C1	85.08 (7)	H15A—C15—H15C	107.2 (12)
C5—C7—C1	86.05 (7)	H15B—C15—H15C	108.2 (11)
C5—C7—H7A	113.1 (8)	N1—C16—H16A	111.0 (9)
C1—C7—H7A	113.2 (8)	N1—C16—H16B	111.9 (9)
C5—C7—H7B	115.2 (8)	H16A—C16—H16B	107.9 (12)
C1—C7—H7B	117.4 (7)	N1—C16—H16C	108.2 (9)
H7A—C7—H7B	110.2 (11)	H16A—C16—H16C	108.2 (12)
C6—C8—H8A	113.8 (8)	H16B—C16—H16C	109.6 (12)
C6—C8—H8B	111.3 (8)
C7—C1—C2—C3	−39.93 (11)	C7—C5—C6—C1	−27.90 (7)
C6—C1—C2—C3	53.92 (10)	C2—C1—C6—C9	38.36 (11)
C7—C1—C2—C10	133.56 (9)	C7—C1—C6—C9	148.03 (8)
C6—C1—C2—C10	−132.58 (8)	C2—C1—C6—C8	165.86 (7)
C7—C1—C2—Li	46.66 (11)	C7—C1—C6—C8	−84.47 (8)
C6—C1—C2—Li	140.52 (8)	C2—C1—C6—C5	−81.85 (8)
C10—C2—C3—C4	177.25 (9)	C7—C1—C6—C5	27.82 (7)
C1—C2—C3—C4	−9.94 (13)	C4—C5—C7—C1	−83.53 (8)
Li—C2—C3—C4	−130.37 (10)	C6—C5—C7—C1	28.15 (7)
C10—C2—C3—Li	−52.38 (10)	C2—C1—C7—C5	81.35 (8)
C1—C2—C3—Li	120.43 (9)	C6—C1—C7—C5	−28.04 (7)
C2—C3—C4—C5	7.46 (13)	C3—C2—C10—Li	53.08 (10)
Li—C3—C4—C5	−81.66 (12)	C1—C2—C10—Li	−119.46 (9)
C3—C4—C5—C7	45.11 (10)	C14—N2—C11—C12	−74.60 (10)
C3—C4—C5—C6	−49.40 (11)	C13—N2—C11—C12	165.20 (8)
C4—C5—C6—C9	−39.25 (11)	Li—N2—C11—C12	40.05 (10)
C7—C5—C6—C9	−147.68 (8)	C15—N1—C12—C11	−80.01 (10)
C4—C5—C6—C8	−168.16 (8)	C16—N1—C12—C11	159.87 (8)
C7—C5—C6—C8	83.41 (9)	Li—N1—C12—C11	42.06 (10)
C4—C5—C6—C1	80.53 (8)	N2—C11—C12—N1	−60.64 (11)