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Acta Cryst. (2009). E65, m493    [ doi:10.1107/S1600536809012185 ]

(Biphenyl-2-yl)bromidobis(2-methyltetrahydrofuran-[kappa]O)magnesium(II)

S. Nordschild, D. Wohlgemuth and M. Bolte

Abstract top

In the title Grignard reagent, [MgBr(C12H9)(C5H10O)2], the Mg centre adopts a distorted tetrahedral MgCO2Br arrangement. The dihedral angle between the two aromatic rings of the biphenyl residue is 44.00 (14)°. Each molecule incorporates one R- and one S-configured 2-methyltetrahydrofuran molecule.

Comment top

The title compound is a Grignard reagent, a kind of compounds which is widely used for C—C bond formation or as base in organic chemistry. The Mg centre is four coordinate in a distorted tetrahedral fashion. The bond angles range from 97.02 (1)° for O—Mg—O to 120.53 (8)° for C—Mg—Br. The bond lengths are 2.4750 (10)Å for Mg—Br, 2.143 (3)Å for Mg—C and 2.022 (2)° and 2.030 (2)Å for the Mg—O bonds. The dihedral angles between the two aromatic rings of the biphenyl residue is 44.00 (14)°.

Related literature top

For background to Grignard-type compounds, see Elschenbroich (2008); Schwetlick (1996); Silverman & Rakita (1996).

Experimental top

This compound is commercially available from Chemetall GmbH (CAS 82214–69-5, Product No. 408562). Colourless blocks of (I) were obtained from a solution due to long term storage at ambient temperature.

Refinement top

The H atoms bonded were geometrically positioned and refined with fixed individual displacement parameters [U(H) = 1.2 Ueq(C) or U(H) = 1.5 Ueq(Cmethyl)] using a riding model with Caromatic—H = 0.95 Å, Cmethyl—H = 0.98 Å, Cmethylene—H = 0.99Å and Ctertiary—H = 1.00 Å.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Perspective view of (I) with displacement ellipsoids drawn at the 50% probability level; H atoms omitted for clarity.
(Biphenyl-2-yl)bromidobis(2-methyltetrahydrofuran-κO)magnesium(II) top
Crystal data top
[MgBr(C12H9)(C5H10O)2]F(000) = 896
Mr = 429.67Dx = 1.269 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 40381 reflections
a = 11.6887 (5) Åθ = 3.6–26.6°
b = 16.8061 (9) ŵ = 1.87 mm−1
c = 11.7888 (5) ÅT = 173 K
β = 103.757 (4)°Block, colourless
V = 2249.38 (18) Å30.29 × 0.28 × 0.26 mm
Z = 4
Data collection top
Stoe IPDSII two-circle
diffractometer		4107 independent reflections
Radiation source: fine-focus sealed tube3484 reflections with I > 2σ(I)
graphiteRint = 0.069
ω scansθmax = 25.4°, θmin = 3.6°
Absorption correction: multi-scan
(MULABS; Spek, 2003; Blessing, 1995)		h = −14→14
Tmin = 0.614, Tmax = 0.642k = −20→20
54470 measured reflectionsl = −14→14
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.108 w = 1/[σ2(Fo2) + (0.0462P)2 + 2.3133P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
4107 reflectionsΔρmax = 0.76 e Å−3
236 parametersΔρmin = −0.41 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0043 (6)
Crystal data top
[MgBr(C12H9)(C5H10O)2]V = 2249.38 (18) Å3
Mr = 429.67Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.6887 (5) ŵ = 1.87 mm−1
b = 16.8061 (9) ÅT = 173 K
c = 11.7888 (5) Å0.29 × 0.28 × 0.26 mm
β = 103.757 (4)°
Data collection top
Stoe IPDSII two-circle
diffractometer		4107 independent reflections
Absorption correction: multi-scan
(MULABS; Spek, 2003; Blessing, 1995)		3484 reflections with I > 2σ(I)
Tmin = 0.614, Tmax = 0.642Rint = 0.069
54470 measured reflectionsθmax = 25.4°
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.108Δρmax = 0.76 e Å−3
S = 1.05Δρmin = −0.41 e Å−3
4107 reflectionsAbsolute structure: ?
236 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mg10.56815 (8)0.31486 (6)0.70780 (8)0.0349 (2)
Br10.60093 (3)0.24360 (2)0.89652 (3)0.05398 (15)
O10.4214 (2)0.38260 (15)0.6841 (2)0.0572 (6)
C20.4112 (4)0.4578 (4)0.6045 (5)0.0967 (17)
H2A0.48980.47810.60110.116*
H2B0.36490.44650.52430.116*
C30.3515 (7)0.5122 (4)0.6625 (8)0.159 (4)
H3A0.31140.55420.60850.190*
H3B0.40670.53760.72960.190*
C40.2618 (6)0.4595 (5)0.7036 (7)0.145 (3)
H4A0.23120.48600.76530.173*
H4B0.19510.44500.63790.173*
C50.3367 (5)0.3866 (6)0.7512 (5)0.143 (3)
H50.37630.39480.83540.172*
C60.2702 (6)0.3147 (6)0.7372 (7)0.170 (4)
H6A0.32120.27050.77200.256*
H6B0.23830.30440.65390.256*
H6C0.20520.31990.77620.256*
O110.50159 (19)0.23129 (11)0.58553 (18)0.0412 (5)
C120.4587 (3)0.2531 (2)0.4632 (3)0.0536 (8)
H12A0.49400.30400.44640.064*
H12B0.37180.25870.44300.064*
C130.4955 (5)0.1870 (3)0.3968 (4)0.0852 (15)
H13A0.43550.17770.32310.102*
H13B0.57130.19980.37740.102*
C140.5080 (4)0.1158 (2)0.4719 (4)0.0672 (11)
H14A0.58330.08840.47320.081*
H14B0.44260.07820.44220.081*
C150.5056 (3)0.14444 (18)0.5944 (3)0.0521 (9)
H150.57990.12790.65080.063*
C160.4023 (4)0.1148 (3)0.6359 (4)0.0790 (13)
H16A0.40650.13510.71470.119*
H16B0.40320.05650.63730.119*
H16C0.32940.13340.58290.119*
C210.7121 (2)0.37048 (16)0.6550 (2)0.0341 (6)
C220.7636 (2)0.44648 (17)0.6866 (3)0.0395 (7)
C230.8611 (3)0.4719 (2)0.6460 (3)0.0549 (9)
H230.89280.52340.66660.066*
C240.9121 (3)0.4234 (3)0.5767 (4)0.0627 (11)
H240.97940.44110.55180.075*
C250.8648 (3)0.3495 (2)0.5439 (3)0.0542 (9)
H250.89860.31590.49590.065*
C260.7668 (3)0.32490 (18)0.5821 (3)0.0419 (7)
H260.73450.27410.55770.050*
C310.6804 (3)0.4711 (2)0.8611 (3)0.0483 (8)
H310.69140.41630.88020.058*
C320.7136 (3)0.50025 (17)0.7624 (3)0.0442 (8)
C330.6971 (4)0.5819 (2)0.7384 (3)0.0638 (11)
H330.72050.60390.67320.077*
C340.6474 (5)0.6307 (2)0.8081 (4)0.0854 (16)
H340.63540.68550.78900.102*
C350.6154 (4)0.6014 (3)0.9041 (4)0.0853 (16)
H350.58210.63560.95170.102*
C360.6318 (4)0.5206 (2)0.9319 (3)0.0656 (11)
H360.60990.49970.99860.079*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mg10.0308 (5)0.0364 (5)0.0377 (5)−0.0051 (4)0.0085 (4)−0.0023 (4)
Br10.0496 (2)0.0716 (3)0.0401 (2)−0.01271 (17)0.00923 (14)0.00894 (16)
O10.0412 (13)0.0673 (16)0.0586 (15)0.0132 (11)0.0029 (11)−0.0154 (12)
C20.059 (3)0.116 (4)0.106 (4)0.027 (3)0.002 (3)0.014 (3)
C30.129 (6)0.114 (5)0.174 (8)0.051 (5)−0.082 (6)−0.039 (5)
C40.103 (5)0.204 (8)0.133 (6)0.102 (6)0.039 (4)−0.001 (5)
C50.080 (4)0.269 (10)0.082 (4)0.081 (5)0.023 (3)−0.001 (5)
C60.086 (5)0.277 (12)0.145 (7)−0.072 (6)0.022 (4)0.027 (7)
O110.0477 (12)0.0308 (11)0.0408 (11)−0.0064 (9)0.0017 (9)0.0021 (8)
C120.065 (2)0.0477 (19)0.0407 (17)−0.0002 (17)−0.0019 (15)0.0043 (15)
C130.137 (5)0.065 (3)0.054 (2)−0.002 (3)0.024 (3)−0.013 (2)
C140.072 (3)0.050 (2)0.075 (3)0.0072 (19)0.009 (2)−0.0172 (19)
C150.054 (2)0.0317 (16)0.061 (2)−0.0068 (14)−0.0061 (16)0.0057 (15)
C160.090 (3)0.069 (3)0.073 (3)−0.043 (2)0.010 (2)0.003 (2)
C210.0299 (13)0.0292 (14)0.0409 (15)0.0013 (11)0.0038 (11)0.0036 (12)
C220.0312 (14)0.0343 (15)0.0451 (17)−0.0061 (12)−0.0063 (12)0.0082 (13)
C230.0436 (19)0.054 (2)0.058 (2)−0.0204 (16)−0.0055 (16)0.0150 (17)
C240.0345 (17)0.086 (3)0.067 (2)−0.0100 (18)0.0113 (16)0.025 (2)
C250.0435 (18)0.066 (2)0.057 (2)0.0104 (17)0.0198 (16)0.0174 (18)
C260.0397 (16)0.0364 (16)0.0507 (18)0.0063 (13)0.0129 (14)0.0064 (13)
C310.0481 (18)0.0392 (17)0.0478 (19)0.0046 (14)−0.0079 (14)−0.0072 (14)
C320.0417 (16)0.0341 (16)0.0450 (18)−0.0045 (13)−0.0132 (13)−0.0052 (13)
C330.082 (3)0.0333 (18)0.055 (2)−0.0038 (17)−0.0242 (19)−0.0040 (16)
C340.124 (4)0.038 (2)0.065 (3)0.015 (2)−0.035 (3)−0.017 (2)
C350.103 (4)0.064 (3)0.066 (3)0.033 (2)−0.025 (3)−0.034 (2)
C360.069 (2)0.068 (2)0.049 (2)0.013 (2)−0.0076 (18)−0.0172 (18)
Geometric parameters (Å, °) top
Mg1—O12.022 (2)C14—H14A0.9900
Mg1—O112.030 (2)C14—H14B0.9900
Mg1—C212.143 (3)C15—C161.492 (5)
Mg1—Br12.4750 (10)C15—H151.0000
O1—C51.408 (6)C16—H16A0.9800
O1—C21.562 (6)C16—H16B0.9800
C2—C31.421 (9)C16—H16C0.9800
C2—H2A0.9900C21—C261.412 (4)
C2—H2B0.9900C21—C221.424 (4)
C3—C41.536 (11)C22—C231.403 (5)
C3—H3A0.9900C22—C321.485 (5)
C3—H3B0.9900C23—C241.385 (6)
C4—C51.533 (9)C23—H230.9500
C4—H4A0.9900C24—C251.377 (6)
C4—H4B0.9900C24—H240.9500
C5—C61.425 (11)C25—C261.390 (4)
C5—H51.0000C25—H250.9500
C6—H6A0.9800C26—H260.9500
C6—H6B0.9800C31—C361.393 (5)
C6—H6C0.9800C31—C321.399 (5)
O11—C121.456 (4)C31—H310.9500
O11—C151.463 (4)C32—C331.404 (4)
C12—C131.481 (5)C33—C341.384 (6)
C12—H12A0.9900C33—H330.9500
C12—H12B0.9900C34—C351.366 (7)
C13—C141.475 (6)C34—H340.9500
C13—H13A0.9900C35—C361.398 (6)
C13—H13B0.9900C35—H350.9500
C14—C151.529 (5)C36—H360.9500
O1—Mg1—O1197.02 (10)C13—C14—C15106.8 (3)
O1—Mg1—C21114.41 (11)C13—C14—H14A110.4
O11—Mg1—C21106.87 (11)C15—C14—H14A110.4
O1—Mg1—Br1109.97 (9)C13—C14—H14B110.4
O11—Mg1—Br1104.75 (7)C15—C14—H14B110.4
C21—Mg1—Br1120.53 (8)H14A—C14—H14B108.6
C5—O1—C2109.6 (4)O11—C15—C16110.0 (3)
C5—O1—Mg1129.5 (3)O11—C15—C14104.7 (3)
C2—O1—Mg1118.7 (2)C16—C15—C14113.8 (3)
C3—C2—O1102.0 (5)O11—C15—H15109.4
C3—C2—H2A111.4C16—C15—H15109.4
O1—C2—H2A111.4C14—C15—H15109.4
C3—C2—H2B111.4C15—C16—H16A109.5
O1—C2—H2B111.4C15—C16—H16B109.5
H2A—C2—H2B109.2H16A—C16—H16B109.5
C2—C3—C4103.3 (6)C15—C16—H16C109.5
C2—C3—H3A111.1H16A—C16—H16C109.5
C4—C3—H3A111.1H16B—C16—H16C109.5
C2—C3—H3B111.1C26—C21—C22114.9 (3)
C4—C3—H3B111.1C26—C21—Mg1116.1 (2)
H3A—C3—H3B109.1C22—C21—Mg1128.9 (2)
C5—C4—C3101.7 (5)C23—C22—C21120.8 (3)
C5—C4—H4A111.4C23—C22—C32119.2 (3)
C3—C4—H4A111.4C21—C22—C32120.0 (3)
C5—C4—H4B111.4C24—C23—C22121.3 (3)
C3—C4—H4B111.4C24—C23—H23119.3
H4A—C4—H4B109.3C22—C23—H23119.3
O1—C5—C6109.4 (6)C25—C24—C23119.7 (3)
O1—C5—C4104.4 (6)C25—C24—H24120.1
C6—C5—C4112.8 (7)C23—C24—H24120.1
O1—C5—H5110.0C24—C25—C26119.0 (3)
C6—C5—H5110.0C24—C25—H25120.5
C4—C5—H5110.0C26—C25—H25120.5
C5—C6—H6A109.5C25—C26—C21124.2 (3)
C5—C6—H6B109.5C25—C26—H26117.9
H6A—C6—H6B109.5C21—C26—H26117.9
C5—C6—H6C109.5C36—C31—C32121.6 (3)
H6A—C6—H6C109.5C36—C31—H31119.2
H6B—C6—H6C109.5C32—C31—H31119.2
C12—O11—C15108.6 (2)C31—C32—C33117.2 (3)
C12—O11—Mg1120.80 (18)C31—C32—C22121.0 (3)
C15—O11—Mg1129.73 (19)C33—C32—C22121.8 (3)
O11—C12—C13105.0 (3)C34—C33—C32121.1 (4)
O11—C12—H12A110.7C34—C33—H33119.5
C13—C12—H12A110.7C32—C33—H33119.5
O11—C12—H12B110.7C35—C34—C33121.0 (4)
C13—C12—H12B110.7C35—C34—H34119.5
H12A—C12—H12B108.8C33—C34—H34119.5
C14—C13—C12106.9 (3)C34—C35—C36119.7 (4)
C14—C13—H13A110.3C34—C35—H35120.1
C12—C13—H13A110.3C36—C35—H35120.1
C14—C13—H13B110.3C31—C36—C35119.4 (4)
C12—C13—H13B110.3C31—C36—H36120.3
H13A—C13—H13B108.6C35—C36—H36120.3
O11—Mg1—O1—C5101.5 (5)C13—C14—C15—C16115.6 (4)
C21—Mg1—O1—C5−146.4 (5)O1—Mg1—C21—C26−130.5 (2)
Br1—Mg1—O1—C5−7.1 (5)O11—Mg1—C21—C26−24.4 (2)
O11—Mg1—O1—C2−97.5 (3)Br1—Mg1—C21—C2694.8 (2)
C21—Mg1—O1—C214.7 (3)O1—Mg1—C21—C2252.0 (3)
Br1—Mg1—O1—C2154.0 (3)O11—Mg1—C21—C22158.2 (2)
C5—O1—C2—C320.6 (6)Br1—Mg1—C21—C22−82.6 (3)
Mg1—O1—C2—C3−144.0 (4)C26—C21—C22—C230.3 (4)
O1—C2—C3—C4−38.6 (5)Mg1—C21—C22—C23177.7 (2)
C2—C3—C4—C543.7 (7)C26—C21—C22—C32179.6 (3)
C2—O1—C5—C6127.7 (6)Mg1—C21—C22—C32−2.9 (4)
Mg1—O1—C5—C6−69.9 (7)C21—C22—C23—C24−1.6 (5)
C2—O1—C5—C46.8 (7)C32—C22—C23—C24179.0 (3)
Mg1—O1—C5—C4169.2 (4)C22—C23—C24—C251.7 (5)
C3—C4—C5—O1−29.7 (8)C23—C24—C25—C26−0.4 (5)
C3—C4—C5—C6−148.4 (7)C24—C25—C26—C21−1.0 (5)
O1—Mg1—O11—C1260.3 (3)C22—C21—C26—C251.1 (4)
C21—Mg1—O11—C12−57.9 (3)Mg1—C21—C26—C25−176.7 (2)
Br1—Mg1—O11—C12173.1 (2)C36—C31—C32—C330.8 (5)
O1—Mg1—O11—C15−131.4 (3)C36—C31—C32—C22−179.0 (3)
C21—Mg1—O11—C15110.4 (3)C23—C22—C32—C31−136.9 (3)
Br1—Mg1—O11—C15−18.6 (3)C21—C22—C32—C3143.7 (4)
C15—O11—C12—C13−28.8 (4)C23—C22—C32—C3343.3 (4)
Mg1—O11—C12—C13141.7 (3)C21—C22—C32—C33−136.1 (3)
O11—C12—C13—C1425.2 (5)C31—C32—C33—C34−1.6 (5)
C12—C13—C14—C15−12.7 (5)C22—C32—C33—C34178.2 (3)
C12—O11—C15—C16−102.0 (3)C32—C33—C34—C351.6 (6)
Mg1—O11—C15—C1688.6 (3)C33—C34—C35—C36−0.7 (7)
C12—O11—C15—C1420.7 (4)C32—C31—C36—C350.1 (5)
Mg1—O11—C15—C14−148.7 (2)C34—C35—C36—C31−0.1 (6)
C13—C14—C15—O11−4.6 (4)
Table 1
Selected geometric parameters (Å, °) top
Mg1—O12.022 (2)Mg1—C212.143 (3)
Mg1—O112.030 (2)Mg1—Br12.4750 (10)
O1—Mg1—O1197.02 (10)O1—Mg1—Br1109.97 (9)
O1—Mg1—C21114.41 (11)O11—Mg1—Br1104.75 (7)
O11—Mg1—C21106.87 (11)C21—Mg1—Br1120.53 (8)
Acknowledgements top

none

references
References top

Blessing, R. H. (1995). Acta Cryst. A51, 33–38.

Elschenbroich, C. (2008). In Organometallchemie. Stuttgart: Teubner BG.

Schwetlick, K. (1996). In Organikum. Heidelberg: Johann Ambrosius Barth.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Silverman, G. S. & Rakita, P. E. (1996). In Handbook of Grignard Reagents. New York: Dekker.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.