Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105033858/av1265sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105033858/av1265Isup2.hkl |
CCDC reference: 294307
The title complex, [HgCl2(C15H26N2)], was prepared by the direct reaction of mercury(II) chloride with a stoichiometric amount of (-)-L-sparteine in an ethanol–triethylorthoformate (5:1 v/v) solution. The resulting colourless precipitate was filtered off, washed with cold absolute ethanol and dried in a vacuum. Single crystals of (I) were obtained by recrystallization at room temperature in a dichloromethane–triethylorthoformate (5:1 v/v) solution. Analysis, calculated for HgC15H26N2Cl2: C 35.61, H 5.18, N 5.54%; found C 35.69, H 5.23, N 5.65%.
The H atoms of the sparteine ligand were positioned geometrically and constrained to ride on their attached atoms, with C—H distances in the range 0.97–0.98 Å and with Uiso(H) = 1.2Ueq(C). [Please check amended text]
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. A diagram of (I), showing the atom-numbering scheme and 30% probability displacement ellipsoids. H atoms are drawn as small spheres of arbitrary radii. |
[HgCl2(C15H26N2)] | F(000) = 976 |
Mr = 505.87 | Dx = 1.955 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 23 reflections |
a = 11.191 (3) Å | θ = 11.5–12.7° |
b = 12.1156 (11) Å | µ = 9.26 mm−1 |
c = 12.6742 (10) Å | T = 293 K |
V = 1718.4 (5) Å3 | Block, colourless |
Z = 4 | 0.26 × 0.23 × 0.2 mm |
Enraf–Nonius CAD-4 diffractometer | 3052 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.047 |
Graphite monochromator | θmax = 27.5°, θmin = 2.3° |
Non–profiled ω/2θ scans | h = −14→14 |
Absorption correction: ψ scan (North et al., 1968) | k = −1→15 |
Tmin = 0.099, Tmax = 0.154 | l = −1→16 |
5070 measured reflections | 3 standard reflections every 400 reflections |
3935 independent reflections | intensity decay: 2% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0309P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
3935 reflections | Δρmax = 1.37 e Å−3 |
181 parameters | Δρmin = −0.70 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 1694 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.001 (14) |
[HgCl2(C15H26N2)] | V = 1718.4 (5) Å3 |
Mr = 505.87 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.191 (3) Å | µ = 9.26 mm−1 |
b = 12.1156 (11) Å | T = 293 K |
c = 12.6742 (10) Å | 0.26 × 0.23 × 0.2 mm |
Enraf–Nonius CAD-4 diffractometer | 3052 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.047 |
Tmin = 0.099, Tmax = 0.154 | 3 standard reflections every 400 reflections |
5070 measured reflections | intensity decay: 2% |
3935 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.082 | Δρmax = 1.37 e Å−3 |
S = 1.01 | Δρmin = −0.70 e Å−3 |
3935 reflections | Absolute structure: Flack (1983), with 1694 Friedel pairs |
181 parameters | Absolute structure parameter: −0.001 (14) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Hg | 0.80449 (3) | 0.23667 (3) | 0.10368 (3) | 0.03363 (11) | |
Cl1 | 0.8267 (4) | 0.0505 (2) | 0.0428 (2) | 0.0732 (11) | |
Cl2 | 0.7951 (4) | 0.3995 (2) | −0.0001 (2) | 0.0641 (8) | |
N1 | 0.6964 (8) | 0.2107 (5) | 0.2610 (5) | 0.0315 (16) | |
C2 | 0.5727 (8) | 0.1768 (9) | 0.2285 (8) | 0.046 (3) | |
H2A | 0.5260 | 0.1593 | 0.2907 | 0.055* | |
H2B | 0.5771 | 0.1111 | 0.1850 | 0.055* | |
C3 | 0.5118 (8) | 0.2685 (10) | 0.1673 (8) | 0.053 (3) | |
H3A | 0.5532 | 0.2793 | 0.1008 | 0.063* | |
H3B | 0.4303 | 0.2466 | 0.1515 | 0.063* | |
C4 | 0.5102 (10) | 0.3747 (10) | 0.2268 (10) | 0.056 (3) | |
H4A | 0.4550 | 0.3689 | 0.2856 | 0.068* | |
H4B | 0.4825 | 0.4334 | 0.1810 | 0.068* | |
C5 | 0.6337 (9) | 0.4027 (9) | 0.2679 (9) | 0.048 (3) | |
H5A | 0.6843 | 0.4227 | 0.2088 | 0.058* | |
H5B | 0.6279 | 0.4665 | 0.3139 | 0.058* | |
C6 | 0.6907 (11) | 0.3108 (8) | 0.3268 (8) | 0.044 (2) | |
H6 | 0.6370 | 0.2934 | 0.3855 | 0.053* | |
C7 | 0.8124 (9) | 0.3368 (8) | 0.3760 (7) | 0.038 (2) | |
H7 | 0.8012 | 0.4000 | 0.4232 | 0.046* | |
C8 | 0.8701 (10) | 0.1436 (9) | 0.3712 (8) | 0.040 (3) | |
H8 | 0.8924 | 0.0799 | 0.4146 | 0.048* | |
N9 | 0.9538 (6) | 0.2708 (6) | 0.2346 (5) | 0.0289 (16) | |
C10 | 1.0583 (7) | 0.3005 (9) | 0.1684 (8) | 0.040 (3) | |
H10A | 1.0438 | 0.3721 | 0.1366 | 0.048* | |
H10B | 1.0653 | 0.2471 | 0.1117 | 0.048* | |
C11 | 1.1764 (10) | 0.3049 (9) | 0.2279 (8) | 0.056 (3) | |
H11A | 1.2411 | 0.3205 | 0.1793 | 0.068* | |
H11B | 1.1739 | 0.3634 | 0.2802 | 0.068* | |
C12 | 1.1976 (10) | 0.1953 (8) | 0.2815 (7) | 0.048 (3) | |
H12A | 1.2052 | 0.1377 | 0.2289 | 0.058* | |
H12B | 1.2713 | 0.1982 | 0.3217 | 0.058* | |
C13 | 1.0956 (9) | 0.1698 (10) | 0.3534 (7) | 0.048 (3) | |
H13A | 1.0922 | 0.2250 | 0.4087 | 0.058* | |
H13B | 1.1091 | 0.0987 | 0.3864 | 0.058* | |
C14 | 0.9760 (9) | 0.1674 (7) | 0.2951 (7) | 0.030 (2) | |
H14 | 0.9794 | 0.1066 | 0.2442 | 0.036* | |
C15 | 0.7521 (9) | 0.1163 (8) | 0.3180 (8) | 0.041 (3) | |
H15A | 0.7651 | 0.0566 | 0.2683 | 0.050* | |
H15B | 0.6965 | 0.0901 | 0.3711 | 0.050* | |
C16 | 0.9142 (9) | 0.3659 (8) | 0.3010 (8) | 0.035 (2) | |
H16A | 0.8885 | 0.4255 | 0.2551 | 0.042* | |
H16B | 0.9816 | 0.3924 | 0.3418 | 0.042* | |
C17 | 0.8499 (8) | 0.2392 (11) | 0.4444 (6) | 0.049 (3) | |
H17A | 0.9226 | 0.2564 | 0.4826 | 0.059* | |
H17B | 0.7877 | 0.2217 | 0.4950 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg | 0.04195 (18) | 0.03382 (17) | 0.02511 (14) | −0.00029 (19) | −0.00381 (19) | 0.00046 (17) |
Cl1 | 0.131 (3) | 0.0409 (15) | 0.0473 (17) | 0.0093 (19) | −0.009 (2) | −0.0194 (13) |
Cl2 | 0.105 (3) | 0.0481 (15) | 0.0388 (14) | 0.009 (2) | −0.0020 (19) | 0.0164 (12) |
N1 | 0.030 (4) | 0.036 (4) | 0.028 (3) | 0.004 (4) | 0.007 (4) | 0.001 (3) |
C2 | 0.017 (5) | 0.073 (8) | 0.049 (6) | −0.017 (5) | 0.003 (5) | −0.014 (6) |
C3 | 0.015 (4) | 0.085 (9) | 0.057 (6) | −0.002 (6) | −0.002 (4) | −0.015 (7) |
C4 | 0.043 (7) | 0.063 (8) | 0.064 (8) | 0.011 (6) | −0.005 (6) | −0.027 (6) |
C5 | 0.033 (6) | 0.055 (7) | 0.056 (7) | 0.013 (5) | −0.011 (5) | −0.022 (6) |
C6 | 0.034 (5) | 0.060 (6) | 0.038 (5) | −0.001 (7) | −0.003 (6) | −0.006 (5) |
C7 | 0.027 (5) | 0.048 (5) | 0.039 (6) | 0.009 (5) | −0.004 (6) | −0.023 (4) |
C8 | 0.041 (6) | 0.048 (6) | 0.032 (6) | 0.002 (5) | −0.003 (5) | 0.016 (5) |
N9 | 0.031 (4) | 0.033 (4) | 0.022 (3) | 0.001 (4) | 0.000 (3) | −0.008 (4) |
C10 | 0.017 (5) | 0.050 (6) | 0.052 (6) | 0.004 (4) | 0.007 (4) | 0.005 (5) |
C11 | 0.038 (8) | 0.073 (8) | 0.058 (7) | −0.001 (6) | 0.012 (6) | −0.015 (6) |
C12 | 0.027 (5) | 0.069 (7) | 0.049 (6) | 0.023 (6) | −0.013 (6) | −0.021 (5) |
C13 | 0.042 (6) | 0.070 (8) | 0.032 (5) | 0.022 (6) | −0.018 (5) | −0.001 (5) |
C14 | 0.044 (6) | 0.022 (5) | 0.023 (5) | 0.011 (4) | −0.005 (4) | −0.008 (4) |
C15 | 0.043 (6) | 0.044 (6) | 0.037 (6) | −0.013 (5) | 0.005 (5) | 0.021 (5) |
C16 | 0.026 (5) | 0.033 (5) | 0.048 (6) | −0.004 (5) | 0.001 (5) | −0.020 (5) |
C17 | 0.035 (5) | 0.090 (9) | 0.023 (4) | 0.005 (7) | −0.001 (4) | −0.014 (6) |
Hg—N1 | 2.353 (7) | C8—C15 | 1.519 (13) |
Hg—N9 | 2.391 (6) | C8—C14 | 1.555 (13) |
Hg—Cl1 | 2.397 (3) | C8—H8 | 0.9800 |
Hg—Cl2 | 2.374 (2) | N9—C10 | 1.483 (10) |
N1—C6 | 1.473 (11) | N9—C14 | 1.490 (11) |
N1—C15 | 1.489 (11) | N9—C16 | 1.494 (11) |
N1—C2 | 1.501 (12) | C10—C11 | 1.522 (14) |
C2—C3 | 1.516 (15) | C10—H10A | 0.9700 |
C2—H2A | 0.9700 | C10—H10B | 0.9700 |
C2—H2B | 0.9700 | C11—C12 | 1.510 (14) |
C3—C4 | 1.492 (14) | C11—H11A | 0.9700 |
C3—H3A | 0.9700 | C11—H11B | 0.9700 |
C3—H3B | 0.9700 | C12—C13 | 1.493 (15) |
C4—C5 | 1.515 (15) | C12—H12A | 0.9700 |
C4—H4A | 0.9700 | C12—H12B | 0.9700 |
C4—H4B | 0.9700 | C13—C14 | 1.529 (13) |
C5—C6 | 1.485 (14) | C13—H13A | 0.9700 |
C5—H5A | 0.9700 | C13—H13B | 0.9700 |
C5—H5B | 0.9700 | C14—H14 | 0.9800 |
C6—C7 | 1.531 (14) | C15—H15A | 0.9700 |
C6—H6 | 0.9800 | C15—H15B | 0.9700 |
C7—C17 | 1.524 (14) | C16—H16A | 0.9700 |
C7—C16 | 1.525 (13) | C16—H16B | 0.9700 |
C7—H7 | 0.9800 | C17—H17A | 0.9700 |
C8—C17 | 1.501 (14) | C17—H17B | 0.9700 |
N1—Hg—N9 | 78.2 (3) | C10—N9—C14 | 111.4 (7) |
N1—Hg—Cl1 | 101.55 (18) | C10—N9—C16 | 111.4 (7) |
N1—Hg—Cl2 | 123.90 (19) | C14—N9—C16 | 114.1 (6) |
N9—Hg—Cl1 | 108.3 (2) | C10—N9—Hg | 101.6 (5) |
N9—Hg—Cl2 | 105.8 (2) | C14—N9—Hg | 109.2 (5) |
Cl1—Hg—Cl2 | 127.48 (11) | C16—N9—Hg | 108.4 (5) |
C6—N1—C15 | 112.1 (7) | N9—C10—C11 | 114.3 (8) |
C6—N1—C2 | 109.9 (8) | N9—C10—H10A | 108.7 |
C15—N1—C2 | 108.0 (7) | C11—C10—H10A | 108.7 |
C6—N1—Hg | 113.0 (6) | N9—C10—H10B | 108.7 |
C15—N1—Hg | 107.4 (6) | C11—C10—H10B | 108.7 |
C2—N1—Hg | 106.1 (5) | H10A—C10—H10B | 107.6 |
N1—C2—C3 | 110.8 (8) | C12—C11—C10 | 109.2 (10) |
N1—C2—H2A | 109.5 | C12—C11—H11A | 109.8 |
C3—C2—H2A | 109.5 | C10—C11—H11A | 109.8 |
N1—C2—H2B | 109.5 | C12—C11—H11B | 109.8 |
C3—C2—H2B | 109.5 | C10—C11—H11B | 109.8 |
H2A—C2—H2B | 108.1 | H11A—C11—H11B | 108.3 |
C4—C3—C2 | 112.2 (9) | C13—C12—C11 | 109.7 (10) |
C4—C3—H3A | 109.2 | C13—C12—H12A | 109.7 |
C2—C3—H3A | 109.2 | C11—C12—H12A | 109.7 |
C4—C3—H3B | 109.2 | C13—C12—H12B | 109.7 |
C2—C3—H3B | 109.2 | C11—C12—H12B | 109.7 |
H3A—C3—H3B | 107.9 | H12A—C12—H12B | 108.2 |
C3—C4—C5 | 110.9 (9) | C12—C13—C14 | 112.2 (8) |
C3—C4—H4A | 109.5 | C12—C13—H13A | 109.2 |
C5—C4—H4A | 109.5 | C14—C13—H13A | 109.2 |
C3—C4—H4B | 109.5 | C12—C13—H13B | 109.2 |
C5—C4—H4B | 109.5 | C14—C13—H13B | 109.2 |
H4A—C4—H4B | 108.1 | H13A—C13—H13B | 107.9 |
C6—C5—C4 | 113.4 (10) | N9—C14—C13 | 112.2 (8) |
C6—C5—H5A | 108.9 | N9—C14—C8 | 110.4 (7) |
C4—C5—H5A | 108.9 | C13—C14—C8 | 111.8 (8) |
C6—C5—H5B | 108.9 | N9—C14—H14 | 107.4 |
C4—C5—H5B | 108.9 | C13—C14—H14 | 107.4 |
H5A—C5—H5B | 107.7 | C8—C14—H14 | 107.4 |
N1—C6—C5 | 110.6 (8) | N1—C15—C8 | 114.3 (8) |
N1—C6—C7 | 111.2 (9) | N1—C15—H15A | 108.7 |
C5—C6—C7 | 115.7 (9) | C8—C15—H15A | 108.7 |
N1—C6—H6 | 106.2 | N1—C15—H15B | 108.7 |
C5—C6—H6 | 106.2 | C8—C15—H15B | 108.7 |
C7—C6—H6 | 106.2 | H15A—C15—H15B | 107.6 |
C17—C7—C16 | 109.2 (8) | N9—C16—C7 | 113.2 (7) |
C17—C7—C6 | 108.5 (8) | N9—C16—H16A | 108.9 |
C16—C7—C6 | 117.2 (8) | C7—C16—H16A | 108.9 |
C17—C7—H7 | 107.2 | N9—C16—H16B | 108.9 |
C16—C7—H7 | 107.2 | C7—C16—H16B | 108.9 |
C6—C7—H7 | 107.2 | H16A—C16—H16B | 107.7 |
C17—C8—C15 | 108.2 (9) | C8—C17—C7 | 106.8 (7) |
C17—C8—C14 | 110.8 (8) | C8—C17—H17A | 110.4 |
C15—C8—C14 | 115.3 (8) | C7—C17—H17A | 110.4 |
C17—C8—H8 | 107.4 | C8—C17—H17B | 110.4 |
C15—C8—H8 | 107.4 | C7—C17—H17B | 110.4 |
C14—C8—H8 | 107.4 | H17A—C17—H17B | 108.6 |
Cl2—Hg—N1—C6 | −39.3 (8) | Cl2—Hg—N9—C16 | 62.0 (6) |
N9—Hg—N1—C6 | 61.9 (7) | Cl1—Hg—N9—C16 | −158.6 (5) |
Cl1—Hg—N1—C6 | 168.4 (7) | C14—N9—C10—C11 | −52.2 (11) |
Cl2—Hg—N1—C15 | −163.4 (5) | C16—N9—C10—C11 | 76.4 (11) |
N9—Hg—N1—C15 | −62.2 (6) | Hg—N9—C10—C11 | −168.3 (7) |
Cl1—Hg—N1—C15 | 44.3 (6) | N9—C10—C11—C12 | 56.1 (12) |
Cl2—Hg—N1—C2 | 81.3 (6) | C10—C11—C12—C13 | −57.4 (10) |
N9—Hg—N1—C2 | −177.6 (6) | C11—C12—C13—C14 | 57.7 (11) |
Cl1—Hg—N1—C2 | −71.1 (6) | C10—N9—C14—C13 | 49.6 (9) |
C6—N1—C2—C3 | 58.9 (9) | C16—N9—C14—C13 | −77.6 (10) |
C15—N1—C2—C3 | −178.5 (8) | Hg—N9—C14—C13 | 160.9 (6) |
Hg—N1—C2—C3 | −63.6 (8) | C10—N9—C14—C8 | 175.0 (8) |
N1—C2—C3—C4 | −54.9 (11) | C16—N9—C14—C8 | 47.8 (10) |
C2—C3—C4—C5 | 50.0 (13) | Hg—N9—C14—C8 | −73.7 (7) |
C3—C4—C5—C6 | −51.1 (14) | C12—C13—C14—N9 | −53.9 (11) |
C15—N1—C6—C5 | −179.4 (8) | C12—C13—C14—C8 | −178.6 (9) |
C2—N1—C6—C5 | −59.3 (11) | C17—C8—C14—N9 | −56.9 (10) |
Hg—N1—C6—C5 | 59.1 (11) | C15—C8—C14—N9 | 66.4 (10) |
C15—N1—C6—C7 | 50.6 (11) | C17—C8—C14—C13 | 68.8 (10) |
C2—N1—C6—C7 | 170.7 (8) | C15—C8—C14—C13 | −167.9 (9) |
Hg—N1—C6—C7 | −70.9 (8) | C6—N1—C15—C8 | −49.5 (12) |
C4—C5—C6—N1 | 56.1 (13) | C2—N1—C15—C8 | −170.8 (8) |
C4—C5—C6—C7 | −176.3 (9) | Hg—N1—C15—C8 | 75.2 (8) |
N1—C6—C7—C17 | −59.9 (10) | C17—C8—C15—N1 | 56.0 (10) |
C5—C6—C7—C17 | 172.9 (8) | C14—C8—C15—N1 | −68.6 (11) |
N1—C6—C7—C16 | 64.3 (11) | C10—N9—C16—C7 | −175.9 (7) |
C5—C6—C7—C16 | −62.9 (12) | C14—N9—C16—C7 | −48.8 (11) |
N1—Hg—N9—C10 | −177.7 (6) | Hg—N9—C16—C7 | 73.1 (8) |
Cl2—Hg—N9—C10 | −55.4 (6) | C17—C7—C16—N9 | 55.7 (10) |
Cl1—Hg—N9—C10 | 83.9 (6) | C6—C7—C16—N9 | −68.2 (11) |
N1—Hg—N9—C14 | 64.7 (5) | C15—C8—C17—C7 | −63.0 (10) |
Cl2—Hg—N9—C14 | −173.1 (5) | C14—C8—C17—C7 | 64.3 (11) |
Cl1—Hg—N9—C14 | −33.8 (5) | C16—C7—C17—C8 | −62.8 (10) |
N1—Hg—N9—C16 | −60.2 (6) | C6—C7—C17—C8 | 66.1 (10) |
Experimental details
Crystal data | |
Chemical formula | [HgCl2(C15H26N2)] |
Mr | 505.87 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 11.191 (3), 12.1156 (11), 12.6742 (10) |
V (Å3) | 1718.4 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 9.26 |
Crystal size (mm) | 0.26 × 0.23 × 0.2 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.099, 0.154 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5070, 3935, 3052 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.082, 1.01 |
No. of reflections | 3935 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.37, −0.70 |
Absolute structure | Flack (1983), with 1694 Friedel pairs |
Absolute structure parameter | −0.001 (14) |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Hg—N1 | 2.353 (7) | Hg—Cl1 | 2.397 (3) |
Hg—N9 | 2.391 (6) | Hg—Cl2 | 2.374 (2) |
N1—Hg—N9 | 78.2 (3) | N9—Hg—Cl1 | 108.3 (2) |
N1—Hg—Cl1 | 101.55 (18) | N9—Hg—Cl2 | 105.8 (2) |
N1—Hg—Cl2 | 123.90 (19) | Cl1—Hg—Cl2 | 127.48 (11) |
Cl···H | Hg—Cl···H | |
Hg—Cl1···H15Bi | 2.776 | 145.1 |
Hg—Cl2···H7ii | 2.829 | 157.1 |
Symmetry codes: (i) 3/2 − x, −y, z − 1/2; (ii) 3/2 − x, −y, z − 1/2. |
(-)-Sparteine, C15H26N2, a naturally occurring tertiary diamine, has attracted research attention. It has been intensively utilized in medicinal chemistry (Cady et al., 1977), in the asymmetric synthesis of chiral compounds (Beak et al., 1996; Kretchmer, 1972; Mason & Peacock, 1973) and in the preparation of a model compound for the type I copper(II) site in metalloproteins (Kim et al., 2001). The structures of several metal(II) sparteine dichloride complexes of the type [MX2(C15H26N2)] (M = FeII, CoII, NiII, CuII or ZnII, and X = Cl− or Br−) have been reported, and the metal moieties in these compounds are known to have a distorted tetrahedral geometry (Kang, Choi et al., 2004; Kang, Lee et al. 2004; Kuroda & Mason, 1979; Lee et al., 2002, 2003; Lopez et al., 1998; Lorber et al., 2002).
The zinc(II) ion has a closed-shell electronic structure of d10, and consequently the molecular structure of [ZnCl2(C15H26N2)] (Lee et al., 2003) is thought to be determined solely by the steric effect of the (-)-sparteine ligand operating on the ZnCl2 unit. The two Zn—N bond distances in [ZnCl2(C15H26N2)] [2.085 (7) and 2.087 (7) Å] are nearly equal and the dihedral angle between the N1—Zn—N9 and Cl1—Zn—Cl2 planes is 82.2 (2)°, only 7.8° smaller than the value of 90° for a perfect tetrahedron. Although the two Cu—N bond distances [2.003 (13) and 2.021 (11) Å] in [CuCl2(C15H26N2)] (Lopez et al., 1998) are equal within two standard deviations, a smaller dihedral angle of 67.0° was observed between N1—Cu—N9 and Cl1—Cu—Cl2. This is definitely the result of the balance of the electronic effect of the d9 system and the steric effect imposed by the bulky (-)-sparteine ligand. The electronic effect of d9 configuration on the geometry of four-coordinate CuII complexes tends to prefer a square-planar to a tetrahedral structure (Figgis, 1966).
The synthesis of the title compound, (I), was prompted by our interest in the preparation of a momomeric and tetrahedral HgII compound and a desire to compare the coordination geometry and bonding parameters of (I) with the analogous CuII and ZnII sparteine dichloride complexes for which structures are already known (Lee et al., 2003; Lopez et al., 1998).
The crystal structure of complex (I) was determined, and selected bond distances and angles for (I) are listed in Table 1. The complex is monomeric and shows the expected overall geometric features, with the (-)-sparteine molecule acting as a bidentate ligand in its all-chair conformation. The coordination around the HgII atom in (I) is well described by a slightly distorted tetrahedron. The mid-point of the N1···N9 line of the sparteine ligand does not lie in the Cl1—Hg—Cl2 plane, but is tilted towards atom N1 by 0.346 Å (23.1% of half of the N1···N9 distance). Similarly, the mid-point of the Cl1···Cl2 line is tilted toward atom Cl2 by 0.163 Å (7.6% of half of the Cl1···Cl2 distance). The N1—Hg—Cl1 bite angle is 4.35° smaller than the N9—Hg—Cl2 bite angle. However, the N1—Hg—Cl2 bite angle is 5.6° larger than the N9—Hg—Cl1 bite angle.
The dihedral angle between the N1—Hg—N9 and Cl1—Hg—Cl2 planes in (I) is 81.1 (2)°, which is quite similar to that between the N1—Zn—N9 and Cl1—Zn—Cl2 planes in [ZnCl2(C15H26N2)]. However, the two Hg—N and the two Hg—Cl bond distances in (I) differ significantly (Table 1), whereas the two Zn—N and the two Zn—Cl bond distances in [ZnCl2(C15H26N2)] are nearly identical, respectively (Lee et al., 2003). Asymmetry in the two MII—N bond distances was also observed in [CoCl2(C15H26N2)] [2.040 (7) and 2.068 (8) Å; Kuroda & Mason, 1979], and was considered to be attributed to the cis- and trans-ring junctions of the ring including atoms N1 and N9, respectively (Lorber et al., 2002). However, the observation of the asymmetry in the two HgII—N bond distances in the d10 compound, (I), is somewhat surprising, since the two MII—N bond distances in another d10 complex, [ZnCl2(C15H26N2)], and in a high-spin d5 complex, [FeCl2(C15H26N2)] (Lee et al., 2003; Lorber et al., 2002), in which the electronic effect on the coordination geometry is not operative, are almost identical.
The crystal structure of (I) is stabilized through two interatomic Cl···H contacts involving two Cl atoms and the methylene or methine H atoms of the (-)-sparteine ligand, namely Hg—Cl1···H15Bi and Hg—Cl2···H7ii (Table 2). The Cl···H separations are then 0.22 and 0.17 Å shorter, respectively, than the sum of the Cl and H van der Waals radii (Pauling, 1960).
The asymmetry in the two Hg—N bond distances in (I) might be attributable either to the poorer Lewis acidity of HgII or to the intermolecular Cl···H interaction in the crystalline packing structure.