Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102020425/ob1088sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102020425/ob1088Isup2.hkl |
CCDC reference: 201284
The precursor complex, [Cu(C15H26N2)(ClO4)2] was prepared by mixing a solution of copper(II) perchlorate in ethanol–triethylorthoformate (3:1 v/v) with a stoichiometric amount of (-)-l-sparteine, (6R,7S,9S,11S)-C15H26N2. The resulting dark-blue solution was added to a stoichiometric amount of potassium fluoride. CuF2 salts were immediately precipitated and were removed from the solution by filtration. Single crystals of (I) were obtained by slow evaporation from the solution at room temperature. Analysis calculated for C15H27ClN2O4: C 53.81, H 8.13, N 8.37%; found: C 53.63, H 8.00, N 8.34%.
The positional parameters of the H atoms were calculated geometrically (C—H = 0.96–0.98 Å) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(CH and CH2). The H atom on N1 was located in a difference map and refined isotropically.
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).
C15H27N2+·ClO4− | F(000) = 720 |
Mr = 334.84 | Dx = 1.348 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 8.029 (2) Å | θ = 11.3–14.1° |
b = 13.4196 (16) Å | µ = 0.25 mm−1 |
c = 15.3094 (16) Å | T = 293 K |
V = 1649.6 (5) Å3 | Block, yellow |
Z = 4 | 0.33 × 0.3 × 0.3 mm |
Enraf-Nonius CAD-4 diffractometer | 1559 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.012 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
non–profiled ω/2θ scans | h = −1→10 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→17 |
Tmin = 0.887, Tmax = 0.926 | l = 0→19 |
2438 measured reflections | 3 standard reflections every 300 min |
2402 independent reflections | intensity decay: 1% |
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)] = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0533P)2 + 0.3075P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2402 reflections | Δρmax = 0.25 e Å−3 |
203 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 232 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (13) |
C15H27N2+·ClO4− | V = 1649.6 (5) Å3 |
Mr = 334.84 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.029 (2) Å | µ = 0.25 mm−1 |
b = 13.4196 (16) Å | T = 293 K |
c = 15.3094 (16) Å | 0.33 × 0.3 × 0.3 mm |
Enraf-Nonius CAD-4 diffractometer | 1559 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.012 |
Tmin = 0.887, Tmax = 0.926 | 3 standard reflections every 300 min |
2438 measured reflections | intensity decay: 1% |
2402 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.128 | Δρmax = 0.25 e Å−3 |
S = 1.02 | Δρmin = −0.24 e Å−3 |
2402 reflections | Absolute structure: Flack (1983), 232 Friedel pairs |
203 parameters | Absolute structure parameter: 0.00 (13) |
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 | ||
N1 | 0.1462 (4) | 0.5025 (3) | 0.43971 (19) | 0.0366 (7) | |
H1 | 0.242 (5) | 0.505 (4) | 0.418 (3) | 0.044 (11)* | |
N16 | 0.3437 (4) | 0.5980 (2) | 0.3186 (2) | 0.0373 (8) | |
C2 | 0.1250 (7) | 0.4216 (3) | 0.5064 (3) | 0.0494 (12) | |
H2A | 0.0163 | 0.4275 | 0.5335 | 0.059* | |
H2B | 0.2087 | 0.4289 | 0.5516 | 0.059* | |
C3 | 0.1414 (7) | 0.3196 (3) | 0.4646 (3) | 0.0575 (13) | |
H3A | 0.2542 | 0.3109 | 0.4432 | 0.069* | |
H3B | 0.1205 | 0.2686 | 0.5081 | 0.069* | |
C4 | 0.0204 (7) | 0.3072 (3) | 0.3898 (3) | 0.0592 (14) | |
H4A | −0.0928 | 0.3090 | 0.4117 | 0.071* | |
H4B | 0.0381 | 0.2432 | 0.3618 | 0.071* | |
C5 | 0.0457 (7) | 0.3906 (3) | 0.3235 (3) | 0.0494 (12) | |
H5A | −0.0340 | 0.3830 | 0.2763 | 0.059* | |
H5B | 0.1566 | 0.3856 | 0.2989 | 0.059* | |
C6 | 0.0237 (5) | 0.4927 (3) | 0.3652 (2) | 0.0376 (8) | |
H6 | −0.0886 | 0.4953 | 0.3902 | 0.045* | |
C7 | 0.0398 (6) | 0.5793 (3) | 0.3018 (3) | 0.0434 (11) | |
H7 | −0.0477 | 0.5730 | 0.2575 | 0.052* | |
C8 | 0.0140 (6) | 0.6777 (3) | 0.3508 (3) | 0.0465 (11) | |
H8A | 0.0173 | 0.7332 | 0.3102 | 0.056* | |
H8B | −0.0933 | 0.6778 | 0.3799 | 0.056* | |
C9 | 0.1532 (6) | 0.6871 (3) | 0.4173 (3) | 0.0426 (10) | |
H9 | 0.1391 | 0.7504 | 0.4484 | 0.051* | |
C10 | 0.1362 (6) | 0.6029 (3) | 0.4833 (2) | 0.0430 (11) | |
H10A | 0.2242 | 0.6083 | 0.5265 | 0.052* | |
H10B | 0.0303 | 0.6089 | 0.5134 | 0.052* | |
C11 | 0.3235 (5) | 0.6882 (3) | 0.3726 (3) | 0.0401 (9) | |
H11 | 0.4070 | 0.6840 | 0.4192 | 0.048* | |
C12 | 0.3593 (6) | 0.7841 (3) | 0.3225 (3) | 0.0495 (11) | |
H12A | 0.3517 | 0.8405 | 0.3619 | 0.059* | |
H12B | 0.2765 | 0.7928 | 0.2770 | 0.059* | |
C13 | 0.5329 (6) | 0.7811 (3) | 0.2815 (3) | 0.0603 (14) | |
H13A | 0.5495 | 0.8401 | 0.2459 | 0.072* | |
H13B | 0.6165 | 0.7810 | 0.3272 | 0.072* | |
C14 | 0.5527 (7) | 0.6893 (3) | 0.2256 (3) | 0.0564 (12) | |
H14A | 0.6665 | 0.6851 | 0.2047 | 0.068* | |
H14B | 0.4798 | 0.6940 | 0.1753 | 0.068* | |
C15 | 0.5104 (6) | 0.5957 (3) | 0.2776 (3) | 0.0492 (12) | |
H15A | 0.5166 | 0.5385 | 0.2389 | 0.059* | |
H15B | 0.5936 | 0.5867 | 0.3229 | 0.059* | |
C17 | 0.2077 (5) | 0.5847 (3) | 0.2555 (3) | 0.0440 (11) | |
H17A | 0.2257 | 0.5239 | 0.2225 | 0.053* | |
H17B | 0.2073 | 0.6400 | 0.2147 | 0.053* | |
Cl | 0.10569 (12) | 0.00084 (9) | 0.46176 (7) | 0.0495 (3) | |
O1 | 0.2009 (5) | −0.0724 (3) | 0.5068 (2) | 0.0729 (11) | |
O2 | 0.0187 (6) | 0.0599 (3) | 0.5240 (3) | 0.0980 (14) | |
O3 | −0.0101 (5) | −0.0503 (3) | 0.4058 (2) | 0.0923 (14) | |
O4 | 0.2127 (6) | 0.0604 (3) | 0.4112 (3) | 0.1147 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0334 (17) | 0.0433 (17) | 0.0332 (16) | 0.000 (2) | 0.0004 (14) | −0.0010 (18) |
N16 | 0.0352 (18) | 0.0418 (19) | 0.0349 (16) | 0.0020 (16) | 0.0025 (16) | −0.0050 (15) |
C2 | 0.049 (3) | 0.059 (3) | 0.040 (2) | −0.008 (3) | 0.001 (2) | 0.012 (2) |
C3 | 0.061 (3) | 0.046 (2) | 0.066 (3) | −0.002 (3) | 0.007 (3) | 0.009 (3) |
C4 | 0.065 (4) | 0.047 (2) | 0.066 (3) | −0.008 (3) | 0.003 (3) | −0.003 (2) |
C5 | 0.051 (3) | 0.052 (2) | 0.045 (2) | −0.007 (3) | −0.005 (2) | −0.009 (2) |
C6 | 0.0322 (19) | 0.045 (2) | 0.0353 (18) | −0.002 (2) | −0.0041 (17) | 0.000 (2) |
C7 | 0.041 (2) | 0.049 (2) | 0.041 (2) | −0.002 (2) | −0.011 (2) | 0.000 (2) |
C8 | 0.037 (3) | 0.048 (2) | 0.054 (3) | 0.007 (2) | 0.001 (2) | 0.006 (2) |
C9 | 0.045 (3) | 0.0334 (19) | 0.050 (2) | 0.003 (2) | 0.006 (2) | −0.009 (2) |
C10 | 0.042 (3) | 0.051 (3) | 0.036 (2) | −0.002 (2) | 0.001 (2) | −0.0129 (19) |
C11 | 0.037 (2) | 0.043 (2) | 0.041 (2) | 0.001 (2) | −0.001 (2) | −0.010 (2) |
C12 | 0.045 (3) | 0.045 (2) | 0.058 (3) | −0.003 (2) | 0.007 (2) | −0.006 (2) |
C13 | 0.052 (3) | 0.054 (3) | 0.075 (3) | −0.011 (3) | 0.015 (3) | 0.001 (2) |
C14 | 0.054 (3) | 0.057 (3) | 0.058 (3) | −0.005 (3) | 0.017 (3) | 0.002 (2) |
C15 | 0.043 (3) | 0.052 (3) | 0.053 (3) | 0.006 (2) | 0.007 (2) | −0.007 (2) |
C17 | 0.055 (3) | 0.043 (2) | 0.033 (2) | −0.003 (2) | 0.000 (2) | −0.0010 (19) |
Cl | 0.0376 (5) | 0.0537 (5) | 0.0572 (6) | 0.0023 (7) | 0.0040 (5) | 0.0115 (6) |
O1 | 0.074 (3) | 0.067 (2) | 0.078 (2) | 0.017 (2) | −0.024 (2) | 0.0033 (18) |
O2 | 0.094 (3) | 0.080 (2) | 0.120 (3) | 0.022 (3) | 0.027 (3) | −0.015 (2) |
O3 | 0.060 (3) | 0.140 (4) | 0.077 (2) | −0.012 (3) | −0.021 (2) | 0.002 (2) |
O4 | 0.094 (4) | 0.120 (3) | 0.130 (3) | −0.033 (3) | 0.032 (3) | 0.052 (3) |
N1—C2 | 1.500 (5) | C8—H8B | 0.9700 |
N1—C6 | 1.512 (5) | C9—C10 | 1.522 (5) |
N1—C10 | 1.506 (5) | C9—C11 | 1.529 (6) |
N1—H1 | 0.84 (4) | C9—H9 | 0.9800 |
N16—C11 | 1.475 (5) | C10—H10A | 0.9700 |
N16—C15 | 1.479 (5) | C10—H10B | 0.9700 |
N16—C17 | 1.469 (5) | C11—C12 | 1.526 (6) |
C2—C3 | 1.516 (6) | C11—H11 | 0.9800 |
C2—H2A | 0.9700 | C12—C13 | 1.529 (6) |
C2—H2B | 0.9700 | C12—H12A | 0.9700 |
C3—C4 | 1.511 (7) | C12—H12B | 0.9700 |
C3—H3A | 0.9700 | C13—C14 | 1.509 (6) |
C3—H3B | 0.9700 | C13—H13A | 0.9700 |
C4—C5 | 1.523 (6) | C13—H13B | 0.9700 |
C4—H4A | 0.9700 | C14—C15 | 1.525 (5) |
C4—H4B | 0.9700 | C14—H14A | 0.9700 |
C5—C6 | 1.522 (5) | C14—H14B | 0.9700 |
C5—H5A | 0.9700 | C15—H15A | 0.9700 |
C5—H5B | 0.9700 | C15—H15B | 0.9700 |
C6—C7 | 1.519 (5) | C17—H17A | 0.9700 |
C6—H6 | 0.9800 | C17—H17B | 0.9700 |
C7—C17 | 1.525 (6) | Cl—O1 | 1.423 (3) |
C7—C8 | 1.533 (5) | Cl—O2 | 1.423 (4) |
C7—H7 | 0.9800 | Cl—O3 | 1.439 (4) |
C8—C9 | 1.518 (6) | Cl—O4 | 1.406 (4) |
C8—H8A | 0.9700 | ||
C2—N1—C6 | 112.2 (3) | C10—C9—C11 | 112.6 (4) |
C2—N1—C10 | 109.9 (3) | C8—C9—H9 | 108.2 |
C6—N1—C10 | 112.2 (3) | C10—C9—H9 | 108.2 |
C2—N1—H1 | 114 (3) | C11—C9—H9 | 108.2 |
C6—N1—H1 | 107 (3) | N1—C10—C9 | 111.4 (3) |
C10—N1—H1 | 101 (4) | N1—C10—H10A | 109.3 |
C11—N16—C15 | 110.8 (3) | C9—C10—H10A | 109.3 |
C11—N16—C17 | 112.7 (3) | N1—C10—H10B | 109.3 |
C15—N16—C17 | 113.0 (3) | C9—C10—H10B | 109.3 |
N1—C2—C3 | 110.9 (3) | H10A—C10—H10B | 108.0 |
N1—C2—H2A | 109.5 | N16—C11—C12 | 112.9 (3) |
C3—C2—H2A | 109.5 | N16—C11—C9 | 109.9 (3) |
N1—C2—H2B | 109.5 | C12—C11—C9 | 113.7 (4) |
C3—C2—H2B | 109.5 | N16—C11—H11 | 106.6 |
H2A—C2—H2B | 108.1 | C12—C11—H11 | 106.6 |
C4—C3—C2 | 111.3 (4) | C9—C11—H11 | 106.6 |
C4—C3—H3A | 109.4 | C11—C12—C13 | 110.9 (4) |
C2—C3—H3A | 109.4 | C11—C12—H12A | 109.5 |
C4—C3—H3B | 109.4 | C13—C12—H12A | 109.5 |
C2—C3—H3B | 109.4 | C11—C12—H12B | 109.5 |
H3A—C3—H3B | 108.0 | C13—C12—H12B | 109.5 |
C3—C4—C5 | 109.8 (4) | H12A—C12—H12B | 108.1 |
C3—C4—H4A | 109.7 | C14—C13—C12 | 110.5 (4) |
C5—C4—H4A | 109.7 | C14—C13—H13A | 109.6 |
C3—C4—H4B | 109.7 | C12—C13—H13A | 109.6 |
C5—C4—H4B | 109.7 | C14—C13—H13B | 109.6 |
H4A—C4—H4B | 108.2 | C12—C13—H13B | 109.6 |
C4—C5—C6 | 111.5 (3) | H13A—C13—H13B | 108.1 |
C4—C5—H5A | 109.3 | C13—C14—C15 | 110.7 (3) |
C6—C5—H5A | 109.3 | C13—C14—H14A | 109.5 |
C4—C5—H5B | 109.3 | C15—C14—H14A | 109.5 |
C6—C5—H5B | 109.3 | C13—C14—H14B | 109.5 |
H5A—C5—H5B | 108.0 | C15—C14—H14B | 109.5 |
N1—C6—C7 | 111.1 (3) | H14A—C14—H14B | 108.1 |
N1—C6—C5 | 108.6 (3) | N16—C15—C14 | 113.9 (4) |
C7—C6—C5 | 114.3 (3) | N16—C15—H15A | 108.8 |
N1—C6—H6 | 107.5 | C14—C15—H15A | 108.8 |
C7—C6—H6 | 107.5 | N16—C15—H15B | 108.8 |
C5—C6—H6 | 107.5 | C14—C15—H15B | 108.8 |
C6—C7—C17 | 114.1 (3) | H15A—C15—H15B | 107.7 |
C6—C7—C8 | 109.6 (3) | N16—C17—C7 | 110.9 (3) |
C17—C7—C8 | 107.8 (4) | N16—C17—H17A | 109.5 |
C6—C7—H7 | 108.4 | C7—C17—H17A | 109.5 |
C17—C7—H7 | 108.4 | N16—C17—H17B | 109.5 |
C8—C7—H7 | 108.4 | C7—C17—H17B | 109.5 |
C7—C8—C9 | 107.5 (4) | H17A—C17—H17B | 108.0 |
C9—C8—H8A | 110.2 | O1—Cl—O2 | 108.9 (2) |
C7—C8—H8A | 110.2 | O1—Cl—O3 | 107.8 (2) |
C9—C8—H8B | 110.2 | O1—Cl—O4 | 109.3 (3) |
C7—C8—H8B | 110.2 | O2—Cl—O3 | 110.3 (3) |
H8A—C8—H8B | 108.5 | O2—Cl—O4 | 110.6 (3) |
C8—C9—C10 | 108.6 (4) | O3—Cl—O4 | 109.8 (3) |
C8—C9—C11 | 111.0 (3) | ||
C10—N1—C2—C3 | −177.7 (4) | C8—C9—C10—N1 | 59.4 (5) |
C6—N1—C2—C3 | 56.7 (5) | C11—C9—C10—N1 | −63.9 (5) |
N1—C2—C3—C4 | −55.5 (5) | C17—N16—C11—C12 | −73.6 (4) |
C2—C3—C4—C5 | 55.8 (5) | C15—N16—C11—C12 | 54.1 (4) |
C3—C4—C5—C6 | −57.8 (5) | C17—N16—C11—C9 | 54.6 (4) |
C2—N1—C6—C7 | 176.2 (3) | C15—N16—C11—C9 | −177.7 (3) |
C10—N1—C6—C7 | 51.9 (4) | C8—C9—C11—N16 | −56.4 (4) |
C2—N1—C6—C5 | −57.3 (4) | C10—C9—C11—N16 | 65.6 (4) |
C10—N1—C6—C5 | 178.5 (3) | C8—C9—C11—C12 | 71.3 (4) |
C4—C5—C6—N1 | 57.8 (5) | C10—C9—C11—C12 | −166.7 (3) |
C4—C5—C6—C7 | −177.5 (4) | N16—C11—C12—C13 | −55.3 (5) |
N1—C6—C7—C17 | 63.8 (4) | C9—C11—C12—C13 | 178.6 (4) |
C5—C6—C7—C17 | −59.5 (5) | C11—C12—C13—C14 | 54.4 (5) |
N1—C6—C7—C8 | −57.1 (4) | C12—C13—C14—C15 | −53.6 (6) |
C5—C6—C7—C8 | 179.5 (4) | C17—N16—C15—C14 | 73.7 (4) |
C6—C7—C8—C9 | 63.3 (4) | C11—N16—C15—C14 | −53.9 (4) |
C17—C7—C8—C9 | −61.4 (4) | C13—C14—C15—N16 | 54.5 (5) |
C7—C8—C9—C10 | −63.8 (4) | C11—N16—C17—C7 | −58.0 (4) |
C7—C8—C9—C11 | 60.5 (4) | C15—N16—C17—C7 | 175.4 (3) |
C2—N1—C10—C9 | −178.7 (4) | C6—C7—C17—N16 | −61.2 (4) |
C6—N1—C10—C9 | −53.2 (5) | C8—C7—C17—N16 | 60.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.84 (4) | 2.54 (4) | 3.155 (6) | 130 (4) |
N1—H1···N16 | 0.84 (4) | 2.13 (5) | 2.755 (5) | 131 (4) |
Symmetry code: (i) x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C15H27N2+·ClO4− |
Mr | 334.84 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 8.029 (2), 13.4196 (16), 15.3094 (16) |
V (Å3) | 1649.6 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.33 × 0.3 × 0.3 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.887, 0.926 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2438, 2402, 1559 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.128, 1.02 |
No. of reflections | 2402 |
No. of parameters | 203 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.24 |
Absolute structure | Flack (1983), 232 Friedel pairs |
Absolute structure parameter | 0.00 (13) |
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).
N1—C2 | 1.500 (5) | N16—C17 | 1.469 (5) |
N1—C6 | 1.512 (5) | Cl—O1 | 1.423 (3) |
N1—C10 | 1.506 (5) | Cl—O2 | 1.423 (4) |
N1—H1 | 0.84 (4) | Cl—O3 | 1.439 (4) |
N16—C11 | 1.475 (5) | Cl—O4 | 1.406 (4) |
N16—C15 | 1.479 (5) | ||
C2—N1—C6 | 112.2 (3) | C10—N1—H1 | 101 (4) |
C2—N1—C10 | 109.9 (3) | C11—N16—C15 | 110.8 (3) |
C6—N1—C10 | 112.2 (3) | C11—N16—C17 | 112.7 (3) |
C2—N1—H1 | 114 (3) | C15—N16—C17 | 113.0 (3) |
C6—N1—H1 | 107 (3) | C7—C8—C9 | 107.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.84 (4) | 2.54 (4) | 3.155 (6) | 130 (4) |
N1—H1···N16 | 0.84 (4) | 2.13 (5) | 2.755 (5) | 131 (4) |
Symmetry code: (i) x+1/2, −y+1/2, −z+1. |
The crystal structure of sparteinium monoperchlorate, (I), has been determined previously (Borovyak et al., 1973). However, the refinement of the structure was not complete and the structural data collected was very limited; the H-atom and ClO4- positions were not determined. We redetermined the crystal structure of (I) for two reasons: (i) there is a need for the complete and well refined crystal structure of (-)-sparteine in order to understand the structural features of many previously reported metal–sparteine complexes (Kim et al., 2001; Kuroda & Mason, 1979; Lee et al., 1998, 2000, 2002; Lopez et al., 1998; Motevalli et al., 1993), and (ii) compound (I) has attracted research attention and has been intensively utilized in medicinal chemistry (Cady et al., 1977) and asymmetric synthesis (Beak et al., 1996; Kretchmer, 1972; Mason & Peacock, 1973).
The neutral dialkaloid sparteine structure is composed of four rings, two of which (A and B) form a double-chair system of trans-quinolizidine, which is relatively resistant to conformation–configuration change upon protonation. However, the second system of rings (C and D) is much more susceptible to inversion on an N-donor atom (N16) and inversion may occur in a trans-boat-chair or cis-double-chair conformation. The outer rings (A and D) are directed upward (cis) or downward (trans) with respect to the methylene bridge, i.e. the H atoms on C6 and C11 are in trans–trans or cis–cis positions, respectively. The conformation and configuration of the spartenium cation in (I) was found to be the same as reportedpreviously (Borovyak et al., 1973).
Based on 13C NMR and IR studies, Boczon & Koziol (1997) suggested that sparteine and its isomers and derivatives can undergo conformational–configurational rearrangements in solution. It is well known that, in the case of the monoprotonated base, viz. C15H27N2+, in solution, a tautomeric equilibrium takes place, with the contributions of cations N1—H1···N16 and N1···H1—N16 being 1:1.25 (Boczon & Koziol, 1997). However, in the solid state, the H atom bonds to atom N1 and the compound crystallizes exclusively in the N1—H1···N16 tautomeric form (Fig. 1 and Table 1). The H atom also interacts with perchlorate atom O2 to form a rare three-centered hydrogen bond (bifurcated hydrogen bonding), as shown in Fig. 2. The four hydrogen-bonding atoms (N1, N16, H1 and O2) are nearly in the same plane, as the sum of three angles N1—H1···N16, N1—H1···O2 and N16···H1···O2 is approximately 358°. Atom H1 on protonated atom N1 is axial relative to rings A and B, as is usually observed (Boczon & Koziol, 1997). The N1···N16 distance is 2.755 (5) Å, which is considerably less than the sum of the van der Waals radii of 3.16 Å and confirms the participation of the two N atoms in a bifurcated intramolecular hydrogen bond (Table 2).
The (-)-sparteine conformation in metal(II)–(-)-sparteine complexes is almost identical to the conformations in free and monoprotonated (-)-sparteine. In the complexes, there is a relationship between N—M—N bite angle and M—N distance, i.e. if the N—M—N bite angle is smaller then the M—N bond is longer (Lee et al., 2002). In fact, the N—M—N bite angle in the metal(II)–(-)-sparteine complexes affects the N···N distance of the coordinated (-)-sparteine ligand. The N1···N16 distance of (I) is shorter than those observed in the metal complexes due to the intramolecular N—H···N hydrogen bond and the cation size.