
Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802017154/tk6078sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536802017154/tk6078Isup2.hkl |
CCDC reference: 198315
(S)-(-)-Nicotine (0.24 g, 1.5 mmol) dissolved in an ethanol-triethylorthoformate mixture (15.0 ml; 5:1 v/v) was added to an excess of concentrated HCl. To this solution, 1.0 mmol of anhydrous CuCl2 dissolved in an ethanol-triethlyorthoformate mixture (5.0 ml; 5:1 v/v) was added. The resulting solution was stirred vigorously for 2 h at room temperature and was then refrigerated overnight. The bright yellow precipitate which appeared was collected by filtration and washed with cold absolute ethanol and dried under vacuum. The yield of the product was 0.28 g (76.03%) based on CuCl2. The orange crystals used for analysis were obtained by recrystallization from absolute ethanol. Analysis calculated for C10H16Cl4CuN2: C 32.50, H 4.36, N 7.58%; found: C 32.70, H 4.39, N 7.63%.
The positional parameters of the H atoms were calculated geometrically (C—H = 0.96–0.98 Å and N—H = 0.86–0.91 Å) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(CH, CH2, and NH) or 1.5Ueq(CH3). Intensity statistics suggested non-centrosymmetric space group P1 with |E2-1| = 0.725 and proved correct from the successful refinement.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
(C10H16N2)[CuCl4] | Z = 2 |
Mr = 369.59 | F(000) = 374 |
Triclinic, P1 | Dx = 1.602 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6919 (8) Å | Cell parameters from 50 reflections |
b = 8.1526 (9) Å | θ = 5.0–15.3° |
c = 12.2337 (15) Å | µ = 2.10 mm−1 |
α = 87.249 (9)° | T = 293 K |
β = 88.694 (8)° | Block, orange |
γ = 89.414 (7)° | 0.50 × 0.45 × 0.26 mm |
V = 766.05 (15) Å3 |
Bruker P4 diffractometer | 3327 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
2θ/ω scans | h = −1→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −10→10 |
Tmin = 0.663, Tmax = 0.988 | l = −15→15 |
4302 measured reflections | 3 standard reflections every 97 reflections |
4302 independent reflections | intensity decay: none |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + (0.0406P)2 + 0.6259P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.099 | (Δ/σ)max = 0.001 |
S = 1.05 | Δρmax = 0.70 e Å−3 |
4302 reflections | Δρmin = −0.71 e Å−3 |
290 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
4 restraints | Extinction coefficient: 0.0251 (16) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 781 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.037 (17) |
(C10H16N2)[CuCl4] | γ = 89.414 (7)° |
Mr = 369.59 | V = 766.05 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.6919 (8) Å | Mo Kα radiation |
b = 8.1526 (9) Å | µ = 2.10 mm−1 |
c = 12.2337 (15) Å | T = 293 K |
α = 87.249 (9)° | 0.50 × 0.45 × 0.26 mm |
β = 88.694 (8)° |
Bruker P4 diffractometer | 3327 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.663, Tmax = 0.988 | 3 standard reflections every 97 reflections |
4302 measured reflections | intensity decay: none |
4302 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.099 | Δρmax = 0.70 e Å−3 |
S = 1.05 | Δρmin = −0.71 e Å−3 |
4302 reflections | Absolute structure: Flack (1983), 781 Friedel pairs |
290 parameters | Absolute structure parameter: −0.037 (17) |
4 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 | ||
Cu1 | 0.45109 (9) | 0.47409 (8) | 0.68886 (6) | 0.0483 (2) | |
Cu2 | −0.04690 (10) | −0.09647 (9) | 1.20718 (6) | 0.0521 (2) | |
Cl1 | 0.5423 (2) | 0.66843 (19) | 0.56747 (13) | 0.0559 (4) | |
Cl2 | 0.5420 (2) | 0.2158 (2) | 0.74059 (16) | 0.0645 (5) | |
Cl3 | 0.5213 (3) | 0.6052 (3) | 0.84022 (14) | 0.0853 (8) | |
Cl4 | 0.2175 (3) | 0.3936 (2) | 0.60310 (16) | 0.0687 (5) | |
Cl5 | 0.0208 (3) | −0.2799 (2) | 1.08265 (15) | 0.0652 (5) | |
Cl6 | −0.3083 (3) | −0.0122 (3) | 1.1496 (2) | 0.0934 (8) | |
Cl7 | 0.0524 (3) | −0.2349 (3) | 1.35607 (14) | 0.0823 (7) | |
Cl8 | 0.0597 (3) | 0.1536 (2) | 1.23306 (16) | 0.0700 (5) | |
N1 | 0.6252 (7) | 0.1280 (6) | 0.3943 (4) | 0.0479 (12) | |
H1 | 0.6784 | 0.1113 | 0.3285 | 0.057* | |
C2 | 0.6276 (9) | 0.3097 (7) | 0.4135 (5) | 0.0411 (13) | |
H2 | 0.5493 | 0.3299 | 0.4758 | 0.049* | |
C3 | 0.8127 (9) | 0.3346 (8) | 0.4494 (6) | 0.0556 (17) | |
H3A | 0.8884 | 0.3608 | 0.3866 | 0.067* | |
H3B | 0.8173 | 0.4233 | 0.4992 | 0.067* | |
C4 | 0.8680 (14) | 0.1736 (10) | 0.5061 (8) | 0.0801 (18) | |
H4A | 0.9814 | 0.1395 | 0.4787 | 0.096* | |
H4B | 0.8745 | 0.1855 | 0.5844 | 0.096* | |
C5 | 0.7342 (12) | 0.0505 (10) | 0.4820 (6) | 0.0659 (15) | |
H5A | 0.6636 | 0.0233 | 0.5469 | 0.079* | |
H5B | 0.7890 | −0.0492 | 0.4573 | 0.079* | |
C6 | 0.4454 (13) | 0.0581 (12) | 0.3933 (8) | 0.090 (2) | |
H6A | 0.3815 | 0.1111 | 0.3348 | 0.135* | |
H6B | 0.3868 | 0.0761 | 0.4619 | 0.135* | |
H6C | 0.4529 | −0.0576 | 0.3825 | 0.135* | |
C7 | 0.5632 (8) | 0.4099 (7) | 0.3159 (5) | 0.0441 (14) | |
C8 | 0.4058 (9) | 0.4876 (8) | 0.3194 (5) | 0.0492 (15) | |
H8 | 0.3367 | 0.4786 | 0.3828 | 0.059* | |
N9 | 0.3504 (9) | 0.5762 (7) | 0.2329 (5) | 0.0598 (16) | |
H9 | 0.2511 | 0.6250 | 0.2373 | 0.072* | |
C10 | 0.4428 (11) | 0.5926 (9) | 0.1392 (6) | 0.0625 (19) | |
H10 | 0.3979 | 0.6543 | 0.0803 | 0.075* | |
C11 | 0.6015 (11) | 0.5199 (10) | 0.1293 (6) | 0.063 (2) | |
H11 | 0.6674 | 0.5325 | 0.0649 | 0.076* | |
C12 | 0.6633 (10) | 0.4250 (9) | 0.2197 (6) | 0.0569 (17) | |
H12 | 0.7709 | 0.3723 | 0.2151 | 0.068* | |
N13 | 0.2330 (8) | 0.1530 (7) | 0.9112 (4) | 0.0609 (16) | |
H13 | 0.2844 | 0.1724 | 0.8441 | 0.073* | |
C14 | 0.0515 (9) | 0.1013 (8) | 0.8941 (5) | 0.0522 (15) | |
H14 | 0.0016 | 0.0580 | 0.9639 | 0.063* | |
C15 | −0.0365 (14) | 0.2655 (10) | 0.8633 (8) | 0.092 (3) | |
H15A | −0.0332 | 0.2859 | 0.7845 | 0.111* | |
H15B | −0.1569 | 0.2653 | 0.8886 | 0.111* | |
C16 | 0.0625 (13) | 0.3942 (10) | 0.9176 (8) | 0.0801 (18) | |
H16A | 0.0969 | 0.4809 | 0.8647 | 0.096* | |
H16B | −0.0086 | 0.4420 | 0.9746 | 0.096* | |
C17 | 0.2154 (11) | 0.3137 (9) | 0.9645 (6) | 0.0659 (15) | |
H17A | 0.2003 | 0.2965 | 1.0431 | 0.079* | |
H17B | 0.3180 | 0.3799 | 0.9495 | 0.079* | |
C18 | 0.3390 (13) | 0.0304 (12) | 0.9712 (9) | 0.090 (2) | |
H18A | 0.3417 | −0.0698 | 0.9330 | 0.135* | |
H18B | 0.2897 | 0.0100 | 1.0433 | 0.135* | |
H18C | 0.4552 | 0.0705 | 0.9766 | 0.135* | |
C19 | 0.0348 (8) | −0.0264 (7) | 0.8094 (5) | 0.0411 (13) | |
C20 | −0.1145 (10) | −0.1155 (9) | 0.8152 (6) | 0.0588 (18) | |
H20 | −0.1935 | −0.1035 | 0.8730 | 0.071* | |
N21 | −0.1472 (9) | −0.2209 (7) | 0.7369 (6) | 0.0656 (17) | |
H21 | −0.2427 | −0.2750 | 0.7416 | 0.079* | |
C22 | −0.0383 (11) | −0.2457 (9) | 0.6523 (7) | 0.065 (2) | |
H22 | −0.0672 | −0.3162 | 0.5981 | 0.078* | |
C23 | 0.1148 (11) | −0.1655 (9) | 0.6476 (6) | 0.0618 (19) | |
H23 | 0.1968 | −0.1856 | 0.5927 | 0.074* | |
C24 | 0.1481 (9) | −0.0529 (8) | 0.7256 (6) | 0.0551 (16) | |
H24 | 0.2510 | 0.0061 | 0.7203 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0495 (5) | 0.0505 (4) | 0.0454 (4) | −0.0169 (4) | −0.0002 (3) | −0.0037 (3) |
Cu2 | 0.0503 (5) | 0.0578 (4) | 0.0481 (4) | 0.0172 (4) | −0.0036 (4) | −0.0045 (3) |
Cl1 | 0.0618 (11) | 0.0487 (8) | 0.0567 (8) | −0.0152 (8) | 0.0011 (8) | 0.0041 (6) |
Cl2 | 0.0545 (11) | 0.0616 (10) | 0.0757 (11) | −0.0014 (9) | 0.0065 (9) | 0.0103 (8) |
Cl3 | 0.1103 (19) | 0.1024 (15) | 0.0455 (9) | −0.0643 (15) | 0.0119 (11) | −0.0196 (9) |
Cl4 | 0.0524 (11) | 0.0755 (12) | 0.0798 (12) | −0.0191 (9) | −0.0138 (9) | −0.0122 (9) |
Cl5 | 0.0699 (12) | 0.0640 (10) | 0.0635 (10) | 0.0111 (9) | −0.0054 (9) | −0.0216 (8) |
Cl6 | 0.0641 (14) | 0.1025 (16) | 0.1170 (17) | 0.0317 (13) | −0.0425 (13) | −0.0296 (14) |
Cl7 | 0.1011 (17) | 0.0976 (14) | 0.0455 (8) | 0.0541 (13) | 0.0062 (10) | 0.0098 (9) |
Cl8 | 0.0693 (13) | 0.0683 (11) | 0.0734 (11) | 0.0073 (10) | −0.0063 (10) | −0.0137 (9) |
N1 | 0.049 (3) | 0.043 (3) | 0.053 (3) | −0.004 (2) | −0.008 (3) | −0.007 (2) |
C2 | 0.045 (3) | 0.041 (3) | 0.038 (3) | 0.007 (3) | −0.010 (3) | −0.002 (2) |
C3 | 0.046 (4) | 0.052 (4) | 0.071 (4) | −0.003 (3) | −0.015 (3) | −0.013 (3) |
C4 | 0.086 (5) | 0.071 (4) | 0.085 (4) | −0.004 (3) | −0.008 (4) | −0.014 (3) |
C5 | 0.084 (4) | 0.063 (3) | 0.051 (3) | −0.020 (3) | 0.000 (3) | −0.011 (2) |
C6 | 0.072 (4) | 0.095 (5) | 0.103 (5) | −0.017 (4) | −0.033 (4) | 0.013 (4) |
C7 | 0.039 (3) | 0.047 (3) | 0.045 (3) | 0.007 (3) | −0.003 (3) | −0.004 (3) |
C8 | 0.044 (4) | 0.055 (4) | 0.048 (3) | 0.009 (3) | −0.003 (3) | −0.005 (3) |
N9 | 0.053 (4) | 0.064 (3) | 0.063 (4) | 0.018 (3) | −0.013 (3) | 0.000 (3) |
C10 | 0.062 (5) | 0.060 (4) | 0.064 (4) | 0.005 (4) | −0.014 (4) | 0.010 (3) |
C11 | 0.060 (5) | 0.075 (5) | 0.053 (4) | 0.010 (4) | 0.012 (4) | 0.014 (3) |
C12 | 0.045 (4) | 0.063 (4) | 0.062 (4) | 0.014 (3) | −0.001 (3) | 0.005 (3) |
N13 | 0.062 (4) | 0.080 (4) | 0.042 (3) | −0.034 (3) | −0.006 (3) | −0.002 (3) |
C14 | 0.045 (4) | 0.060 (4) | 0.052 (3) | −0.009 (3) | −0.002 (3) | −0.009 (3) |
C15 | 0.100 (7) | 0.070 (5) | 0.110 (7) | 0.017 (5) | −0.016 (6) | −0.040 (5) |
C16 | 0.086 (5) | 0.071 (4) | 0.085 (4) | −0.004 (3) | −0.008 (4) | −0.014 (3) |
C17 | 0.084 (4) | 0.063 (3) | 0.051 (3) | −0.020 (3) | 0.000 (3) | −0.011 (2) |
C18 | 0.072 (4) | 0.095 (5) | 0.103 (5) | −0.017 (4) | −0.033 (4) | 0.013 (4) |
C19 | 0.038 (3) | 0.045 (3) | 0.041 (3) | −0.002 (3) | −0.006 (3) | 0.000 (2) |
C20 | 0.045 (4) | 0.058 (4) | 0.074 (5) | −0.015 (3) | 0.006 (4) | −0.006 (3) |
N21 | 0.049 (4) | 0.062 (4) | 0.087 (5) | −0.017 (3) | −0.001 (3) | −0.015 (3) |
C22 | 0.060 (5) | 0.059 (4) | 0.077 (5) | −0.008 (4) | −0.017 (4) | −0.018 (4) |
C23 | 0.060 (5) | 0.061 (4) | 0.067 (4) | −0.005 (4) | 0.000 (4) | −0.022 (3) |
C24 | 0.040 (4) | 0.062 (4) | 0.064 (4) | −0.014 (3) | 0.000 (3) | −0.007 (3) |
Cu1—Cl1 | 2.2264 (17) | N9—H9 | 0.8600 |
Cu1—Cl2 | 2.2774 (19) | C10—C11 | 1.357 (11) |
Cu1—Cl3 | 2.2605 (18) | C10—H10 | 0.9300 |
Cu1—Cl4 | 2.2216 (19) | C11—C12 | 1.407 (9) |
Cu1—Cl7i | 5.577 (2) | C11—H11 | 0.9300 |
Cu1—Cu2ii | 7.6910 (13) | C12—H12 | 0.9300 |
Cu2—Cl5 | 2.2349 (18) | N13—C14 | 1.485 (9) |
Cu2—Cl6 | 2.236 (2) | N13—C17 | 1.495 (9) |
Cu2—Cl7 | 2.2412 (18) | N13—C18 | 1.464 (11) |
Cu2—Cl8 | 2.244 (2) | N13—H13 | 0.9100 |
Cl4—Cl7i | 4.375 (3) | C14—C15 | 1.529 (11) |
N1—C2 | 1.511 (7) | C14—C19 | 1.512 (8) |
N1—C5 | 1.489 (10) | C14—H14 | 0.9800 |
N1—C6 | 1.502 (11) | C15—C16 | 1.493 (12) |
N1—H1 | 0.9100 | C15—H15A | 0.9700 |
N1—Cl6iii | 3.282 (6) | C15—H15B | 0.9700 |
N1—Cl8iii | 3.844 (6) | C16—C17 | 1.456 (11) |
C2—C3 | 1.518 (9) | C16—H16A | 0.9700 |
C2—C7 | 1.505 (8) | C16—H16B | 0.9700 |
C2—H2 | 0.9800 | C17—H17A | 0.9700 |
C3—C4 | 1.516 (11) | C17—H17B | 0.9700 |
C3—H3A | 0.9700 | C18—H18A | 0.9600 |
C3—H3B | 0.9700 | C18—H18B | 0.9600 |
C4—C5 | 1.489 (11) | C18—H18C | 0.9600 |
C4—H4A | 0.9700 | C19—C24 | 1.354 (9) |
C4—H4B | 0.9700 | C19—C20 | 1.363 (9) |
C5—H5A | 0.9700 | C20—N21 | 1.346 (9) |
C5—H5B | 0.9700 | C20—H20 | 0.9300 |
C6—H6A | 0.9600 | N21—C22 | 1.338 (10) |
C6—H6B | 0.9600 | N21—H21 | 0.8600 |
C6—H6C | 0.9600 | C22—C23 | 1.351 (11) |
C7—C8 | 1.361 (9) | C22—H22 | 0.9300 |
C7—C12 | 1.393 (9) | C23—C24 | 1.386 (9) |
C8—N9 | 1.329 (8) | C23—H23 | 0.9300 |
C8—H8 | 0.9300 | C24—H24 | 0.9300 |
N9—C10 | 1.336 (10) | ||
Cl1—Cu1—Cl2 | 135.32 (8) | N9—C8—C7 | 120.3 (6) |
Cl1—Cu1—Cl3 | 96.68 (7) | N9—C8—H8 | 119.8 |
Cl1—Cu1—Cl4 | 98.89 (7) | C7—C8—H8 | 119.8 |
Cl2—Cu1—Cl3 | 99.20 (9) | C8—N9—C10 | 122.7 (6) |
Cl2—Cu1—Cl4 | 95.22 (8) | C8—N9—H9 | 118.6 |
Cl3—Cu1—Cl4 | 139.84 (9) | C10—N9—H9 | 118.6 |
Cl1—Cu1—Cl7i | 54.66 (6) | N9—C10—C11 | 120.6 (6) |
Cl2—Cu1—Cl7i | 136.81 (6) | N9—C10—H10 | 119.7 |
Cl3—Cu1—Cl7i | 122.95 (8) | C11—C10—H10 | 119.7 |
Cl4—Cu1—Cl7i | 47.00 (6) | C10—C11—C12 | 118.0 (7) |
Cl1—Cu1—Cu2ii | 19.19 (5) | C10—C11—H11 | 121.0 |
Cl2—Cu1—Cu2ii | 116.44 (5) | C12—C11—H11 | 121.0 |
Cl3—Cu1—Cu2ii | 106.45 (5) | C7—C12—C11 | 119.9 (6) |
Cl4—Cu1—Cu2ii | 100.06 (6) | C7—C12—H12 | 120.0 |
Cl7i—Cu1—Cu2ii | 63.50 (3) | C11—C12—H12 | 120.0 |
Cl5—Cu2—Cl6 | 100.44 (9) | C18—N13—C14 | 114.2 (6) |
Cl5—Cu2—Cl7 | 98.73 (8) | C18—N13—C17 | 114.4 (6) |
Cl5—Cu2—Cl8 | 131.17 (9) | C14—N13—C17 | 104.7 (6) |
Cl6—Cu2—Cl7 | 135.29 (11) | C14—N13—H13 | 107.7 |
Cl6—Cu2—Cl8 | 96.80 (9) | C17—N13—H13 | 107.7 |
Cl7—Cu2—Cl8 | 100.20 (9) | C18—N13—H13 | 107.7 |
Cu1—Cl4—Cl7i | 111.20 (8) | N13—C14—C19 | 114.1 (6) |
C5—N1—C6 | 112.9 (6) | N13—C14—C15 | 101.5 (6) |
C5—N1—C2 | 105.0 (5) | C19—C14—C15 | 114.1 (6) |
C6—N1—C2 | 113.6 (6) | N13—C14—H14 | 109.0 |
C5—N1—Cl6iii | 115.3 (4) | C19—C14—H14 | 109.0 |
C6—N1—Cl6iii | 88.0 (5) | C15—C14—H14 | 109.0 |
C2—N1—Cl6iii | 121.7 (4) | C16—C15—C14 | 106.5 (7) |
C5—N1—Cl8iii | 83.5 (4) | C16—C15—H15A | 110.4 |
C6—N1—Cl8iii | 143.2 (5) | C14—C15—H15A | 110.4 |
C2—N1—Cl8iii | 91.6 (4) | C16—C15—H15B | 110.4 |
Cl6iii—N1—Cl8iii | 55.41 (10) | C14—C15—H15B | 110.4 |
C2—N1—H1 | 108.4 | H15A—C15—H15B | 108.6 |
C5—N1—H1 | 108.4 | C17—C16—C15 | 106.9 (7) |
C6—N1—H1 | 108.4 | C17—C16—H16A | 110.3 |
Cl6iii—N1—H1 | 20.6 | C15—C16—H16A | 110.3 |
Cl8iii—N1—H1 | 35.5 | C17—C16—H16B | 110.3 |
C7—C2—N1 | 111.6 (5) | C15—C16—H16B | 110.3 |
C7—C2—C3 | 118.5 (6) | H16A—C16—H16B | 108.6 |
N1—C2—C3 | 102.4 (5) | C16—C17—N13 | 106.0 (6) |
C7—C2—H2 | 107.9 | C16—C17—H17A | 110.5 |
N1—C2—H2 | 107.9 | N13—C17—H17A | 110.5 |
C3—C2—H2 | 107.9 | C16—C17—H17B | 110.5 |
C4—C3—C2 | 105.9 (6) | N13—C17—H17B | 110.5 |
C4—C3—H3A | 110.5 | H17A—C17—H17B | 108.7 |
C2—C3—H3A | 110.5 | N13—C18—H18A | 109.5 |
C4—C3—H3B | 110.5 | N13—C18—H18B | 109.5 |
C2—C3—H3B | 110.5 | H18A—C18—H18B | 109.5 |
H3A—C3—H3B | 108.7 | N13—C18—H18C | 109.5 |
C5—C4—C3 | 106.7 (7) | H18A—C18—H18C | 109.5 |
C5—C4—H4A | 110.4 | H18B—C18—H18C | 109.5 |
C3—C4—H4A | 110.4 | C24—C19—C20 | 117.6 (6) |
C5—C4—H4B | 110.4 | C24—C19—C14 | 126.2 (6) |
C3—C4—H4B | 110.4 | C20—C19—C14 | 116.0 (6) |
H4A—C4—H4B | 108.6 | N21—C20—C19 | 119.8 (7) |
C4—C5—N1 | 106.3 (6) | N21—C20—H20 | 120.1 |
C4—C5—H5A | 110.5 | C19—C20—H20 | 120.1 |
N1—C5—H5A | 110.5 | C20—N21—C22 | 123.2 (7) |
C4—C5—H5B | 110.5 | C20—N21—H21 | 118.4 |
N1—C5—H5B | 110.5 | C22—N21—H21 | 118.4 |
H5A—C5—H5B | 108.7 | N21—C22—C23 | 118.2 (7) |
N1—C6—H6A | 109.5 | N21—C22—H22 | 120.9 |
N1—C6—H6B | 109.5 | C23—C22—H22 | 120.9 |
H6A—C6—H6B | 109.5 | C22—C23—C24 | 119.1 (8) |
N1—C6—H6C | 109.5 | C22—C23—H23 | 120.4 |
H6A—C6—H6C | 109.5 | C24—C23—H23 | 120.4 |
H6B—C6—H6C | 109.5 | C19—C24—C23 | 121.8 (7) |
C8—C7—C12 | 118.5 (6) | C19—C24—H24 | 119.1 |
C8—C7—C2 | 120.8 (6) | C23—C24—H24 | 119.1 |
C12—C7—C2 | 120.6 (6) | ||
Cl1—Cu1—Cl4—Cl7i | −18.84 (8) | C8—N9—C10—C11 | −1.1 (11) |
Cl3—Cu1—Cl4—Cl7i | 92.75 (13) | N9—C10—C11—C12 | 1.2 (12) |
Cl2—Cu1—Cl4—Cl7i | −156.32 (7) | C8—C7—C12—C11 | 0.5 (10) |
Cu2ii—Cu1—Cl4—Cl7i | −38.27 (7) | C2—C7—C12—C11 | −179.7 (7) |
C5—N1—C2—C7 | 165.2 (6) | C10—C11—C12—C7 | −0.9 (11) |
C6—N1—C2—C7 | −71.0 (8) | C18—N13—C14—C19 | −73.3 (8) |
Cl6iii—N1—C2—C7 | 32.0 (7) | C17—N13—C14—C19 | 160.8 (6) |
Cl8iii—N1—C2—C7 | 81.5 (5) | C18—N13—C14—C15 | 163.6 (7) |
C5—N1—C2—C3 | 37.4 (7) | C17—N13—C14—C15 | 37.6 (7) |
C6—N1—C2—C3 | 161.2 (6) | N13—C14—C15—C16 | −28.1 (9) |
Cl6iii—N1—C2—C3 | −95.8 (5) | C19—C14—C15—C16 | −151.2 (7) |
Cl8iii—N1—C2—C3 | −46.3 (4) | C14—C15—C16—C17 | 7.8 (11) |
C7—C2—C3—C4 | −153.2 (6) | C15—C16—C17—N13 | 15.8 (10) |
N1—C2—C3—C4 | −29.9 (7) | C18—N13—C17—C16 | −160.2 (8) |
C2—C3—C4—C5 | 11.7 (9) | C14—N13—C17—C16 | −34.3 (8) |
C3—C4—C5—N1 | 11.7 (9) | N13—C14—C19—C24 | −24.8 (9) |
C6—N1—C5—C4 | −155.1 (8) | C15—C14—C19—C24 | 91.2 (9) |
C2—N1—C5—C4 | −30.9 (9) | N13—C14—C19—C20 | 159.6 (6) |
Cl6iii—N1—C5—C4 | 105.8 (6) | C15—C14—C19—C20 | −84.4 (8) |
Cl8iii—N1—C5—C4 | 59.1 (6) | C24—C19—C20—N21 | −2.2 (10) |
N1—C2—C7—C8 | 108.6 (7) | C14—C19—C20—N21 | 173.8 (6) |
C3—C2—C7—C8 | −132.9 (7) | C19—C20—N21—C22 | 0.8 (11) |
N1—C2—C7—C12 | −71.2 (8) | C20—N21—C22—C23 | 2.6 (12) |
C3—C2—C7—C12 | 47.3 (8) | N21—C22—C23—C24 | −4.4 (12) |
C12—C7—C8—N9 | −0.3 (10) | C20—C19—C24—C23 | 0.3 (10) |
C2—C7—C8—N9 | 179.8 (6) | C14—C19—C24—C23 | −175.3 (7) |
C7—C8—N9—C10 | 0.7 (10) | C22—C23—C24—C19 | 3.1 (12) |
Symmetry codes: (i) x, y+1, z−1; (ii) x+1, y+1, z−1; (iii) x+1, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl6iii | 0.91 | 2.45 | 3.282 (6) | 152 |
N9—H9···Cl7i | 0.86 | 2.40 | 3.145 (7) | 145 |
N9—H9···Cl5i | 0.86 | 2.70 | 3.336 (6) | 132 |
N13—H13···Cl2 | 0.91 | 2.35 | 3.156 (6) | 148 |
N21—H21···Cl3iv | 0.86 | 2.35 | 3.141 (7) | 153 |
N21—H21···Cl1iv | 0.86 | 2.78 | 3.357 (7) | 125 |
Symmetry codes: (i) x, y+1, z−1; (iii) x+1, y, z−1; (iv) x−1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | (C10H16N2)[CuCl4] |
Mr | 369.59 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.6919 (8), 8.1526 (9), 12.2337 (15) |
α, β, γ (°) | 87.249 (9), 88.694 (8), 89.414 (7) |
V (Å3) | 766.05 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.10 |
Crystal size (mm) | 0.50 × 0.45 × 0.26 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.663, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4302, 4302, 3327 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.099, 1.05 |
No. of reflections | 4302 |
No. of parameters | 290 |
No. of restraints | 4 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.70, −0.71 |
Absolute structure | Flack (1983), 781 Friedel pairs |
Absolute structure parameter | −0.037 (17) |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
Cu1—Cl1 | 2.2264 (17) | N1—C5 | 1.489 (10) |
Cu1—Cl2 | 2.2774 (19) | N1—C6 | 1.502 (11) |
Cu1—Cl3 | 2.2605 (18) | C8—N9 | 1.329 (8) |
Cu1—Cl4 | 2.2216 (19) | N9—C10 | 1.336 (10) |
Cu2—Cl5 | 2.2349 (18) | N13—C14 | 1.485 (9) |
Cu2—Cl6 | 2.236 (2) | N13—C17 | 1.495 (9) |
Cu2—Cl7 | 2.2412 (18) | N13—C18 | 1.464 (11) |
Cu2—Cl8 | 2.244 (2) | C20—N21 | 1.346 (9) |
N1—C2 | 1.511 (7) | N21—C22 | 1.338 (10) |
Cl1—Cu1—Cl2 | 135.32 (8) | Cl5—Cu2—Cl7 | 98.73 (8) |
Cl1—Cu1—Cl3 | 96.68 (7) | Cl5—Cu2—Cl8 | 131.17 (9) |
Cl1—Cu1—Cl4 | 98.89 (7) | Cl6—Cu2—Cl7 | 135.29 (11) |
Cl2—Cu1—Cl3 | 99.20 (9) | Cl6—Cu2—Cl8 | 96.80 (9) |
Cl2—Cu1—Cl4 | 95.22 (8) | Cl7—Cu2—Cl8 | 100.20 (9) |
Cl3—Cu1—Cl4 | 139.84 (9) | C8—N9—C10 | 122.7 (6) |
Cl5—Cu2—Cl6 | 100.44 (9) | C20—N21—C22 | 123.2 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl6i | 0.91 | 2.45 | 3.282 (6) | 152 |
N9—H9···Cl7ii | 0.86 | 2.40 | 3.145 (7) | 145 |
N9—H9···Cl5ii | 0.86 | 2.70 | 3.336 (6) | 132 |
N13—H13···Cl2 | 0.91 | 2.35 | 3.156 (6) | 148 |
N21—H21···Cl3iii | 0.86 | 2.35 | 3.141 (7) | 153 |
N21—H21···Cl1iii | 0.86 | 2.78 | 3.357 (7) | 125 |
Symmetry codes: (i) x+1, y, z−1; (ii) x, y+1, z−1; (iii) x−1, y−1, z. |
Considerable interest has been shown in recent years in tetrahalocuprate complexes containing various organic counter-cations (Desjardins et al., 1983; Halvorson et al., 1990; McDonald et al., 1988; Straatman et al., 1984). It is known that their hydrogen-bonding interactions (Glenn et al., 1995; Marzotto et al., 2001) and π-interactions between the aromatic rings of the organic cations (Luque et al., 2002; Sertucha et al., 1998) stabilize their crystal structures. These types of interactions control molecular recognition and self-assembly processes, and exercise important effects on solid-state structure and the properties of many compounds relevant to biological and material sciences (Desiraju & Steiner, 1999; Robinson et al., 2000). In this work, we report the preparation and crystal structure of the title compound, (I). The doubly protonated nicotinium cation, [C10H16N2H2]2+, contains two sites capable of forming hydrogen-bonding interactions with Cl atoms of the [CuCl4]2− anion and the pyridine ring is capable of establishing a π-interaction in the crystalline state.
The crystal structure (Fig. 1) of (I) comprises two nicotinium cations and two discrete [CuCl4]2− anions held together by N—H···Cl hydrogen bonds. The [CuCl4]2− anions are crystallographically non-equivalent and are approximately D2 d flattened as a result of hydrogen-bonding interactions with nicotinium cations. The two nicotinium cations are protonated at the atoms N1 and N9, and N13 and N21. The protonated pyridinium N atoms exclusively form a rare three-center hydrogen bond (bifurcated hydrogen bond) with two cis-Cl atoms of both [CuCl4]2− units. On the other hand, each of the protonated pyrrolidinium N atoms exclusively forms a common two-center hydrogen bond with a Cl atom of a [CuCl4]2− unit. As a result, three Cl atoms of each [CuCl4]2− anion participate in the hydrogen bonding with nicotinium cations. The hydrogen-bonding interactions are shown in Fig. 2.
The Cu1 and Cu2 centres are each coordinated by four Cl atoms, at average distances of 2.2465 (18) and 2.2390 (19) Å, respectively. These values are close to those observed in similar complexes (Halvorson et al., 1990). The mean N···Cl distance of about 3.24 Å for the three-center hydrogen bond in both of the Cu1 and Cu2 sites is appreciably shorter than the mean distance of 3.40 Å suggested by previous works (Glenn et al., 1995) for this type of hydrogen bond. There are no important bonding interactions among the tetrachlorocuprate anionic units, with the nearest non-bonded Cu···Cl distance in the unit cell being 5.577 (2) Å and the nearest Cu···Cu distance being 7.691 (1) Å. The nearest Cl···Cl contact distance of 4.375 (3) Å is considerably longer than the sum of their van der Waals radii. The aromatic pyridine rings of the cations are nearly perfectly planar, but the pyridine rings stacked in the parallel fashion are well separated from each other by the cell-unit distance, making a π-interaction among them impossible.