supplementary materials
Bis(4-amino-1-hexylpyridinium) bis(1,2-dicyanoethene-1,2-dithiolato)cuprate(II)
The complete complex anion in the title salt, (C11H19N2)2[Cu(C4N2S2)2], has 2/m symmetry while the complete cation is generated by mirror symmetry with the non-H atoms of the alkyl chain lying on the plane. A square-planar geometry based on an S4 donor set is found in the anion; the Cu-S distance is 2.2663 (5) Å. In the crystal, intermolecular N-H
N hydrogen bonds link the ions into layers in the bc plane comprising alternating rows of cations and anions.
Disodium maleonitriledithiolate (468 mg, 2.5 mmol) and cupric nitrate trihydrate
(302 mg, 1.25 mmol) were mixed under stirring in water (20 mL) at room
temperature. Subsequently, a solution of 1-hexyl-4-aminopyridinium iodide (765 mg, 2.5 mmol) in water (10 mL) was added to the mixture. The brown precipitate
that formed immediately was filtered off and washed with water. The crude
product was recrystallized from acetone (20 mL) to give brown crystals. The
crystals suitable for X-ray diffraction measurements were obtained by
diffusing diethyl ether into the solution of the salt in acetone for 6 days.
The C-bound H atoms were geometrically placed (C—H = 0.93 or 0.96 Å) and
refined as riding with Uiso(H) = 1.2-1.5Ueq(C). The N-bound
H atom was refined freely.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Bis(4-amino-1-hexylpyridinium) bis(1,2-dicyanoethene-1,2-dithiolato)cuprate(II)
top
Crystal data top
| (C11H19N2)2[Cu(C4N2S2)2] | F(000) = 734 |
| Mr = 702.51 | Dx = 1.348 Mg m−3 |
| Monoclinic, C2/m | Melting point = 430–432 K |
| Hall symbol: -C 2y | Mo Kα radiation, λ = 0.71073 Å |
| a = 13.3648 (9) Å | Cell parameters from 2059 reflections |
| b = 10.0768 (4) Å | θ = 3.1–29.2° |
| c = 13.8550 (8) Å | µ = 0.91 mm−1 |
| β = 111.902 (8)° | T = 293 K |
| V = 1731.24 (17) Å3 | Block, brown |
| Z = 2 | 0.3 × 0.2 × 0.1 mm |
Data collection top
Siemens SMART CCD area-detector
diffractometer | 1805 independent reflections |
| Radiation source: fine-focus sealed tube | 1299 reflections with I > 2σ(I) |
| graphite | Rint = 0.019 |
| φ and ω scans | θmax = 26.0°, θmin = 3.1° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | h = −12→16 |
| Tmin = 0.939, Tmax = 1.000 | k = −11→12 |
| 4194 measured reflections | l = −17→16 |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.074 | H atoms treated by a mixture of independent and constrained refinement |
| S = 0.92 | w = 1/[σ2(Fo2) + (0.0411P)2]
where P = (Fo2 + 2Fc2)/3 |
| 1805 reflections | (Δ/σ)max < 0.001 |
| 117 parameters | Δρmax = 0.22 e Å−3 |
| 0 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
| (C11H19N2)2[Cu(C4N2S2)2] | V = 1731.24 (17) Å3 |
| Mr = 702.51 | Z = 2 |
| Monoclinic, C2/m | Mo Kα radiation |
| a = 13.3648 (9) Å | µ = 0.91 mm−1 |
| b = 10.0768 (4) Å | T = 293 K |
| c = 13.8550 (8) Å | 0.3 × 0.2 × 0.1 mm |
| β = 111.902 (8)° | |
Data collection top
Siemens SMART CCD area-detector
diffractometer | 1805 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | 1299 reflections with I > 2σ(I) |
| Tmin = 0.939, Tmax = 1.000 | Rint = 0.019 |
| 4194 measured reflections | θmax = 26.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.074 | Δρmax = 0.22 e Å−3 |
| S = 0.92 | Δρmin = −0.17 e Å−3 |
| 1805 reflections | Absolute structure: ? |
| 117 parameters | Flack parameter: ? |
| 0 restraints | Rogers 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| | x | y | z | Uiso*/Ueq | |
| Cu1 | 0.0000 | 0.5000 | 0.0000 | 0.04510 (17) | |
| S1 | 0.04362 (5) | 0.66007 (5) | 0.12376 (4) | 0.0623 (2) | |
| N1 | 0.12555 (15) | 0.7075 (2) | 0.40284 (14) | 0.0721 (6) | |
| N2 | 0.3513 (2) | 0.5000 | 0.5099 (2) | 0.0615 (8) | |
| N3 | 0.39247 (19) | 0.5000 | 0.23171 (18) | 0.0536 (6) | |
| C1 | 0.07750 (14) | 0.56692 (18) | 0.23653 (14) | 0.0445 (4) | |
| C2 | 0.10516 (16) | 0.6424 (2) | 0.33068 (15) | 0.0507 (5) | |
| C3 | 0.3637 (2) | 0.5000 | 0.4193 (2) | 0.0472 (7) | |
| C4 | 0.37096 (16) | 0.38155 (19) | 0.36957 (15) | 0.0544 (5) | |
| H4A | 0.3666 | 0.3005 | 0.3998 | 0.065* | |
| C5 | 0.38435 (18) | 0.3850 (2) | 0.27783 (17) | 0.0586 (6) | |
| H5A | 0.3881 | 0.3054 | 0.2454 | 0.070* | |
| C6 | 0.4079 (3) | 0.5000 | 0.1312 (2) | 0.0678 (9) | |
| H6A | 0.4487 | 0.4229 | 0.1280 | 0.081* | |
| C7 | 0.3047 (3) | 0.5000 | 0.0398 (3) | 0.0810 (10) | |
| H7A | 0.2635 | 0.4226 | 0.0414 | 0.097* | |
| C8 | 0.3282 (3) | 0.5000 | −0.0612 (3) | 0.0819 (11) | |
| H8A | 0.3740 | 0.4117 | −0.0657 | 0.098* | |
| C9 | 0.2314 (3) | 0.5000 | −0.1571 (3) | 0.0917 (12) | |
| H9A | 0.1892 | 0.4230 | −0.1569 | 0.110* | |
| C10 | 0.2529 (4) | 0.5000 | −0.2572 (3) | 0.0930 (12) | |
| H10A | 0.2950 | 0.4229 | −0.2577 | 0.112* | |
| C11 | 0.1534 (3) | 0.5000 | −0.3517 (3) | 0.0931 (12) | |
| H11A | 0.1716 | 0.5000 | −0.4125 | 0.140* | |
| H11B | 0.1119 | 0.4222 | −0.3519 | 0.140* | |
| H2A | 0.3461 (18) | 0.432 (2) | 0.5381 (16) | 0.075 (8)* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cu1 | 0.0613 (3) | 0.0335 (3) | 0.0420 (3) | 0.000 | 0.0211 (2) | 0.000 |
| S1 | 0.1042 (5) | 0.0323 (3) | 0.0463 (3) | 0.0005 (3) | 0.0235 (3) | 0.0001 (2) |
| N1 | 0.0822 (14) | 0.0679 (13) | 0.0574 (11) | 0.0058 (11) | 0.0159 (10) | −0.0184 (10) |
| N2 | 0.076 (2) | 0.0505 (19) | 0.0559 (16) | 0.000 | 0.0218 (15) | 0.000 |
| N3 | 0.0594 (15) | 0.0435 (14) | 0.0669 (15) | 0.000 | 0.0340 (13) | 0.000 |
| C1 | 0.0492 (11) | 0.0407 (10) | 0.0423 (10) | 0.0004 (9) | 0.0155 (9) | −0.0020 (8) |
| C2 | 0.0538 (13) | 0.0454 (11) | 0.0486 (11) | 0.0054 (10) | 0.0143 (10) | 0.0004 (10) |
| C3 | 0.0386 (16) | 0.0423 (17) | 0.0544 (17) | 0.000 | 0.0100 (14) | 0.000 |
| C4 | 0.0649 (14) | 0.0343 (11) | 0.0652 (14) | 0.0001 (10) | 0.0257 (12) | 0.0042 (10) |
| C5 | 0.0692 (15) | 0.0352 (11) | 0.0769 (15) | 0.0012 (10) | 0.0338 (13) | −0.0054 (11) |
| C6 | 0.080 (2) | 0.058 (2) | 0.083 (2) | 0.000 | 0.051 (2) | 0.000 |
| C7 | 0.090 (3) | 0.096 (3) | 0.070 (2) | 0.000 | 0.045 (2) | 0.000 |
| C8 | 0.092 (3) | 0.087 (3) | 0.079 (2) | 0.000 | 0.046 (2) | 0.000 |
| C9 | 0.108 (3) | 0.096 (3) | 0.084 (3) | 0.000 | 0.051 (3) | 0.000 |
| C10 | 0.114 (3) | 0.099 (3) | 0.080 (3) | 0.000 | 0.053 (3) | 0.000 |
| C11 | 0.122 (3) | 0.073 (3) | 0.097 (3) | 0.000 | 0.055 (3) | 0.000 |
Geometric parameters (Å, °) top
| Cu1—S1i | 2.2663 (5) | C4—C5 | 1.349 (3) |
| Cu1—S1 | 2.2663 (5) | C4—H4A | 0.9300 |
| Cu1—S1ii | 2.2663 (5) | C5—H5A | 0.9300 |
| Cu1—S1iii | 2.2663 (5) | C6—C7 | 1.483 (4) |
| S1—C1 | 1.7319 (19) | C6—H6A | 0.9600 |
| N1—C2 | 1.141 (2) | C7—C8 | 1.545 (4) |
| N2—C3 | 1.327 (4) | C7—H7A | 0.9600 |
| N2—H2A | 0.80 (2) | C8—C9 | 1.468 (5) |
| N3—C5 | 1.347 (2) | C8—H8A | 1.0943 |
| N3—C5iii | 1.347 (2) | C9—C10 | 1.519 (4) |
| N3—C6 | 1.482 (3) | C9—H9A | 0.9601 |
| C1—C1iii | 1.349 (4) | C10—C11 | 1.478 (5) |
| C1—C2 | 1.434 (3) | C10—H10A | 0.9600 |
| C3—C4 | 1.399 (2) | C11—H11A | 0.9600 |
| C3—C4iii | 1.399 (2) | C11—H11B | 0.9600 |
| | | |
| S1i—Cu1—S1 | 180.00 (2) | N3—C5—C4 | 122.1 (2) |
| S1i—Cu1—S1ii | 90.75 (3) | N3—C5—H5A | 118.9 |
| S1—Cu1—S1ii | 89.25 (3) | C4—C5—H5A | 118.9 |
| S1i—Cu1—S1iii | 89.25 (3) | N3—C6—C7 | 113.0 (2) |
| S1—Cu1—S1iii | 90.75 (3) | N3—C6—H6A | 108.9 |
| S1ii—Cu1—S1iii | 180.00 (3) | C7—C6—H6A | 108.9 |
| C1—S1—Cu1 | 101.76 (6) | C6—C7—C8 | 109.6 (3) |
| C3—N2—H2A | 121.7 (17) | C6—C7—H7A | 109.8 |
| C5—N3—C5iii | 118.7 (2) | C8—C7—H7A | 109.5 |
| C5—N3—C6 | 120.65 (12) | C9—C8—C7 | 114.3 (3) |
| C5iii—N3—C6 | 120.65 (12) | C9—C8—H8A | 105.7 |
| C1iii—C1—C2 | 122.02 (11) | C7—C8—H8A | 111.0 |
| C1iii—C1—S1 | 122.82 (6) | C8—C9—C10 | 115.0 (3) |
| C2—C1—S1 | 115.16 (14) | C8—C9—H9A | 108.5 |
| N1—C2—C1 | 176.9 (2) | C10—C9—H9A | 108.3 |
| N2—C3—C4 | 121.46 (13) | C11—C10—C9 | 113.2 (3) |
| N2—C3—C4iii | 121.46 (13) | C11—C10—H10A | 109.3 |
| C4—C3—C4iii | 117.1 (3) | C9—C10—H10A | 108.5 |
| C5—C4—C3 | 120.0 (2) | C10—C11—H11A | 109.8 |
| C5—C4—H4A | 120.0 | C10—C11—H11B | 109.3 |
| C3—C4—H4A | 120.0 | H11A—C11—H11B | 109.5 |
| Symmetry codes: (i) −x, −y+1, −z; (ii) −x, y, −z; (iii) x, −y+1, z. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···N1iv | 0.81 (2) | 2.39 (2) | 3.157 (2) | 160 (2) |
| Symmetry codes: (iv) −x+1/2, y−1/2, −z+1. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···N1i | 0.81 (2) | 2.39 (2) | 3.157 (2) | 160 (2) |
| Symmetry codes: (i) −x+1/2, y−1/2, −z+1. |
The authors thank the Science and Technology Department of Jiangsu Province,
People's Republic of China, for support.
Cassoux, P., Valade, L., Kobayashi, H., Kobayashi, A., Clark, R. A. & Underhill, A. E. (1991). Coord. Chem. Rev. 110, 115–160.
Robertson, N. & Cronin, L. (2002). Coord. Chem. Rev. 227, 93–127.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
![[Figure 1]](./tk2752fig1thm.gif)
![[Figure 2]](./tk2752fig2thm.gif)
Square-planar M[dithiolene]2 complexes have attracted extensive interest in the areas of conducting and magnetic materials, dyes, non-linear optics and catalysis (Robertson et al., 2002; Cassoux et al., 1991). Herein, we report the crystal structure of the title compound, Fig.1.
The [Cu(mnt)2]2- dianion is located about a site of symmetry 2/m. The 1-hexyl-4-aminopyridinium cation lies on a mirror plane whereby the non-H atoms of the alkyl chain lie on the plane which bisects the 1,4 atoms of the benzene ring.
In the crystal structure, intermolecular N—H···N hydrogen bonds (Table 1) link the cations and anions to form a layer in the bc plane comprising alternating cations and anions.