supplementary materials
Bis(cyanido-![[kappa]](/logos/entities/kappa_rmgif.gif)
C)(ethane-1,2-diamine-2N,N')silver(II)
The title compound, [Ag(CN)2(C2H8N2)], was obtained from the reaction of ethane-1,2-diamine (en) with K[Ag(CN)2]. The compound crystallizes as an inversion twin, the ratio of the twin components being 0.72 (4):0.28 (4). The AgII atom is in a slightly disorted square-planar environment. The chelate ring has an envelope conformation. The AgII-N(en) bond lengths are 2.071 (2) and 2.078 (2) Å. In the crystal structure, symmetry-related molecules are linked by N-H
N hydrogen bonds to form a three-dimensional network.
The title compound was prepared by the addition of ethane-1,2-diamine in methanol to an equimolar amount of K[Ag(CN)2] in water. The solution was stirred for 15 min then filtered and allowed to evaporate slowly in air. Colourless crystals appeared along with some black deposits on the walls of the vessel, which suggested disproportionation of silver(I) to give silver(II) and silver(0).
The H-atoms were included in calculated positions and treated as riding atoms: N—H = 0.92 Å and C—H = 0.99 Å, with Uiso(H) = 1.2Ueq(N or C).
Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-RED32 (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Bis(cyanido-
κC)(ethane-1,2-diamine-
κ2N,
N')silver(II)
top
Crystal data top
| [Ag(CN)2(C2H8N2)] | F000 = 428 |
| Mr = 220.01 | Dx = 2.050 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation
λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 6960 reflections |
| a = 6.9140 (8) Å | θ = 1.8–28.7º |
| b = 9.3481 (11) Å | µ = 2.74 mm−1 |
| c = 11.0289 (11) Å | T = 173 (2) K |
| V = 712.83 (14) Å3 | Needle, colourless |
| Z = 4 | 0.50 × 0.20 × 0.10 mm |
Data collection top
Stoe IPDS II
diffractometer | 1913 independent reflections |
| Radiation source: fine-focus sealed tube | 1889 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.022 |
| T = 173(2) K | θmax = 29.1º |
| φ and ω scans | θmin = 2.9º |
Absorption correction: multi-scan
(MULABS in PLATON; Spek, 2003) | h = −9→9 |
| Tmin = 0.539, Tmax = 0.760 | k = −12→12 |
| 6842 measured reflections | l = −14→15 |
Refinement top
| Refinement on F2 | H-atom parameters constrained |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0247P)2 + 0.4752P]
where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.016 | (Δ/σ)max = 0.001 |
| wR(F2) = 0.042 | Δρmax = 0.46 e Å−3 |
| S = 1.08 | Δρmin = −0.51 e Å−3 |
| 1913 reflections | Extinction correction: SHELXL 97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 84 parameters | Extinction coefficient: 0.0269 (10) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with 784 Friedel pairs (99.7%) |
| Secondary atom site location: difference Fourier map | Flack parameter: 0.28 (4) |
| Hydrogen site location: inferred from neighbouring sites | |
Crystal data top
| [Ag(CN)2(C2H8N2)] | V = 712.83 (14) Å3 |
| Mr = 220.01 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα |
| a = 6.9140 (8) Å | µ = 2.74 mm−1 |
| b = 9.3481 (11) Å | T = 173 (2) K |
| c = 11.0289 (11) Å | 0.50 × 0.20 × 0.10 mm |
Data collection top
Stoe IPDS II
diffractometer | 1913 independent reflections |
Absorption correction: multi-scan
(MULABS in PLATON; Spek, 2003) | 1889 reflections with I > 2σ(I) |
| Tmin = 0.539, Tmax = 0.760 | Rint = 0.022 |
| 6842 measured reflections | |
Refinement top
| R[F2 > 2σ(F2)] = 0.016 | H-atom parameters constrained |
| wR(F2) = 0.042 | Δρmax = 0.46 e Å−3 |
| S = 1.08 | Δρmin = −0.51 e Å−3 |
| 1913 reflections | Absolute structure: Flack (1983), with 784 Friedel pairs (99.7%) |
| 84 parameters | Flack parameter: 0.28 (4) |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | |
| Ag1 | 0.31636 (2) | 0.86283 (2) | 0.26335 (1) | 0.0170 (1) | |
| N1 | 0.1329 (3) | 0.7590 (2) | 0.3838 (2) | 0.0200 (6) | |
| N2 | 0.1723 (3) | 0.7398 (2) | 0.13599 (18) | 0.0198 (5) | |
| N3 | 0.5059 (3) | 1.0508 (2) | 0.4625 (2) | 0.0265 (6) | |
| N4 | 0.5486 (4) | 1.0323 (3) | 0.0698 (2) | 0.0269 (6) | |
| C1 | −0.0334 (4) | 0.7046 (3) | 0.3122 (2) | 0.0247 (6) | |
| C2 | 0.0448 (4) | 0.6364 (3) | 0.1993 (2) | 0.0268 (6) | |
| C3 | 0.4387 (4) | 0.9800 (2) | 0.3892 (2) | 0.0196 (6) | |
| C4 | 0.4706 (4) | 0.9651 (3) | 0.1414 (2) | 0.0204 (6) | |
| H1NA | 0.19650 | 0.68450 | 0.42100 | 0.0240* | |
| H1A | −0.12130 | 0.78440 | 0.29080 | 0.0300* | |
| H1B | −0.10710 | 0.63360 | 0.36010 | 0.0300* | |
| H1NB | 0.09080 | 0.82150 | 0.44250 | 0.0240* | |
| H2A | 0.11910 | 0.54940 | 0.22070 | 0.0320* | |
| H2B | −0.06310 | 0.60800 | 0.14550 | 0.0320* | |
| H2NA | 0.09970 | 0.79770 | 0.08630 | 0.0240* | |
| H2NB | 0.26030 | 0.69130 | 0.08880 | 0.0240* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Ag1 | 0.0170 (1) | 0.0154 (1) | 0.0187 (1) | −0.0005 (1) | 0.0004 (1) | 0.0002 (1) |
| N1 | 0.0218 (10) | 0.0187 (9) | 0.0195 (10) | −0.0020 (7) | 0.0021 (7) | 0.0031 (8) |
| N2 | 0.0204 (9) | 0.0184 (9) | 0.0207 (9) | −0.0039 (9) | −0.0009 (9) | −0.0017 (7) |
| N3 | 0.0250 (11) | 0.0283 (11) | 0.0261 (11) | −0.0039 (8) | −0.0002 (8) | −0.0037 (9) |
| N4 | 0.0252 (10) | 0.0304 (11) | 0.0252 (11) | −0.0051 (10) | 0.0005 (9) | 0.0003 (9) |
| C1 | 0.0223 (10) | 0.0255 (11) | 0.0264 (12) | −0.0071 (9) | 0.0016 (9) | 0.0010 (10) |
| C2 | 0.0318 (11) | 0.0209 (9) | 0.0278 (11) | −0.0119 (11) | 0.0012 (10) | −0.0019 (11) |
| C3 | 0.0182 (10) | 0.0195 (10) | 0.0210 (11) | −0.0009 (9) | 0.0016 (9) | 0.0028 (9) |
| C4 | 0.0173 (10) | 0.0228 (10) | 0.0212 (11) | −0.0023 (9) | −0.0005 (9) | −0.0006 (9) |
Geometric parameters (Å, °) top
| Ag1—N1 | 2.078 (2) | N1—H1NB | 0.9200 |
| Ag1—N2 | 2.071 (2) | N2—H2NA | 0.9200 |
| Ag1—C3 | 1.960 (2) | N2—H2NB | 0.9200 |
| Ag1—C4 | 1.965 (3) | C1—C2 | 1.500 (3) |
| N1—C1 | 1.485 (3) | C1—H1A | 0.9900 |
| N2—C2 | 1.483 (3) | C1—H1B | 0.9900 |
| N3—C3 | 1.143 (3) | C2—H2A | 0.9900 |
| N4—C4 | 1.144 (4) | C2—H2B | 0.9900 |
| N1—H1NA | 0.9200 | | |
| | | |
| N1—Ag1—N2 | 83.14 (8) | C2—N2—H2NA | 110.00 |
| N1—Ag1—C3 | 94.12 (9) | C2—N2—H2NB | 110.00 |
| N1—Ag1—C4 | 175.20 (10) | N1—C1—C2 | 107.9 (2) |
| N2—Ag1—C3 | 176.69 (10) | N2—C2—C1 | 109.2 (2) |
| N2—Ag1—C4 | 93.84 (9) | Ag1—C3—N3 | 178.2 (2) |
| C3—Ag1—C4 | 88.78 (10) | Ag1—C4—N4 | 174.6 (3) |
| Ag1—N1—C1 | 107.03 (15) | N1—C1—H1A | 110.00 |
| Ag1—N2—C2 | 109.18 (14) | N1—C1—H1B | 110.00 |
| C1—N1—H1NB | 110.00 | C2—C1—H1A | 110.00 |
| H1NA—N1—H1NB | 109.00 | C2—C1—H1B | 110.00 |
| Ag1—N1—H1NB | 110.00 | H1A—C1—H1B | 108.00 |
| C1—N1—H1NA | 110.00 | N2—C2—H2A | 110.00 |
| Ag1—N1—H1NA | 110.00 | N2—C2—H2B | 110.00 |
| Ag1—N2—H2NA | 110.00 | C1—C2—H2A | 110.00 |
| Ag1—N2—H2NB | 110.00 | C1—C2—H2B | 110.00 |
| H2NA—N2—H2NB | 108.00 | H2A—C2—H2B | 108.00 |
| | | |
| N2—Ag1—N1—C1 | −20.61 (15) | Ag1—N1—C1—C2 | 45.1 (2) |
| C3—Ag1—N1—C1 | 157.53 (16) | Ag1—N2—C2—C1 | 34.7 (2) |
| N1—Ag1—N2—C2 | −7.65 (16) | N1—C1—C2—N2 | −53.5 (3) |
| C4—Ag1—N2—C2 | 176.10 (17) | | |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1NA···N4i | 0.92 | 2.27 | 3.099 (3) | 150 |
| N1—H1NB···N4ii | 0.92 | 2.18 | 3.097 (3) | 172 |
| N2—H2NA···N3iii | 0.92 | 2.10 | 3.002 (3) | 167 |
| N2—H2NB···N3i | 0.92 | 2.16 | 3.042 (3) | 161 |
| Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1/2, −y+2, z+1/2; (iii) −x+1/2, −y+2, z−1/2. |
Table 1
Selected geometric parameters (Å, °) top| Ag1—N1 | 2.078 (2) | Ag1—C3 | 1.960 (2) |
| Ag1—N2 | 2.071 (2) | Ag1—C4 | 1.965 (3) |
| | | |
| N1—Ag1—N2 | 83.14 (8) | N2—Ag1—C4 | 93.84 (9) |
| N1—Ag1—C3 | 94.12 (9) | C3—Ag1—C4 | 88.78 (10) |
| N1—Ag1—C4 | 175.20 (10) | Ag1—N1—C1 | 107.03 (15) |
| N2—Ag1—C3 | 176.69 (10) | Ag1—N2—C2 | 109.18 (14) |
Table 2
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1NA···N4i | 0.92 | 2.27 | 3.099 (3) | 150 |
| N1—H1NB···N4ii | 0.92 | 2.18 | 3.097 (3) | 172 |
| N2—H2NA···N3iii | 0.92 | 2.10 | 3.002 (3) | 167 |
| N2—H2NB···N3i | 0.92 | 2.16 | 3.042 (3) | 161 |
| Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1/2, −y+2, z+1/2; (iii) −x+1/2, −y+2, z−1/2. |
Financial support from the Pakistan Council for Science and Technology, Islamabad, is gratefully acknowledged.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Po, H. N., Brinkman, E. & Doedens, R. J. (1991). Acta Cryst. C47, 2310–2312.
Pretsch, T. & Hartl, H. (2005). Inorg. Chim. Acta, 358, 1179–1185.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
Stoe & Cie. (2005). X-AREA (Version 1.26) and X-RED32 (Version 1.26). Stoe & Cie, Darmstadt, Germany.
Wang, Q.-M., Kay Lee, H. & Mak, T. C. W. (2002). New J. Chem. 26, 513–515.
![[Figure 1]](./lh2497fig1thm.gif)
![[Figure 2]](./lh2497fig2thm.gif)
The molecular stucture of the title compound is shown in Fig. 1. The compound crystallized in the chiral space group P212121 as an inversion twin; the refined BASF value is 0.28 (4).
The AgII atom has an almost perfect square planar environement (Table 1). The five-membered chelate ring has an envelope conformation with atom C1 at the flap.
The AgII—N(en) bond distances of 2.071 (2) and 2.078 (2) Å are significantly shorter than the same distances observed in some silver(II) 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane macrocyclic complexes; 2.185 (5) to 2.195 (6) Å (Wang et al., 2002) and 2.194 (3) to 2.196 (3) Å (Po et al., 1991). In the corresponding silver(I) complex, [Ag(CN)en)], prepared solvothermally, the AgI—N(en) distances are 2.283 (6) and 2.355 (6) Å (Pretsch & Hartl, 2005).
In the crystal structure symmetry related molecules are linked by N—H···N(CN) hydrogen bonds to form a three-dimensional network (Fig. 2).