Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031108/hg2236sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031108/hg2236Isup2.hkl |
CCDC reference: 657526
Key indicators
- Single-crystal X-ray study
- T = 290 K
- Mean (C-C) = 0.005 Å
- R factor = 0.024
- wR factor = 0.065
- Data-to-parameter ratio = 14.1
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT063_ALERT_3_B Crystal Probably too Large for Beam Size ....... 1.00 mm
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (1) 1.20
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
A methanolic solution of 4,4'-bipyridine (0.25 ml, 1.0 M) and aqueous KAg(CN)2 (2.5 ml, 0.2 M) were added to an aqueous solution of CuSO4 (2.5 ml, 0.1 M). This resulted in the precipitation of a blue powder, which was then dissolved by the addition of 2.5 ml of a concentrated NH3 (26%) solution. The solution was left for 5 days, resulting in dark blue crystals of the title compound suitable for single-crystal X-ray analysis.
H atoms were placed in calculated positions and allowed to ride during subsequent refinement, with Uiso(H) = 1.2Ueq(C) and C—H distances of 0.93 Å.
Numerous dicyanoargentates have been prepared in recent years due to their interesting structural and magnetic properties (Černák et al., 2002; Lefebvre & Leznoff, 2005). By incorporating various amine ligands along with Cu2+ cations and dicyanoargentate anions, structure types containing molecular units, Cu(pn)2Ag2(CN)4 (pn = 1,2-diaminopropane) (Triščíková et al., 2004), one-dimensional chains, Cu(bpy)2Ag2(CN)4.H2O (bpy = 2,2'-bipyridine) (Černák et al., 1993), two-dimensional sheets, [Cu(en)2][Ag2(CN)3][Ag(CN)2] (en = ethylenediamine) (Shorrock et al., 2002), and three-dimensional networks, [Cu2(C4H12N2)2{Ag(CN)2}4(NH3)].2H2O (Potočňák et al., 2003) have all been prepared. Numerous other metal organic compounds containing various transition metal cations, amine ligands, and dicyanoargentate anions have also been prepared. One such structure-type type containing 4,4'-bipyridine (bpy), M(bpy)2[Ag(CN)2]2, where M is Mn (Dong et al., 2003), Fe (Niel et al., 2002), or Cd (Soma et al., 1994) has been prepared. This structure contains a distorted octahedral coordination polyhedron for the M(II) cations, bridging 4,4'-bipyridine ligands, and a three coordinate Ag atom. The title compound, bis(µ-4,4'-bipyridine)bis[µ-dicyanoargentate(I)]copper(II), was prepared in order to determine (1) if the same structure was possible with copper(II) and (2) to probe the effects on the structure.
There is one symmetrically unique copper atom in the structure of Cu(bpy)2[Ag(CN)2]2 and it is located on an inversion center. The coordination geometry around the Cu atoms (Fig. 1) is composed of six nitrogen atoms in a tetragonal bipyramidal arrangement. Two bridging bipyridine ligands and two nitrogen-bound dicyanoargentate anions account for the nitrogen atoms located in the equatorial plane, while the apical positions are occupied by two nitrogen atoms from bridging dicyanoargentate anions. A significant Jahn-Teller distortion is evident in the lengthened Cu—N distance (2.563 (3) Å) of the apical nitrogen atoms as compared to the equatorial Cu—N distances (1.961 (3) and 2.056 (3) Å). In the previously reported Mn, Fe, and Cd structures, the coordination geometries of these metals can be described as distorted octahedral and the M—N bond distances showed much less variation. In Cd(bpy)2[Ag(CN)2]2 the three unique Cd—N bond distances are 2.288, 2.369, and 2.377 Å, in Fe(bpy)2[Ag(CN)2]2 the three Fe—N bond distances are 2.129, 2.188, and 2.248 Å, and in Mn(bpy)2[Ag(CN)2]2 the three Mn—N bond distances are 2.193, 2.264, and 2.320 Å.
There are no unusual features in the bond distances found in the dicyanoargentate anions in Cu(bpy)2[Ag(CN)2]2, although there is a significant bond angle decrease from linearity, C1—Ag1—C2 angle of 157.40 (13)°, as also observed in the previous Mn, Fe, and Cd structures, which have angles of 153.9°, 154.2°, and 153.6°, respectively. The three-dimensional double penetrating framework (Fig 2.) (Soma et al., 1994) built up by the bridging 4,4'-bipyridine and dicyanoargentate anions is preserved in the structure of Cu(bpy)2[Ag(CN)2]2.
For related literature, see: Dong et al. (2003); Lefebvre & Leznoff (2005); Niel et al. (2002); Potočňák et al. (2003); Shorrock et al. (2002); Soma et al. (1994); Triščíková et al. (2004); Černák et al. (1993, 2002).
Data collection: CAD-4-PC Software (Enraf–Nonius, 1993); cell refinement: CAD-4-PC Software; data reduction: XCAD4PC (Harms, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: publCIF (Westrip, 2007).
[Ag2Cu(CN)4(C10H8N2)2] | F(000) = 678 |
Mr = 695.73 | Dx = 1.873 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 8.9056 (9) Å | θ = 8.7–12.0° |
b = 11.4712 (10) Å | µ = 2.46 mm−1 |
c = 12.5918 (11) Å | T = 290 K |
β = 106.484 (8)° | Irregular prism, dark blue |
V = 1233.5 (2) Å3 | 1.00 × 0.51 × 0.42 mm |
Z = 2 |
Enraf–Nonius CAD-4 diffractometer | 1969 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 25.4°, θmin = 2.5° |
θ/2θ scans | h = 0→10 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→13 |
Tmin = 0.255, Tmax = 0.353 | l = −15→14 |
2418 measured reflections | 3 standard reflections every 120 min |
2267 independent reflections | intensity decay: none |
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)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.065 | w = 1/[σ2(Fo2) + (0.0257P)2 + 1.3204P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.001 |
2267 reflections | Δρmax = 0.45 e Å−3 |
161 parameters | Δρmin = −0.38 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0043 (4) |
[Ag2Cu(CN)4(C10H8N2)2] | V = 1233.5 (2) Å3 |
Mr = 695.73 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.9056 (9) Å | µ = 2.46 mm−1 |
b = 11.4712 (10) Å | T = 290 K |
c = 12.5918 (11) Å | 1.00 × 0.51 × 0.42 mm |
β = 106.484 (8)° |
Enraf–Nonius CAD-4 diffractometer | 1969 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.022 |
Tmin = 0.255, Tmax = 0.353 | 3 standard reflections every 120 min |
2418 measured reflections | intensity decay: none |
2267 independent reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.065 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.45 e Å−3 |
2267 reflections | Δρmin = −0.38 e Å−3 |
161 parameters |
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 > 2σ(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 | ||
Ag1 | 0.17340 (3) | 0.82881 (2) | 0.67239 (2) | 0.04213 (12) | |
Cu1 | 0.0000 | 1.0000 | 1.0000 | 0.04178 (18) | |
N1 | 0.0760 (3) | 0.9291 (3) | 0.8833 (2) | 0.0374 (6) | |
N2 | 0.1216 (4) | 1.1913 (3) | 0.9593 (3) | 0.0479 (7) | |
N3 | 0.2061 (3) | 0.9593 (3) | 1.1172 (2) | 0.0395 (6) | |
N4 | 0.9171 (3) | 0.8550 (3) | 1.5329 (2) | 0.0475 (7) | |
C1 | 0.1135 (4) | 0.8918 (3) | 0.8110 (3) | 0.0370 (7) | |
C2 | 0.1904 (4) | 1.2467 (3) | 0.9156 (3) | 0.0408 (8) | |
C3 | 0.3430 (4) | 0.9961 (4) | 1.1058 (3) | 0.0510 (10) | |
H3A | 0.3437 | 1.0357 | 1.0415 | 0.061* | |
C4 | 0.4829 (4) | 0.9777 (4) | 1.1853 (3) | 0.0492 (9) | |
H4A | 0.5754 | 1.0053 | 1.1741 | 0.059* | |
C5 | 0.4869 (4) | 0.9184 (3) | 1.2819 (3) | 0.0373 (7) | |
C6 | 0.3451 (4) | 0.8779 (3) | 1.2912 (3) | 0.0427 (8) | |
H6A | 0.3415 | 0.8355 | 1.3533 | 0.051* | |
C7 | 0.2092 (4) | 0.9001 (3) | 1.2089 (3) | 0.0432 (8) | |
H7A | 0.1152 | 0.8726 | 1.2176 | 0.052* | |
C8 | 0.6358 (4) | 0.8986 (3) | 1.3694 (3) | 0.0349 (7) | |
C9 | 0.7772 (4) | 0.8921 (3) | 1.3440 (3) | 0.0394 (8) | |
H9A | 0.7809 | 0.9030 | 1.2716 | 0.047* | |
C10 | 0.9128 (4) | 0.8692 (3) | 1.4276 (3) | 0.0459 (9) | |
H10A | 1.0063 | 0.8634 | 1.4089 | 0.055* | |
C11 | 0.7813 (4) | 0.8638 (4) | 1.5570 (3) | 0.0474 (9) | |
H11A | 0.7821 | 0.8560 | 1.6307 | 0.057* | |
C12 | 0.6401 (4) | 0.8835 (3) | 1.4798 (3) | 0.0423 (8) | |
H12A | 0.5483 | 0.8867 | 1.5010 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.04338 (18) | 0.04940 (19) | 0.03717 (17) | 0.00608 (12) | 0.01719 (12) | −0.00403 (11) |
Cu1 | 0.0309 (3) | 0.0685 (4) | 0.0239 (3) | 0.0119 (3) | 0.0044 (2) | −0.0064 (3) |
N1 | 0.0332 (14) | 0.0481 (17) | 0.0309 (14) | 0.0011 (12) | 0.0091 (12) | −0.0005 (13) |
N2 | 0.0454 (17) | 0.0549 (19) | 0.0482 (18) | −0.0031 (15) | 0.0213 (15) | 0.0052 (15) |
N3 | 0.0309 (14) | 0.0556 (18) | 0.0306 (14) | 0.0032 (13) | 0.0064 (12) | −0.0008 (13) |
N4 | 0.0367 (16) | 0.063 (2) | 0.0383 (16) | 0.0033 (14) | 0.0038 (13) | 0.0012 (14) |
C1 | 0.0333 (16) | 0.0432 (19) | 0.0343 (17) | 0.0037 (14) | 0.0094 (14) | 0.0011 (14) |
C2 | 0.0380 (17) | 0.049 (2) | 0.0346 (17) | −0.0039 (16) | 0.0096 (15) | 0.0002 (16) |
C3 | 0.0386 (19) | 0.073 (3) | 0.0389 (19) | 0.0012 (18) | 0.0075 (15) | 0.0181 (19) |
C4 | 0.0309 (17) | 0.067 (3) | 0.046 (2) | −0.0084 (17) | 0.0056 (15) | 0.0126 (18) |
C5 | 0.0349 (17) | 0.0399 (18) | 0.0344 (17) | −0.0007 (14) | 0.0054 (14) | 0.0018 (14) |
C6 | 0.0362 (17) | 0.056 (2) | 0.0340 (17) | −0.0029 (16) | 0.0070 (14) | 0.0093 (16) |
C7 | 0.0292 (16) | 0.062 (2) | 0.0390 (18) | −0.0035 (16) | 0.0106 (14) | 0.0030 (16) |
C8 | 0.0321 (16) | 0.0333 (17) | 0.0358 (17) | −0.0029 (13) | 0.0038 (14) | −0.0007 (13) |
C9 | 0.0382 (17) | 0.049 (2) | 0.0296 (16) | −0.0027 (15) | 0.0069 (14) | −0.0025 (14) |
C10 | 0.0336 (18) | 0.060 (2) | 0.043 (2) | 0.0023 (16) | 0.0098 (15) | −0.0037 (17) |
C11 | 0.0406 (19) | 0.067 (2) | 0.0318 (18) | 0.0020 (17) | 0.0055 (15) | 0.0057 (17) |
C12 | 0.0335 (17) | 0.056 (2) | 0.0363 (18) | 0.0006 (15) | 0.0078 (14) | 0.0032 (16) |
Ag1—C2i | 2.086 (4) | C3—H3A | 0.9300 |
Ag1—C1 | 2.093 (3) | C4—C5 | 1.385 (5) |
Ag1—N4ii | 2.472 (3) | C4—H4A | 0.9300 |
Cu1—N1iii | 1.961 (3) | C5—C6 | 1.381 (5) |
Cu1—N1 | 1.961 (3) | C5—C8 | 1.481 (4) |
Cu1—N3iii | 2.056 (3) | C6—C7 | 1.376 (5) |
Cu1—N3 | 2.056 (3) | C6—H6A | 0.9300 |
Cu1—N2 | 2.563 (3) | C7—H7A | 0.9300 |
N1—C1 | 1.138 (4) | C8—C9 | 1.386 (5) |
N2—C2 | 1.128 (4) | C8—C12 | 1.391 (5) |
N3—C7 | 1.333 (5) | C9—C10 | 1.384 (5) |
N3—C3 | 1.336 (5) | C9—H9A | 0.9300 |
N4—C10 | 1.325 (5) | C10—H10A | 0.9300 |
N4—C11 | 1.332 (5) | C11—C12 | 1.372 (5) |
N4—Ag1iv | 2.472 (3) | C11—H11A | 0.9300 |
C2—Ag1v | 2.086 (4) | C12—H12A | 0.9300 |
C3—C4 | 1.375 (5) | ||
C2i—Ag1—C1 | 157.40 (13) | C4—C3—H3A | 118.7 |
C2i—Ag1—N4ii | 103.67 (12) | C3—C4—C5 | 120.5 (3) |
C1—Ag1—N4ii | 98.52 (12) | C3—C4—H4A | 119.8 |
N1—Cu1—N1iii | 180 | C5—C4—H4A | 119.8 |
N1—Cu1—N3iii | 89.09 (11) | C6—C5—C4 | 116.3 (3) |
N1iii—Cu1—N3iii | 90.91 (11) | C6—C5—C8 | 122.2 (3) |
N1—Cu1—N3 | 90.91 (11) | C4—C5—C8 | 121.5 (3) |
N1iii—Cu1—N3 | 89.09 (11) | C7—C6—C5 | 120.3 (3) |
N3iii—Cu1—N3 | 180 | C7—C6—H6A | 119.9 |
N1—Cu1—N2iii | 92.88 (11) | C5—C6—H6A | 119.9 |
N1iii—Cu1—N2iii | 87.12 (11) | N3—C7—C6 | 123.0 (3) |
N3iii—Cu1—N2iii | 89.78 (11) | N3—C7—H7A | 118.5 |
N3—Cu1—N2iii | 90.22 (11) | C6—C7—H7A | 118.5 |
N1—Cu1—N2 | 87.12 (11) | C9—C8—C12 | 117.1 (3) |
N1iii—Cu1—N2 | 92.88 (11) | C9—C8—C5 | 121.1 (3) |
N3iii—Cu1—N2 | 90.22 (11) | C12—C8—C5 | 121.8 (3) |
N3—Cu1—N2 | 89.78 (11) | C10—C9—C8 | 119.3 (3) |
N2iii—Cu1—N2 | 180 | C10—C9—H9A | 120.4 |
C1—N1—Cu1 | 175.9 (3) | C8—C9—H9A | 120.4 |
C7—N3—C3 | 117.3 (3) | N4—C10—C9 | 123.8 (3) |
C7—N3—Cu1 | 122.2 (2) | N4—C10—H10A | 118.1 |
C3—N3—Cu1 | 120.5 (2) | C9—C10—H10A | 118.1 |
C10—N4—C11 | 116.6 (3) | N4—C11—C12 | 124.0 (3) |
C10—N4—Ag1iv | 119.0 (2) | N4—C11—H11A | 118.0 |
C11—N4—Ag1iv | 124.2 (2) | C12—C11—H11A | 118.0 |
N1—C1—Ag1 | 176.9 (3) | C11—C12—C8 | 119.2 (3) |
N2—C2—Ag1v | 172.6 (3) | C11—C12—H12A | 120.4 |
N3—C3—C4 | 122.7 (3) | C8—C12—H12A | 120.4 |
N3—C3—H3A | 118.7 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x−1, y, z−1; (iii) −x, −y+2, −z+2; (iv) x+1, y, z+1; (v) −x+1/2, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Ag2Cu(CN)4(C10H8N2)2] |
Mr | 695.73 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 290 |
a, b, c (Å) | 8.9056 (9), 11.4712 (10), 12.5918 (11) |
β (°) | 106.484 (8) |
V (Å3) | 1233.5 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.46 |
Crystal size (mm) | 1.00 × 0.51 × 0.42 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.255, 0.353 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2418, 2267, 1969 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.603 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.065, 1.11 |
No. of reflections | 2267 |
No. of parameters | 161 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.38 |
Computer programs: CAD-4-PC Software (Enraf–Nonius, 1993), CAD-4-PC Software, XCAD4PC (Harms, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), publCIF (Westrip, 2007).
Numerous dicyanoargentates have been prepared in recent years due to their interesting structural and magnetic properties (Černák et al., 2002; Lefebvre & Leznoff, 2005). By incorporating various amine ligands along with Cu2+ cations and dicyanoargentate anions, structure types containing molecular units, Cu(pn)2Ag2(CN)4 (pn = 1,2-diaminopropane) (Triščíková et al., 2004), one-dimensional chains, Cu(bpy)2Ag2(CN)4.H2O (bpy = 2,2'-bipyridine) (Černák et al., 1993), two-dimensional sheets, [Cu(en)2][Ag2(CN)3][Ag(CN)2] (en = ethylenediamine) (Shorrock et al., 2002), and three-dimensional networks, [Cu2(C4H12N2)2{Ag(CN)2}4(NH3)].2H2O (Potočňák et al., 2003) have all been prepared. Numerous other metal organic compounds containing various transition metal cations, amine ligands, and dicyanoargentate anions have also been prepared. One such structure-type type containing 4,4'-bipyridine (bpy), M(bpy)2[Ag(CN)2]2, where M is Mn (Dong et al., 2003), Fe (Niel et al., 2002), or Cd (Soma et al., 1994) has been prepared. This structure contains a distorted octahedral coordination polyhedron for the M(II) cations, bridging 4,4'-bipyridine ligands, and a three coordinate Ag atom. The title compound, bis(µ-4,4'-bipyridine)bis[µ-dicyanoargentate(I)]copper(II), was prepared in order to determine (1) if the same structure was possible with copper(II) and (2) to probe the effects on the structure.
There is one symmetrically unique copper atom in the structure of Cu(bpy)2[Ag(CN)2]2 and it is located on an inversion center. The coordination geometry around the Cu atoms (Fig. 1) is composed of six nitrogen atoms in a tetragonal bipyramidal arrangement. Two bridging bipyridine ligands and two nitrogen-bound dicyanoargentate anions account for the nitrogen atoms located in the equatorial plane, while the apical positions are occupied by two nitrogen atoms from bridging dicyanoargentate anions. A significant Jahn-Teller distortion is evident in the lengthened Cu—N distance (2.563 (3) Å) of the apical nitrogen atoms as compared to the equatorial Cu—N distances (1.961 (3) and 2.056 (3) Å). In the previously reported Mn, Fe, and Cd structures, the coordination geometries of these metals can be described as distorted octahedral and the M—N bond distances showed much less variation. In Cd(bpy)2[Ag(CN)2]2 the three unique Cd—N bond distances are 2.288, 2.369, and 2.377 Å, in Fe(bpy)2[Ag(CN)2]2 the three Fe—N bond distances are 2.129, 2.188, and 2.248 Å, and in Mn(bpy)2[Ag(CN)2]2 the three Mn—N bond distances are 2.193, 2.264, and 2.320 Å.
There are no unusual features in the bond distances found in the dicyanoargentate anions in Cu(bpy)2[Ag(CN)2]2, although there is a significant bond angle decrease from linearity, C1—Ag1—C2 angle of 157.40 (13)°, as also observed in the previous Mn, Fe, and Cd structures, which have angles of 153.9°, 154.2°, and 153.6°, respectively. The three-dimensional double penetrating framework (Fig 2.) (Soma et al., 1994) built up by the bridging 4,4'-bipyridine and dicyanoargentate anions is preserved in the structure of Cu(bpy)2[Ag(CN)2]2.