Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104002380/fa1048sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104002380/fa1048Isup2.hkl |
CCDC reference: 235327
Yellow 1,3-bis(2-fluorophenyl)triazene (46.6 mg, 0.2 mmol) was dissolved in methanol (20 ml) and treated with two pellets of KOH, whereupon the solution changed colour to deep red. A solution of cadmium(II) acetate dihydrate (26.7 mg, 0.1 mmol) in methanol (10 ml) was added slowly with continuous stirring while the reaction mixture changed colour to orange–red. The mixture was stirred for 1 h at room temperature, after which pyridine (2 ml) was added and the mixture was stirred for a further 24 h. Orange–red prism-shaped crystals of (I), suitable for X-ray analysis, were obtained by slow evaporation of the solvent at room temperature (yield 42.6 mg, 58%; m.p. 413 K).
The positional parameters of the H atoms were obtained geometrically and the H atoms were treated as riding on their respective C atoms (C–H = 0.93 Å for Csp2 atoms), with a isotropic displacement parameters of 1.2Ueq of the attached Csp2 atom. Friedel pairs were not averaged before refinement. The Flack (1983) parameter was obtained by refinement, including 1829 Friedel pairs. The fluoro F atoms show a large thermal motion, indicated by their elongated displacement ellipsoids (Fig. 1). Split peaks for these atoms were not observed and consequently a disorder model was not used.
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) and DIAMOND (Brandenburg, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Cd(C12H8F2N3)2(C5H5N)2] | F(000) = 1480 |
Mr = 735.03 | Dx = 1.541 Mg m−3 |
Orthorhombic, Iba2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: I 2 -2c | Cell parameters from 25 reflections |
a = 9.835 (3) Å | θ = 7.7–14.0° |
b = 19.229 (2) Å | µ = 0.75 mm−1 |
c = 16.750 (6) Å | T = 208 K |
V = 3167.6 (15) Å3 | Prism, orange–red |
Z = 4 | 0.35 × 0.30 × 0.20 mm |
Enraf–Nonius CAD-4 diffractometer | 3233 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 28.0°, θmin = 3.2° |
θ/2θ scans | h = −1→12 |
Absorption correction: ψ scan (Spek, 1990) | k = −1→25 |
Tmin = 0.779, Tmax = 0.864 | l = −22→22 |
4462 measured reflections | 3 standard reflections every 60 min |
3800 independent reflections | intensity decay: 1% |
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0256P)2 + 0.7633P] where P = (Fo2 + 2Fc2)/3 |
Least-squares matrix: full | (Δ/σ)max < 0.001 |
R[F2 > 2σ(F2)] = 0.021 | Δρmax = 0.25 e Å−3 |
wR(F2) = 0.053 | Δρmin = −0.24 e Å−3 |
S = 1.03 | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
3800 reflections | Extinction coefficient: 0.00193 (13) |
214 parameters | Absolute structure: Flack (1983), 1829 Friedel pairs |
1 restraint | Absolute structure parameter: −0.03 (2) |
H-atom parameters constrained |
[Cd(C12H8F2N3)2(C5H5N)2] | V = 3167.6 (15) Å3 |
Mr = 735.03 | Z = 4 |
Orthorhombic, Iba2 | Mo Kα radiation |
a = 9.835 (3) Å | µ = 0.75 mm−1 |
b = 19.229 (2) Å | T = 208 K |
c = 16.750 (6) Å | 0.35 × 0.30 × 0.20 mm |
Enraf–Nonius CAD-4 diffractometer | 3233 reflections with I > 2σ(I) |
Absorption correction: ψ scan (Spek, 1990) | Rint = 0.017 |
Tmin = 0.779, Tmax = 0.864 | 3 standard reflections every 60 min |
4462 measured reflections | intensity decay: 1% |
3800 independent reflections |
R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.053 | Δρmax = 0.25 e Å−3 |
S = 1.03 | Δρmin = −0.24 e Å−3 |
3800 reflections | Absolute structure: Flack (1983), 1829 Friedel pairs |
214 parameters | Absolute structure parameter: −0.03 (2) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
Cd | 0.0000 | 0.5000 | 0.15184 (2) | 0.03215 (6) | |
F1 | −0.33216 (14) | 0.46022 (7) | 0.10125 (8) | 0.0443 (3) | |
F2 | 0.31412 (15) | 0.46036 (9) | 0.24216 (11) | 0.0613 (5) | |
N11 | −0.13961 (18) | 0.40780 (9) | 0.19869 (10) | 0.0299 (4) | |
N12 | −0.0601 (2) | 0.38504 (10) | 0.25583 (10) | 0.0307 (4) | |
N13 | 0.0556 (2) | 0.41796 (10) | 0.25311 (10) | 0.0297 (4) | |
N31 | 0.1070 (2) | 0.43196 (10) | 0.05402 (11) | 0.0345 (4) | |
C11 | −0.2649 (2) | 0.37376 (11) | 0.19365 (12) | 0.0301 (4) | |
C12 | −0.3632 (2) | 0.40201 (11) | 0.14298 (15) | 0.0337 (4) | |
C13 | −0.4899 (3) | 0.37369 (14) | 0.13303 (12) | 0.0412 (6) | |
H13 | −0.5523 | 0.3944 | 0.0988 | 0.049* | |
C14 | −0.5241 (3) | 0.31382 (15) | 0.17462 (15) | 0.0464 (7) | |
H14 | −0.6097 | 0.2939 | 0.1686 | 0.056* | |
C15 | −0.4290 (3) | 0.28393 (13) | 0.22534 (14) | 0.0419 (5) | |
H15 | −0.4514 | 0.2438 | 0.2535 | 0.050* | |
C16 | −0.3019 (2) | 0.31285 (11) | 0.23453 (13) | 0.0353 (5) | |
H16 | −0.2394 | 0.2917 | 0.2684 | 0.042* | |
C21 | 0.1468 (2) | 0.40016 (11) | 0.31434 (12) | 0.0315 (4) | |
C22 | 0.2802 (2) | 0.42252 (13) | 0.30704 (15) | 0.0423 (5) | |
C23 | 0.3797 (3) | 0.40804 (17) | 0.36286 (19) | 0.0574 (7) | |
H23 | 0.4685 | 0.4233 | 0.3552 | 0.069* | |
C24 | 0.3453 (3) | 0.37071 (17) | 0.42978 (17) | 0.0581 (8) | |
H24 | 0.4109 | 0.3603 | 0.4680 | 0.070* | |
C25 | 0.2126 (3) | 0.34857 (15) | 0.44014 (16) | 0.0518 (7) | |
H25 | 0.1891 | 0.3238 | 0.4858 | 0.062* | |
C26 | 0.1148 (2) | 0.36281 (12) | 0.38349 (12) | 0.0384 (5) | |
H26 | 0.0262 | 0.3474 | 0.3914 | 0.046* | |
C32 | 0.1659 (3) | 0.45526 (13) | −0.01303 (13) | 0.0399 (5) | |
H32 | 0.1585 | 0.5023 | −0.0253 | 0.048* | |
C33 | 0.2367 (3) | 0.41286 (14) | −0.06455 (15) | 0.0457 (6) | |
H33 | 0.2760 | 0.4308 | −0.1107 | 0.055* | |
C34 | 0.2483 (3) | 0.34292 (16) | −0.04616 (15) | 0.0503 (7) | |
H34 | 0.2965 | 0.3131 | −0.0795 | 0.060* | |
C35 | 0.1875 (3) | 0.31804 (14) | 0.02228 (15) | 0.0479 (6) | |
H35 | 0.1935 | 0.2712 | 0.0357 | 0.057* | |
C36 | 0.1176 (3) | 0.36399 (12) | 0.07044 (14) | 0.0404 (5) | |
H36 | 0.0760 | 0.3470 | 0.1163 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd | 0.04344 (10) | 0.02300 (8) | 0.03001 (9) | 0.00282 (11) | 0.000 | 0.000 |
F1 | 0.0439 (8) | 0.0441 (8) | 0.0448 (7) | −0.0073 (7) | −0.0085 (6) | 0.0156 (7) |
F2 | 0.0391 (8) | 0.0712 (12) | 0.0736 (11) | −0.0006 (8) | 0.0023 (8) | 0.0242 (10) |
N11 | 0.0304 (9) | 0.0288 (9) | 0.0306 (8) | 0.0025 (7) | −0.0020 (7) | 0.0014 (7) |
N12 | 0.0344 (9) | 0.0281 (9) | 0.0295 (8) | 0.0040 (8) | 0.0003 (7) | −0.0019 (7) |
N13 | 0.0303 (9) | 0.0300 (9) | 0.0288 (9) | 0.0040 (8) | −0.0017 (7) | 0.0001 (7) |
N31 | 0.0373 (11) | 0.0298 (10) | 0.0365 (10) | 0.0001 (8) | 0.0008 (8) | −0.0021 (8) |
C11 | 0.0334 (11) | 0.0279 (10) | 0.0291 (10) | −0.0004 (9) | 0.0025 (8) | −0.0025 (8) |
C12 | 0.0377 (10) | 0.0324 (9) | 0.0311 (12) | −0.0038 (8) | −0.0012 (10) | 0.0022 (10) |
C13 | 0.0349 (11) | 0.0501 (12) | 0.0386 (15) | −0.0006 (11) | −0.0045 (9) | 0.0035 (8) |
C14 | 0.0408 (15) | 0.0524 (15) | 0.0460 (14) | −0.0143 (11) | 0.0008 (9) | −0.0019 (10) |
C15 | 0.0478 (14) | 0.0343 (12) | 0.0437 (13) | −0.0082 (11) | 0.0072 (11) | 0.0038 (10) |
C16 | 0.0416 (12) | 0.0288 (10) | 0.0354 (10) | 0.0006 (9) | 0.0000 (10) | 0.0007 (9) |
C21 | 0.0349 (10) | 0.0269 (10) | 0.0328 (10) | 0.0087 (9) | −0.0045 (9) | −0.0038 (8) |
C22 | 0.0378 (12) | 0.0393 (12) | 0.0499 (13) | 0.0072 (10) | −0.0038 (10) | −0.0003 (11) |
C23 | 0.0393 (14) | 0.0616 (19) | 0.0713 (18) | 0.0063 (14) | −0.0172 (13) | −0.0084 (15) |
C24 | 0.0579 (17) | 0.0639 (18) | 0.0524 (14) | 0.0246 (15) | −0.0223 (13) | −0.0072 (14) |
C25 | 0.0656 (19) | 0.0494 (15) | 0.0404 (13) | 0.0202 (14) | −0.0067 (13) | 0.0050 (11) |
C26 | 0.0419 (12) | 0.0366 (11) | 0.0368 (13) | 0.0099 (10) | −0.0009 (9) | 0.0022 (8) |
C32 | 0.0410 (13) | 0.0401 (13) | 0.0388 (11) | −0.0066 (11) | 0.0002 (9) | −0.0001 (10) |
C33 | 0.0403 (13) | 0.0584 (16) | 0.0386 (11) | −0.0074 (12) | 0.0046 (10) | −0.0024 (12) |
C34 | 0.0474 (14) | 0.0614 (17) | 0.0420 (12) | 0.0157 (13) | 0.0025 (11) | −0.0155 (12) |
C35 | 0.0620 (16) | 0.0393 (13) | 0.0423 (13) | 0.0128 (12) | −0.0025 (12) | −0.0068 (11) |
C36 | 0.0535 (15) | 0.0335 (12) | 0.0343 (10) | 0.0049 (11) | 0.0019 (10) | −0.0014 (9) |
Cd—N31 | 2.3461 (19) | C15—C16 | 1.377 (3) |
Cd—N31i | 2.3461 (19) | C15—H15 | 0.9300 |
Cd—N11i | 2.3757 (18) | C16—H16 | 0.9300 |
Cd—N11 | 2.3757 (18) | C21—C22 | 1.385 (3) |
Cd—N13i | 2.3800 (19) | C21—C26 | 1.399 (3) |
Cd—N13 | 2.3800 (19) | C22—C23 | 1.382 (4) |
F1—C12 | 1.354 (2) | C23—C24 | 1.374 (4) |
F1—C24ii | 3.351 (3) | C23—H23 | 0.9300 |
F2—C22 | 1.350 (3) | C24—C25 | 1.384 (4) |
F2—C13iii | 3.136 (3) | C24—H24 | 0.9300 |
N11—N12 | 1.311 (2) | C25—C26 | 1.378 (3) |
N11—C11 | 1.398 (3) | C25—H25 | 0.9300 |
N12—N13 | 1.303 (3) | C26—H26 | 0.9300 |
N13—C21 | 1.405 (3) | C32—C33 | 1.377 (3) |
N31—C36 | 1.340 (3) | C32—H32 | 0.9300 |
N31—C32 | 1.341 (3) | C33—C34 | 1.384 (4) |
C11—C12 | 1.397 (3) | C33—H33 | 0.9300 |
C11—C16 | 1.405 (3) | C34—C35 | 1.379 (4) |
C12—C13 | 1.370 (3) | C34—H34 | 0.9300 |
C13—C14 | 1.387 (4) | C35—C36 | 1.380 (3) |
C13—H13 | 0.9300 | C35—H35 | 0.9300 |
C14—C15 | 1.388 (4) | C36—H36 | 0.9300 |
C14—H14 | 0.9300 | ||
N31—Cd—N31i | 91.40 (10) | C15—C16—C11 | 121.2 (2) |
N31—Cd—N11 | 94.24 (6) | C15—C16—H16 | 119.4 |
N31i—Cd—N11 | 112.80 (6) | C11—C16—H16 | 119.4 |
N11i—Cd—N11 | 141.42 (8) | C22—C21—C26 | 116.5 (2) |
N31—Cd—N13i | 166.03 (6) | C22—C21—N13 | 117.7 (2) |
N31—Cd—N13 | 91.44 (6) | C26—C21—N13 | 125.8 (2) |
N11i—Cd—N13 | 97.26 (6) | F2—C22—C23 | 118.6 (2) |
N11—Cd—N13 | 53.33 (6) | F2—C22—C21 | 118.2 (2) |
N13i—Cd—N13 | 89.09 (9) | C23—C22—C21 | 123.3 (3) |
C12—F1—C24ii | 90.53 (13) | C24—C23—C22 | 118.8 (3) |
C22—F2—C13iii | 109.57 (14) | C24—C23—H23 | 120.6 |
N12—N11—C11 | 114.43 (17) | C22—C23—H23 | 120.6 |
N12—N11—Cd | 98.37 (13) | C23—C24—C25 | 119.7 (3) |
C11—N11—Cd | 147.03 (13) | C23—C24—H24 | 120.1 |
N13—N12—N11 | 109.46 (17) | C25—C24—H24 | 120.1 |
N12—N13—C21 | 114.45 (18) | C26—C25—C24 | 120.7 (3) |
N12—N13—Cd | 98.42 (12) | C26—C25—H25 | 119.6 |
C21—N13—Cd | 145.93 (16) | C24—C25—H25 | 119.6 |
C36—N31—C32 | 117.7 (2) | C25—C26—C21 | 121.0 (2) |
C36—N31—Cd | 115.82 (16) | C25—C26—H26 | 119.5 |
C32—N31—Cd | 126.33 (16) | C21—C26—H26 | 119.5 |
C12—C11—N11 | 117.70 (18) | N31—C32—C33 | 123.1 (2) |
C12—C11—C16 | 116.2 (2) | N31—C32—H32 | 118.5 |
N11—C11—C16 | 126.11 (19) | C33—C32—H32 | 118.5 |
F1—C12—C13 | 118.1 (2) | C32—C33—C34 | 118.5 (2) |
F1—C12—C11 | 118.62 (18) | C32—C33—H33 | 120.7 |
C13—C12—C11 | 123.3 (2) | C34—C33—H33 | 120.7 |
C12—C13—C14 | 119.3 (2) | C35—C34—C33 | 119.1 (2) |
C12—C13—H13 | 120.4 | C35—C34—H34 | 120.4 |
C14—C13—H13 | 120.4 | C33—C34—H34 | 120.4 |
C13—C14—C15 | 119.2 (2) | C34—C35—C36 | 118.7 (2) |
C13—C14—H14 | 120.4 | C34—C35—H35 | 120.7 |
C15—C14—H14 | 120.4 | C36—C35—H35 | 120.7 |
C16—C15—C14 | 120.9 (2) | N31—C36—C35 | 122.9 (2) |
C16—C15—H15 | 119.6 | N31—C36—H36 | 118.5 |
C14—C15—H15 | 119.6 | C35—C36—H36 | 118.5 |
Symmetry codes: (i) −x, −y+1, z; (ii) −x, y, z−1/2; (iii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C12H8F2N3)2(C5H5N)2] |
Mr | 735.03 |
Crystal system, space group | Orthorhombic, Iba2 |
Temperature (K) | 208 |
a, b, c (Å) | 9.835 (3), 19.229 (2), 16.750 (6) |
V (Å3) | 3167.6 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.75 |
Crystal size (mm) | 0.35 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (Spek, 1990) |
Tmin, Tmax | 0.779, 0.864 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4462, 3800, 3233 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.053, 1.03 |
No. of reflections | 3800 |
No. of parameters | 214 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.24 |
Absolute structure | Flack (1983), 1829 Friedel pairs |
Absolute structure parameter | −0.03 (2) |
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) and DIAMOND (Brandenburg, 1996), WinGX (Farrugia, 1999).
Cd—N31 | 2.3461 (19) | N11—C11 | 1.398 (3) |
Cd—N11 | 2.3757 (18) | N12—N13 | 1.303 (3) |
Cd—N13 | 2.3800 (19) | N13—C21 | 1.405 (3) |
N11—N12 | 1.311 (2) | ||
N31—Cd—N31i | 91.40 (10) | N31—Cd—N13 | 91.44 (6) |
N31—Cd—N11 | 94.24 (6) | N11i—Cd—N13 | 97.26 (6) |
N31i—Cd—N11 | 112.80 (6) | N11—Cd—N13 | 53.33 (6) |
N11i—Cd—N11 | 141.42 (8) | N13i—Cd—N13 | 89.09 (9) |
N31—Cd—N13i | 166.03 (6) | N13—N12—N11 | 109.46 (17) |
Symmetry code: (i) −x, −y+1, z. |
The synthesis of the first cadmium(II) 1,3-diaryl-substituted triazenide complex, Cd(ArNNNAr)2 (Ar = p-C6H4NO2) was reported in 1887, whereas the analogous complex with 1,3-diphenyltriazene was prepared in 1963 (Moore & Robinson, 1986, and references therein). More recently, cadmium(II) diaryltriazenide complexes have received attention in connection with the spectrophotometric determination of cadmium based on the chromogenic behavior of triazene derivatives (Hayashibe & Sayama, 1996). To date, only two diaryltriazenide cadmium(II) complexes have been characterized by single-crystal X-ray diffraction, namely [Cd{PhN3(H)C6H4– N3(H)Ph}{PhN3C6H4N3(H)Ph}2], hereafter (II), in which the Cd atom is coordinated by one neutral chelating 1,2-bis(phenyltriazene)benzene ligand and two monodentate 1-phenyltriazenide-2-phenyltriazene benzene anions in a distorted-tetrahedral arrangement, and K[Cd(O2NC6H4NNNC6H4NO2)3], (III), an anionic cadmium complex in which the Cd atom is coordinated in a trigonal-prismatic arrangement by three chelating deprotonated 1,3-bis(4-nitrophenyl)triazenide ions (Hörner et al., 1996, 2003a). In this work, we report the synthesis and structural characterization of the title complex, (I), an axially symmetric mononuclear CdII complex with a symmetrically disubstituted 1,3-diaryltriazenide ion and pyridine (py) as ligands.
Complex (I) has a structure analogous to that of the related CoII complex, [Co(C12H10N3)2(C5H5N)2], hereafter (IV) (Peng et al., 1985). The crystal structure of (I) consists of discrete mononuclear complexes in which the CdII ion has a rhombically distorted-octahedral coordination geometry. Two deprotonated 1,3-bis(2-fluorophenyl)triazenide ions act as (N11)-η1,(N13)-η1 bidentate (four-electron donor) ligands, while two neutral pyridine molecules are coordinated cis to one another (Fig. 1).
In the molecule of (I), which has site symmetry 2, the CdII ion is inserted in a distorted square-planar base formed by atoms N13, N13i, N31 and N31i [r.m.s. deviation 0.286 Å; symmetry code (i): −x, −y + 1, z]. The crystallographic twofold-symmetry axis bisects the N13—Cd—N13i [89.09 (9)°] and N31—Cd—N31i [91.40 (10)°] angles and the N11—Cd—N11i axial angle [141.42 (8)°; symmetry code (i): −x, −y + 1, z]. These values are in good agreement with the angles found in the related compound (IV) [N3—Co—N3i = 90.3 (1)°, N4—Co—N4i = 89.6 (1)° and N1—Co—N1i = 149.6 (1)°, respectively; symmetry code (i): −x, −y + 1, z; i.e. Co is also on a twofold axis; Peng et al., 1985).
As a result of the bidentate coordination mode of the triazenide ligand, the N—N bond lengths are equal to within three standard deviations, with a mean value of 1.307 (4) Å (Table 1). These bond lengths are longer than the typical value for a double bond (1.24 Å; International Tables for Crystallography, 1995, Vol. C), and are similar to the N—N distances observed in the anionic triazenido complex (II) [1.310 (5) and 1.317 (6) Å]. On the other hand, both the N11—C11 [1.398 (3) Å] and N13—C21 [1.405 (3) Å] bonds are shorter than expected for an N—Caryl single bond (1.452 Å for secondary amines, NHR2, with R = Csp2; Orpen et al., 1989). These values, together with the observed N—N bond distances, which imply partial double-bond character, provide evidence for the delocalization of the π electrons on the N—N=N triad towards the terminal 2-fluorophenyl substituents.
The Cd—N11 [2.3757 (18) Å] and Cd—N13 [2.3800 (19) Å] bonds are both longer than the sum of the covalent radii (2.27 Å; Allen et al., 1987; Teatum et al., 1960) and correspond to covalent single bonds. These values are in good agreement with those found in (II) [2.350 (5) and 2.397 (4) Å] and (III) [2.350 (4) and 2.376 (4) Å].
The bidentate coordination mode of the triazenide ligand, together with the acute N11—Cd—N13 angle [53.33 (6)°] give rise to a strained Cd/N11–N13 four-membered ring. The bond angle of the triazenide moiety [109.46 (17)°] deviates only slightly from the angles observed in complexes such trans-[Pd(FC6H4—N=N—NC6H4NO2)2(C5H5N)2] [111.0 (3)°; Hörner et al., 2002] and {Au(O2NC6H4N=N—N—C6H4NO2)[P(C6H5)3]} [110.0 (4)°; Hörner et al., 2003b], in which the triazenide ligand is monodentate.
The terminal 2-fluorophenyl substituents form a dihedral angle of 24.6 (1)°, indicating the lack of planarity of the triazenide ligand.
The crystal structure of (I) reveals molecules linked into chains along the [001] direction via intermolecular C—H···F interactions [C24ii···F1 = 3.351 (3) Å; C24ii—H24ii···F1 = 101.12°; symmetry code: (ii) −x, y, −0.5 + z]; these chains, related by the axial c-glide plane, generate sheets of molecules in the (010) plane (Fig. 2). These values are comparable to that found for C—H···F interactions in the crystal structure of the fluorobenzene C6HF5 [C6···F11 = 3.46 Å; C6—H1···F11 = 120.4°; Thalladi et al., 1998].
The pyridine ring (N31/C32–C36) makes a dihedral angle of 56.4 (6)° with the N11—Cd—N11i moiety [symmetry code: (i) −x, −y + 1, z]. The Cd—N31 bond distance [2.3461 (19) Å] in (I) is longer than the sum of the covalent radii (2.27 Å; Allen et al., 1987; Teatum et al., 1960) and is comparable to the avarage Cd—N bond length found in Cd(py)4Cr2O7 [2.347 (5) Å; Norquist et al., 2001].