Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104020499/sk1763sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104020499/sk1763Isup2.hkl |
CCDC reference: 254913
Copper(I) di(methanesulfonyl)amide was prepared by the method of Linoh (1989), dissolved in excess 2-picoline and the solution overlayered with diethyl ether. Despite considerable decomposition, a few colourless crystals of (I) formed. Clearly, the method needs thorough optimization before it can be used as a reliable synthetic procedure.
Methyl H atoms were clearly identified in difference syntheses, idealized and refined as rigid groups allowed to rotate but not tip. Other H atoms were included using a riding model. C—H bond lengths were fixed at 0.98 (methyl) or 0.95 Å (aromatic), and methyl H—C—H angles at 109.5°. Uiso(H) values were fixed at 1.2U(eq) of the parent atom.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
[Cu(C2H6NO4S2)(C6H7N)2] | F(000) = 872 |
Mr = 421.99 | Dx = 1.570 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7138 reflections |
a = 10.2353 (6) Å | θ = 2–30.5° |
b = 7.7684 (4) Å | µ = 1.48 mm−1 |
c = 23.0287 (14) Å | T = 133 K |
β = 102.780 (4)° | Block, colourless |
V = 1785.69 (18) Å3 | 0.39 × 0.25 × 0.17 mm |
Z = 4 |
Bruker SMART 1000 CCD area-detector diffractometer | 5215 independent reflections |
Radiation source: fine-focus sealed tube | 4267 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 8.192 pixels mm-1 | θmax = 30.0°, θmin = 1.8° |
ω and ϕ scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −10→10 |
Tmin = 0.625, Tmax = 0.746 | l = −31→32 |
35736 measured reflections |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0432P)2] where P = (Fo2 + 2Fc2)/3 |
5215 reflections | (Δ/σ)max = 0.002 |
221 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
[Cu(C2H6NO4S2)(C6H7N)2] | V = 1785.69 (18) Å3 |
Mr = 421.99 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.2353 (6) Å | µ = 1.48 mm−1 |
b = 7.7684 (4) Å | T = 133 K |
c = 23.0287 (14) Å | 0.39 × 0.25 × 0.17 mm |
β = 102.780 (4)° |
Bruker SMART 1000 CCD area-detector diffractometer | 5215 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 4267 reflections with I > 2σ(I) |
Tmin = 0.625, Tmax = 0.746 | Rint = 0.030 |
35736 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.43 e Å−3 |
5215 reflections | Δρmin = −0.33 e Å−3 |
221 parameters |
Experimental. {Di(methanesulfonyl)amido-N}bis(2-picolino)copper(I) |
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 | ||
C1 | 0.70655 (15) | 0.1471 (2) | 0.51204 (6) | 0.0249 (3) | |
H1A | 0.7838 | 0.0691 | 0.5196 | 0.030* | |
H1B | 0.7365 | 0.2641 | 0.5058 | 0.030* | |
H1C | 0.6416 | 0.1090 | 0.4764 | 0.030* | |
C2 | 0.80651 (15) | −0.0639 (2) | 0.70031 (7) | 0.0263 (3) | |
H2A | 0.8825 | −0.1232 | 0.7259 | 0.032* | |
H2B | 0.7574 | −0.1447 | 0.6707 | 0.032* | |
H2C | 0.7467 | −0.0198 | 0.7247 | 0.032* | |
N1 | 0.73750 (10) | 0.21799 (16) | 0.63011 (5) | 0.0186 (2) | |
O1 | 0.52550 (10) | 0.27237 (16) | 0.56227 (4) | 0.0307 (3) | |
O2 | 0.59185 (11) | −0.02973 (15) | 0.58231 (5) | 0.0305 (3) | |
O3 | 0.93869 (10) | 0.22316 (14) | 0.70889 (4) | 0.0274 (2) | |
O4 | 0.93988 (10) | 0.03526 (15) | 0.62317 (5) | 0.0276 (2) | |
S1 | 0.63064 (3) | 0.14510 (5) | 0.573639 (15) | 0.01933 (8) | |
S2 | 0.86576 (3) | 0.10869 (5) | 0.663756 (15) | 0.01823 (8) | |
Cu | 0.747080 (16) | 0.48750 (2) | 0.639749 (7) | 0.01940 (6) | |
N11 | 0.82445 (11) | 0.59523 (16) | 0.57854 (5) | 0.0194 (2) | |
C12 | 0.95650 (14) | 0.63068 (19) | 0.58710 (6) | 0.0210 (3) | |
C13 | 1.00977 (15) | 0.7048 (2) | 0.54267 (7) | 0.0263 (3) | |
H13 | 1.1028 | 0.7298 | 0.5500 | 0.032* | |
C14 | 0.92847 (16) | 0.7424 (2) | 0.48787 (7) | 0.0290 (3) | |
H14 | 0.9644 | 0.7924 | 0.4571 | 0.035* | |
C15 | 0.79310 (16) | 0.7052 (2) | 0.47895 (7) | 0.0289 (3) | |
H15 | 0.7342 | 0.7283 | 0.4417 | 0.035* | |
C16 | 0.74509 (14) | 0.6341 (2) | 0.52514 (7) | 0.0248 (3) | |
H16 | 0.6518 | 0.6116 | 0.5190 | 0.030* | |
C17 | 1.04282 (15) | 0.5863 (2) | 0.64671 (7) | 0.0296 (3) | |
H17A | 1.0047 | 0.6373 | 0.6782 | 0.036* | |
H17B | 1.1333 | 0.6316 | 0.6494 | 0.036* | |
H17C | 1.0469 | 0.4609 | 0.6515 | 0.036* | |
N21 | 0.67708 (12) | 0.54473 (16) | 0.70996 (5) | 0.0202 (2) | |
C22 | 0.55320 (14) | 0.61205 (19) | 0.70606 (7) | 0.0248 (3) | |
C23 | 0.51098 (17) | 0.6591 (2) | 0.75719 (8) | 0.0343 (4) | |
H23 | 0.4240 | 0.7062 | 0.7540 | 0.041* | |
C24 | 0.59436 (18) | 0.6381 (3) | 0.81256 (8) | 0.0404 (4) | |
H24 | 0.5656 | 0.6701 | 0.8475 | 0.049* | |
C25 | 0.72076 (17) | 0.5693 (3) | 0.81626 (7) | 0.0357 (4) | |
H25 | 0.7807 | 0.5537 | 0.8538 | 0.043* | |
C26 | 0.75772 (15) | 0.5239 (2) | 0.76394 (7) | 0.0254 (3) | |
H26 | 0.8441 | 0.4758 | 0.7664 | 0.031* | |
C27 | 0.46708 (16) | 0.6334 (2) | 0.64483 (8) | 0.0335 (4) | |
H27A | 0.5118 | 0.7101 | 0.6215 | 0.040* | |
H27B | 0.3807 | 0.6833 | 0.6476 | 0.040* | |
H27C | 0.4523 | 0.5209 | 0.6252 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0248 (7) | 0.0317 (9) | 0.0190 (7) | −0.0039 (6) | 0.0066 (5) | −0.0020 (6) |
C2 | 0.0267 (7) | 0.0225 (8) | 0.0278 (8) | −0.0019 (6) | 0.0019 (6) | 0.0079 (6) |
N1 | 0.0188 (6) | 0.0169 (6) | 0.0179 (5) | 0.0011 (4) | −0.0008 (4) | −0.0004 (4) |
O1 | 0.0212 (5) | 0.0453 (7) | 0.0241 (5) | 0.0103 (5) | 0.0018 (4) | 0.0048 (5) |
O2 | 0.0307 (6) | 0.0322 (7) | 0.0258 (6) | −0.0157 (5) | 0.0002 (5) | 0.0012 (4) |
O3 | 0.0276 (5) | 0.0235 (6) | 0.0253 (5) | −0.0037 (4) | −0.0065 (4) | −0.0026 (4) |
O4 | 0.0228 (5) | 0.0318 (6) | 0.0288 (6) | 0.0064 (4) | 0.0066 (4) | −0.0008 (5) |
S1 | 0.01599 (15) | 0.0243 (2) | 0.01710 (16) | −0.00216 (12) | 0.00241 (12) | 0.00144 (12) |
S2 | 0.01779 (15) | 0.01625 (17) | 0.01905 (16) | −0.00044 (12) | 0.00064 (12) | −0.00038 (12) |
Cu | 0.01858 (9) | 0.02048 (11) | 0.02020 (10) | −0.00104 (6) | 0.00658 (7) | 0.00125 (6) |
N11 | 0.0197 (5) | 0.0173 (6) | 0.0220 (6) | 0.0006 (4) | 0.0061 (4) | 0.0008 (4) |
C12 | 0.0211 (6) | 0.0211 (8) | 0.0218 (7) | −0.0009 (5) | 0.0072 (5) | −0.0012 (5) |
C13 | 0.0228 (7) | 0.0326 (9) | 0.0260 (7) | −0.0037 (6) | 0.0105 (6) | 0.0004 (6) |
C14 | 0.0334 (8) | 0.0309 (9) | 0.0265 (7) | 0.0002 (7) | 0.0148 (6) | 0.0060 (6) |
C15 | 0.0323 (8) | 0.0317 (9) | 0.0225 (7) | 0.0047 (7) | 0.0056 (6) | 0.0078 (6) |
C16 | 0.0214 (7) | 0.0254 (8) | 0.0270 (7) | 0.0020 (6) | 0.0039 (6) | 0.0048 (6) |
C17 | 0.0228 (7) | 0.0413 (10) | 0.0240 (8) | −0.0052 (7) | 0.0036 (6) | 0.0033 (7) |
N21 | 0.0216 (6) | 0.0161 (6) | 0.0248 (6) | −0.0033 (4) | 0.0094 (5) | −0.0014 (5) |
C22 | 0.0233 (7) | 0.0175 (8) | 0.0363 (8) | −0.0037 (5) | 0.0127 (6) | −0.0009 (6) |
C23 | 0.0283 (8) | 0.0295 (9) | 0.0515 (11) | −0.0035 (6) | 0.0224 (8) | −0.0091 (8) |
C24 | 0.0433 (10) | 0.0473 (12) | 0.0382 (10) | −0.0114 (8) | 0.0250 (8) | −0.0165 (8) |
C25 | 0.0380 (9) | 0.0453 (11) | 0.0256 (8) | −0.0095 (8) | 0.0107 (7) | −0.0087 (7) |
C26 | 0.0235 (7) | 0.0269 (9) | 0.0269 (8) | −0.0046 (6) | 0.0079 (6) | −0.0027 (6) |
C27 | 0.0241 (7) | 0.0329 (10) | 0.0437 (10) | 0.0022 (7) | 0.0077 (7) | 0.0069 (7) |
C1—S1 | 1.7618 (14) | C14—C15 | 1.385 (2) |
C1—H1A | 0.9800 | C14—H14 | 0.9500 |
C1—H1B | 0.9800 | C15—C16 | 1.382 (2) |
C1—H1C | 0.9800 | C15—H15 | 0.9500 |
C2—S2 | 1.7606 (15) | C16—H16 | 0.9500 |
C2—H2A | 0.9800 | C17—H17A | 0.9800 |
C2—H2B | 0.9800 | C17—H17B | 0.9800 |
C2—H2C | 0.9800 | C17—H17C | 0.9800 |
N1—S1 | 1.6059 (11) | N21—C26 | 1.3412 (19) |
N1—S2 | 1.6107 (11) | N21—C22 | 1.3561 (18) |
O1—S1 | 1.4421 (11) | C22—C23 | 1.390 (2) |
O2—S1 | 1.4412 (11) | C22—C27 | 1.498 (2) |
O3—S2 | 1.4440 (10) | C23—C24 | 1.378 (3) |
O4—S2 | 1.4451 (11) | C23—H23 | 0.9500 |
Cu—N1 | 2.1054 (12) | C24—C25 | 1.385 (2) |
Cu—N11 | 1.9514 (12) | C24—H24 | 0.9500 |
Cu—N21 | 1.9589 (12) | C25—C26 | 1.386 (2) |
N11—C16 | 1.3497 (18) | C25—H25 | 0.9500 |
N11—C12 | 1.3504 (17) | C26—H26 | 0.9500 |
C12—C13 | 1.386 (2) | C27—H27A | 0.9800 |
C12—C17 | 1.499 (2) | C27—H27B | 0.9800 |
C13—C14 | 1.381 (2) | C27—H27C | 0.9800 |
C13—H13 | 0.9500 | ||
N11—Cu—N21 | 141.24 (5) | C13—C14—C15 | 118.18 (14) |
N11—Cu—N1 | 111.54 (5) | C13—C14—H14 | 120.9 |
N21—Cu—N1 | 107.20 (5) | C15—C14—H14 | 120.9 |
S1—C1—H1A | 109.5 | C16—C15—C14 | 118.91 (14) |
S1—C1—H1B | 109.5 | C16—C15—H15 | 120.5 |
H1A—C1—H1B | 109.5 | C14—C15—H15 | 120.5 |
S1—C1—H1C | 109.5 | N11—C16—C15 | 123.10 (14) |
H1A—C1—H1C | 109.5 | N11—C16—H16 | 118.4 |
H1B—C1—H1C | 109.5 | C15—C16—H16 | 118.4 |
S2—C2—H2A | 109.5 | C12—C17—H17A | 109.5 |
S2—C2—H2B | 109.5 | C12—C17—H17B | 109.5 |
H2A—C2—H2B | 109.5 | H17A—C17—H17B | 109.5 |
S2—C2—H2C | 109.5 | C12—C17—H17C | 109.5 |
H2A—C2—H2C | 109.5 | H17A—C17—H17C | 109.5 |
H2B—C2—H2C | 109.5 | H17B—C17—H17C | 109.5 |
S1—N1—S2 | 122.70 (8) | C26—N21—C22 | 118.86 (13) |
S1—N1—Cu | 116.32 (6) | C26—N21—Cu | 118.37 (10) |
S2—N1—Cu | 117.36 (6) | C22—N21—Cu | 122.70 (10) |
O2—S1—O1 | 116.99 (7) | N21—C22—C23 | 120.45 (15) |
O1—S1—N1 | 104.63 (7) | N21—C22—C27 | 116.87 (14) |
O3—S2—N1 | 104.96 (6) | C23—C22—C27 | 122.68 (14) |
O2—S1—N1 | 112.29 (6) | C24—C23—C22 | 120.50 (15) |
O4—S2—N1 | 112.68 (6) | C24—C23—H23 | 119.7 |
O2—S1—C1 | 107.68 (7) | C22—C23—H23 | 119.7 |
O1—S1—C1 | 106.99 (7) | C23—C24—C25 | 118.79 (15) |
N1—S1—C1 | 107.84 (6) | C23—C24—H24 | 120.6 |
O3—S2—O4 | 116.54 (7) | C25—C24—H24 | 120.6 |
O3—S2—C2 | 107.62 (7) | C24—C25—C26 | 118.40 (16) |
O4—S2—C2 | 107.12 (8) | C24—C25—H25 | 120.8 |
N1—S2—C2 | 107.53 (7) | C26—C25—H25 | 120.8 |
C16—N11—C12 | 117.93 (12) | N21—C26—C25 | 123.00 (15) |
C16—N11—Cu | 119.71 (9) | N21—C26—H26 | 118.5 |
C12—N11—Cu | 122.35 (10) | C25—C26—H26 | 118.5 |
N11—C12—C13 | 121.42 (13) | C22—C27—H27A | 109.5 |
N11—C12—C17 | 117.05 (12) | C22—C27—H27B | 109.5 |
C13—C12—C17 | 121.53 (13) | H27A—C27—H27B | 109.5 |
C14—C13—C12 | 120.43 (14) | C22—C27—H27C | 109.5 |
C14—C13—H13 | 119.8 | H27A—C27—H27C | 109.5 |
C12—C13—H13 | 119.8 | H27B—C27—H27C | 109.5 |
S2—N1—S1—O2 | 45.26 (11) | Cu—N11—C12—C17 | −1.01 (19) |
Cu—N1—S1—O2 | −156.78 (7) | N11—C12—C13—C14 | −0.8 (2) |
S2—N1—S1—O1 | 173.13 (8) | C17—C12—C13—C14 | 179.14 (15) |
Cu—N1—S1—O1 | −28.91 (8) | C12—C13—C14—C15 | 0.5 (2) |
S2—N1—S1—C1 | −73.22 (10) | C13—C14—C15—C16 | 0.6 (2) |
Cu—N1—S1—C1 | 84.75 (8) | C12—N11—C16—C15 | 1.2 (2) |
S1—N1—S2—O3 | 176.71 (8) | Cu—N11—C16—C15 | −177.81 (13) |
Cu—N1—S2—O3 | 18.96 (8) | C14—C15—C16—N11 | −1.5 (3) |
S1—N1—S2—O4 | 48.91 (11) | N11—Cu—N21—C26 | −98.97 (13) |
Cu—N1—S2—O4 | −108.84 (8) | N1—Cu—N21—C26 | 79.16 (11) |
S1—N1—S2—C2 | −68.90 (10) | N11—Cu—N21—C22 | 77.78 (14) |
Cu—N1—S2—C2 | 133.35 (8) | N1—Cu—N21—C22 | −104.09 (12) |
S1—N1—Cu—N11 | −70.08 (8) | C26—N21—C22—C23 | 0.2 (2) |
S2—N1—Cu—N11 | 89.10 (7) | Cu—N21—C22—C23 | −176.49 (11) |
S1—N1—Cu—N21 | 111.18 (7) | C26—N21—C22—C27 | 179.78 (14) |
S2—N1—Cu—N21 | −89.64 (7) | Cu—N21—C22—C27 | 3.05 (19) |
N21—Cu—N11—C16 | −96.18 (13) | N21—C22—C23—C24 | 0.0 (2) |
N1—Cu—N11—C16 | 85.74 (12) | C27—C22—C23—C24 | −179.52 (16) |
N21—Cu—N11—C12 | 84.91 (13) | C22—C23—C24—C25 | 0.0 (3) |
N1—Cu—N11—C12 | −93.17 (12) | C23—C24—C25—C26 | −0.3 (3) |
C16—N11—C12—C13 | 0.0 (2) | C22—N21—C26—C25 | −0.5 (2) |
Cu—N11—C12—C13 | 178.95 (11) | Cu—N21—C26—C25 | 176.36 (13) |
C16—N11—C12—C17 | −179.94 (14) | C24—C25—C26—N21 | 0.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C24—H24···O1i | 0.95 | 2.58 | 3.531 (2) | 176 |
C27—H27A···O2ii | 0.98 | 2.43 | 3.371 (2) | 161 |
C14—H14···O4iii | 0.95 | 2.64 | 3.5863 (19) | 174 |
C15—H15···O1iv | 0.95 | 2.64 | 3.1930 (18) | 118 |
C16—H16···O1iv | 0.95 | 2.47 | 3.1278 (17) | 126 |
C17—H17A···O3v | 0.98 | 2.62 | 3.4563 (19) | 143 |
C1—H1C···O2vi | 0.98 | 2.55 | 3.4560 (18) | 154 |
C2—H2A···O3vii | 0.98 | 2.41 | 3.3908 (18) | 177 |
C2—H2B···Cuviii | 0.98 | 2.94 | 3.7529 (17) | 141 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, y+1, z; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x+2, y+1/2, −z+3/2; (vi) −x+1, −y, −z+1; (vii) −x+2, y−1/2, −z+3/2; (viii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2H6NO4S2)(C6H7N)2] |
Mr | 421.99 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 133 |
a, b, c (Å) | 10.2353 (6), 7.7684 (4), 23.0287 (14) |
β (°) | 102.780 (4) |
V (Å3) | 1785.69 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.48 |
Crystal size (mm) | 0.39 × 0.25 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.625, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 35736, 5215, 4267 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.073, 1.06 |
No. of reflections | 5215 |
No. of parameters | 221 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.33 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
Cu—N1 | 2.1054 (12) | Cu—N21 | 1.9589 (12) |
Cu—N11 | 1.9514 (12) | ||
N11—Cu—N21 | 141.24 (5) | O2—S1—N1 | 112.29 (6) |
N11—Cu—N1 | 111.54 (5) | O4—S2—N1 | 112.68 (6) |
N21—Cu—N1 | 107.20 (5) | C16—N11—C12 | 117.93 (12) |
O1—S1—N1 | 104.63 (7) | C26—N21—C22 | 118.86 (13) |
O3—S2—N1 | 104.96 (6) | ||
S2—N1—S1—O1 | 173.13 (8) | S1—N1—S2—O3 | 176.71 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C24—H24···O1i | 0.95 | 2.58 | 3.531 (2) | 176 |
C27—H27A···O2ii | 0.98 | 2.43 | 3.371 (2) | 161 |
C14—H14···O4iii | 0.95 | 2.64 | 3.5863 (19) | 174 |
C15—H15···O1iv | 0.95 | 2.64 | 3.1930 (18) | 118 |
C16—H16···O1iv | 0.95 | 2.47 | 3.1278 (17) | 126 |
C17—H17A···O3v | 0.98 | 2.62 | 3.4563 (19) | 143 |
C1—H1C···O2vi | 0.98 | 2.55 | 3.4560 (18) | 154 |
C2—H2A···O3vii | 0.98 | 2.41 | 3.3908 (18) | 177 |
C2—H2B···Cuviii | 0.98 | 2.94 | 3.7529 (17) | 141 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, y+1, z; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x+2, y+1/2, −z+3/2; (vi) −x+1, −y, −z+1; (vii) −x+2, y−1/2, −z+3/2; (viii) x, y−1, z. |
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We are interested in the synthesis and structure of complexes of the coinage metals with N ligands. We have been able to show that amine complexes of gold(I) are much more stable than normally assumed on the basis of hard/soft incompatibility, and that they can be stabilized further by using disulfonylamides (RSO2)2N−, especially di(methanesulfonyl)amide (R = CH3; henceforth DMS), as counterions (Ahrens et al., 2000, and references therein). Amine complexes of silver(I) disulfonylamides are easier to prepare (Zerbe & Jones, 2004) because the silver salts are available as stable starting materials, whereas homoleptic gold(I) disulfonylamides are not known. The disulfonylamides can coordinate to silver(I), but rarely to gold(I), which has little tendency to increase its coordination number beyond two.
We now wished to extend our studies to complexes of copper(I). The starting material, copper(I) DMS, is available (Linoh, 1989) but is of limited stability. Nevertheless, an initial synthesis and structure, that of the title compound, (I) (2-picoline is 2-methylpyridine), proved successful. The molecule of (I) is shown in Fig. 1. \sch
The Cu centre of (I) exhibits planar three-coordination by two picoline N atoms and the N atom of the amide (r.m.s. deviation of four atoms 0.007 Å), but the coordination is far from regular, with the Cu—Namide bond being 0.15 Å longer than the Cu—Npicoline bond. Consistent with this, the angle opposite Cu—Namide is (by far) the largest (Table 1).
The dimensions of the picoline ligands may be regarded as normal. The ring angles at N are slightly less than the ideal 120° (Table 1).
All three ligands are essentially perpendicular to the CuN3 plane, with interplanar angles of 85.37 (5)° from the first picoline, 78.34 (5)° from the second and 80.34 (3)° from the SNS plane of the amide.
A search of the Cambridge Structural Database (Version 5.25; Allen, 2002) showed that there are few examples of monomeric copper(I) complexes with three monodentate N ligands. Habiyakare et al. (1992) presented the structures of seven [CuL3]+ complexes (L are various methylpyridines). In each case, the coordination geometry was planar but with considerable variation in angles, from almost regular (all three angles 120°) to irregular (106–141°). Particularly wide angles tended to be associated with ligands that were approximately coplanar with the CuN3 plane, and with weak axial contacts from the Cu centres to the counteranions. The Cu—N bond lengths clustered around 2.00 Å, but with a range of 1.962 (4)–2.10 (1) Å; the C—N—C angles showed a slight tendency to be less than 120°, with an average value of 118.6°, but again with appreciable scatter (115.9–124.9°). Näther & Beck (2004) have recently presented the structure of the neutral molecule chlorobis(piperidine)copper(I), which is also trigonal planar at Cu, with a wide N—Cu—N angle of 135.37 (7)°.
The DMS group in (I) displays the usual conformation, with approximate C2 symmetry, whereby the local twofold axis is the bisector of the S—N—S angle. As a measure of the deviation from ideal symmetry, we use the average absolute difference ΔτSN between equivalent torsion angles about the S—N bonds; here, the value is 3.8°. A further general feature is the presence of two antiperiplanar S—N—S—Oap groupings that together form a W-shaped sequence of five atoms. The two Oap atoms, which as usual form the narrower O—S—N angles (as in the essentially `free' DMS anion in its 1-aza-4-azoniabicyclo[2.2.2]octane salt; Henschel et al., 1997), are involved in short intramolecular contacts to the copper atom, with Cu···O1 3.0545 (12) and Cu···O3 3.0360 (11) Å.
In a long series of publications, we have established that the O atoms of the DMS group are versatile hydrogen-bond acceptors (e.g. Wijaya et al., 2004, and references therein). However, the current structure contains no classical hydrogen-bond donors. In such cases, `weak' hydrogen bonds of the form C—H···O (Desiraju & Steiner, 1999) would be expected, and are indeed observed (Table 2). In the following discussion, the numbering refers to the order in Table 2.
The complete hydrogen-bonding pattern in (I) is three-dimensional and complex, but may be analysed in terms of layer formation in two directions. Hydrogen bonds 1–3, including one from each para H atom of the picoline ligands, combine to form layers parallel to (101) (Fig. 2). The remaining hydrogen bonds 4–8, of which 4 and 5 form a bifurcated (C—H···)2O unit, and 7 and 8 represent hydrogen bonds between DMS units (as we have commonly observed, e.g. Wijaya et al., 2004), combine to form layers parallel to (102) (Fig. 3). The final interaction in Table 2 is included as a reminder that metal atoms may also fulfil the criteria for hydrogen-bond acceptors.