Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103011454/de1212sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103011454/de1212Isup2.hkl |
CCDC reference: 221064
A solution of L (20 mg, 0.09 mmol) in methanol (1 ml) was added to a solution of CaTf2 (17.6 mg, 0.09 mmol) in methanol (1 ml) and the mixture was heated for 2 h at 333 K. Single crystals of the LCaTf2 complex were obtained by slow diffusion of diisopropyl ether as non-solvent into the resulting methanol solution at room temperature.
For simplicity, the atoms were positioned in the cell so that the π–π interaction was between molecules of the ligand L related by the inversion centre at (1/2,0.5, 1/2). All H atoms were located in difference maps and subsequently allowed for as riding atoms, with C—H = 0.93 and 0.96 Å, N—H = 0.86 Å and O—H = 0.82 Å.
Data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2002); data reduction: CrysAlis RED (2002); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Watkin et al., 2001), SHELXL97 (Sheldrick, 1997) and WinGX (Version 1.64.05; Farrugia, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
Ca2+·2CF3O3S−·2C11H10N4O·4CH4O | Z = 1 |
Mr = 894.84 | F(000) = 462 |
Triclinic, P1 | Dx = 1.497 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.157 (1) Å | Cell parameters from 4175 reflections |
b = 9.768 (1) Å | θ = 1.8–23.2° |
c = 11.366 (2) Å | µ = 0.36 mm−1 |
α = 98.95 (1)° | T = 173 K |
β = 97.14 (1)° | Prism, colourless |
γ = 94.03 (1)° | 0.30 × 0.30 × 0.25 mm |
V = 992.3 (2) Å3 |
Xcalibur CCD diffractometer | 2931 reflections with I > 2σ(I) |
Detector resolution: 17 pixels mm-1 | Rint = 0.030 |
area–detector scans | θmax = 28.5°, θmin = 3.2° |
Absorption correction: gaussian (Schwarzenbach & Flack, 1991) | h = −13→12 |
Tmin = 0.900, Tmax = 0.910 | k = −12→13 |
17908 measured reflections | l = −17→16 |
5013 independent reflections |
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)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.023P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.70 | (Δ/σ)max = 0.002 |
6255 reflections | Δρmax = 0.26 e Å−3 |
264 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0018 (4) |
Ca2+·2CF3O3S−·2C11H10N4O·4CH4O | γ = 94.03 (1)° |
Mr = 894.84 | V = 992.3 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.157 (1) Å | Mo Kα radiation |
b = 9.768 (1) Å | µ = 0.36 mm−1 |
c = 11.366 (2) Å | T = 173 K |
α = 98.95 (1)° | 0.30 × 0.30 × 0.25 mm |
β = 97.14 (1)° |
Xcalibur CCD diffractometer | 5013 independent reflections |
Absorption correction: gaussian (Schwarzenbach & Flack, 1991) | 2931 reflections with I > 2σ(I) |
Tmin = 0.900, Tmax = 0.910 | Rint = 0.030 |
17908 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 0.70 | Δρmax = 0.26 e Å−3 |
6255 reflections | Δρmin = −0.31 e Å−3 |
264 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. |
x | y | z | Uiso*/Ueq | ||
Ca1 | 1.0000 | 0.0000 | 0.0000 | 0.02014 (11) | |
O2 | 1.13628 (12) | 0.20800 (12) | −0.01142 (11) | 0.0316 (3) | |
H2 | 1.1087 | 0.2472 | −0.0679 | 0.047* | |
C2 | 1.28346 (19) | 0.26111 (19) | 0.03850 (17) | 0.0423 (5) | |
H2B | 1.3085 | 0.2300 | 0.1139 | 0.063* | |
H2C | 1.2907 | 0.3610 | 0.0511 | 0.063* | |
H2D | 1.3504 | 0.2282 | −0.0159 | 0.063* | |
O3 | 0.85768 (12) | 0.01471 (11) | −0.18068 (10) | 0.0302 (3) | |
H3 | 0.8003 | 0.0748 | −0.1867 | 0.045* | |
C3 | 0.8362 (2) | −0.08435 (19) | −0.28842 (16) | 0.0440 (5) | |
H3A | 0.8893 | −0.1634 | −0.2762 | 0.066* | |
H3B | 0.8719 | −0.0429 | −0.3518 | 0.066* | |
H3C | 0.7327 | −0.1137 | −0.3100 | 0.066* | |
S1 | 0.75716 (5) | 0.20720 (4) | 0.18066 (4) | 0.02909 (11) | |
F1 | 0.56130 (14) | 0.12817 (13) | 0.30814 (11) | 0.0658 (4) | |
F2 | 0.69659 (14) | −0.03200 (12) | 0.24689 (12) | 0.0649 (4) | |
F3 | 0.52539 (13) | 0.02686 (12) | 0.12473 (11) | 0.0585 (3) | |
O11 | 0.82191 (13) | 0.13343 (12) | 0.08232 (11) | 0.0384 (3) | |
O12 | 0.85742 (13) | 0.24608 (13) | 0.29065 (11) | 0.0479 (4) | |
O13 | 0.66623 (13) | 0.31371 (12) | 0.14929 (11) | 0.0397 (3) | |
C4 | 0.6278 (2) | 0.07484 (19) | 0.21640 (17) | 0.0372 (4) | |
O1 | 0.68198 (14) | 0.62088 (12) | 0.57166 (10) | 0.0406 (3) | |
N1 | 0.80701 (14) | 0.44014 (13) | 0.49423 (12) | 0.0264 (3) | |
H1 | 0.8211 | 0.3903 | 0.4280 | 0.032* | |
N2 | 0.64656 (14) | 0.54022 (13) | 0.36927 (11) | 0.0247 (3) | |
H2A | 0.6717 | 0.4784 | 0.3148 | 0.030* | |
C1 | 0.70925 (17) | 0.54100 (16) | 0.48560 (14) | 0.0249 (4) | |
N11 | 1.04683 (17) | 0.33489 (17) | 0.80203 (15) | 0.0443 (4) | |
C12 | 1.0463 (2) | 0.2641 (2) | 0.69164 (19) | 0.0440 (5) | |
H12 | 1.1012 | 0.1875 | 0.6834 | 0.053* | |
C13 | 0.97008 (19) | 0.29712 (18) | 0.58935 (17) | 0.0366 (4) | |
H13 | 0.9749 | 0.2445 | 0.5146 | 0.044* | |
C14 | 0.88485 (18) | 0.41131 (16) | 0.59933 (15) | 0.0273 (4) | |
C15 | 0.8866 (2) | 0.48728 (18) | 0.71277 (16) | 0.0369 (4) | |
H15A | 0.8344 | 0.5655 | 0.7239 | 0.044* | |
C16 | 0.9673 (2) | 0.4449 (2) | 0.80916 (17) | 0.0453 (5) | |
H16 | 0.9665 | 0.4968 | 0.8849 | 0.054* | |
N21 | 0.34134 (15) | 0.80415 (13) | 0.23998 (12) | 0.0290 (3) | |
C22 | 0.39556 (18) | 0.70308 (17) | 0.16774 (15) | 0.0298 (4) | |
H22 | 0.3638 | 0.6915 | 0.0856 | 0.036* | |
C23 | 0.49556 (18) | 0.61560 (16) | 0.20837 (14) | 0.0268 (4) | |
H23 | 0.5292 | 0.5473 | 0.1544 | 0.032* | |
C24 | 0.54559 (17) | 0.63065 (15) | 0.33099 (14) | 0.0221 (3) | |
C25 | 0.49125 (17) | 0.73559 (16) | 0.40699 (15) | 0.0274 (4) | |
H25 | 0.5216 | 0.7505 | 0.4895 | 0.033* | |
C26 | 0.39121 (18) | 0.81690 (17) | 0.35664 (15) | 0.0309 (4) | |
H26 | 0.3558 | 0.8862 | 0.4085 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ca1 | 0.0210 (2) | 0.0206 (2) | 0.0195 (2) | 0.00650 (19) | 0.00356 (19) | 0.00260 (19) |
O2 | 0.0278 (6) | 0.0319 (7) | 0.0356 (7) | −0.0010 (5) | −0.0039 (5) | 0.0152 (5) |
C2 | 0.0313 (10) | 0.0484 (12) | 0.0451 (12) | −0.0030 (9) | −0.0015 (9) | 0.0096 (10) |
O3 | 0.0346 (7) | 0.0272 (6) | 0.0269 (6) | 0.0134 (5) | −0.0039 (5) | 0.0005 (5) |
C3 | 0.0479 (12) | 0.0412 (11) | 0.0366 (11) | 0.0204 (10) | −0.0074 (9) | −0.0102 (9) |
S1 | 0.0281 (2) | 0.0289 (2) | 0.0310 (2) | 0.01003 (19) | 0.00934 (19) | −0.00035 (19) |
F1 | 0.0703 (9) | 0.0724 (9) | 0.0609 (8) | 0.0060 (7) | 0.0448 (7) | 0.0022 (7) |
F2 | 0.0687 (9) | 0.0522 (8) | 0.0868 (10) | 0.0212 (7) | 0.0182 (8) | 0.0386 (7) |
F3 | 0.0474 (7) | 0.0568 (8) | 0.0645 (8) | −0.0099 (6) | −0.0034 (6) | 0.0042 (6) |
O11 | 0.0409 (7) | 0.0378 (7) | 0.0403 (7) | 0.0154 (6) | 0.0215 (6) | 0.0006 (6) |
O12 | 0.0359 (8) | 0.0566 (9) | 0.0434 (8) | 0.0092 (7) | −0.0030 (6) | −0.0116 (7) |
O13 | 0.0471 (8) | 0.0317 (7) | 0.0452 (8) | 0.0209 (6) | 0.0145 (6) | 0.0073 (6) |
C4 | 0.0368 (11) | 0.0424 (11) | 0.0369 (11) | 0.0136 (9) | 0.0131 (9) | 0.0090 (9) |
O1 | 0.0569 (9) | 0.0375 (7) | 0.0254 (7) | 0.0237 (7) | −0.0039 (6) | −0.0026 (6) |
N1 | 0.0299 (8) | 0.0268 (7) | 0.0235 (7) | 0.0098 (6) | 0.0020 (6) | 0.0058 (6) |
N2 | 0.0290 (8) | 0.0246 (7) | 0.0207 (7) | 0.0120 (6) | 0.0018 (6) | 0.0017 (6) |
C1 | 0.0271 (9) | 0.0214 (8) | 0.0267 (9) | 0.0038 (7) | 0.0005 (7) | 0.0070 (7) |
N11 | 0.0397 (10) | 0.0460 (10) | 0.0483 (11) | −0.0028 (8) | −0.0086 (8) | 0.0262 (9) |
C12 | 0.0330 (11) | 0.0436 (12) | 0.0604 (14) | 0.0092 (9) | −0.0010 (10) | 0.0273 (11) |
C13 | 0.0324 (10) | 0.0391 (11) | 0.0418 (11) | 0.0109 (9) | 0.0022 (9) | 0.0162 (9) |
C14 | 0.0252 (9) | 0.0257 (9) | 0.0326 (10) | −0.0001 (7) | 0.0007 (7) | 0.0136 (7) |
C15 | 0.0460 (12) | 0.0319 (10) | 0.0322 (10) | 0.0040 (9) | −0.0047 (9) | 0.0108 (8) |
C16 | 0.0584 (13) | 0.0417 (12) | 0.0336 (11) | −0.0018 (10) | −0.0090 (10) | 0.0141 (9) |
N21 | 0.0297 (8) | 0.0268 (8) | 0.0321 (8) | 0.0086 (6) | 0.0021 (7) | 0.0088 (6) |
C22 | 0.0339 (10) | 0.0293 (9) | 0.0264 (9) | 0.0053 (8) | 0.0007 (8) | 0.0069 (7) |
C23 | 0.0323 (9) | 0.0242 (8) | 0.0243 (9) | 0.0085 (7) | 0.0031 (7) | 0.0031 (7) |
C24 | 0.0228 (8) | 0.0194 (8) | 0.0249 (9) | 0.0027 (6) | 0.0039 (7) | 0.0053 (7) |
C25 | 0.0299 (9) | 0.0286 (9) | 0.0234 (9) | 0.0087 (7) | 0.0013 (7) | 0.0026 (7) |
C26 | 0.0338 (10) | 0.0268 (9) | 0.0335 (10) | 0.0111 (8) | 0.0070 (8) | 0.0032 (8) |
Ca1—O2 | 2.3384 (11) | N2—C1 | 1.3731 (19) |
Ca1—O3 | 2.3215 (11) | N2—C24 | 1.3996 (18) |
Ca1—O11 | 2.3521 (11) | N2—H2A | 0.86 |
O2—C2 | 1.4239 (19) | N11—C12 | 1.334 (2) |
O2—H2 | 0.82 | N11—C16 | 1.337 (2) |
C2—H2B | 0.96 | C12—C13 | 1.375 (2) |
C2—H2C | 0.96 | C12—H12 | 0.93 |
C2—H2D | 0.96 | C13—C14 | 1.404 (2) |
O3—C3 | 1.4209 (19) | C13—H13 | 0.93 |
O3—H3 | 0.82 | C14—C15 | 1.382 (2) |
C3—H3A | 0.96 | C15—C16 | 1.379 (2) |
C3—H3B | 0.96 | C15—H15A | 0.93 |
C3—H3C | 0.96 | C16—H16 | 0.93 |
S1—O13 | 1.4375 (11) | N21—C26 | 1.331 (2) |
S1—O12 | 1.4381 (13) | N21—C22 | 1.3466 (19) |
S1—O11 | 1.4471 (11) | C22—C23 | 1.382 (2) |
S1—C4 | 1.818 (2) | C22—H22 | 0.93 |
F1—C4 | 1.3280 (19) | C23—C24 | 1.394 (2) |
F2—C4 | 1.3252 (19) | C23—H23 | 0.93 |
F3—C4 | 1.315 (2) | C24—C25 | 1.395 (2) |
O1—C1 | 1.2160 (18) | C25—C26 | 1.382 (2) |
N1—C1 | 1.3834 (18) | C25—H25 | 0.93 |
N1—C14 | 1.3913 (19) | C26—H26 | 0.93 |
N1—H1 | 0.86 | ||
O3—Ca1—O2 | 89.42 (4) | C1—N2—H2A | 116.9 |
O3—Ca1—O11 | 83.08 (4) | C24—N2—H2A | 116.9 |
O2—Ca1—O11 | 88.24 (4) | O1—C1—N2 | 124.02 (14) |
O3i—Ca1—O11 | 96.92 (4) | O1—C1—N1 | 123.58 (15) |
O2i—Ca1—O11 | 91.76 (4) | N2—C1—N1 | 112.40 (14) |
O11i—Ca1—O11 | 180 | C12—N11—C16 | 115.60 (16) |
C2—O2—H2 | 109.5 | N11—C12—C13 | 124.31 (17) |
O2—C2—H2B | 109.5 | N11—C12—H12 | 117.8 |
O2—C2—H2C | 109.5 | C13—C12—H12 | 117.8 |
H2B—C2—H2C | 109.5 | C12—C13—C14 | 119.08 (18) |
O2—C2—H2D | 109.5 | C12—C13—H13 | 120.5 |
H2B—C2—H2D | 109.5 | C14—C13—H13 | 120.5 |
H2C—C2—H2D | 109.5 | C15—C14—N1 | 125.20 (14) |
C3—O3—H3 | 109.5 | C15—C14—C13 | 117.27 (16) |
O3—C3—H3A | 109.5 | N1—C14—C13 | 117.53 (15) |
O3—C3—H3B | 109.5 | C16—C15—C14 | 118.72 (17) |
H3A—C3—H3B | 109.5 | C16—C15—H15A | 120.6 |
O3—C3—H3C | 109.5 | C14—C15—H15A | 120.6 |
H3A—C3—H3C | 109.5 | N11—C16—C15 | 124.99 (18) |
H3B—C3—H3C | 109.5 | N11—C16—H16 | 117.5 |
O13—S1—O12 | 114.92 (8) | C15—C16—H16 | 117.5 |
O13—S1—O11 | 114.99 (7) | C26—N21—C22 | 115.56 (13) |
O12—S1—O11 | 114.24 (7) | N21—C22—C23 | 123.95 (15) |
O13—S1—C4 | 104.20 (8) | N21—C22—H22 | 118.0 |
O12—S1—C4 | 103.04 (9) | C23—C22—H22 | 118.0 |
O11—S1—C4 | 103.28 (8) | C22—C23—C24 | 119.40 (15) |
S1—O11—Ca1 | 153.75 (8) | C22—C23—H23 | 120.3 |
F3—C4—F2 | 107.80 (16) | C24—C23—H23 | 120.3 |
F3—C4—F1 | 108.07 (15) | C23—C24—C25 | 117.36 (14) |
F2—C4—F1 | 108.13 (15) | C23—C24—N2 | 117.99 (13) |
F3—C4—S1 | 111.69 (13) | C25—C24—N2 | 124.64 (14) |
F2—C4—S1 | 111.16 (13) | C26—C25—C24 | 118.38 (15) |
F1—C4—S1 | 109.87 (13) | C26—C25—H25 | 120.8 |
C1—N1—C14 | 126.53 (14) | C24—C25—H25 | 120.8 |
C1—N1—H1 | 116.7 | N21—C26—C25 | 125.36 (15) |
C14—N1—H1 | 116.7 | N21—C26—H26 | 117.3 |
C1—N2—C24 | 126.11 (13) | C25—C26—H26 | 117.3 |
O13—S1—O11—Ca1 | 156.19 (15) | N11—C12—C13—C14 | −0.8 (3) |
O12—S1—O11—Ca1 | 20.2 (2) | C1—N1—C14—C15 | −5.8 (3) |
C4—S1—O11—Ca1 | −90.98 (18) | C1—N1—C14—C13 | 175.15 (16) |
O3i—Ca1—O11—S1 | −0.18 (18) | C12—C13—C14—C15 | 2.0 (3) |
O2i—Ca1—O11—S1 | 89.45 (17) | C12—C13—C14—N1 | −178.86 (16) |
O13—S1—C4—F3 | 59.24 (14) | N1—C14—C15—C16 | 179.02 (16) |
O12—S1—C4—F3 | 179.56 (12) | C13—C14—C15—C16 | −1.9 (3) |
O11—S1—C4—F3 | −61.25 (14) | C12—N11—C16—C15 | 0.6 (3) |
O13—S1—C4—F2 | 179.69 (13) | C14—C15—C16—N11 | 0.6 (3) |
O12—S1—C4—F2 | −60.00 (14) | C26—N21—C22—C23 | 0.4 (2) |
O11—S1—C4—F2 | 59.19 (15) | N21—C22—C23—C24 | −0.2 (3) |
O13—S1—C4—F1 | −60.66 (14) | C22—C23—C24—C25 | −0.3 (2) |
O12—S1—C4—F1 | 59.65 (14) | C22—C23—C24—N2 | 179.86 (14) |
O11—S1—C4—F1 | 178.84 (12) | C1—N2—C24—C23 | 178.92 (15) |
C24—N2—C1—O1 | 1.3 (3) | C1—N2—C24—C25 | −0.9 (3) |
C24—N2—C1—N1 | −178.88 (14) | C23—C24—C25—C26 | 0.4 (2) |
C14—N1—C1—O1 | 1.9 (3) | N2—C24—C25—C26 | −179.70 (15) |
C14—N1—C1—N2 | −177.95 (14) | C22—N21—C26—C25 | −0.3 (3) |
C16—N11—C12—C13 | −0.6 (3) | C24—C25—C26—N21 | −0.2 (3) |
Symmetry code: (i) −x+2, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O12 | 0.86 | 2.01 | 2.8608 (18) | 170 |
N2—H2A···O13 | 0.86 | 2.27 | 3.1025 (17) | 163 |
C3—H3A···O12i | 0.96 | 2.52 | 3.316 (2) | 140 |
O2—H2···N11ii | 0.82 | 1.87 | 2.6891 (18) | 179 |
O3—H3···N21iii | 0.82 | 1.92 | 2.7250 (16) | 167 |
Symmetry codes: (i) −x+2, −y, −z; (ii) x, y, z−1; (iii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | Ca2+·2CF3O3S−·2C11H10N4O·4CH4O |
Mr | 894.84 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 9.157 (1), 9.768 (1), 11.366 (2) |
α, β, γ (°) | 98.95 (1), 97.14 (1), 94.03 (1) |
V (Å3) | 992.3 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.30 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Xcalibur CCD diffractometer |
Absorption correction | Gaussian (Schwarzenbach & Flack, 1991) |
Tmin, Tmax | 0.900, 0.910 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17908, 5013, 2931 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.671 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.066, 0.70 |
No. of reflections | 6255 |
No. of parameters | 264 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.31 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2002), CrysAlis RED (Oxford Diffraction, 2002), CrysAlis RED (2002), SIR92 (Altomare et al., 1994), CRYSTALS (Watkin et al., 2001), SHELXL97 (Sheldrick, 1997) and WinGX (Version 1.64.05; Farrugia, 1997), PLATON (Spek, 2003), PLATON.
Ca1—O2 | 2.3384 (11) | N1—C1 | 1.3834 (18) |
Ca1—O3 | 2.3215 (11) | N1—C14 | 1.3913 (19) |
Ca1—O11 | 2.3521 (11) | N2—C1 | 1.3731 (19) |
O1—C1 | 1.2160 (18) | N2—C24 | 1.3996 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O12 | 0.86 | 2.01 | 2.8608 (18) | 170 |
N2—H2A···O13 | 0.86 | 2.27 | 3.1025 (17) | 163 |
C3—H3A···O12i | 0.96 | 2.52 | 3.316 (2) | 140 |
O2—H2···N11ii | 0.82 | 1.87 | 2.6891 (18) | 179 |
O3—H3···N21iii | 0.82 | 1.92 | 2.7250 (16) | 167 |
Symmetry codes: (i) −x+2, −y, −z; (ii) x, y, z−1; (iii) −x+1, −y+1, −z. |
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Functional supramolecular architectures as constitutionally dynamic adaptative materials have emerged as a major field in supramolecular chemistry, geared towards the design of self-organizing nanosystems of increasing complexity (Lehn, 2000a,b, 2002; Funeriu et al., 2001). The self-assembly of different entities is based both on the implementation of ligands containing specific molecular information stored in the arrangement of suitable binding sites and on complexed ions reading out the structural information through the algorithm defined by their recognition geometry. Of special interest are so-called hereon–heteroditopic ligand systems, containing different binding units that can combine to form different superstructures according to the specific interaction involved (Funeriu et al., 2001).
We consider in this context the 1,3-di-4-pyridylurea ligand, L, in which the available urea and pyridine moities are covalently linked. We reasoned that, by an appropriate choice of these binding units and of a specific metal salt, we could obtain, under specific conditions, a supramolecular structure (output device). The different interaction types (subprograms) involved are (a) pyridine–metal coordination (Scudder et al., 1999; Lu et al., 2001), (b) metal–anion association (coordination), (c) urea–anion complexation (Scheerder et al., 1996) and (d) urea head-to-tail association (Etter, 1990). These interactions combine either in an independent way (linear combination) or by a crossover with interference between the individual subprograms.
The structure of the complex of L with CaTf2(methanol)4 (Tf− = CF3SO3−) was determined from a crystal obtained in a methanol/diisopropyl ether (1:1) solution at room temperature. This complex proves to be an intriguing coordination polymer with a novel architecture and results from the crossover of the simultaneous independent trifluoromethanesulfonate–urea and trifluoromethanesulfonate–Ca2+ complexation subprograms.
The molecular structure of (I) is presented in Fig. 1. The unit cell contains two L ligands, one Ca2+ cation on an inversion centre, two trifluoromethanesulfonate counter-ions and four methanol molecules. The unique L ligand has an almost planar conformation; the angle between the two pyridyl rings is 4.28 (10)°. Two inversion-related Tf− ions are coordinated to the Ca2+ cation and octahedral coordination at Ca is completed by two pairs of inversion-relate methanol molecules; pertinent dimensions are given in Table 1. The inversion-related L ligands are linked to the Tf− ion by pairs of N—H···O hydrogen bonds, as shown in Fig. 1; hydrogen-bond geometry details are given in Table 2. Possibly assisting the retention of this structure are C—H···O contacts (Table 2) between C3—H3A and O12 (at 2 − x, −y, −z)
The crystal structure contains sheets of molecules lying in the (110) plane (Fig. 2). A feature of this sheet structure is the R(32)44 (Bernstein et al., 1995) hydrogen-bonded ring system, which is shown in more detail in Fig. 3. Infinite chains are thus generated which are further linked to yield the sheet structure by Tf−–Ca2+–Tf− moieties. The R(32)44 ring is stabilized by significant π–π interactions between inversion-related L ligands; details of the overlap are shown in Fig. 4, where the shortest intermolecular C···C distance is 3.388 (2) Å between C14 and C26 at (1 − x, 1 − y, 1 − z).