Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807059399/bt2622sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807059399/bt2622Isup2.hkl |
CCDC reference: 672761
Key indicators
- Single-crystal X-ray study
- T = 183 K
- Mean (C-C)= 0.004 Å
- R factor = 0.024
- wR factor = 0.069
- Data-to-parameter ratio = 24.2
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
All manipulations were carried out in an atmosphere of argon using standard Schlenk techniques. DME was dried (Na/benzophenone) and distilled prior to use. 1-Naphthylcalcium(thf)4 iodide was prepared according to a literature procedure (Gärtner et al. (2007)). Recrystallization of 1-naphthylcalcium(thf)4 iodide from 1,2-dimethoxyethane led to the formation of single crystals of the title compound at -25 °C due to a Schlenk equilibrium. The yield is approx. 50%. Bis(1-naphthyl)calcium remained in solution.
All hydrogen atoms were set to idealized positions and were refined with 1.2 times (1.5 for methyl groups) the isotropic displacement parameter of the corresponding carbon atom. The methyl groups were allowed to rotate but not to tip.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Siemens, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[CaI2(C4H8O)(C4H10O2)2] | F(000) = 1064 |
Mr = 546.22 | Dx = 1.804 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C2yc | Cell parameters from 6625 reflections |
a = 12.8976 (4) Å | θ = 2.5–27.5° |
b = 11.2682 (4) Å | µ = 3.39 mm−1 |
c = 15.2359 (5) Å | T = 183 K |
β = 114.715 (2)° | Prism, colourless |
V = 2011.44 (12) Å3 | 0.04 × 0.04 × 0.03 mm |
Z = 4 |
KappaCCD diffractometer | 1892 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
ϕ and ω scan | h = −16→16 |
6625 measured reflections | k = −14→14 |
2279 independent reflections | l = −16→19 |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0318P)2 + 3.2686P] where P = (Fo2 + 2Fc2)/3 |
2279 reflections | (Δ/σ)max = 0.002 |
94 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.94 e Å−3 |
[CaI2(C4H8O)(C4H10O2)2] | V = 2011.44 (12) Å3 |
Mr = 546.22 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 12.8976 (4) Å | µ = 3.39 mm−1 |
b = 11.2682 (4) Å | T = 183 K |
c = 15.2359 (5) Å | 0.04 × 0.04 × 0.03 mm |
β = 114.715 (2)° |
KappaCCD diffractometer | 1892 reflections with I > 2σ(I) |
6625 measured reflections | Rint = 0.020 |
2279 independent reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.36 e Å−3 |
2279 reflections | Δρmin = −0.94 e Å−3 |
94 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 > 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 | ||
Ca1 | 0.5000 | 0.24628 (5) | 0.7500 | 0.02044 (15) | |
I1 | 0.582761 (14) | 0.248498 (14) | 0.583681 (11) | 0.03409 (9) | |
O1 | 0.29341 (13) | 0.29633 (16) | 0.65423 (12) | 0.0271 (3) | |
O2 | 0.38695 (14) | 0.07448 (15) | 0.66082 (13) | 0.0311 (4) | |
O3 | 0.5000 | 0.45785 (19) | 0.7500 | 0.0277 (5) | |
C1 | 0.2241 (2) | 0.1915 (2) | 0.63757 (19) | 0.0326 (5) | |
H1A | 0.1443 | 0.2097 | 0.5928 | 0.039* | |
H1B | 0.2248 | 0.1629 | 0.6992 | 0.039* | |
C2 | 0.2712 (2) | 0.0987 (2) | 0.59491 (18) | 0.0338 (5) | |
H2A | 0.2250 | 0.0254 | 0.5831 | 0.041* | |
H2B | 0.2686 | 0.1266 | 0.5324 | 0.041* | |
C3 | 0.4316 (3) | −0.0220 (3) | 0.6253 (3) | 0.0512 (8) | |
H3A | 0.3846 | −0.0929 | 0.6180 | 0.077* | |
H3B | 0.5103 | −0.0385 | 0.6712 | 0.077* | |
H3C | 0.4302 | −0.0004 | 0.5625 | 0.077* | |
C4 | 0.2358 (2) | 0.3955 (2) | 0.6731 (2) | 0.0379 (6) | |
H4A | 0.1612 | 0.4062 | 0.6187 | 0.057* | |
H4B | 0.2817 | 0.4674 | 0.6812 | 0.057* | |
H4C | 0.2253 | 0.3807 | 0.7322 | 0.057* | |
C5 | 0.4803 (3) | 0.5323 (2) | 0.6664 (2) | 0.0365 (6) | |
H5A | 0.4118 | 0.5056 | 0.6097 | 0.044* | |
H5B | 0.5468 | 0.5298 | 0.6499 | 0.044* | |
C6 | 0.4632 (3) | 0.6564 (2) | 0.6962 (2) | 0.0451 (7) | |
H6A | 0.4891 | 0.7172 | 0.6629 | 0.054* | |
H6B | 0.3821 | 0.6710 | 0.6822 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ca1 | 0.0186 (3) | 0.0192 (3) | 0.0237 (3) | 0.000 | 0.0090 (3) | 0.000 |
I1 | 0.03470 (13) | 0.04437 (14) | 0.02571 (13) | 0.00171 (7) | 0.01510 (9) | −0.00373 (6) |
O1 | 0.0209 (8) | 0.0271 (8) | 0.0335 (9) | 0.0033 (7) | 0.0116 (7) | 0.0011 (7) |
O2 | 0.0280 (9) | 0.0247 (8) | 0.0379 (9) | −0.0004 (7) | 0.0112 (7) | −0.0074 (7) |
O3 | 0.0344 (12) | 0.0197 (11) | 0.0325 (12) | 0.000 | 0.0173 (10) | 0.000 |
C1 | 0.0200 (11) | 0.0365 (14) | 0.0373 (13) | −0.0038 (10) | 0.0082 (10) | 0.0023 (11) |
C2 | 0.0308 (12) | 0.0327 (13) | 0.0304 (12) | −0.0061 (10) | 0.0053 (10) | −0.0035 (10) |
C3 | 0.0524 (18) | 0.0313 (14) | 0.072 (2) | 0.0023 (13) | 0.0276 (16) | −0.0161 (14) |
C4 | 0.0312 (13) | 0.0371 (14) | 0.0457 (15) | 0.0115 (11) | 0.0163 (12) | 0.0003 (12) |
C5 | 0.0474 (15) | 0.0290 (13) | 0.0384 (14) | 0.0019 (11) | 0.0233 (12) | 0.0059 (11) |
C6 | 0.0598 (18) | 0.0246 (12) | 0.0659 (18) | 0.0087 (12) | 0.0411 (16) | 0.0116 (12) |
Ca1—O3 | 2.384 (2) | C1—H1B | 0.9900 |
Ca1—O2i | 2.4624 (17) | C2—H2A | 0.9900 |
Ca1—O2 | 2.4624 (17) | C2—H2B | 0.9900 |
Ca1—O1 | 2.5092 (16) | C3—H3A | 0.9800 |
Ca1—O1i | 2.5092 (16) | C3—H3B | 0.9800 |
Ca1—I1 | 3.1342 (2) | C3—H3C | 0.9800 |
Ca1—I1i | 3.1342 (2) | C4—H4A | 0.9800 |
O1—C4 | 1.436 (3) | C4—H4B | 0.9800 |
O1—C1 | 1.438 (3) | C4—H4C | 0.9800 |
O2—C2 | 1.434 (3) | C5—C6 | 1.515 (4) |
O2—C3 | 1.438 (3) | C5—H5A | 0.9900 |
O3—C5 | 1.456 (3) | C5—H5B | 0.9900 |
O3—C5i | 1.456 (3) | C6—C6i | 1.512 (6) |
C1—C2 | 1.488 (4) | C6—H6A | 0.9900 |
C1—H1A | 0.9900 | C6—H6B | 0.9900 |
O3—Ca1—O2i | 141.83 (4) | O1—C1—H1B | 110.0 |
O3—Ca1—O2 | 141.83 (4) | C2—C1—H1B | 110.0 |
O2i—Ca1—O2 | 76.34 (8) | H1A—C1—H1B | 108.4 |
O3—Ca1—O1 | 77.01 (4) | O2—C2—C1 | 108.85 (19) |
O2i—Ca1—O1 | 137.52 (6) | O2—C2—H2A | 109.9 |
O2—Ca1—O1 | 67.42 (6) | C1—C2—H2A | 109.9 |
O3—Ca1—O1i | 77.01 (4) | O2—C2—H2B | 109.9 |
O2i—Ca1—O1i | 67.42 (6) | C1—C2—H2B | 109.9 |
O2—Ca1—O1i | 137.51 (6) | H2A—C2—H2B | 108.3 |
O1—Ca1—O1i | 154.02 (8) | O2—C3—H3A | 109.5 |
O3—Ca1—I1 | 89.543 (10) | O2—C3—H3B | 109.5 |
O2i—Ca1—I1 | 97.42 (4) | H3A—C3—H3B | 109.5 |
O2—Ca1—I1 | 83.30 (4) | O2—C3—H3C | 109.5 |
O1—Ca1—I1 | 99.55 (4) | H3A—C3—H3C | 109.5 |
O1i—Ca1—I1 | 80.24 (4) | H3B—C3—H3C | 109.5 |
O3—Ca1—I1i | 89.543 (10) | O1—C4—H4A | 109.5 |
O2i—Ca1—I1i | 83.30 (4) | O1—C4—H4B | 109.5 |
O2—Ca1—I1i | 97.42 (4) | H4A—C4—H4B | 109.5 |
O1—Ca1—I1i | 80.24 (4) | O1—C4—H4C | 109.5 |
O1i—Ca1—I1i | 99.55 (4) | H4A—C4—H4C | 109.5 |
I1—Ca1—I1i | 179.09 (2) | H4B—C4—H4C | 109.5 |
C4—O1—C1 | 109.85 (19) | O3—C5—C6 | 105.3 (2) |
C4—O1—Ca1 | 124.81 (14) | O3—C5—H5A | 110.7 |
C1—O1—Ca1 | 110.38 (14) | C6—C5—H5A | 110.7 |
C2—O2—C3 | 110.1 (2) | O3—C5—H5B | 110.7 |
C2—O2—Ca1 | 116.08 (14) | C6—C5—H5B | 110.7 |
C3—O2—Ca1 | 124.35 (16) | H5A—C5—H5B | 108.8 |
C5—O3—C5i | 109.6 (3) | C6i—C6—C5 | 102.74 (19) |
C5—O3—Ca1 | 125.19 (13) | C6i—C6—H6A | 111.2 |
C5i—O3—Ca1 | 125.19 (13) | C5—C6—H6A | 111.2 |
O1—C1—C2 | 108.5 (2) | C6i—C6—H6B | 111.2 |
O1—C1—H1A | 110.0 | C5—C6—H6B | 111.2 |
C2—C1—H1A | 110.0 | H6A—C6—H6B | 109.1 |
Symmetry code: (i) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [CaI2(C4H8O)(C4H10O2)2] |
Mr | 546.22 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 183 |
a, b, c (Å) | 12.8976 (4), 11.2682 (4), 15.2359 (5) |
β (°) | 114.715 (2) |
V (Å3) | 2011.44 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.39 |
Crystal size (mm) | 0.04 × 0.04 × 0.03 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6625, 2279, 1892 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.069, 1.06 |
No. of reflections | 2279 |
No. of parameters | 94 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.94 |
Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Siemens, 1990).
There are only a few molecular structures of calcium diiodides with ether ligands in literature. At first, Tesh et al. (1994) and Henderson et al. (2005) investigated the structure of (thf)4CaI2, which was used for metathesis reactions with potassium compounds (e.g. potassium cyclopentadienides). Later, Fromm and coworkers were able to charaterize calcium iodides with 1,2-dimethoxyethane (dme) and diglycoldimethylether (diglyme) as ligands such as (dme)(diglyme)CaI2 (diglyme = diglycoldimethylether) (Fromm, 2002), (dme)3CaI(I) (Fromm & Maudez, 2003), and (diglyme)2CaI(I) (Fromm & Maudez, 2003). Single crystals of the later compound were difficult to grow, so a molecular structure does not exist. Junk & Steed (2007) prepared the 15-crown-5 or 18-crown-6 complexes of the heavy alkaline earth metal chlorides, bromides, iodides, and perchlorates and determined their molecular structures. The presence of water leads to the formation of polymers via hydrogen bridges (Fromm, 2001, Fromm, Goesmann et al., 2000), Fromm, Bernardinelli et al., 2000).