The crystal structures of two crown-ether-coordinated caesium halogen salt hydrates, namely di-μ-bromido-bis[aqua(1,4,7,10,13,16-hexaoxacyclooctadecane)caesium(I)] dihydrate, [Cs2Br2(C12H24O6)2(H2O)2]·2H2O, (I), and poly[[diaquadi-μ-chlorido-μ-(1,4,7,10,13,16-hexaoxacyclooctadecane)dicaesium(I)] dihydrate], {[Cs2Cl2(C12H24O6)(H2O)2]·2H2O}n, (II), are reported. In (I), all atoms are located on general positions. In (II), the Cs+ cation is located on a mirror plane perpendicular to the a axis, the chloride anion is located on a mirror plane perpendicular to the c axis and the crown-ether ring is located around a special position with site symmetry 2/m, with two opposite O atoms exactly on the mirror plane perpendicular to the a axis; of one water molecule, only the O atom is located on a mirror plane perpendicular on the a axis, while the other water molecule is completely located on a mirror plane perpendicular to the c axis. Whereas in (I), hydrogen bonds between bromide ligands and water molecules lead to one-dimensional chains running along the b axis, in (II) two-dimensional sheets of water molecules and chloride ligands are formed which combine with the polymeric caesium–crown polymer to give a three-dimensional network. Although both compounds have a similar composition, i.e. a Cs+ cation with a halogen, an 18-crown-6 ether and a water ligand, the crystal structures are rather different. On the other hand, it is remarkable that (I) is isomorphous with the already published iodide compound.
Supporting information
CCDC references: 994052; 994053
For both structures, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Di-µ-bromido-bis[aqua(1,4,7,10,13,16-hexaoxacyclooctadecane)caesium(I)]
dihydrate (I)
top
Crystal data top
[Cs2Br2(C12H24O6)2(H2O)2]·2H2O | F(000) = 1016 |
Mr = 1026.31 | Dx = 1.771 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.7379 (5) Å | Cell parameters from 44249 reflections |
b = 8.4198 (3) Å | θ = 2.3–30.6° |
c = 21.4724 (11) Å | µ = 4.03 mm−1 |
β = 97.618 (4)° | T = 173 K |
V = 1924.21 (15) Å3 | Block, colourless |
Z = 2 | 0.28 × 0.23 × 0.18 mm |
Data collection top
Stoe IPDSII two-circle diffractometer | 5351 reflections with I > 2σ(I) |
Radiation source: Genix 3D IµS microfocus X-ray source | Rint = 0.073 |
ω scans | θmax = 30.2°, θmin = 2.6° |
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001) | h = −15→15 |
Tmin = 0.398, Tmax = 0.531 | k = −11→11 |
32488 measured reflections | l = −30→30 |
5665 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.035 | w = 1/[σ2(Fo2) + (0.0468P)2 + 1.741P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.090 | (Δ/σ)max = 0.001 |
S = 1.09 | Δρmax = 1.18 e Å−3 |
5665 reflections | Δρmin = −1.17 e Å−3 |
216 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
4 restraints | Extinction coefficient: 0.0154 (7) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cs1 | 0.83923 (2) | 0.52538 (2) | 0.60297 (2) | 0.02701 (8) | |
Br1 | 1.12489 (3) | 0.32691 (4) | 0.56604 (2) | 0.03532 (9) | |
O1 | 0.76052 (19) | 0.8885 (2) | 0.60244 (9) | 0.0328 (4) | |
O2 | 0.57087 (19) | 0.6532 (3) | 0.57151 (10) | 0.0369 (4) | |
O3 | 0.58421 (17) | 0.3840 (2) | 0.65021 (9) | 0.0296 (4) | |
O4 | 0.82764 (16) | 0.2818 (2) | 0.70794 (9) | 0.0276 (3) | |
O5 | 1.01419 (17) | 0.5182 (2) | 0.73457 (10) | 0.0296 (4) | |
O6 | 1.00371 (18) | 0.7926 (2) | 0.66133 (10) | 0.0328 (4) | |
C1 | 0.6713 (3) | 0.8918 (4) | 0.54736 (13) | 0.0382 (6) | |
H1A | 0.7042 | 0.8324 | 0.5133 | 0.046* | |
H1B | 0.6560 | 1.0030 | 0.5333 | 0.046* | |
C2 | 0.5507 (3) | 0.8183 (4) | 0.56094 (14) | 0.0385 (6) | |
H2A | 0.5232 | 0.8683 | 0.5985 | 0.046* | |
H2B | 0.4842 | 0.8349 | 0.5249 | 0.046* | |
C3 | 0.4621 (3) | 0.5731 (4) | 0.58557 (14) | 0.0392 (6) | |
H3A | 0.3933 | 0.5850 | 0.5503 | 0.047* | |
H3B | 0.4339 | 0.6190 | 0.6238 | 0.047* | |
C4 | 0.4935 (3) | 0.4011 (4) | 0.59591 (14) | 0.0384 (6) | |
H4A | 0.4166 | 0.3410 | 0.6016 | 0.046* | |
H4B | 0.5273 | 0.3577 | 0.5587 | 0.046* | |
C5 | 0.6208 (3) | 0.2228 (3) | 0.66045 (14) | 0.0322 (5) | |
H5A | 0.6596 | 0.1830 | 0.6241 | 0.039* | |
H5B | 0.5460 | 0.1570 | 0.6647 | 0.039* | |
C6 | 0.7126 (2) | 0.2104 (3) | 0.71876 (13) | 0.0303 (5) | |
H6A | 0.6791 | 0.2649 | 0.7539 | 0.036* | |
H6B | 0.7267 | 0.0974 | 0.7303 | 0.036* | |
C7 | 0.9171 (2) | 0.2806 (3) | 0.76312 (12) | 0.0298 (5) | |
H7A | 0.9333 | 0.1699 | 0.7775 | 0.036* | |
H7B | 0.8837 | 0.3402 | 0.7970 | 0.036* | |
C8 | 1.0373 (2) | 0.3555 (3) | 0.74917 (13) | 0.0305 (5) | |
H8A | 1.1026 | 0.3458 | 0.7861 | 0.037* | |
H8B | 1.0677 | 0.3010 | 0.7132 | 0.037* | |
C9 | 1.1250 (2) | 0.6014 (4) | 0.72459 (15) | 0.0349 (6) | |
H9A | 1.1578 | 0.5590 | 0.6870 | 0.042* | |
H9B | 1.1903 | 0.5873 | 0.7612 | 0.042* | |
C10 | 1.0941 (3) | 0.7744 (4) | 0.71551 (15) | 0.0354 (6) | |
H10A | 1.0601 | 0.8164 | 0.7529 | 0.043* | |
H10B | 1.1711 | 0.8348 | 0.7102 | 0.043* | |
C11 | 0.9668 (3) | 0.9538 (3) | 0.65176 (17) | 0.0372 (6) | |
H11A | 1.0414 | 1.0204 | 0.6480 | 0.045* | |
H11B | 0.9273 | 0.9923 | 0.6881 | 0.045* | |
C12 | 0.8754 (3) | 0.9662 (4) | 0.59298 (17) | 0.0406 (7) | |
H12A | 0.8588 | 1.0793 | 0.5824 | 0.049* | |
H12B | 0.9110 | 0.9156 | 0.5576 | 0.049* | |
O1W | 0.8425 (2) | 0.2870 (3) | 0.47605 (13) | 0.0459 (5) | |
H1WA | 0.9145 (17) | 0.272 (5) | 0.4954 (16) | 0.034 (9)* | |
H1WB | 0.852 (4) | 0.361 (3) | 0.4510 (15) | 0.038 (10)* | |
O2W | 0.7235 (3) | 0.0336 (4) | 0.39410 (14) | 0.0499 (6) | |
H2WA | 0.753 (5) | −0.055 (3) | 0.406 (3) | 0.080 (18)* | |
H2WB | 0.761 (5) | 0.101 (6) | 0.419 (2) | 0.09 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cs1 | 0.02688 (10) | 0.02713 (11) | 0.02730 (10) | 0.00380 (5) | 0.00463 (6) | 0.00055 (5) |
Br1 | 0.03321 (14) | 0.03525 (16) | 0.03854 (16) | 0.00666 (10) | 0.00860 (11) | −0.00002 (11) |
O1 | 0.0365 (9) | 0.0316 (10) | 0.0311 (9) | 0.0053 (8) | 0.0072 (7) | 0.0067 (7) |
O2 | 0.0330 (9) | 0.0371 (11) | 0.0395 (11) | 0.0106 (8) | 0.0005 (8) | 0.0005 (8) |
O3 | 0.0277 (8) | 0.0315 (9) | 0.0282 (8) | −0.0009 (7) | −0.0009 (7) | −0.0038 (7) |
O4 | 0.0264 (8) | 0.0298 (9) | 0.0263 (8) | −0.0015 (7) | 0.0027 (6) | 0.0027 (7) |
O5 | 0.0226 (8) | 0.0269 (9) | 0.0390 (10) | −0.0001 (6) | 0.0033 (7) | −0.0006 (7) |
O6 | 0.0331 (9) | 0.0243 (9) | 0.0413 (10) | 0.0005 (7) | 0.0062 (8) | −0.0013 (8) |
C1 | 0.0522 (16) | 0.0338 (14) | 0.0276 (12) | 0.0159 (12) | 0.0015 (11) | 0.0034 (10) |
C2 | 0.0427 (14) | 0.0412 (16) | 0.0284 (12) | 0.0197 (12) | −0.0066 (11) | −0.0028 (11) |
C3 | 0.0266 (11) | 0.0551 (18) | 0.0337 (13) | 0.0077 (12) | −0.0043 (10) | −0.0032 (13) |
C4 | 0.0314 (12) | 0.0476 (17) | 0.0333 (13) | −0.0039 (11) | −0.0056 (10) | −0.0058 (12) |
C5 | 0.0307 (11) | 0.0297 (12) | 0.0367 (13) | −0.0033 (10) | 0.0065 (10) | −0.0051 (10) |
C6 | 0.0306 (11) | 0.0294 (12) | 0.0318 (12) | −0.0028 (9) | 0.0077 (9) | 0.0050 (10) |
C7 | 0.0324 (11) | 0.0279 (12) | 0.0285 (11) | 0.0028 (9) | 0.0017 (9) | 0.0031 (9) |
C8 | 0.0267 (11) | 0.0309 (13) | 0.0327 (12) | 0.0045 (9) | −0.0002 (9) | 0.0022 (10) |
C9 | 0.0221 (10) | 0.0373 (15) | 0.0450 (15) | −0.0016 (9) | 0.0035 (10) | −0.0004 (11) |
C10 | 0.0283 (11) | 0.0335 (14) | 0.0445 (15) | −0.0065 (10) | 0.0048 (10) | −0.0027 (11) |
C11 | 0.0379 (14) | 0.0227 (12) | 0.0540 (18) | 0.0005 (10) | 0.0174 (13) | 0.0006 (11) |
C12 | 0.0479 (17) | 0.0308 (15) | 0.0472 (17) | 0.0066 (12) | 0.0216 (14) | 0.0097 (12) |
O1W | 0.0459 (12) | 0.0426 (13) | 0.0481 (13) | 0.0005 (10) | 0.0020 (10) | 0.0012 (11) |
O2W | 0.0449 (13) | 0.0547 (17) | 0.0491 (14) | 0.0102 (11) | 0.0025 (11) | 0.0058 (12) |
Geometric parameters (Å, º) top
Cs1—O6 | 3.028 (2) | C2—H2B | 0.9900 |
Cs1—O4 | 3.0622 (18) | C3—C4 | 1.496 (5) |
Cs1—O2 | 3.066 (2) | C3—H3A | 0.9900 |
Cs1—O1 | 3.172 (2) | C3—H3B | 0.9900 |
Cs1—O5 | 3.180 (2) | C4—H4A | 0.9900 |
Cs1—O3 | 3.2682 (19) | C4—H4B | 0.9900 |
Cs1—O1W | 3.388 (3) | C5—C6 | 1.491 (4) |
Cs1—Br1 | 3.6708 (3) | C5—H5A | 0.9900 |
Cs1—C1 | 3.692 (3) | C5—H5B | 0.9900 |
Cs1—C12 | 3.741 (3) | C6—H6A | 0.9900 |
Cs1—C5 | 3.779 (3) | C6—H6B | 0.9900 |
Cs1—C9 | 3.810 (3) | C7—C8 | 1.502 (4) |
Cs1—H1WA | 3.32 (4) | C7—H7A | 0.9900 |
Br1—Cs1i | 3.9032 (4) | C7—H7B | 0.9900 |
O1—C1 | 1.420 (3) | C8—H8A | 0.9900 |
O1—C12 | 1.434 (4) | C8—H8B | 0.9900 |
O2—C3 | 1.416 (4) | C9—C10 | 1.501 (4) |
O2—C2 | 1.420 (4) | C9—H9A | 0.9900 |
O3—C5 | 1.422 (3) | C9—H9B | 0.9900 |
O3—C4 | 1.424 (3) | C10—H10A | 0.9900 |
O4—C6 | 1.420 (3) | C10—H10B | 0.9900 |
O4—C7 | 1.423 (3) | C11—C12 | 1.496 (5) |
O5—C8 | 1.420 (3) | C11—H11A | 0.9900 |
O5—C9 | 1.421 (3) | C11—H11B | 0.9900 |
O6—C10 | 1.421 (4) | C12—H12A | 0.9900 |
O6—C11 | 1.421 (3) | C12—H12B | 0.9900 |
C1—C2 | 1.498 (5) | O1W—H1WA | 0.838 (10) |
C1—H1A | 0.9900 | O1W—H1WB | 0.839 (10) |
C1—H1B | 0.9900 | O2W—H2WA | 0.840 (10) |
C2—H2A | 0.9900 | O2W—H2WB | 0.840 (10) |
| | | |
O6—Cs1—O4 | 105.75 (5) | C2—C1—Cs1 | 89.39 (16) |
O6—Cs1—O2 | 108.05 (6) | O1—C1—H1A | 109.8 |
O4—Cs1—O2 | 105.58 (5) | C2—C1—H1A | 109.8 |
O6—Cs1—O1 | 54.94 (5) | Cs1—C1—H1A | 67.0 |
O4—Cs1—O1 | 127.70 (5) | O1—C1—H1B | 109.8 |
O2—Cs1—O1 | 54.45 (6) | C2—C1—H1B | 109.8 |
O6—Cs1—O5 | 53.33 (5) | Cs1—C1—H1B | 160.4 |
O4—Cs1—O5 | 53.84 (5) | H1A—C1—H1B | 108.2 |
O2—Cs1—O5 | 129.03 (5) | O2—C2—C1 | 108.5 (2) |
O1—Cs1—O5 | 98.47 (5) | O2—C2—H2A | 110.0 |
O6—Cs1—O3 | 127.52 (5) | C1—C2—H2A | 110.0 |
O4—Cs1—O3 | 53.85 (5) | O2—C2—H2B | 110.0 |
O2—Cs1—O3 | 52.75 (6) | C1—C2—H2B | 110.0 |
O1—Cs1—O3 | 96.80 (5) | H2A—C2—H2B | 108.4 |
O5—Cs1—O3 | 97.92 (5) | O2—C3—C4 | 108.5 (2) |
O6—Cs1—O1W | 134.87 (6) | O2—C3—H3A | 110.0 |
O4—Cs1—O1W | 101.60 (6) | C4—C3—H3A | 110.0 |
O2—Cs1—O1W | 98.07 (6) | O2—C3—H3B | 110.0 |
O1—Cs1—O1W | 126.82 (6) | C4—C3—H3B | 110.0 |
O5—Cs1—O1W | 129.47 (6) | H3A—C3—H3B | 108.4 |
O3—Cs1—O1W | 97.60 (6) | O3—C4—C3 | 109.6 (2) |
O6—Cs1—Br1 | 88.25 (4) | O3—C4—Cs1 | 56.12 (13) |
O4—Cs1—Br1 | 88.32 (3) | C3—C4—Cs1 | 86.56 (17) |
O2—Cs1—Br1 | 154.16 (4) | O3—C4—H4A | 109.7 |
O1—Cs1—Br1 | 131.91 (4) | C3—C4—H4A | 109.7 |
O5—Cs1—Br1 | 76.77 (4) | Cs1—C4—H4A | 162.2 |
O3—Cs1—Br1 | 131.28 (4) | O3—C4—H4B | 109.7 |
O1W—Cs1—Br1 | 57.22 (4) | C3—C4—H4B | 109.7 |
O6—Cs1—C1 | 75.28 (6) | Cs1—C4—H4B | 71.1 |
O4—Cs1—C1 | 137.06 (6) | H4A—C4—H4B | 108.2 |
O2—Cs1—C1 | 39.71 (7) | O3—C5—C6 | 109.6 (2) |
O1—Cs1—C1 | 22.27 (6) | O3—C5—Cs1 | 58.47 (12) |
O5—Cs1—C1 | 120.61 (6) | C6—C5—Cs1 | 87.24 (15) |
O3—Cs1—C1 | 90.64 (6) | O3—C5—H5A | 109.8 |
O1W—Cs1—C1 | 106.95 (6) | C6—C5—H5A | 109.8 |
Br1—Cs1—C1 | 134.19 (5) | Cs1—C5—H5A | 68.1 |
O6—Cs1—C12 | 39.39 (7) | O3—C5—H5B | 109.8 |
O4—Cs1—C12 | 136.17 (7) | C6—C5—H5B | 109.8 |
O2—Cs1—C12 | 74.97 (7) | Cs1—C5—H5B | 162.5 |
O1—Cs1—C12 | 22.03 (6) | H5A—C5—H5B | 108.2 |
O5—Cs1—C12 | 90.93 (7) | O4—C6—C5 | 109.0 (2) |
O3—Cs1—C12 | 118.47 (6) | O4—C6—H6A | 109.9 |
O1W—Cs1—C12 | 121.96 (7) | C5—C6—H6A | 109.9 |
Br1—Cs1—C12 | 110.08 (5) | O4—C6—H6B | 109.9 |
C1—Cs1—C12 | 37.08 (8) | C5—C6—H6B | 109.9 |
O6—Cs1—C5 | 135.98 (6) | H6A—C6—H6B | 108.3 |
O4—Cs1—C5 | 38.79 (6) | O4—C7—C8 | 109.5 (2) |
O2—Cs1—C5 | 72.71 (6) | O4—C7—H7A | 109.8 |
O1—Cs1—C5 | 118.32 (6) | C8—C7—H7A | 109.8 |
O5—Cs1—C5 | 90.92 (6) | O4—C7—H7B | 109.8 |
O3—Cs1—C5 | 21.76 (5) | C8—C7—H7B | 109.8 |
O1W—Cs1—C5 | 86.35 (6) | H7A—C7—H7B | 108.2 |
Br1—Cs1—C5 | 109.65 (4) | O5—C8—C7 | 108.7 (2) |
C1—Cs1—C5 | 111.79 (7) | O5—C8—Cs1 | 52.89 (12) |
C12—Cs1—C5 | 139.56 (6) | C7—C8—Cs1 | 85.53 (14) |
O6—Cs1—C9 | 38.64 (6) | O5—C8—H8A | 110.0 |
O4—Cs1—C9 | 73.48 (6) | C7—C8—H8A | 110.0 |
O2—Cs1—C9 | 137.71 (6) | Cs1—C8—H8A | 161.0 |
O1—Cs1—C9 | 91.75 (6) | O5—C8—H8B | 110.0 |
O5—Cs1—C9 | 21.08 (6) | C7—C8—H8B | 110.0 |
O3—Cs1—C9 | 118.69 (6) | Cs1—C8—H8B | 74.8 |
O1W—Cs1—C9 | 123.89 (6) | H8A—C8—H8B | 108.3 |
Br1—Cs1—C9 | 66.71 (5) | O5—C9—C10 | 108.9 (2) |
C1—Cs1—C9 | 113.31 (7) | O5—C9—Cs1 | 53.59 (13) |
C12—Cs1—C9 | 78.02 (8) | C10—C9—Cs1 | 85.99 (16) |
C5—Cs1—C9 | 111.57 (6) | O5—C9—H9A | 109.9 |
O6—Cs1—H1WA | 125.6 (5) | C10—C9—H9A | 109.9 |
O4—Cs1—H1WA | 96.8 (6) | Cs1—C9—H9A | 73.8 |
O2—Cs1—H1WA | 112.36 (19) | O5—C9—H9B | 109.9 |
O1—Cs1—H1WA | 134.9 (6) | C10—C9—H9B | 109.9 |
O5—Cs1—H1WA | 115.9 (3) | Cs1—C9—H9B | 161.2 |
O3—Cs1—H1WA | 105.8 (6) | H9A—C9—H9B | 108.3 |
O1W—Cs1—H1WA | 14.30 (17) | O6—C10—C9 | 109.0 (2) |
Br1—Cs1—H1WA | 43.1 (2) | O6—C10—H10A | 109.9 |
C1—Cs1—H1WA | 117.7 (5) | C9—C10—H10A | 109.9 |
C12—Cs1—H1WA | 124.1 (7) | O6—C10—H10B | 109.9 |
C5—Cs1—H1WA | 90.7 (6) | C9—C10—H10B | 109.9 |
C9—Cs1—H1WA | 109.7 (2) | H10A—C10—H10B | 108.3 |
Cs1—Br1—Cs1i | 104.126 (8) | O6—C11—C12 | 109.2 (3) |
C1—O1—C12 | 111.8 (2) | O6—C11—H11A | 109.8 |
C1—O1—Cs1 | 99.90 (16) | C12—C11—H11A | 109.8 |
C12—O1—Cs1 | 101.91 (15) | O6—C11—H11B | 109.8 |
C3—O2—C2 | 112.8 (2) | C12—C11—H11B | 109.8 |
C3—O2—Cs1 | 124.30 (17) | H11A—C11—H11B | 108.3 |
C2—O2—Cs1 | 119.86 (18) | O1—C12—C11 | 109.2 (2) |
C5—O3—C4 | 111.6 (2) | O1—C12—Cs1 | 56.06 (13) |
C5—O3—Cs1 | 99.77 (14) | C11—C12—Cs1 | 86.77 (16) |
C4—O3—Cs1 | 102.67 (16) | O1—C12—H12A | 109.8 |
C6—O4—C7 | 111.50 (19) | C11—C12—H12A | 109.8 |
C6—O4—Cs1 | 121.67 (14) | Cs1—C12—H12A | 162.0 |
C7—O4—Cs1 | 121.93 (15) | O1—C12—H12B | 109.8 |
C8—O5—C9 | 112.6 (2) | C11—C12—H12B | 109.8 |
C8—O5—Cs1 | 106.26 (15) | Cs1—C12—H12B | 70.8 |
C9—O5—Cs1 | 105.33 (16) | H12A—C12—H12B | 108.3 |
C10—O6—C11 | 111.6 (2) | Cs1—O1W—H1WA | 78 (3) |
C10—O6—Cs1 | 123.81 (16) | Cs1—O1W—H1WB | 95 (3) |
C11—O6—Cs1 | 120.90 (18) | H1WA—O1W—H1WB | 104 (4) |
O1—C1—C2 | 109.6 (2) | H2WA—O2W—H2WB | 106 (6) |
O1—C1—Cs1 | 57.83 (13) | | |
| | | |
C12—O1—C1—C2 | −176.5 (2) | C6—O4—C7—C8 | 179.4 (2) |
Cs1—O1—C1—C2 | 76.3 (2) | Cs1—O4—C7—C8 | −25.0 (3) |
C12—O1—C1—Cs1 | 107.2 (2) | C9—O5—C8—C7 | 176.2 (2) |
C3—O2—C2—C1 | 179.3 (2) | Cs1—O5—C8—C7 | −69.0 (2) |
Cs1—O2—C2—C1 | 18.1 (3) | C9—O5—C8—Cs1 | −114.8 (2) |
O1—C1—C2—O2 | −68.3 (3) | O4—C7—C8—O5 | 65.1 (3) |
Cs1—C1—C2—O2 | −12.9 (2) | O4—C7—C8—Cs1 | 16.76 (18) |
C2—O2—C3—C4 | −179.9 (2) | C8—O5—C9—C10 | −174.7 (2) |
Cs1—O2—C3—C4 | −19.7 (3) | Cs1—O5—C9—C10 | 69.9 (2) |
C5—O3—C4—C3 | −177.6 (2) | C8—O5—C9—Cs1 | 115.4 (2) |
Cs1—O3—C4—C3 | −71.6 (2) | C11—O6—C10—C9 | 177.6 (2) |
C5—O3—C4—Cs1 | −106.04 (19) | Cs1—O6—C10—C9 | 19.1 (3) |
O2—C3—C4—O3 | 65.0 (3) | O5—C9—C10—O6 | −61.8 (3) |
O2—C3—C4—Cs1 | 12.9 (2) | Cs1—C9—C10—O6 | −12.51 (19) |
C4—O3—C5—C6 | −178.2 (2) | C10—O6—C11—C12 | 178.0 (2) |
Cs1—O3—C5—C6 | 73.8 (2) | Cs1—O6—C11—C12 | −22.8 (3) |
C4—O3—C5—Cs1 | 107.9 (2) | C1—O1—C12—C11 | −178.0 (2) |
C7—O4—C6—C5 | 177.1 (2) | Cs1—O1—C12—C11 | −72.2 (2) |
Cs1—O4—C6—C5 | 21.4 (3) | C1—O1—C12—Cs1 | −105.9 (2) |
O3—C5—C6—O4 | −69.7 (3) | O6—C11—C12—O1 | 67.9 (3) |
Cs1—C5—C6—O4 | −14.61 (19) | O6—C11—C12—Cs1 | 15.7 (2) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···Br1 | 0.84 (1) | 2.59 (2) | 3.390 (3) | 160 (4) |
O1W—H1WB···Br1i | 0.84 (1) | 2.67 (2) | 3.405 (3) | 147 (4) |
O2W—H2WA···Br1ii | 0.84 (1) | 2.67 (2) | 3.497 (3) | 170 (5) |
O2W—H2WB···O1W | 0.84 (1) | 2.11 (1) | 2.947 (4) | 174 (6) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y, −z+1. |
Poly[[diaquadi-µ-chlorido-µ-(1,4,7,10,13,16-hexaoxacyclooctadecane)-dicaesium(I)] dihydrate] (II)
top
Crystal data top
[Cs2Cl2(C12H24O6)(H2O)2]·2H2O | Dx = 1.870 Mg m−3 |
Mr = 673.09 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Cmcm | Cell parameters from 51072 reflections |
a = 14.2567 (6) Å | θ = 2.5–30.8° |
b = 10.4542 (4) Å | µ = 3.31 mm−1 |
c = 16.0386 (5) Å | T = 173 K |
V = 2390.43 (16) Å3 | Block, colourless |
Z = 4 | 0.23 × 0.17 × 0.13 mm |
F(000) = 1312 | |
Data collection top
Stoe IPDSII two-circle diffractometer | 1905 reflections with I > 2σ(I) |
Radiation source: Genix 3D IµS microfocus X-ray source | Rint = 0.082 |
ω scans | θmax = 30.4°, θmin = 2.4° |
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001) | h = −20→20 |
Tmin = 0.516, Tmax = 0.673 | k = −14→14 |
31362 measured reflections | l = −22→22 |
1911 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.030 | w = 1/[σ2(Fo2) + (0.0379P)2 + 6.3049P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.083 | (Δ/σ)max = 0.001 |
S = 1.21 | Δρmax = 0.66 e Å−3 |
1911 reflections | Δρmin = −1.05 e Å−3 |
78 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0144 (6) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cs1 | 0.5000 | 0.59962 (2) | 0.60079 (2) | 0.02645 (13) | |
Cl1 | 0.32395 (7) | 0.61640 (8) | 0.7500 | 0.02649 (18) | |
O1 | 0.5000 | 0.7086 (3) | 0.38765 (19) | 0.0313 (6) | |
O2 | 0.33290 (14) | 0.62067 (18) | 0.46040 (13) | 0.0294 (4) | |
C1 | 0.4177 (2) | 0.7842 (3) | 0.38969 (18) | 0.0341 (6) | |
H1A | 0.4166 | 0.8428 | 0.3413 | 0.041* | |
H1B | 0.4164 | 0.8362 | 0.4412 | 0.041* | |
C2 | 0.3342 (2) | 0.6976 (3) | 0.38717 (18) | 0.0326 (5) | |
H2A | 0.2761 | 0.7491 | 0.3839 | 0.039* | |
H2B | 0.3374 | 0.6423 | 0.3372 | 0.039* | |
C3 | 0.25343 (18) | 0.5382 (3) | 0.46063 (16) | 0.0308 (5) | |
H3A | 0.2560 | 0.4802 | 0.4119 | 0.037* | |
H3B | 0.1952 | 0.5894 | 0.4569 | 0.037* | |
O1W | 0.5000 | 0.8914 (3) | 0.6284 (3) | 0.0420 (7) | |
H1WA | 0.547 (5) | 0.908 (5) | 0.657 (4) | 0.08 (2)* | |
O2W | 0.6480 (2) | 0.9205 (3) | 0.7500 | 0.0377 (6) | |
H2WA | 0.706 (5) | 0.960 (7) | 0.7500 | 0.058 (18)* | |
H2WB | 0.673 (5) | 0.849 (6) | 0.7500 | 0.052 (17)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cs1 | 0.02644 (16) | 0.02666 (16) | 0.02626 (16) | 0.000 | 0.000 | −0.00422 (7) |
Cl1 | 0.0276 (4) | 0.0258 (4) | 0.0261 (4) | −0.0003 (3) | 0.000 | 0.000 |
O1 | 0.0316 (13) | 0.0212 (12) | 0.0412 (14) | 0.000 | 0.000 | 0.0025 (10) |
O2 | 0.0267 (9) | 0.0299 (8) | 0.0315 (9) | 0.0002 (7) | −0.0073 (7) | 0.0013 (7) |
C1 | 0.0402 (14) | 0.0202 (11) | 0.0421 (14) | 0.0040 (10) | −0.0039 (11) | 0.0032 (9) |
C2 | 0.0347 (13) | 0.0273 (11) | 0.0359 (12) | 0.0038 (10) | −0.0100 (10) | 0.0018 (10) |
C3 | 0.0223 (10) | 0.0387 (13) | 0.0312 (11) | −0.0001 (9) | −0.0032 (9) | −0.0039 (10) |
O1W | 0.0419 (19) | 0.0340 (16) | 0.050 (2) | 0.000 | 0.000 | −0.0028 (14) |
O2W | 0.0272 (13) | 0.0314 (13) | 0.0543 (19) | −0.0010 (11) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Cs1—O1W | 3.082 (3) | O1—Cs1i | 3.227 (3) |
Cs1—O1i | 3.227 (3) | O2—C2 | 1.424 (3) |
Cs1—O2 | 3.2853 (19) | O2—C3 | 1.424 (3) |
Cs1—O2ii | 3.2853 (19) | O2—Cs1i | 3.456 (2) |
Cs1—O2iii | 3.456 (2) | C1—C2 | 1.495 (4) |
Cs1—O2i | 3.456 (2) | C1—H1A | 0.9900 |
Cs1—Cl1iv | 3.4724 (7) | C1—H1B | 0.9900 |
Cs1—Cl1 | 3.4724 (7) | C2—Cs1i | 3.909 (3) |
Cs1—O1 | 3.603 (3) | C2—H2A | 0.9900 |
Cs1—Cs1i | 3.8458 (4) | C2—H2B | 0.9900 |
Cs1—C2iii | 3.909 (3) | C3—C3iii | 1.494 (5) |
Cs1—C2i | 3.909 (3) | C3—H3A | 0.9900 |
Cs1—H1WA | 3.41 (5) | C3—H3B | 0.9900 |
Cl1—Cs1v | 3.4724 (7) | O1W—H1WA | 0.83 (7) |
O1—C1ii | 1.415 (3) | O2W—H2WA | 0.92 (7) |
O1—C1 | 1.415 (3) | O2W—H2WB | 0.83 (7) |
| | | |
O1W—Cs1—O1i | 168.43 (11) | O2ii—Cs1—C2i | 69.43 (6) |
O1W—Cs1—O2 | 91.85 (7) | O2iii—Cs1—C2i | 84.32 (5) |
O1i—Cs1—O2 | 96.10 (5) | O2i—Cs1—C2i | 21.16 (5) |
O1W—Cs1—O2ii | 91.85 (7) | Cl1iv—Cs1—C2i | 64.48 (4) |
O1i—Cs1—O2ii | 96.10 (5) | Cl1—Cs1—C2i | 116.30 (5) |
O2—Cs1—O2ii | 92.96 (7) | O1—Cs1—C2i | 107.35 (6) |
O1W—Cs1—O2iii | 134.45 (4) | Cs1i—Cs1—C2i | 67.11 (4) |
O1i—Cs1—O2iii | 49.53 (4) | C2iii—Cs1—C2i | 74.40 (9) |
O2—Cs1—O2iii | 49.47 (7) | O1W—Cs1—H1WA | 13.5 (11) |
O2ii—Cs1—O2iii | 110.48 (4) | O1i—Cs1—H1WA | 158.1 (11) |
O1W—Cs1—O2i | 134.45 (4) | O2—Cs1—H1WA | 105.1 (11) |
O1i—Cs1—O2i | 49.53 (4) | O2ii—Cs1—H1WA | 88.6 (11) |
O2—Cs1—O2i | 110.48 (4) | O2iii—Cs1—H1WA | 147.1 (11) |
O2ii—Cs1—O2i | 49.47 (7) | O2i—Cs1—H1WA | 124.7 (11) |
O2iii—Cs1—O2i | 87.16 (6) | Cl1iv—Cs1—H1WA | 68.2 (11) |
O1W—Cs1—Cl1iv | 81.42 (6) | Cl1—Cs1—H1WA | 85.0 (11) |
O1i—Cs1—Cl1iv | 90.62 (4) | O1—Cs1—H1WA | 87.2 (11) |
O2—Cs1—Cl1iv | 173.26 (4) | Cs1i—Cs1—H1WA | 137.2 (11) |
O2ii—Cs1—Cl1iv | 86.84 (4) | C2iii—Cs1—H1WA | 148.9 (11) |
O2iii—Cs1—Cl1iv | 136.69 (4) | C2i—Cs1—H1WA | 128.2 (11) |
O2i—Cs1—Cl1iv | 74.40 (4) | Cs1v—Cl1—Cs1 | 87.13 (2) |
O1W—Cs1—Cl1 | 81.42 (6) | C1ii—O1—C1 | 112.1 (3) |
O1i—Cs1—Cl1 | 90.62 (4) | C1ii—O1—Cs1i | 123.78 (16) |
O2—Cs1—Cl1 | 86.84 (4) | C1—O1—Cs1i | 123.78 (16) |
O2ii—Cs1—Cl1 | 173.26 (4) | C1ii—O1—Cs1 | 98.89 (17) |
O2iii—Cs1—Cl1 | 74.40 (4) | C1—O1—Cs1 | 98.89 (17) |
O2i—Cs1—Cl1 | 136.69 (4) | Cs1i—O1—Cs1 | 68.28 (5) |
Cl1iv—Cs1—Cl1 | 92.57 (2) | C2—O2—C3 | 110.8 (2) |
O1W—Cs1—O1 | 79.84 (10) | C2—O2—Cs1 | 126.41 (16) |
O1i—Cs1—O1 | 111.72 (5) | C3—O2—Cs1 | 122.32 (15) |
O2—Cs1—O1 | 47.83 (4) | C2—O2—Cs1i | 97.64 (16) |
O2ii—Cs1—O1 | 47.83 (4) | C3—O2—Cs1i | 98.37 (14) |
O2iii—Cs1—O1 | 86.63 (5) | Cs1—O2—Cs1i | 69.52 (4) |
O2i—Cs1—O1 | 86.63 (5) | O1—C1—C2 | 108.7 (2) |
Cl1iv—Cs1—O1 | 129.63 (2) | O1—C1—H1A | 109.9 |
Cl1—Cs1—O1 | 129.63 (2) | C2—C1—H1A | 109.9 |
O1W—Cs1—Cs1i | 131.06 (9) | O1—C1—H1B | 109.9 |
O1i—Cs1—Cs1i | 60.50 (5) | C2—C1—H1B | 109.9 |
O2—Cs1—Cs1i | 57.33 (4) | H1A—C1—H1B | 108.3 |
O2ii—Cs1—Cs1i | 57.33 (4) | O2—C2—C1 | 109.3 (2) |
O2iii—Cs1—Cs1i | 53.16 (3) | O2—C2—Cs1i | 61.20 (13) |
O2i—Cs1—Cs1i | 53.16 (3) | C1—C2—Cs1i | 89.93 (16) |
Cl1iv—Cs1—Cs1i | 127.355 (13) | O2—C2—H2A | 109.8 |
Cl1—Cs1—Cs1i | 127.355 (13) | C1—C2—H2A | 109.8 |
O1—Cs1—Cs1i | 51.22 (5) | Cs1i—C2—H2A | 160.3 |
O1W—Cs1—C2iii | 141.23 (5) | O2—C2—H2B | 109.8 |
O1i—Cs1—C2iii | 37.20 (4) | C1—C2—H2B | 109.8 |
O2—Cs1—C2iii | 69.43 (6) | Cs1i—C2—H2B | 63.1 |
O2ii—Cs1—C2iii | 121.70 (5) | H2A—C2—H2B | 108.3 |
O2iii—Cs1—C2iii | 21.16 (5) | O2—C3—C3iii | 109.01 (18) |
O2i—Cs1—C2iii | 84.32 (5) | O2—C3—H3A | 109.9 |
Cl1iv—Cs1—C2iii | 116.30 (5) | C3iii—C3—H3A | 109.9 |
Cl1—Cs1—C2iii | 64.48 (4) | O2—C3—H3B | 109.9 |
O1—Cs1—C2iii | 107.35 (6) | C3iii—C3—H3B | 109.9 |
Cs1i—Cs1—C2iii | 67.11 (4) | H3A—C3—H3B | 108.3 |
O1W—Cs1—C2i | 141.23 (5) | Cs1—O1W—H1WA | 107 (3) |
O1i—Cs1—C2i | 37.20 (4) | H2WA—O2W—H2WB | 91 (6) |
O2—Cs1—C2i | 121.70 (5) | | |
| | | |
C1ii—O1—C1—C2 | 179.88 (19) | Cs1—O2—C2—Cs1i | 70.14 (13) |
Cs1i—O1—C1—C2 | −6.9 (3) | O1—C1—C2—O2 | 64.0 (3) |
Cs1—O1—C1—C2 | −76.7 (2) | O1—C1—C2—Cs1i | 4.8 (2) |
C3—O2—C2—C1 | 179.2 (2) | C2—O2—C3—C3iii | −178.5 (2) |
Cs1—O2—C2—C1 | −8.7 (3) | Cs1—O2—C3—C3iii | 8.9 (3) |
Cs1i—O2—C2—C1 | −78.8 (2) | Cs1i—O2—C3—C3iii | 79.9 (2) |
C3—O2—C2—Cs1i | −102.01 (19) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, z; (iii) x, −y+1, −z+1; (iv) −x+1, y, −z+3/2; (v) x, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···Cl1vi | 0.99 | 2.94 | 3.702 (3) | 135 |
C3—H3A···Cl1vii | 0.99 | 2.95 | 3.877 (3) | 156 |
O1W—H1WA···O2W | 0.83 (7) | 2.08 (7) | 2.889 (4) | 166 (6) |
O2W—H2WA···Cl1viii | 0.92 (7) | 2.35 (7) | 3.239 (3) | 162 (6) |
O2W—H2WB···Cl1iv | 0.83 (7) | 2.43 (7) | 3.205 (3) | 156 (6) |
Symmetry codes: (iv) −x+1, y, −z+3/2; (vi) −x+1/2, −y+3/2, −z+1; (vii) x, −y+1, z−1/2; (viii) x+1/2, y+1/2, z. |
Atomic ratios of Cs, Cl and Br as determined by EDX analysis topCompound | Element | at.% |
(I) | Cs | 51.6 |
(I) | Br | 48.4 |
(II) | Cs | 48.2 |
(II) | Cl | 51.8 |