Two crown-ether-coordinated caesium halogen salts

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.

Computing details

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)

Crystal data

[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) Å^3	Block, colourless
Z = 2	0.28 × 0.23 × 0.18 mm

Data collection

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

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.0468P)^2 + 1.741P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/sin(2θ)]^-1/4
4 restraints	Extinction coefficient: 0.0154 (7)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—Cs1^i	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—Cs1^i	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)

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···Br1^i	0.84 (1)	2.67 (2)	3.405 (3)	147 (4)
O2W—H2WA···Br1^ii	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)

Crystal data

[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) Å^3	Block, colourless
Z = 4	0.23 × 0.17 × 0.13 mm
F(000) = 1312

Data collection

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

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.030	w = 1/[σ^2(Fo^2) + (0.0379P)^2 + 6.3049P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0144 (6)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Cs1—O1W	3.082 (3)	O1—Cs1^i	3.227 (3)
Cs1—O1^i	3.227 (3)	O2—C2	1.424 (3)
Cs1—O2	3.2853 (19)	O2—C3	1.424 (3)
Cs1—O2^ii	3.2853 (19)	O2—Cs1^i	3.456 (2)
Cs1—O2^iii	3.456 (2)	C1—C2	1.495 (4)
Cs1—O2^i	3.456 (2)	C1—H1A	0.9900
Cs1—Cl1^iv	3.4724 (7)	C1—H1B	0.9900
Cs1—Cl1	3.4724 (7)	C2—Cs1^i	3.909 (3)
Cs1—O1	3.603 (3)	C2—H2A	0.9900
Cs1—Cs1^i	3.8458 (4)	C2—H2B	0.9900
Cs1—C2^iii	3.909 (3)	C3—C3^iii	1.494 (5)
Cs1—C2^i	3.909 (3)	C3—H3A	0.9900
Cs1—H1WA	3.41 (5)	C3—H3B	0.9900
Cl1—Cs1^v	3.4724 (7)	O1W—H1WA	0.83 (7)
O1—C1^ii	1.415 (3)	O2W—H2WA	0.92 (7)
O1—C1	1.415 (3)	O2W—H2WB	0.83 (7)
O1W—Cs1—O1^i	168.43 (11)	O2^ii—Cs1—C2^i	69.43 (6)
O1W—Cs1—O2	91.85 (7)	O2^iii—Cs1—C2^i	84.32 (5)
O1^i—Cs1—O2	96.10 (5)	O2^i—Cs1—C2^i	21.16 (5)
O1W—Cs1—O2^ii	91.85 (7)	Cl1^iv—Cs1—C2^i	64.48 (4)
O1^i—Cs1—O2^ii	96.10 (5)	Cl1—Cs1—C2^i	116.30 (5)
O2—Cs1—O2^ii	92.96 (7)	O1—Cs1—C2^i	107.35 (6)
O1W—Cs1—O2^iii	134.45 (4)	Cs1^i—Cs1—C2^i	67.11 (4)
O1^i—Cs1—O2^iii	49.53 (4)	C2^iii—Cs1—C2^i	74.40 (9)
O2—Cs1—O2^iii	49.47 (7)	O1W—Cs1—H1WA	13.5 (11)
O2^ii—Cs1—O2^iii	110.48 (4)	O1^i—Cs1—H1WA	158.1 (11)
O1W—Cs1—O2^i	134.45 (4)	O2—Cs1—H1WA	105.1 (11)
O1^i—Cs1—O2^i	49.53 (4)	O2^ii—Cs1—H1WA	88.6 (11)
O2—Cs1—O2^i	110.48 (4)	O2^iii—Cs1—H1WA	147.1 (11)
O2^ii—Cs1—O2^i	49.47 (7)	O2^i—Cs1—H1WA	124.7 (11)
O2^iii—Cs1—O2^i	87.16 (6)	Cl1^iv—Cs1—H1WA	68.2 (11)
O1W—Cs1—Cl1^iv	81.42 (6)	Cl1—Cs1—H1WA	85.0 (11)
O1^i—Cs1—Cl1^iv	90.62 (4)	O1—Cs1—H1WA	87.2 (11)
O2—Cs1—Cl1^iv	173.26 (4)	Cs1^i—Cs1—H1WA	137.2 (11)
O2^ii—Cs1—Cl1^iv	86.84 (4)	C2^iii—Cs1—H1WA	148.9 (11)
O2^iii—Cs1—Cl1^iv	136.69 (4)	C2^i—Cs1—H1WA	128.2 (11)
O2^i—Cs1—Cl1^iv	74.40 (4)	Cs1^v—Cl1—Cs1	87.13 (2)
O1W—Cs1—Cl1	81.42 (6)	C1^ii—O1—C1	112.1 (3)
O1^i—Cs1—Cl1	90.62 (4)	C1^ii—O1—Cs1^i	123.78 (16)
O2—Cs1—Cl1	86.84 (4)	C1—O1—Cs1^i	123.78 (16)
O2^ii—Cs1—Cl1	173.26 (4)	C1^ii—O1—Cs1	98.89 (17)
O2^iii—Cs1—Cl1	74.40 (4)	C1—O1—Cs1	98.89 (17)
O2^i—Cs1—Cl1	136.69 (4)	Cs1^i—O1—Cs1	68.28 (5)
Cl1^iv—Cs1—Cl1	92.57 (2)	C2—O2—C3	110.8 (2)
O1W—Cs1—O1	79.84 (10)	C2—O2—Cs1	126.41 (16)
O1^i—Cs1—O1	111.72 (5)	C3—O2—Cs1	122.32 (15)
O2—Cs1—O1	47.83 (4)	C2—O2—Cs1^i	97.64 (16)
O2^ii—Cs1—O1	47.83 (4)	C3—O2—Cs1^i	98.37 (14)
O2^iii—Cs1—O1	86.63 (5)	Cs1—O2—Cs1^i	69.52 (4)
O2^i—Cs1—O1	86.63 (5)	O1—C1—C2	108.7 (2)
Cl1^iv—Cs1—O1	129.63 (2)	O1—C1—H1A	109.9
Cl1—Cs1—O1	129.63 (2)	C2—C1—H1A	109.9
O1W—Cs1—Cs1^i	131.06 (9)	O1—C1—H1B	109.9
O1^i—Cs1—Cs1^i	60.50 (5)	C2—C1—H1B	109.9
O2—Cs1—Cs1^i	57.33 (4)	H1A—C1—H1B	108.3
O2^ii—Cs1—Cs1^i	57.33 (4)	O2—C2—C1	109.3 (2)
O2^iii—Cs1—Cs1^i	53.16 (3)	O2—C2—Cs1^i	61.20 (13)
O2^i—Cs1—Cs1^i	53.16 (3)	C1—C2—Cs1^i	89.93 (16)
Cl1^iv—Cs1—Cs1^i	127.355 (13)	O2—C2—H2A	109.8
Cl1—Cs1—Cs1^i	127.355 (13)	C1—C2—H2A	109.8
O1—Cs1—Cs1^i	51.22 (5)	Cs1^i—C2—H2A	160.3
O1W—Cs1—C2^iii	141.23 (5)	O2—C2—H2B	109.8
O1^i—Cs1—C2^iii	37.20 (4)	C1—C2—H2B	109.8
O2—Cs1—C2^iii	69.43 (6)	Cs1^i—C2—H2B	63.1
O2^ii—Cs1—C2^iii	121.70 (5)	H2A—C2—H2B	108.3
O2^iii—Cs1—C2^iii	21.16 (5)	O2—C3—C3^iii	109.01 (18)
O2^i—Cs1—C2^iii	84.32 (5)	O2—C3—H3A	109.9
Cl1^iv—Cs1—C2^iii	116.30 (5)	C3^iii—C3—H3A	109.9
Cl1—Cs1—C2^iii	64.48 (4)	O2—C3—H3B	109.9
O1—Cs1—C2^iii	107.35 (6)	C3^iii—C3—H3B	109.9
Cs1^i—Cs1—C2^iii	67.11 (4)	H3A—C3—H3B	108.3
O1W—Cs1—C2^i	141.23 (5)	Cs1—O1W—H1WA	107 (3)
O1^i—Cs1—C2^i	37.20 (4)	H2WA—O2W—H2WB	91 (6)
O2—Cs1—C2^i	121.70 (5)
C1^ii—O1—C1—C2	179.88 (19)	Cs1—O2—C2—Cs1^i	70.14 (13)
Cs1^i—O1—C1—C2	−6.9 (3)	O1—C1—C2—O2	64.0 (3)
Cs1—O1—C1—C2	−76.7 (2)	O1—C1—C2—Cs1^i	4.8 (2)
C3—O2—C2—C1	179.2 (2)	C2—O2—C3—C3^iii	−178.5 (2)
Cs1—O2—C2—C1	−8.7 (3)	Cs1—O2—C3—C3^iii	8.9 (3)
Cs1^i—O2—C2—C1	−78.8 (2)	Cs1^i—O2—C3—C3^iii	79.9 (2)
C3—O2—C2—Cs1^i	−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)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cl1^vi	0.99	2.94	3.702 (3)	135
C3—H3A···Cl1^vii	0.99	2.95	3.877 (3)	156
O1W—H1WA···O2W	0.83 (7)	2.08 (7)	2.889 (4)	166 (6)
O2W—H2WA···Cl1^viii	0.92 (7)	2.35 (7)	3.239 (3)	162 (6)
O2W—H2WB···Cl1^iv	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.