Poly­[[di­aqua­cerium(III)]-μ5-propane-1,2,3-tri­carboxyl­ato]

Armstrong, J.A.; Barnes, J.C.

doi:10.1107/S1600536804011389

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 60| Part 6| June 2004| Pages m791-m793

https://doi.org/10.1107/S1600536804011389

Poly[[diaquacerium(III)]-μ₅-propane-1,2,3-tricarboxylato]

Jennifer A. Armstrong ^a and John C. Barnes ^a ^*

^aDepartment of Chemistry, University of Dundee, Perth Road, Dundee DD1 4HN, Scotland
^*Correspondence e-mail: j.c.barnes@dundee.ac.uk

(Received 22 April 2004; accepted 11 May 2004; online 15 May 2004)

Crystals of polymeric cerium(III) 1,2,3-propanetricarboxylate dihydrate, [Ce(C₆H₅O₆)(H₂O)₂]_n, were grown under hydrothermal conditions. The nine-coordinate Ce atoms occur as centrosymmetric pairs. Two bidentate and three monodentate carboxylate groups, each from a different anion, and two water molecules are coordinated to each cerium ion. Ce—O distances range from 2.390 (3) to 2.637 (2) Å. Each anion is joined to five cerium ions, forming a three-dimensional network.

Comment

Metal salts of polycarboxylic acids can often be prepared only as powders by precipitation from aqueous solution. The very low solubilities of these powders frequently defeat attempts to grow single crystals from solution. For example, in spite of many attempts in this laboratory, only one metal salt of tetrahydrofuran tetracarboxylic acid has been obtained with crystals adequate for structure determination (Barnes & Paton, 1982 ). The exploitation of hydrothermal recrystallization by Yaghi et al. (1996 ) and Plater et al. (1997 ) offers a new route to these crystals. These workers have used the relatively rigid 1,3,5-benzenetricarboxylate anion in attempts to stabilize open-network structures. In the present work, we report the hydrothermal recrystallization and structure of a cerium(III) salt, (I), of the very flexible 1,3,5-propanetricarboxylate anion (tca).

Barnes & Paton (1988 ) reported the crystal structure of 1,2,3-propanetricarboxylic acid (H₃tca) at 298 K. A redetermination at 150 K, using better crystals, shows that no phase changes occur over this temperature range (Barnes, 2004 ).

Gupta & Powel (1963 , 1964 ) prepared powdered samples of lanthanide–tca salts by precipitation from solutions at pH 4–5. They reported that, at room temperature, lanthanum formed La(tca)·5H₂O, but all other lanthanides studied gave Ln(tca)·4H₂O. From thermogravimetric analysis (TGA) measurements, they concluded that Ln(tca)·nH₄O lost water by several different sequences to give anhydrous Ln(tca) between 423 and 473 K.

Solution studies by Barnes & Bristow (1969 ) showed the existence of of LnHtca⁺ and Lntca in the pH range 2–5. Almost quantitative precipitation occurs above pH 5.0.

In the present work, hydrothermal recrystallization of Ce(tca)·4H₂O powder gave crystals shown by thermogravimetry and structural analysis to be Ce(tca)·2H₂O, (I). Data were collected at 150 and 298 K using different crystals. There were no significant structural differences but the room-temperature crystal proved to be of much better quality; R is 0.028 compared with 0.055 for the low-temperature crystal. The low-temperature cell has a = 6.840 (6) Å, b = 8.687 (11) Å, c = 8.819 (14) Å, α = 99.72 (17)°, β = 110.25 (7)° and γ = 110.25 (7)°.

Fig. 1 shows that the Ce atoms occur as centrosymmetric pairs, bridged by the O8 atoms of two bidentate carboxylate groups. The nine-coordinate Ce³⁺ ion has an unusual 2–5–2 geometry, with trans bidentate carboxylate groups (C7/O8/O9 and C10/O11/O12) from different ligands. The angle between these carboxylate planes is 89.3 (4)°. Atoms O5, O6 and O8 from three more ligands and two water molecules O13 and O14 make up a pentagonal median plane (r.m.s. deviation = 0.344 Å) at 88.4 (3)° to the plane Ce/O11/O12. (A more familiar but less precise visualization is a monocapped square antiprism with O9 as the cap.) Ce—O distances are in the ranges 2.390 (3)–2.489 (2) Å (monodentate), 2.505 (3)–2.516 (2) Å (water) and 2.544 (2)–2.637 (2) Å (bidentate carboxylate groups).

The tca anion is shown in Fig. 2, with torsion angles in Table 1. Each anion is joined to five Ce atoms to form a three-dimensional network. This flexible anion allows the formation of a framework with no significant volumes of free space, unlike the open-network structures reported by Plater et al. (1997) for complexes of the rigid 1,3,5-benzenetricarboxylate anion.

The coordinated water molecules contribute to the network by inter-unit hydrogen bonding (Table 2).

X-ray powder diffraction showed that the powder sample of Ce(tca)·2H₂O prepared at room temperature is identical to the observations of Ce(tca)·2H₂O crystals. TGA studies on Ce(tca)·4H₂O confirmed the observation of Gupta & Powel (1963, 1964) that Ce(tca)·2H₂O is not formed by dehydration of Ce(tca)·4H₂O at atmospheric pressure. In the present work, highly crystalline Ce(tca)·4H₂O was converted at 423 K into the monohydrate which had not been not observed by Gupta & Powel. This Ce(tca)·H₂O is of very low crystallinity. Ce(tca)·2H₂O was thermally stable to 400 K, forming crystalline anhydrous Ce(tca) by 430 K.

Figure 1
The structure of Ce(tca)·2H₂O, viewed down a.

Figure 2
The tca anion and the water molecules, showing 50% probability displacement ellipsoids.

Experimental

Two samples of hydrated Ce(tca) salts were prepared by mixing aqueous CeCl₃ and H₃tca solutions (0.01 mol) at room temperature and adjusting the pH to 5.5 with NaOH. The resulting fine precipitates were collected after stirring for 1 h. Analysis showed that one sample was Ce(tca)·4H₂O and the other Ce(tca)·2H₂O, in spite of no intentional differences in preparation.

Analytical data for Ce(tca)·4H₂O: Ce found by edta titration: 37.92%; required: 38.14%. Thermogravimetry: weight loss to 423 K = 14.53%, required for Ce(tca)·H₂O = 14.72%; weight loss to 1200 K = 51.68%, required for CeO₂ = 52.05%

Analytical data for Ce(tca)·2H₂O: Ce found by edta titration 39.83%, required = 40.11%. Thermogravimetry: weight loss to 430 K = 10.42%, required for Ce(tca) = 10.31%, weight loss to 1200 K = 49.83%, required for CeO₂ = 49.58%.

Using a Parr model 4745 bomb with a PTFE liner, 0.5 g of Ce(tca)·4H₂O and 15 ml of water were heated to 423 K for 16 h, cooled at 7.5 K h⁻¹ to 363 K and then allowed to cool naturally to room temperature. Colourless poorly shaped crystals were obtained.

Crystal data

[Ce(C₆H₅O₆)(H₂O)₂]
M_r = 349.25
Triclinic, $[P\overline 1]$
a = 6.9084 (2) Å
b = 8.7738 (4) Å
c = 8.8162 (4) Å
α = 99.552 (2)°
β = 110.209 (2)°
γ = 104.461 (2)°
V = 466.51 (3) Å³
Z = 2
D_x = 2.486 Mg m⁻³
Mo Kα radiation
Cell parameters from 5965 reflections
θ = 2.6–27.5°
μ = 4.90 mm⁻¹
T = 150 (2) K
Block, colourless
0.30 × 0.20 × 0.10 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.353, T_max = 0.613
5965 measured reflections
2091 independent reflections
2046 reflections with I > 2σ(I)
R_int = 0.045
θ_max = 27.5°
h = −8 → 8
k = −11 → 9
l = −11 → 11

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.064
S = 1.13
2091 reflections
148 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0331P)² + 0.7556P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.018
Δρ_max = 1.05 e Å⁻³
Δρ_min = −2.89 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ce1—O5ⁱ	2.390 (3)
Ce1—O6	2.489 (2)
Ce1—O14	2.505 (3)
Ce1—O13	2.518 (2)
Ce1—O12ⁱⁱ	2.544 (2)
Ce1—O8ⁱⁱⁱ	2.572 (2)
Ce1—O9^iv	2.611 (2)
Ce1—O8^iv	2.619 (2)
Ce1—O11ⁱⁱ	2.637 (2)
C1—C4	1.510 (4)
C1—C2	1.539 (4)
C2—C7	1.517 (5)
C2—C3	1.537 (5)
C3—C10	1.513 (5)
C4—O5	1.237 (4)
C4—O6	1.267 (4)
C7—O9	1.251 (4)
C7—O8	1.272 (4)
C10—O12	1.257 (4)
C10—O11	1.270 (4)

O5—C4—C1—C2	−126.3 (3)
C4—C1—C2—C3	−176.7 (3)
C1—C2—C3—C10	72.6 (4)
C2—C3—C10—O11	−4.9 (5)
O5—C4—C1—C2	−126.3 (3)
C4—C1—C2—C7	61.7 (4)
C1—C2—C7—O8	−151.6 (3)
Symmetry codes: (i) -x,2-y,1-z; (ii) x,y-1,z; (iii) -1-x,2-y,-z; (iv) 1+x,y,z.

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H131⋯O11^v	0.86 (5)	1.95 (5)	2.810 (3)	174 (5)
O13—H132⋯O6^v	0.79 (5)	1.99 (3)	2.741 (4)	160 (5)
O14—H141⋯O9ⁱ	0.89 (5)	1.96 (5)	2.830 (4)	165 (5)
O14—H142⋯O12^vi	0.83 (5)	1.91 (5)	2.718 (4)	165 (5)
Symmetry codes: (i) -x,2-y,1-z; (v) -x,2-y,-z; (vi) 1+x,y-1,z.

H atoms of the tricarballylate anion were placed in calculated positions with U_iso values set at 1.3 times the U_eq value of the parent atom and the C—H distance set at 0.97 Å. H atoms of water were located in a difference synthesis and the coordinates were refined with U_iso values set at 1.3 times the U_eq value of the parent atom; the O—H distances were not constrained. The highest difference map peak was 0.83 Å from Ce1 and the deepest hole was 0.86 Å from Ce1.

Data collection: DENZO (Otwinowski & Minor, 1997 ) and COLLECT (Hooft, 1998 ); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: PLATON (Spek, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536804011389/hg6042sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804011389/hg6042Isup2.hkl

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1992).

Poly[[diaquacerium(III)]-µ₅-propane-1,2,3-tricarboxylato] top

Crystal data top

[Ce(C₆H₅O₆)(H₂O)₂]	Z = 2
M_r = 349.25	F(000) = 334
Triclinic, P1	D_x = 2.486 Mg m⁻³
a = 6.9084 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7738 (4) Å	Cell parameters from 5965 reflections
c = 8.8162 (4) Å	θ = 2.6–27.5°
α = 99.552 (2)°	µ = 4.90 mm⁻¹
β = 110.209 (2)°	T = 150 K
γ = 104.461 (2)°	Block, colourless
V = 466.51 (3) Å³	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius KappaCCD area-detector diffractometer	2091 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	2046 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 9.091 pixels/mm pixels mm^-1	θ_max = 27.5°, θ_min = 2.6°
π and ω scans	h = −8→8
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −11→9
T_min = 0.353, T_max = 0.613	l = −11→11
5965 measured reflections

Refinement top

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: mixed
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0331P)² + 0.7556P] where P = (F_o² + 2F_c²)/3
2091 reflections	(Δ/σ)_max = 0.018
148 parameters	Δρ_max = 1.05 e Å⁻³
1 restraint	Δρ_min = −2.89 e Å⁻³

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.

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.

H atoms of tricarballylate anion placed on calculated positions with U(iso) set to 1.3 times that of parent atom. H atoms of water located on a difference synthesis, coordinates refined with U(iso) set to 1.3 times that of parent atom. The O - H distances were not constrained.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ce1	0.02449 (2)	0.876953 (16)	0.199738 (17)	0.00936 (9)
C1	−0.2152 (5)	1.3184 (4)	0.3811 (4)	0.0125 (6)
H1A	−0.0956	1.4050	0.3820	0.016*
H1B	−0.2354	1.3532	0.4833	0.016*
C2	−0.4245 (5)	1.2984 (4)	0.2294 (4)	0.0142 (7)
H2	−0.4044	1.2626	0.1262	0.018*
C3	−0.4664 (6)	1.4628 (4)	0.2342 (5)	0.0161 (7)
H3A	−0.6153	1.4417	0.1558	0.021*
H3B	−0.4552	1.5095	0.3459	0.021*
C4	−0.1505 (5)	1.1664 (4)	0.3843 (4)	0.0135 (6)
O5	−0.1194 (5)	1.1165 (3)	0.5111 (3)	0.0265 (6)
O6	−0.1279 (4)	1.0985 (3)	0.2560 (3)	0.0203 (5)
C7	−0.6234 (5)	1.1717 (4)	0.2242 (4)	0.0130 (7)
O8	−0.7802 (3)	1.0940 (3)	0.0821 (3)	0.0155 (5)
O9	−0.6356 (4)	1.1430 (3)	0.3555 (3)	0.0250 (6)
C10	−0.3142 (6)	1.5888 (4)	0.1922 (4)	0.0153 (7)
O11	−0.1532 (4)	1.5636 (3)	0.1668 (3)	0.0217 (5)
O12	−0.3486 (4)	1.7220 (3)	0.1851 (3)	0.0221 (5)
O13	0.0587 (5)	0.7143 (3)	−0.0477 (3)	0.0239 (6)
H131	0.091 (8)	0.628 (6)	−0.077 (6)	0.031*
H132	0.107 (7)	0.764 (5)	−0.100 (5)	0.031*
O14	0.3613 (5)	0.7979 (4)	0.3020 (4)	0.0280 (6)
H141	0.434 (8)	0.827 (6)	0.414 (7)	0.036*
H142	0.436 (8)	0.777 (6)	0.250 (6)	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce1	0.01162 (13)	0.00675 (12)	0.01070 (13)	0.00144 (8)	0.00547 (9)	0.00535 (8)
C1	0.0079 (13)	0.0101 (13)	0.0159 (15)	−0.0011 (11)	0.0039 (11)	0.0026 (11)
C2	0.0164 (15)	0.0114 (14)	0.0148 (16)	0.0034 (12)	0.0065 (13)	0.0056 (12)
C3	0.0164 (17)	0.0137 (15)	0.0232 (18)	0.0063 (13)	0.0102 (14)	0.0109 (14)
C4	0.0124 (14)	0.0155 (14)	0.0110 (14)	0.0019 (11)	0.0044 (11)	0.0042 (11)
O5	0.0443 (16)	0.0342 (14)	0.0174 (12)	0.0263 (13)	0.0173 (11)	0.0181 (11)
O6	0.0350 (14)	0.0186 (12)	0.0179 (11)	0.0151 (10)	0.0162 (10)	0.0098 (9)
C7	0.0123 (15)	0.0086 (14)	0.0179 (17)	0.0022 (12)	0.0053 (13)	0.0067 (12)
O8	0.0137 (10)	0.0128 (10)	0.0138 (11)	−0.0010 (8)	0.0018 (8)	0.0047 (8)
O9	0.0225 (12)	0.0269 (13)	0.0160 (12)	−0.0060 (10)	0.0044 (10)	0.0113 (10)
C10	0.0129 (15)	0.0131 (16)	0.0167 (16)	−0.0006 (12)	0.0056 (13)	0.0041 (13)
O11	0.0258 (13)	0.0118 (11)	0.0357 (14)	0.0059 (10)	0.0202 (11)	0.0113 (10)
O12	0.0226 (12)	0.0144 (11)	0.0394 (15)	0.0074 (9)	0.0199 (11)	0.0150 (10)
O13	0.0448 (16)	0.0201 (13)	0.0247 (13)	0.0185 (12)	0.0257 (12)	0.0140 (10)
O14	0.0253 (14)	0.0452 (17)	0.0171 (13)	0.0199 (12)	0.0079 (11)	0.0063 (12)

Geometric parameters (Å, º) top

Ce1—O5ⁱ	2.390 (3)	C2—C3	1.537 (5)
Ce1—O6	2.489 (2)	C2—H2	0.9800
Ce1—O14	2.505 (3)	C3—C10	1.513 (5)
Ce1—O13	2.518 (2)	C3—H3A	0.9700
Ce1—O12ⁱⁱ	2.544 (2)	C3—H3B	0.9700
Ce1—O8ⁱⁱⁱ	2.572 (2)	C4—O5	1.237 (4)
Ce1—O9^iv	2.611 (2)	C4—O6	1.267 (4)
Ce1—O8^iv	2.619 (2)	C7—O9	1.251 (4)
Ce1—O11ⁱⁱ	2.637 (2)	C7—O8	1.272 (4)
Ce1—C10ⁱⁱ	2.958 (4)	C10—O12	1.257 (4)
Ce1—C7^iv	2.994 (3)	C10—O11	1.270 (4)
C1—C4	1.510 (4)	O13—H131	0.86 (5)
C1—C2	1.539 (4)	O13—H132	0.79 (5)
C1—H1A	0.9700	O14—H141	0.89 (5)
C1—H1B	0.9700	O14—H142	0.83 (5)
C2—C7	1.517 (5)

O5ⁱ—Ce1—O6	86.43 (8)	O9^iv—Ce1—C10ⁱⁱ	152.85 (9)
O5ⁱ—Ce1—O14	71.53 (9)	O8^iv—Ce1—C10ⁱⁱ	157.50 (9)
O6—Ce1—O14	142.83 (9)	O11ⁱⁱ—Ce1—C10ⁱⁱ	25.42 (9)
O5ⁱ—Ce1—O13	136.27 (9)	O5ⁱ—Ce1—C7^iv	101.71 (10)
O6—Ce1—O13	137.29 (8)	O6—Ce1—C7^iv	78.77 (9)
O14—Ce1—O13	70.71 (9)	O14—Ce1—C7^iv	77.01 (10)
O5ⁱ—Ce1—O12ⁱⁱ	80.17 (9)	O13—Ce1—C7^iv	90.53 (9)
O6—Ce1—O12ⁱⁱ	76.77 (8)	O12ⁱⁱ—Ce1—C7^iv	155.30 (8)
O14—Ce1—O12ⁱⁱ	125.86 (10)	O8ⁱⁱⁱ—Ce1—C7^iv	88.34 (8)
O13—Ce1—O12ⁱⁱ	105.21 (9)	O9^iv—Ce1—C7^iv	24.59 (9)
O5ⁱ—Ce1—O8ⁱⁱⁱ	153.05 (8)	O8^iv—Ce1—C7^iv	25.08 (8)
O6—Ce1—O8ⁱⁱⁱ	70.91 (7)	O11ⁱⁱ—Ce1—C7^iv	154.72 (8)
O14—Ce1—O8ⁱⁱⁱ	135.40 (8)	C10ⁱⁱ—Ce1—C7^iv	177.42 (8)
O13—Ce1—O8ⁱⁱⁱ	67.52 (8)	C4—C1—C2	115.1 (2)
O12ⁱⁱ—Ce1—O8ⁱⁱⁱ	80.56 (8)	C4—C1—H1A	108.5
O5ⁱ—Ce1—O9^iv	77.23 (9)	C2—C1—H1A	108.5
O6—Ce1—O9^iv	75.00 (9)	C4—C1—H1B	108.5
O14—Ce1—O9^iv	71.21 (9)	C2—C1—H1B	108.5
O13—Ce1—O9^iv	109.96 (9)	H1A—C1—H1B	107.5
O12ⁱⁱ—Ce1—O9^iv	144.63 (8)	C7—C2—C3	109.0 (3)
O8ⁱⁱⁱ—Ce1—O9^iv	109.35 (7)	C7—C2—C1	112.0 (3)
O5ⁱ—Ce1—O8^iv	126.58 (9)	C3—C2—C1	110.4 (2)
O6—Ce1—O8^iv	79.56 (8)	C7—C2—H2	108.4
O14—Ce1—O8^iv	89.83 (9)	C3—C2—H2	108.4
O13—Ce1—O8^iv	74.36 (8)	C1—C2—H2	108.4
O12ⁱⁱ—Ce1—O8^iv	142.78 (8)	C10—C3—C2	115.6 (3)
O8ⁱⁱⁱ—Ce1—O8^iv	64.65 (8)	C10—C3—H3A	108.4
O9^iv—Ce1—O8^iv	49.36 (7)	C2—C3—H3A	108.4
O5ⁱ—Ce1—O11ⁱⁱ	80.15 (9)	C10—C3—H3B	108.4
O6—Ce1—O11ⁱⁱ	126.43 (8)	C2—C3—H3B	108.4
O14—Ce1—O11ⁱⁱ	79.82 (9)	H3A—C3—H3B	107.4
O13—Ce1—O11ⁱⁱ	72.25 (8)	O5—C4—O6	123.7 (3)
O12ⁱⁱ—Ce1—O11ⁱⁱ	49.96 (7)	O5—C4—C1	119.0 (3)
O8ⁱⁱⁱ—Ce1—O11ⁱⁱ	101.34 (8)	O6—C4—C1	117.3 (3)
O9^iv—Ce1—O11ⁱⁱ	147.60 (8)	O9—C7—O8	119.9 (3)
O8^iv—Ce1—O11ⁱⁱ	146.60 (7)	O9—C7—C2	121.6 (3)
O5ⁱ—Ce1—C10ⁱⁱ	75.71 (10)	O8—C7—C2	118.5 (3)
O6—Ce1—C10ⁱⁱ	101.01 (9)	O12—C10—O11	120.1 (3)
O14—Ce1—C10ⁱⁱ	101.94 (11)	O12—C10—C3	118.2 (3)
O13—Ce1—C10ⁱⁱ	91.34 (9)	O11—C10—C3	121.7 (3)
O12ⁱⁱ—Ce1—C10ⁱⁱ	24.97 (9)	O12—C10—Ce1^v	58.71 (18)
O8ⁱⁱⁱ—Ce1—C10ⁱⁱ	94.03 (9)

O5—C4—C1—C2	−126.3 (3)	O5—C4—C1—C2	−126.3 (3)
C4—C1—C2—C3	−176.7 (3)	C4—C1—C2—C7	61.7 (4)
C1—C2—C3—C10	72.6 (4)	C1—C2—C7—O8	−151.6 (3)
C2—C3—C10—O11	−4.9 (5)

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z; (iii) −x−1, −y+2, −z; (iv) x+1, y, z; (v) x, y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H131···O11^vi	0.86 (5)	1.95 (5)	2.810 (3)	174 (5)
O13—H132···O6^vi	0.79 (5)	1.99 (3)	2.741 (4)	160 (5)
O14—H141···O9ⁱ	0.89 (5)	1.96 (5)	2.830 (4)	165 (5)
O14—H142···O12^vii	0.83 (5)	1.91 (5)	2.718 (4)	165 (5)

Symmetry codes: (i) −x, −y+2, −z+1; (vi) −x, −y+2, −z; (vii) x+1, y−1, z.

Acknowledgements

We thank the EPSRC and Professor M. B. Hursthouse for collection of data at Cardiff and Southampton Universities.

References

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Volume 60| Part 6| June 2004| Pages m791-m793

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