Download citation
Download citation
link to html
The reaction of CaCO3 with isophthalic acid in water yields nona­aqua­penta-[mu]-isophthalato-pentacalcium octahydrate, {[Ca5(C8H4O4)5(H2O)9]·8H2O}n, a complex polymeric one-dimensional column structure bearing metal-carboxyl­ate bonds and Ca-bound terminal and bridging water mol­ecules, in addition to hydrogen-bonded water mol­ecules of crystallization. The asymmetric unit comprises half of the formula unit, with one Ca2+ ion located on a twofold axis, and contains 16 unique strong O-H...O hydrogen bonds, some of which link the columns together.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103023643/tr1070sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103023643/tr1070Isup2.hkl
Contains datablock I

CCDC reference: 229081

Comment top

The benzenepolycarboxylic acid family has been extensively exploited in the challenge of creating functional porous supramolecular architectures (Yaghi et al., 1998; Janiak, 1997). While numerous examples of polymeric metal-organic frameworks (MOFs) exist in the literature, containing the more commonly used terephthalic (e.g. Groeneman et al., 1999) and trimesic (e.g. Yaghi et al., 1995) acids, a search of the Cambridge Structural Database (Version 5.24, July 2003 update; Allen, 2002) has highlighted the use of isophthalic acid (H2IPA, benzene-1,3-dicarboxylic acid), predominantly in mixed-ligand metal complexes, for example in combination with derivatives of 4,4'-bipyridine (Bourne et al., 2001; Tao et al., 2000, 2002). Only two examples exist of solely hydrated salts of H2IPA, namely those of Zn2+ (Otto & Wheeler, 2001) and La3+ (Kim et al., 2001), and this led us to investigate the synthesis of other hydrated metal salts of H2IPA, including the title Ca2+ salt, (I), presented here. \sch

The asymmetric unit of (I), {[Ca(C8H4O4)]5.17H2O}n, contains half of a formula unit, with 2.5 Ca2+ cations, 2.5 IPA2− anionic ligands and 8.5 H2O molecules. The two full-weight Ca2+ ions (Ca1 and Ca2) both have a coordination number of eight, with the coordination sphere of atom Ca1 comprising six metal-carboxylate bonds and two terminal metal-OH2 bonds, while atom Ca2 has six metal-carboxylate bonds, one terminal metal-OH2 bond and one bridging metal-OH2 bond, with the H2O molecule (atom O15) bridging atoms Ca2 and Ca3, which lies on a twofold axis. In contrast, atom Ca3 has a coordination number of nine and makes six metal-carboxylate bonds, in addition to one terminal and two bridging metal-OH2 bonds (Fig. 1 and Table 1). The Ca—O bond lengths are in the range 2.3252 (12)–2.7746 (13) Å for metal-carboxylate bonds and 2.3568 (13)–2.5800 (16) Å for metal-OH2 bonds, which compare well with bond lengths observed in the literature, for example in calcium terephthalate trihydrate (Dale & Elsegood, 2003).

The carboxylate groups of the IPA2− anions and their respective benzene rings lie close to coplanarity, with the greatest twist angle being 10.0 (3)°, while the aromatic rings of the anions lie at angles of roughly 60° to each other [dihedral angles with respect to the C1—C6 ring: carboxyl groups C7/O1/O2 6.5 (2) and C8/O3/O4 4.8 (2)°, and rings C9—C14 63.45 (6) and C17—C20 62.84 (6)°; dihedral angles with respect to the C9—C14 ring: carboxyl groups C15/O5/O6 6.3 (2) and C16/O7/O8 1.0 (2)°, and ring C17—C20 62.15 (5)°; dihedral angle with respect to the C17—C20 ring: carboxyl group C21/O9/O10 10.0 (3)°].

Each unique carboxylate group in (I) chelates one Ca2+ centre, with one of its O atoms also bridging a second Ca2+ centre, producing an η2:η12 motif. This creates an infinte one-dimensional coordination polymer which, viewed end on, approximates to a five-pointed star in cross-section. An extensive array of 16 unique strong O—H···O hydrogen bonds (Table 2) between metal-coordinated water molecules, water molecules of crystallization and carboxyl O atoms produces an extensive hydrogen-bonding network, too complex to describe here in detail. Packing plots reveal that each column (propagating parallel to the crystallographic a axis) is connected, either via direct or water-bridged hydrogen-bond paths, to five neighbouring columns (Fig. 2).

Experimental top

Isophthalic acid (1 equivalent) was refluxed with CaCO3 (1 equivalent) in H2O for 24 h, producing X-ray quality colourless crystals of (I), in quantitative yield, upon slow evaporation of the cooled filtered solution. The crystals were observed to desolvate at 318–323 K. Spectroscopic analysis: IR (KBr, νmax, cm−1): 3442 (br, OH), 3136 and 3118 (aromatic C—H), 1603 and 1533 (asymmetric CO2), 1479, 1448, 1394 (symmetric CO2), 1280, 1163, 1107, 1080 (C—O), 942, 916, 840, 833, 745, 725 (aromatic C—H). Analysis calculated for Ca5C40H55O37: C 36.17, H, 4.17%; found: C 36.39, H 3.63%.

Refinement top

In the refinement of the water molecules 1,2 and 1,3 distances were refined with the SHELX commands SADI 0.005 > and DFIX 1.33 0.005 respectively. Aromatic H atoms were placed in geometric positions (C—H distance = 0.95 Å) using a riding model, while the coordinates of the water H atoms were refined using geometric restraints on the O—H bond lengths and H—O—H bond angles. Uiso(H) values were set to 1.2Ueq for aryl H (1.5Ueq for water H). Atom O14 is disordered over two equally occupied sets of positions close to a twofold axis and restraints were applied to the anisotropic displacment parameters for this atom.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atom-labelling scheme and the completed Ca2+ coordination spheres. Displacement ellipsoids are drawn at the 50% probability level and all H atoms have been omitted for clarity. Atoms with the suffix A are at the symmetry position (-x, y, 1/2 − z), B at (1 − x, y, 1/2 − z) and C at (x + 1, y, z).
[Figure 2] Fig. 2. A packing plot of (I) showing the one-dimensional coordination polymer columns extending parallel to the crystallographic a axis. H atoms have been omitted for clarity and hydrogen-bond O···O contacts are shown by dashed lines.
Nonaaquapenta-µ-isophthalato-pentacalcium octahydrate top
Crystal data top
[Ca5(C8H4O4)5(H2O)9]·8H2OF(000) = 2760
Mr = 1327.24Dx = 1.666 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 9880 reflections
a = 15.6289 (8) Åθ = 2.4–28.9°
b = 21.2640 (11) ŵ = 0.62 mm1
c = 17.1852 (9) ÅT = 150 K
β = 112.134 (2)°Block, colourless
V = 5290.3 (5) Å30.38 × 0.20 × 0.10 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
6434 independent reflections
Radiation source: sealed tube5100 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω rotation with narrow frames scansθmax = 29.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
h = 2021
Tmin = 0.836, Tmax = 0.941k = 2728
23336 measured reflectionsl = 2322
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0373P)2 + 4.8388P]
where P = (Fo2 + 2Fc2)/3
6434 reflections(Δ/σ)max = 0.001
428 parametersΔρmax = 0.46 e Å3
169 restraintsΔρmin = 0.33 e Å3
Crystal data top
[Ca5(C8H4O4)5(H2O)9]·8H2OV = 5290.3 (5) Å3
Mr = 1327.24Z = 4
Monoclinic, C2/cMo Kα radiation
a = 15.6289 (8) ŵ = 0.62 mm1
b = 21.2640 (11) ÅT = 150 K
c = 17.1852 (9) Å0.38 × 0.20 × 0.10 mm
β = 112.134 (2)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
6434 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
5100 reflections with I > 2σ(I)
Tmin = 0.836, Tmax = 0.941Rint = 0.027
23336 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033169 restraints
wR(F2) = 0.083H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.46 e Å3
6434 reflectionsΔρmin = 0.33 e Å3
428 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ca10.07805 (2)0.457932 (16)0.18124 (2)0.01297 (8)
O110.00015 (9)0.55510 (6)0.15074 (9)0.0230 (3)
H11A0.0562 (4)0.5500 (10)0.1297 (12)0.034*
H11B0.0140 (12)0.5817 (8)0.1233 (12)0.034*
O120.12621 (9)0.48871 (7)0.06916 (8)0.0243 (3)
H12A0.1028 (12)0.5119 (9)0.0287 (10)0.036*
H12B0.1808 (5)0.4842 (11)0.0773 (13)0.036*
Ca20.26313 (2)0.350822 (16)0.14830 (2)0.01424 (8)
O130.16860 (9)0.33877 (7)0.00341 (8)0.0226 (3)
H13A0.1127 (5)0.3397 (10)0.0085 (13)0.034*
H13B0.1816 (12)0.3655 (8)0.0246 (12)0.034*
Ca30.50000.29311 (2)0.25000.01577 (11)
O140.5268 (2)0.18294 (12)0.2545 (3)0.0328 (8)0.50
H14A0.50000.1493 (3)0.25000.049*
H14B0.5726 (10)0.1776 (6)0.2431 (17)0.049*0.5
O150.34963 (11)0.26034 (8)0.12884 (12)0.0416 (4)
H15A0.336 (2)0.2240 (5)0.1343 (15)0.062*
H15B0.349 (2)0.2652 (12)0.0814 (8)0.062*
O160.80877 (9)0.55494 (7)0.08166 (8)0.0273 (3)
H16A0.7611 (9)0.5487 (12)0.0410 (7)0.041*
H16B0.7998 (14)0.5464 (12)0.1244 (7)0.041*
O170.63010 (12)0.31325 (8)0.01361 (10)0.0384 (4)
H17A0.5769 (8)0.3056 (12)0.0178 (12)0.058*
H17B0.6430 (15)0.2912 (11)0.0556 (10)0.058*
O180.81026 (12)0.66462 (8)0.25007 (18)0.0710 (7)
H18A0.797 (2)0.6273 (4)0.244 (2)0.107*
H18B0.7630 (13)0.6854 (12)0.230 (2)0.107*
O190.48254 (9)0.15049 (6)0.04840 (8)0.0217 (3)
H19A0.4629 (14)0.1856 (5)0.0651 (13)0.033*
H19B0.4625 (14)0.1394 (9)0.0130 (11)0.033*
C10.20145 (12)0.37312 (8)0.07094 (11)0.0154 (3)
C20.25026 (11)0.35537 (8)0.12087 (11)0.0146 (3)
H20.22850.36800.17810.017*
C30.33079 (11)0.31929 (8)0.08768 (11)0.0154 (3)
C40.36152 (12)0.30049 (8)0.00366 (11)0.0179 (4)
H40.41570.27560.01940.021*
C50.31343 (12)0.31792 (9)0.04639 (11)0.0201 (4)
H50.33480.30480.10340.024*
C60.23420 (12)0.35444 (9)0.01336 (11)0.0184 (4)
H60.20210.36680.04810.022*
C70.11385 (11)0.41116 (8)0.10758 (10)0.0140 (3)
O10.06599 (8)0.42079 (6)0.06309 (7)0.0164 (3)
O20.08804 (8)0.43137 (6)0.18196 (7)0.0161 (2)
C80.38557 (11)0.30216 (8)0.14082 (11)0.0153 (3)
O30.35612 (8)0.31834 (6)0.21711 (7)0.0179 (3)
O40.46099 (8)0.27332 (6)0.10720 (8)0.0204 (3)
C90.46903 (12)0.47596 (8)0.11969 (10)0.0154 (3)
C100.56102 (11)0.46398 (8)0.17083 (10)0.0148 (3)
H100.57610.42730.20480.018*
C110.63094 (11)0.50527 (8)0.17253 (10)0.0145 (3)
C120.60808 (12)0.55805 (8)0.12027 (11)0.0160 (3)
H120.65530.58600.11980.019*
C130.51661 (12)0.56986 (8)0.06888 (11)0.0179 (4)
H130.50170.60570.03320.022*
C140.44682 (12)0.52953 (8)0.06953 (11)0.0172 (4)
H140.38420.53850.03590.021*
C150.39582 (11)0.43069 (8)0.12058 (10)0.0153 (3)
O50.31161 (8)0.44388 (6)0.08099 (8)0.0189 (3)
O60.42038 (8)0.38049 (6)0.16321 (8)0.0169 (3)
C160.72924 (11)0.49231 (8)0.23008 (10)0.0143 (3)
O70.74746 (8)0.44345 (6)0.27512 (7)0.0157 (2)
O80.79235 (8)0.53032 (6)0.23120 (7)0.0171 (3)
C170.05483 (11)0.25618 (8)0.21605 (10)0.0140 (3)
C180.05440 (12)0.19063 (8)0.21597 (11)0.0172 (4)
H180.09160.16840.19250.021*
C190.00000.15749 (12)0.25000.0186 (5)
H190.00000.11280.25000.022*
C200.00000.28929 (11)0.25000.0140 (5)
H200.00000.33400.25000.017*
C210.11630 (11)0.29059 (8)0.18050 (10)0.0147 (3)
O90.10972 (8)0.34960 (6)0.17077 (8)0.0166 (3)
O100.17496 (8)0.25890 (6)0.16277 (8)0.0183 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ca10.01177 (16)0.01394 (17)0.01339 (16)0.00028 (12)0.00496 (13)0.00073 (13)
O110.0155 (6)0.0224 (7)0.0309 (7)0.0017 (5)0.0086 (6)0.0066 (6)
O120.0204 (7)0.0341 (8)0.0211 (7)0.0066 (6)0.0109 (6)0.0106 (6)
Ca20.01200 (16)0.01587 (17)0.01498 (16)0.00110 (13)0.00525 (13)0.00018 (13)
O130.0179 (7)0.0276 (7)0.0212 (7)0.0031 (6)0.0060 (6)0.0026 (6)
Ca30.0138 (2)0.0149 (2)0.0198 (2)0.0000.00779 (19)0.000
O140.044 (3)0.0184 (13)0.0454 (18)0.0050 (11)0.027 (2)0.0012 (14)
O150.0233 (8)0.0412 (10)0.0659 (12)0.0099 (7)0.0234 (8)0.0331 (9)
O160.0159 (7)0.0461 (9)0.0190 (7)0.0008 (6)0.0057 (5)0.0110 (7)
O170.0461 (10)0.0345 (9)0.0266 (8)0.0053 (8)0.0044 (7)0.0028 (7)
O180.0283 (9)0.0231 (9)0.130 (2)0.0008 (7)0.0060 (11)0.0034 (11)
O190.0239 (7)0.0203 (7)0.0251 (7)0.0039 (5)0.0138 (6)0.0053 (6)
C10.0145 (8)0.0163 (8)0.0150 (8)0.0012 (7)0.0050 (7)0.0011 (7)
C20.0143 (8)0.0156 (8)0.0138 (8)0.0015 (6)0.0052 (6)0.0004 (7)
C30.0143 (8)0.0160 (8)0.0160 (8)0.0016 (7)0.0057 (7)0.0005 (7)
C40.0141 (8)0.0190 (9)0.0188 (8)0.0009 (7)0.0042 (7)0.0014 (7)
C50.0189 (9)0.0268 (10)0.0132 (8)0.0003 (7)0.0044 (7)0.0039 (7)
C60.0175 (9)0.0225 (9)0.0166 (8)0.0007 (7)0.0081 (7)0.0010 (7)
C70.0135 (8)0.0143 (8)0.0144 (8)0.0035 (6)0.0056 (6)0.0031 (6)
O10.0144 (6)0.0201 (6)0.0161 (6)0.0008 (5)0.0074 (5)0.0001 (5)
O20.0159 (6)0.0181 (6)0.0141 (6)0.0011 (5)0.0054 (5)0.0004 (5)
C80.0144 (8)0.0132 (8)0.0186 (8)0.0019 (6)0.0065 (7)0.0003 (7)
O30.0181 (6)0.0203 (7)0.0161 (6)0.0019 (5)0.0075 (5)0.0018 (5)
O40.0162 (6)0.0228 (7)0.0219 (6)0.0055 (5)0.0070 (5)0.0036 (5)
C90.0143 (8)0.0170 (8)0.0150 (8)0.0009 (7)0.0058 (7)0.0017 (7)
C100.0163 (8)0.0129 (8)0.0155 (8)0.0003 (6)0.0064 (7)0.0012 (6)
C110.0135 (8)0.0151 (8)0.0157 (8)0.0001 (6)0.0063 (7)0.0017 (7)
C120.0148 (8)0.0151 (8)0.0194 (8)0.0017 (6)0.0079 (7)0.0009 (7)
C130.0183 (9)0.0159 (8)0.0193 (9)0.0028 (7)0.0068 (7)0.0033 (7)
C140.0122 (8)0.0196 (9)0.0183 (8)0.0024 (7)0.0040 (7)0.0003 (7)
C150.0152 (8)0.0191 (9)0.0127 (8)0.0020 (7)0.0064 (7)0.0032 (7)
O50.0123 (6)0.0244 (7)0.0189 (6)0.0012 (5)0.0046 (5)0.0024 (5)
O60.0156 (6)0.0170 (6)0.0180 (6)0.0015 (5)0.0063 (5)0.0012 (5)
C160.0152 (8)0.0145 (8)0.0147 (8)0.0005 (6)0.0074 (7)0.0020 (7)
O70.0137 (6)0.0159 (6)0.0168 (6)0.0009 (5)0.0049 (5)0.0023 (5)
O80.0130 (6)0.0181 (6)0.0191 (6)0.0014 (5)0.0049 (5)0.0026 (5)
C170.0135 (8)0.0148 (8)0.0137 (8)0.0006 (6)0.0050 (6)0.0007 (6)
C180.0174 (9)0.0153 (8)0.0205 (9)0.0022 (7)0.0089 (7)0.0021 (7)
C190.0193 (13)0.0132 (12)0.0233 (13)0.0000.0080 (10)0.000
C200.0137 (11)0.0121 (11)0.0167 (11)0.0000.0063 (9)0.000
C210.0140 (8)0.0163 (8)0.0132 (8)0.0017 (6)0.0044 (6)0.0013 (7)
O90.0178 (6)0.0151 (6)0.0191 (6)0.0004 (5)0.0095 (5)0.0006 (5)
O100.0177 (6)0.0169 (6)0.0241 (6)0.0011 (5)0.0122 (5)0.0011 (5)
Geometric parameters (Å, º) top
Ca1—O112.3568 (13)C1—C71.509 (2)
Ca1—O2i2.3652 (12)C2—C31.399 (2)
Ca1—O92.3772 (12)C2—H20.9500
Ca1—O122.4078 (13)C3—C41.397 (2)
Ca1—O12.5238 (12)C3—C81.513 (2)
Ca1—O8ii2.5377 (12)C4—C51.389 (2)
Ca1—O7ii2.5600 (12)C4—H40.9500
Ca1—O22.6610 (12)C5—C61.389 (2)
O11—H11A0.819 (5)C5—H50.9500
O11—H11B0.819 (5)C6—H60.9500
O12—H12A0.818 (5)C7—O21.262 (2)
O12—H12B0.817 (5)C7—O11.272 (2)
Ca2—O3i2.3252 (12)C8—O41.259 (2)
Ca2—O132.3824 (13)C8—O31.263 (2)
Ca2—O7ii2.4089 (12)C9—C141.391 (2)
Ca2—O152.4457 (16)C9—C101.397 (2)
Ca2—O62.4555 (12)C9—C151.500 (2)
Ca2—O102.4575 (13)C10—C111.393 (2)
Ca2—O52.5473 (13)C10—H100.9500
Ca2—O92.5682 (12)C11—C121.397 (2)
O13—H13A0.819 (5)C11—C161.506 (2)
O13—H13B0.819 (5)C12—C131.391 (2)
Ca3—O142.376 (3)C12—H120.9500
Ca3—O62.4138 (13)C13—C141.391 (2)
Ca3—O3i2.5733 (12)C13—H130.9500
Ca3—O152.5800 (16)C14—H140.9500
Ca3—O4i2.7746 (13)C15—O51.264 (2)
O14—H14A0.818 (5)C15—O61.270 (2)
O14—H14B0.819 (5)C16—O71.262 (2)
O15—H15A0.817 (5)C16—O81.270 (2)
O15—H15B0.817 (5)C17—C181.394 (2)
O16—H16A0.818 (5)C17—C201.395 (2)
O16—H16B0.818 (5)C17—C211.508 (2)
O17—H17A0.819 (5)C18—C191.391 (2)
O17—H17B0.820 (5)C18—H180.9500
O18—H18A0.817 (5)C19—C18i1.391 (2)
O18—H18B0.817 (5)C19—H190.9500
O19—H19A0.818 (5)C20—C17i1.395 (2)
O19—H19B0.817 (5)C20—H200.9500
C1—C21.398 (2)C21—O101.264 (2)
C1—C61.400 (2)C21—O91.265 (2)
O11—Ca1—O2i105.36 (5)O6—Ca3—O4iii78.71 (4)
O11—Ca1—O9159.72 (5)O3i—Ca3—O4iii136.66 (4)
O2i—Ca1—O984.62 (4)O3iii—Ca3—O4iii48.39 (4)
O11—Ca1—O1282.88 (5)O15—Ca3—O4iii71.47 (4)
O2i—Ca1—O12159.49 (5)O15ii—Ca3—O4iii103.64 (5)
O9—Ca1—O1293.79 (5)O4i—Ca3—O4iii162.55 (6)
O11—Ca1—O182.23 (4)Ca3—O14—H14A141.4 (3)
O2i—Ca1—O1115.45 (4)O14ii—O14—H14B155 (2)
O9—Ca1—O177.52 (4)Ca3—O14—H14B106.8 (10)
O12—Ca1—O183.94 (4)H14A—O14—H14B108.6 (10)
O11—Ca1—O8ii80.29 (4)Ca2—O15—Ca393.42 (5)
O2i—Ca1—O8ii79.42 (4)Ca2—O15—H15A123 (2)
O9—Ca1—O8ii119.36 (4)Ca3—O15—H15A111 (2)
O12—Ca1—O8ii83.64 (5)Ca2—O15—H15B104 (2)
O1—Ca1—O8ii159.65 (4)Ca3—O15—H15B116 (2)
O11—Ca1—O7ii125.21 (4)H15A—O15—H15B109.1 (9)
O2i—Ca1—O7ii90.92 (4)H16A—O16—H16B108.9 (10)
O9—Ca1—O7ii71.12 (4)H17A—O17—H17B108.6 (10)
O12—Ca1—O7ii69.36 (4)H18A—O18—H18B109.0 (10)
O1—Ca1—O7ii136.63 (4)H19A—O19—H19B109.1 (10)
O8ii—Ca1—O7ii51.32 (4)C2—C1—C6119.16 (16)
O11—Ca1—O276.24 (4)C2—C1—C7120.53 (15)
O2i—Ca1—O269.14 (5)C6—C1—C7120.30 (15)
O9—Ca1—O291.49 (4)C1—C2—C3120.87 (16)
O12—Ca1—O2131.37 (4)C1—C2—H2119.6
O1—Ca1—O250.31 (4)C3—C2—H2119.6
O8ii—Ca1—O2133.48 (4)C4—C3—C2118.96 (16)
O7ii—Ca1—O2155.02 (4)C4—C3—C8120.17 (15)
Ca1—O11—H11A111.1 (15)C2—C3—C8120.85 (15)
Ca1—O11—H11B120.2 (16)C5—C4—C3120.53 (16)
H11A—O11—H11B108.2 (10)C5—C4—H4119.7
Ca1—O12—H12A132.0 (14)C3—C4—H4119.7
Ca1—O12—H12B116.9 (14)C6—C5—C4120.22 (16)
H12A—O12—H12B108.7 (10)C6—C5—H5119.9
O3i—Ca2—O13156.46 (5)C4—C5—H5119.9
O3i—Ca2—O7ii81.10 (4)C5—C6—C1120.24 (16)
O13—Ca2—O7ii121.05 (5)C5—C6—H6119.9
O3i—Ca2—O1574.44 (6)C1—C6—H6119.9
O13—Ca2—O1585.97 (6)O2—C7—O1121.22 (15)
O7ii—Ca2—O15150.83 (5)O2—C7—C1119.92 (15)
O3i—Ca2—O675.32 (4)O1—C7—C1118.83 (15)
O13—Ca2—O6109.81 (4)C7—O1—Ca196.61 (10)
O7ii—Ca2—O690.28 (4)C7—O2—Ca1i164.64 (11)
O15—Ca2—O668.49 (5)C7—O2—Ca190.44 (10)
O3i—Ca2—O1080.05 (4)Ca1i—O2—Ca1104.76 (4)
O13—Ca2—O1082.51 (4)O4—C8—O3121.40 (16)
O7ii—Ca2—O10116.01 (4)O4—C8—C3119.02 (15)
O15—Ca2—O1075.41 (5)O3—C8—C3119.56 (15)
O6—Ca2—O10140.45 (4)C8—O3—Ca2i163.85 (11)
O3i—Ca2—O5120.08 (4)C8—O3—Ca3iv99.47 (10)
O13—Ca2—O577.43 (4)Ca2i—O3—Ca3iv96.53 (4)
O7ii—Ca2—O572.92 (4)C8—O4—Ca3iv90.00 (10)
O15—Ca2—O5105.94 (5)C14—C9—C10119.77 (16)
O6—Ca2—O552.45 (4)C14—C9—C15121.23 (15)
O10—Ca2—O5159.71 (4)C10—C9—C15119.00 (15)
O3i—Ca2—O996.69 (4)C11—C10—C9120.75 (16)
O13—Ca2—O984.81 (4)C11—C10—H10119.6
O7ii—Ca2—O970.49 (4)C9—C10—H10119.6
O15—Ca2—O9127.45 (5)C10—C11—C12118.95 (15)
O6—Ca2—O9160.27 (4)C10—C11—C16119.75 (15)
O10—Ca2—O952.12 (4)C12—C11—C16121.29 (15)
O5—Ca2—O9122.03 (4)C13—C12—C11120.38 (16)
Ca2—O13—H13A116.2 (16)C13—C12—H12119.8
Ca2—O13—H13B110.3 (15)C11—C12—H12119.8
H13A—O13—H13B108.3 (10)C14—C13—C12120.33 (16)
O14ii—Ca3—O1419.22 (13)C14—C13—H13119.8
O14ii—Ca3—O6ii145.34 (10)C12—C13—H13119.8
O14—Ca3—O6ii134.05 (9)C13—C14—C9119.76 (16)
O14ii—Ca3—O6134.05 (9)C13—C14—H14120.1
O14—Ca3—O6145.34 (10)C9—C14—H14120.1
O6ii—Ca3—O679.34 (6)O5—C15—O6121.62 (16)
O14ii—Ca3—O3i93.12 (7)O5—C15—C9119.70 (15)
O14—Ca3—O3i110.88 (7)O6—C15—C9118.65 (15)
O6ii—Ca3—O3i89.63 (4)C15—O5—Ca290.61 (10)
O6—Ca3—O3i71.68 (4)C15—O6—Ca3167.75 (11)
O14ii—Ca3—O3iii110.88 (7)C15—O6—Ca294.74 (10)
O14—Ca3—O3iii93.12 (7)Ca3—O6—Ca297.43 (4)
O6ii—Ca3—O3iii71.68 (4)O7—C16—O8121.34 (15)
O6—Ca3—O3iii89.63 (4)O7—C16—C11119.45 (15)
O3i—Ca3—O3iii155.94 (6)O8—C16—C11119.19 (15)
O14ii—Ca3—O1567.14 (10)C16—O7—Ca2ii164.13 (11)
O14—Ca3—O1581.71 (10)C16—O7—Ca1ii92.86 (10)
O6ii—Ca3—O15143.83 (5)Ca2ii—O7—Ca1ii102.89 (4)
O6—Ca3—O1566.95 (5)C16—O8—Ca1ii93.71 (10)
O3i—Ca3—O1568.15 (4)C18—C17—C20120.10 (16)
O3iii—Ca3—O15118.99 (5)C18—C17—C21119.24 (15)
O14ii—Ca3—O15ii81.71 (10)C20—C17—C21120.65 (16)
O14—Ca3—O15ii67.14 (10)C19—C18—C17120.63 (17)
O6ii—Ca3—O15ii66.95 (5)C19—C18—H18119.7
O6—Ca3—O15ii143.83 (5)C17—C18—H18119.7
O3i—Ca3—O15ii118.99 (5)C18i—C19—C18119.2 (2)
O3iii—Ca3—O15ii68.15 (4)C18i—C19—H19120.4
O15—Ca3—O15ii148.66 (9)C18—C19—H19120.4
O14ii—Ca3—O4i77.54 (9)C17i—C20—C17119.4 (2)
O14—Ca3—O4i85.21 (9)C17i—C20—H20120.3
O6ii—Ca3—O4i78.71 (4)C17—C20—H20120.3
O6—Ca3—O4i115.43 (4)O10—C21—O9121.82 (16)
O3i—Ca3—O4i48.39 (4)O10—C21—C17118.00 (15)
O3iii—Ca3—O4i136.66 (4)O9—C21—C17120.17 (15)
O15—Ca3—O4i103.64 (5)C21—O9—Ca1163.76 (11)
O15ii—Ca3—O4i71.47 (4)C21—O9—Ca289.77 (10)
O14ii—Ca3—O4iii85.21 (9)Ca1—O9—Ca2103.55 (4)
O14—Ca3—O4iii77.54 (9)C21—O10—Ca294.91 (10)
O6ii—Ca3—O4iii115.43 (4)
O3i—Ca2—O15—Ca339.27 (5)C9—C15—O6—Ca2170.18 (13)
O13—Ca2—O15—Ca3153.91 (6)O14ii—Ca3—O6—C15141.6 (5)
O7ii—Ca2—O15—Ca35.19 (15)O14—Ca3—O6—C15117.2 (5)
O6—Ca2—O15—Ca340.77 (5)O6ii—Ca3—O6—C1549.1 (5)
O10—Ca2—O15—Ca3122.79 (6)O3i—Ca3—O6—C15142.3 (5)
O5—Ca2—O15—Ca378.21 (6)O3iii—Ca3—O6—C1522.3 (5)
O9—Ca2—O15—Ca3125.77 (5)O15—Ca3—O6—C15144.2 (5)
O14ii—Ca3—O15—Ca2139.87 (11)O15ii—Ca3—O6—C1528.0 (6)
O14—Ca3—O15—Ca2152.93 (10)O4i—Ca3—O6—C15121.1 (5)
O6ii—Ca3—O15—Ca219.52 (12)O4iii—Ca3—O6—C1569.7 (5)
O6—Ca3—O15—Ca242.19 (5)O14ii—Ca3—O6—Ca244.98 (12)
O3i—Ca3—O15—Ca236.41 (5)O14—Ca3—O6—Ca269.34 (13)
O3iii—Ca3—O15—Ca2118.08 (5)O6ii—Ca3—O6—Ca2124.28 (6)
O15ii—Ca3—O15—Ca2146.64 (6)O3i—Ca3—O6—Ca231.10 (4)
O4i—Ca3—O15—Ca269.95 (6)O3iii—Ca3—O6—Ca2164.30 (4)
O4iii—Ca3—O15—Ca2127.50 (7)O15—Ca3—O6—Ca242.33 (5)
C6—C1—C2—C30.1 (3)O15ii—Ca3—O6—Ca2145.44 (7)
C7—C1—C2—C3179.03 (15)O4i—Ca3—O6—Ca252.34 (5)
C1—C2—C3—C40.7 (3)O4iii—Ca3—O6—Ca2116.83 (4)
C1—C2—C3—C8177.69 (16)O3i—Ca2—O6—C15144.47 (10)
C2—C3—C4—C50.7 (3)O13—Ca2—O6—C1559.61 (11)
C8—C3—C4—C5177.70 (16)O7ii—Ca2—O6—C1563.76 (10)
C3—C4—C5—C60.1 (3)O15—Ca2—O6—C15136.76 (11)
C4—C5—C6—C11.0 (3)O10—Ca2—O6—C15162.24 (9)
C2—C1—C6—C51.0 (3)O5—Ca2—O6—C154.27 (9)
C7—C1—C6—C5178.19 (16)O9—Ca2—O6—C1576.42 (16)
C2—C1—C7—O25.5 (2)O3i—Ca2—O6—Ca334.13 (4)
C6—C1—C7—O2175.31 (16)O13—Ca2—O6—Ca3121.79 (5)
C2—C1—C7—O1172.60 (16)O7ii—Ca2—O6—Ca3114.85 (4)
C6—C1—C7—O16.6 (2)O15—Ca2—O6—Ca344.64 (6)
O2—C7—O1—Ca112.67 (17)O10—Ca2—O6—Ca319.16 (8)
C1—C7—O1—Ca1165.44 (13)O5—Ca2—O6—Ca3177.13 (7)
O11—Ca1—O1—C785.17 (10)O9—Ca2—O6—Ca3102.18 (12)
O2i—Ca1—O1—C718.19 (11)C10—C11—C16—O71.3 (2)
O9—Ca1—O1—C795.97 (10)C12—C11—C16—O7178.55 (16)
O12—Ca1—O1—C7168.78 (10)C10—C11—C16—O8179.89 (15)
O8ii—Ca1—O1—C7116.13 (13)C12—C11—C16—O80.3 (2)
O7ii—Ca1—O1—C7140.17 (10)O8—C16—O7—Ca2ii164.2 (3)
O2—Ca1—O1—C76.64 (9)C11—C16—O7—Ca2ii17.0 (5)
O1—C7—O2—Ca1i176.2 (3)O8—C16—O7—Ca1ii8.91 (16)
C1—C7—O2—Ca1i5.7 (5)C11—C16—O7—Ca1ii169.88 (13)
O1—C7—O2—Ca111.93 (16)O7—C16—O8—Ca1ii9.00 (17)
C1—C7—O2—Ca1166.16 (14)C11—C16—O8—Ca1ii169.80 (13)
O11—Ca1—O2—C797.93 (10)C20—C17—C18—C190.4 (2)
O2i—Ca1—O2—C7149.42 (8)C21—C17—C18—C19178.58 (13)
O9—Ca1—O2—C765.75 (10)C17—C18—C19—C18i0.19 (11)
O12—Ca1—O2—C730.62 (12)C18—C17—C20—C17i0.19 (11)
O1—Ca1—O2—C76.64 (9)C21—C17—C20—C17i178.75 (17)
O8ii—Ca1—O2—C7159.79 (9)C18—C17—C21—O109.9 (2)
O7ii—Ca1—O2—C7110.45 (12)C20—C17—C21—O10169.07 (13)
O11—Ca1—O2—Ca1i84.30 (5)C18—C17—C21—O9171.56 (16)
O2i—Ca1—O2—Ca1i28.35 (6)C20—C17—C21—O99.5 (2)
O9—Ca1—O2—Ca1i112.02 (5)O10—C21—O9—Ca1157.4 (3)
O12—Ca1—O2—Ca1i151.61 (5)C17—C21—O9—Ca121.1 (5)
O1—Ca1—O2—Ca1i175.59 (7)O10—C21—O9—Ca211.86 (16)
O8ii—Ca1—O2—Ca1i22.44 (8)C17—C21—O9—Ca2166.64 (14)
O7ii—Ca1—O2—Ca1i67.32 (11)O11—Ca1—O9—C2194.7 (4)
C4—C3—C8—O43.2 (2)O2i—Ca1—O9—C2126.1 (4)
C2—C3—C8—O4175.19 (16)O12—Ca1—O9—C21174.4 (4)
C4—C3—C8—O3178.59 (16)O1—Ca1—O9—C2191.4 (4)
C2—C3—C8—O33.0 (2)O8ii—Ca1—O9—C21100.8 (4)
O4—C8—O3—Ca2i162.8 (3)O7ii—Ca1—O9—C21119.0 (4)
C3—C8—O3—Ca2i19.0 (5)O2—Ca1—O9—C2142.7 (4)
O4—C8—O3—Ca3iv9.36 (18)O11—Ca1—O9—Ca2120.91 (12)
C3—C8—O3—Ca3iv168.84 (13)O2i—Ca1—O9—Ca2118.25 (5)
O3—C8—O4—Ca3iv8.56 (17)O12—Ca1—O9—Ca241.24 (5)
C3—C8—O4—Ca3iv169.65 (14)O1—Ca1—O9—Ca2124.17 (5)
C14—C9—C10—C110.3 (3)O8ii—Ca1—O9—Ca243.59 (6)
C15—C9—C10—C11179.24 (15)O7ii—Ca1—O9—Ca225.43 (4)
C9—C10—C11—C121.9 (3)O2—Ca1—O9—Ca2172.87 (4)
C9—C10—C11—C16178.21 (15)O3i—Ca2—O9—C2165.30 (10)
C10—C11—C12—C131.5 (3)O13—Ca2—O9—C2191.07 (10)
C16—C11—C12—C13178.64 (15)O7ii—Ca2—O9—C21143.37 (10)
C11—C12—C13—C140.6 (3)O15—Ca2—O9—C2110.20 (12)
C12—C13—C14—C92.2 (3)O6—Ca2—O9—C21129.91 (13)
C10—C9—C14—C131.8 (3)O10—Ca2—O9—C216.53 (9)
C15—C9—C14—C13178.67 (16)O5—Ca2—O9—C21162.74 (9)
C14—C9—C15—O56.3 (3)O3i—Ca2—O9—Ca1105.33 (5)
C10—C9—C15—O5173.22 (16)O13—Ca2—O9—Ca198.30 (5)
C14—C9—C15—O6175.44 (16)O7ii—Ca2—O9—Ca127.26 (4)
C10—C9—C15—O65.0 (2)O15—Ca2—O9—Ca1179.17 (6)
O6—C15—O5—Ca27.70 (16)O6—Ca2—O9—Ca140.72 (14)
C9—C15—O5—Ca2170.48 (14)O10—Ca2—O9—Ca1177.16 (7)
O3i—Ca2—O5—C1531.19 (11)O5—Ca2—O9—Ca126.63 (6)
O13—Ca2—O5—C15131.81 (10)O9—C21—O10—Ca212.44 (17)
O7ii—Ca2—O5—C1599.78 (10)C17—C21—O10—Ca2166.09 (12)
O15—Ca2—O5—C1549.78 (11)O3i—Ca2—O10—C21100.08 (10)
O6—Ca2—O5—C154.27 (9)O13—Ca2—O10—C2195.80 (10)
O10—Ca2—O5—C15140.76 (13)O7ii—Ca2—O10—C2125.17 (11)
O9—Ca2—O5—C15152.59 (9)O15—Ca2—O10—C21176.44 (11)
O5—C15—O6—Ca3178.5 (4)O6—Ca2—O10—C21152.01 (9)
C9—C15—O6—Ca33.3 (6)O5—Ca2—O10—C2186.99 (15)
O5—C15—O6—Ca28.02 (17)O9—Ca2—O10—C216.56 (9)
Symmetry codes: (i) x, y, z+1/2; (ii) x+1, y, z+1/2; (iii) x+1, y, z; (iv) x1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H11A···O16iv0.82 (2)1.96 (2)2.7670 (18)169 (2)
O11—H11B···O19v0.82 (2)1.96 (2)2.7656 (19)167 (2)
O12—H12A···O1vi0.82 (2)2.05 (2)2.8535 (18)169 (2)
O12—H12B···O50.82 (2)2.20 (2)2.9836 (18)162 (2)
O13—H13A···O19vii0.82 (2)1.90 (2)2.7110 (19)172 (2)
O13—H13B···O16viii0.82 (2)1.99 (2)2.786 (2)164 (2)
O14—H14B···O18ix0.82 (2)1.81 (2)2.606 (3)164 (3)
O15—H15B···O17iii0.82 (2)2.06 (2)2.818 (3)155 (2)
O16—H16A···O5viii0.82 (2)1.98 (2)2.7185 (18)150 (2)
O16—H16B···O80.82 (2)1.91 (2)2.7278 (18)174 (2)
O17—H17A···O40.82 (2)2.00 (2)2.808 (2)167 (3)
O17—H17B···O10vii0.82 (2)2.02 (2)2.839 (2)177 (3)
O18—H18A···O80.82 (2)2.07 (2)2.876 (2)168 (3)
O18—H18B···O10v0.82 (2)2.12 (2)2.890 (2)158 (3)
O19—H19A···O40.82 (2)2.00 (2)2.7747 (18)159 (2)
O19—H19B···O1vii0.82 (2)2.00 (2)2.7639 (18)156 (2)
Symmetry codes: (iii) x+1, y, z; (iv) x1, y, z; (v) x+1/2, y+1/2, z; (vi) x, y+1, z; (vii) x1/2, y+1/2, z; (viii) x+1, y+1, z; (ix) x+3/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Ca5(C8H4O4)5(H2O)9]·8H2O
Mr1327.24
Crystal system, space groupMonoclinic, C2/c
Temperature (K)150
a, b, c (Å)15.6289 (8), 21.2640 (11), 17.1852 (9)
β (°) 112.134 (2)
V3)5290.3 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.62
Crystal size (mm)0.38 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2001)
Tmin, Tmax0.836, 0.941
No. of measured, independent and
observed [I > 2σ(I)] reflections
23336, 6434, 5100
Rint0.027
(sin θ/λ)max1)0.681
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.083, 1.08
No. of reflections6434
No. of parameters428
No. of restraints169
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.46, 0.33

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2000), SHELXTL and local programs.

Selected bond lengths (Å) top
Ca1—O112.3568 (13)Ca2—O152.4457 (16)
Ca1—O2i2.3652 (12)Ca2—O62.4555 (12)
Ca1—O92.3772 (12)Ca2—O102.4575 (13)
Ca1—O122.4078 (13)Ca2—O52.5473 (13)
Ca1—O12.5238 (12)Ca2—O92.5682 (12)
Ca1—O8ii2.5377 (12)Ca3—O142.376 (3)
Ca1—O7ii2.5600 (12)Ca3—O62.4138 (13)
Ca1—O22.6610 (12)Ca3—O3i2.5733 (12)
Ca2—O3i2.3252 (12)Ca3—O152.5800 (16)
Ca2—O132.3824 (13)Ca3—O4i2.7746 (13)
Ca2—O7ii2.4089 (12)
Symmetry codes: (i) x, y, z+1/2; (ii) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H11A···O16iii0.82 (2)1.96 (2)2.7670 (18)169 (2)
O11—H11B···O19iv0.82 (2)1.96 (2)2.7656 (19)167 (2)
O12—H12A···O1v0.82 (2)2.05 (2)2.8535 (18)169 (2)
O12—H12B···O50.82 (2)2.20 (2)2.9836 (18)162 (2)
O13—H13A···O19vi0.82 (2)1.90 (2)2.7110 (19)172 (2)
O13—H13B···O16vii0.82 (2)1.99 (2)2.786 (2)164 (2)
O14—H14B···O18viii0.82 (2)1.81 (2)2.606 (3)164 (3)
O15—H15B···O17ix0.82 (2)2.06 (2)2.818 (3)155 (2)
O16—H16A···O5vii0.82 (2)1.98 (2)2.7185 (18)150 (2)
O16—H16B···O80.82 (2)1.91 (2)2.7278 (18)174 (2)
O17—H17A···O40.82 (2)2.00 (2)2.808 (2)167 (3)
O17—H17B···O10vi0.82 (2)2.02 (2)2.839 (2)177 (3)
O18—H18A···O80.82 (2)2.07 (2)2.876 (2)168 (3)
O18—H18B···O10iv0.82 (2)2.12 (2)2.890 (2)158 (3)
O19—H19A···O40.82 (2)2.00 (2)2.7747 (18)159 (2)
O19—H19B···O1vi0.82 (2)2.00 (2)2.7639 (18)156 (2)
Symmetry codes: (iii) x1, y, z; (iv) x+1/2, y+1/2, z; (v) x, y+1, z; (vi) x1/2, y+1/2, z; (vii) x+1, y+1, z; (viii) x+3/2, y1/2, z+1/2; (ix) x+1, y, z.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds