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Acta Cryst. (2008). E64, m654    [ doi:10.1107/S1600536808009379 ]

Poly[[diaquabis[[mu]-(2,4-dichlorophenoxy)acetato]calcium(II)] monohydrate]

W.-D. Song, X.-H. Huang, J.-B. Yan and D.-Y. Ma

Abstract top

In the title coordination polymer, {[Ca(C8H5Cl2O3)2(H2O)2]·H2O}n, the CaII atom is eight-coordinated by six O atoms from four different (2,4-dichlorophenoxy)acetate ligands and two water molecules, and displays a distorted square-antiprismatic coordination geometry. The compound forms an infinite zigzag chain through connection of the metal centers by (2,4-dichlorphenoxy)acetate ligands and hydrogen bonding of coordinated and interstitial water molecules. These chains are further hydrogen bonded with neighboring chains, forming a supramolecular network.

Comment top

In the structural investigation of 2,4-dichlorophenoxyacetate complexes, it has been found that the (2,4-dichlorphenoxy)acetate functions as a multidentate ligand [Song et al. (2006); Hao et al. (2006)], with versatile binding and coordination modes. In this paper, we report the crystal structure of the title compound, (I), a new Ca complex obtained by the reaction of (2,4-dichlorphenoxy)acetate and calcium chloride in an alkaline aqueous solution.

As illustrated in Figure 1, the CaII atom exists in a distorted square-antiprismatic environment, defined by six O atoms from four different 2,4-dichlorophenoxyacetate ligands and two water molecules. The 2,4-dichlorophenoxyacetate ligands link the calcium ions to form infinite zigzag like chains, which are further stabilized by hydrogen bonding of the coordinated and interstitial water molecules O2W and O3W to carboxylate oxygen atoms (Table 1, Fig. 2). O1W, via a hydrogen bond to the ether oxygen atom O6, also stabilizes the chains, but also forms another intermolecular hydrogen bond to a water molecule O3W that is part of a neighboring chain, thus forming a supramolecular network of H-bonded chains.

Related literature top

For related literature, see: Song et al. (2006); Hao et al. (2006).

Experimental top

A mixture of calcium chloride (1 mmol), 2,4-dichlorophenoxyacetate (1 mmol), NaOH (1.5 mmol) and H2O (12 ml) was placed in a 23 ml Teflon reactor, which was heated to 433 K for three days and then cooled to room temperature at a rate of 10 K h-1. The crystals obtained were washed with water and dryed in air.

Refinement top

Carbon-bound H atoms were placed in calculated positions and were treated as riding on the parent C atoms with C—H = 0.93–0.97 Å, and with Uiso(H) = 1.2 Ueq(C). Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.84 Å and H···H = 1.39 Å, each within a standard deviation of 0.01 Å, and with Uiso(H) = 1.5 Ueq(O)

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atomic numbering scheme. Non-H atoms are shown as 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. A packing view of (I).
Poly[[diaquabis[µ-(2,4-dichlorophenoxy)acetato]calcium(II)] monohydrate] top
Crystal data top
[Ca(C8H5Cl2O3)2(H2O)2]·H2OF000 = 1088
Mr = 534.17Dx = 1.608 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5837 reflections
a = 17.8354 (7) Åθ = 2.8–27.9º
b = 6.8077 (3) ŵ = 0.81 mm−1
c = 18.5276 (8) ÅT = 296 (2) K
β = 101.297 (3)ºBlock, colorless
V = 2206.00 (16) Å30.30 × 0.26 × 0.23 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer		5049 independent reflections
Radiation source: fine-focus sealed tube2962 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.047
T = 296(2) Kθmax = 27.5º
φ and ω scansθmin = 1.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −22→23
Tmin = 0.790, Tmax = 0.840k = −8→8
15522 measured reflectionsl = −23→24
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.158  w = 1/[σ2(Fo2) + (0.0794P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
5049 reflectionsΔρmax = 0.55 e Å−3
289 parametersΔρmin = −0.60 e Å−3
9 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ca(C8H5Cl2O3)2(H2O)2]·H2OV = 2206.00 (16) Å3
Mr = 534.17Z = 4
Monoclinic, P21/cMo Kα
a = 17.8354 (7) ŵ = 0.81 mm−1
b = 6.8077 (3) ÅT = 296 (2) K
c = 18.5276 (8) Å0.30 × 0.26 × 0.23 mm
β = 101.297 (3)º
Data collection top
Bruker APEXII area-detector
diffractometer		5049 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2962 reflections with I > 2σ(I)
Tmin = 0.790, Tmax = 0.840Rint = 0.047
15522 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0509 restraints
wR(F2) = 0.158H atoms treated by a mixture of
independent and constrained refinement
S = 1.00Δρmax = 0.55 e Å−3
5049 reflectionsΔρmin = −0.60 e Å−3
289 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*/Ueq
C10.10806 (18)0.6762 (5)0.41264 (16)0.0380 (7)
C20.18125 (18)0.6618 (5)0.46951 (19)0.0450 (8)
H2A0.17070.60230.51400.054*
H2B0.21750.57900.45100.054*
C30.28244 (17)0.8609 (6)0.53280 (18)0.0448 (9)
C40.3216 (2)1.0370 (6)0.5327 (2)0.0570 (10)
C50.3898 (2)1.0689 (7)0.5798 (3)0.0700 (13)
H50.41561.18740.57910.084*
C60.4196 (2)0.9231 (7)0.6281 (2)0.0621 (11)
C70.3831 (2)0.7454 (7)0.6279 (2)0.0622 (11)
H70.40460.64630.66000.075*
C80.31519 (19)0.7145 (6)0.5804 (2)0.0555 (10)
H80.29080.59370.58010.067*
C9−0.24793 (17)1.0577 (5)0.26633 (18)0.0408 (8)
C10−0.2516 (2)1.2253 (6)0.2240 (2)0.0529 (10)
H10−0.21561.32430.23730.063*
C11−0.3083 (2)1.2475 (7)0.1617 (2)0.0632 (11)
H11−0.31121.36220.13400.076*
C12−0.3600 (2)1.1003 (8)0.1412 (2)0.0655 (12)
C13−0.3568 (2)0.9291 (7)0.1815 (2)0.0638 (12)
H13−0.39190.82890.16680.077*
C14−0.30089 (18)0.9088 (6)0.2439 (2)0.0481 (9)
C15−0.13933 (18)1.1724 (5)0.35198 (17)0.0400 (8)
H15A−0.11351.14850.40230.048*
H15B−0.16371.30010.35020.048*
C16−0.08085 (15)1.1739 (5)0.30233 (15)0.0290 (6)
Ca1−0.02416 (3)0.67481 (9)0.29818 (3)0.03103 (18)
Cl10.28379 (8)1.21602 (17)0.46954 (10)0.1105 (6)
Cl20.50445 (6)0.9670 (2)0.69082 (8)0.1050 (5)
Cl3−0.43126 (7)1.1255 (3)0.06300 (7)0.1062 (5)
Cl4−0.29530 (6)0.69273 (16)0.29402 (7)0.0722 (3)
O10.07745 (13)0.5164 (3)0.39084 (12)0.0501 (6)
O20.08134 (12)0.8394 (3)0.38986 (12)0.0456 (6)
O30.21318 (13)0.8512 (4)0.48578 (14)0.0531 (7)
O4−0.06060 (11)1.0138 (3)0.27914 (11)0.0369 (5)
O5−0.05492 (12)1.3347 (3)0.28650 (12)0.0387 (5)
O6−0.19623 (11)1.0256 (3)0.33051 (12)0.0427 (6)
O1W−0.10329 (14)0.6837 (4)0.38884 (13)0.0494 (6)
H2W−0.1418 (13)0.750 (5)0.3754 (18)0.074*
H1W−0.0840 (18)0.731 (5)0.4291 (12)0.074*
O2W−0.12281 (14)0.6700 (4)0.18973 (12)0.0480 (6)
H3W−0.123 (2)0.766 (3)0.1629 (15)0.072*
H4W−0.122 (2)0.577 (3)0.1615 (14)0.072*
O3W0.0390 (2)0.1918 (4)0.47185 (15)0.0702 (8)
H5W0.047 (3)0.286 (3)0.444 (2)0.105*
H6W0.049 (3)0.084 (3)0.453 (2)0.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0464 (17)0.033 (2)0.0330 (15)−0.0011 (16)0.0041 (13)0.0020 (17)
C20.0487 (18)0.035 (2)0.0459 (17)0.0030 (16)−0.0045 (14)−0.0007 (18)
C30.0376 (16)0.045 (2)0.0480 (18)0.0036 (16)−0.0011 (14)−0.0061 (18)
C40.051 (2)0.038 (2)0.075 (2)0.0067 (18)−0.0046 (18)−0.008 (2)
C50.047 (2)0.053 (3)0.103 (3)−0.003 (2)−0.005 (2)−0.016 (3)
C60.0421 (19)0.069 (3)0.068 (2)0.007 (2)−0.0073 (17)−0.020 (3)
C70.056 (2)0.070 (3)0.055 (2)0.013 (2)−0.0043 (18)0.003 (2)
C80.0472 (19)0.059 (3)0.056 (2)−0.0014 (19)−0.0016 (16)0.005 (2)
C90.0363 (15)0.039 (2)0.0495 (18)0.0025 (15)0.0130 (14)−0.0018 (18)
C100.0451 (18)0.045 (2)0.067 (2)0.0010 (18)0.0072 (17)0.009 (2)
C110.051 (2)0.067 (3)0.070 (3)0.010 (2)0.0087 (19)0.017 (2)
C120.044 (2)0.083 (3)0.067 (2)0.002 (2)0.0049 (18)0.000 (3)
C130.050 (2)0.075 (3)0.066 (2)−0.015 (2)0.0083 (18)−0.014 (3)
C140.0439 (18)0.045 (2)0.058 (2)−0.0077 (17)0.0157 (16)−0.007 (2)
C150.0465 (17)0.0297 (19)0.0453 (17)−0.0031 (15)0.0128 (14)−0.0073 (17)
C160.0321 (13)0.0212 (17)0.0317 (14)−0.0017 (13)0.0012 (11)−0.0023 (15)
Ca10.0361 (3)0.0204 (3)0.0360 (3)−0.0013 (3)0.0055 (2)−0.0010 (3)
Cl10.0981 (9)0.0400 (7)0.1650 (15)−0.0089 (7)−0.0439 (10)0.0245 (8)
Cl20.0585 (6)0.1143 (12)0.1209 (11)0.0061 (7)−0.0348 (6)−0.0308 (10)
Cl30.0697 (7)0.1599 (15)0.0775 (8)0.0059 (8)−0.0140 (6)0.0030 (9)
Cl40.0734 (6)0.0479 (7)0.0945 (8)−0.0211 (5)0.0145 (6)0.0040 (6)
O10.0637 (14)0.0287 (14)0.0493 (13)−0.0065 (12)−0.0102 (11)−0.0002 (12)
O20.0485 (12)0.0296 (14)0.0523 (13)−0.0008 (11)−0.0060 (10)0.0041 (12)
O30.0491 (13)0.0330 (14)0.0660 (15)0.0001 (11)−0.0159 (11)0.0012 (13)
O40.0465 (11)0.0192 (12)0.0479 (12)0.0012 (10)0.0163 (10)−0.0007 (11)
O50.0455 (11)0.0198 (12)0.0528 (13)−0.0056 (10)0.0143 (10)−0.0036 (11)
O60.0399 (11)0.0360 (14)0.0535 (13)−0.0074 (11)0.0121 (10)0.0018 (12)
O1W0.0600 (15)0.0416 (16)0.0490 (13)0.0065 (13)0.0161 (11)0.0002 (13)
O2W0.0533 (13)0.0359 (15)0.0495 (13)0.0035 (13)−0.0031 (11)−0.0039 (12)
O3W0.109 (2)0.0463 (18)0.0554 (16)−0.0093 (19)0.0159 (15)−0.0003 (15)
Geometric parameters (Å, °) top
C1—O11.248 (4)C14—Cl41.732 (4)
C1—O21.250 (4)C15—O61.424 (4)
C1—C21.512 (4)C15—C161.520 (4)
C2—O31.417 (4)C15—H15A0.9700
C2—H2A0.9700C15—H15B0.9700
C2—H2B0.9700C16—O51.246 (3)
C3—O31.367 (4)C16—O41.251 (3)
C3—C81.382 (5)C16—Ca1i2.888 (3)
C3—C41.387 (5)Ca1—O5ii2.379 (2)
C4—C51.370 (5)Ca1—O1W2.397 (2)
C4—Cl11.732 (4)Ca1—O2W2.398 (2)
C5—C61.370 (6)Ca1—O42.405 (2)
C5—H50.9300Ca1—O12.485 (2)
C6—C71.373 (6)Ca1—O4iii2.527 (2)
C6—Cl21.745 (4)Ca1—O22.536 (2)
C7—C81.367 (5)Ca1—O5iii2.550 (2)
C7—H70.9300Ca1—C16iii2.888 (3)
C8—H80.9300Ca1—Ca1iii4.0148 (6)
C9—O61.372 (4)Ca1—Ca1i4.0148 (6)
C9—C101.379 (5)O4—Ca1i2.527 (2)
C9—C141.392 (5)O5—Ca1iv2.379 (2)
C10—C111.386 (5)O5—Ca1i2.550 (2)
C10—H100.9300O1W—H2W0.818 (10)
C11—C121.364 (6)O1W—H1W0.823 (10)
C11—H110.9300O2W—H3W0.822 (10)
C12—C131.379 (6)O2W—H4W0.823 (10)
C12—Cl31.739 (4)O3W—H5W0.850 (10)
C13—C141.379 (5)O3W—H6W0.848 (10)
C13—H130.9300
O1—C1—O2123.5 (3)O2W—Ca1—O1152.75 (8)
O1—C1—C2115.6 (3)O4—Ca1—O1131.10 (8)
O2—C1—C2120.9 (3)O5ii—Ca1—O4iii71.29 (7)
O3—C2—C1110.2 (3)O1W—Ca1—O4iii155.21 (8)
O3—C2—H2A109.6O2W—Ca1—O4iii86.63 (8)
C1—C2—H2A109.6O4—Ca1—O4iii120.50 (6)
O3—C2—H2B109.6O1—Ca1—O4iii76.53 (8)
C1—C2—H2B109.6O5ii—Ca1—O2128.21 (8)
H2A—C2—H2B108.1O1W—Ca1—O288.91 (8)
O3—C3—C8126.0 (3)O2W—Ca1—O2153.37 (8)
O3—C3—C4115.7 (3)O4—Ca1—O279.51 (7)
C8—C3—C4118.3 (3)O1—Ca1—O251.97 (7)
C5—C4—C3121.4 (4)O4iii—Ca1—O297.10 (7)
C5—C4—Cl1119.9 (3)O5ii—Ca1—O5iii120.33 (6)
C3—C4—Cl1118.7 (3)O1W—Ca1—O5iii153.23 (8)
C4—C5—C6118.9 (4)O2W—Ca1—O5iii83.90 (8)
C4—C5—H5120.6O4—Ca1—O5iii70.50 (7)
C6—C5—H5120.6O1—Ca1—O5iii101.18 (8)
C5—C6—C7120.9 (3)O4iii—Ca1—O5iii51.11 (7)
C5—C6—Cl2119.0 (4)O2—Ca1—O5iii78.24 (7)
C7—C6—Cl2120.1 (3)O5ii—Ca1—C16iii96.11 (8)
C8—C7—C6119.8 (4)O1W—Ca1—C16iii175.59 (8)
C8—C7—H7120.1O2W—Ca1—C16iii85.51 (8)
C6—C7—H7120.1O4—Ca1—C16iii95.63 (8)
C7—C8—C3120.7 (4)O1—Ca1—C16iii88.12 (8)
C7—C8—H8119.7O4iii—Ca1—C16iii25.61 (7)
C3—C8—H8119.7O2—Ca1—C16iii86.73 (8)
O6—C9—C10125.0 (3)O5iii—Ca1—C16iii25.52 (7)
O6—C9—C14116.4 (3)O5ii—Ca1—Ca1iii36.91 (5)
C10—C9—C14118.6 (3)O1W—Ca1—Ca1iii122.70 (6)
C9—C10—C11120.6 (4)O2W—Ca1—Ca1iii78.57 (6)
C9—C10—H10119.7O4—Ca1—Ca1iii145.47 (6)
C11—C10—H10119.7O1—Ca1—Ca1iii75.42 (6)
C12—C11—C10119.6 (4)O4iii—Ca1—Ca1iii34.50 (5)
C12—C11—H11120.2O2—Ca1—Ca1iii118.48 (6)
C10—C11—H11120.2O5iii—Ca1—Ca1iii84.01 (5)
C11—C12—C13121.1 (4)C16iii—Ca1—Ca1iii59.25 (7)
C11—C12—Cl3120.2 (4)O5ii—Ca1—Ca1i148.24 (6)
C13—C12—Cl3118.7 (3)O1W—Ca1—Ca1i119.82 (6)
C14—C13—C12119.0 (4)O2W—Ca1—Ca1i79.94 (6)
C14—C13—H13120.5O4—Ca1—Ca1i36.54 (5)
C12—C13—H13120.5O1—Ca1—Ca1i118.95 (6)
C13—C14—C9121.0 (4)O4iii—Ca1—Ca1i84.92 (5)
C13—C14—Cl4119.4 (3)O2—Ca1—Ca1i74.18 (5)
C9—C14—Cl4119.6 (3)O5iii—Ca1—Ca1i34.07 (5)
O6—C15—C16111.8 (2)C16iii—Ca1—Ca1i59.49 (7)
O6—C15—H15A109.3Ca1iii—Ca1—Ca1i115.95 (3)
C16—C15—H15A109.3C1—O1—Ca193.37 (19)
O6—C15—H15B109.3C1—O2—Ca190.98 (19)
C16—C15—H15B109.3C3—O3—C2117.1 (3)
H15A—C15—H15B107.9C16—O4—Ca1150.93 (19)
O5—C16—O4122.7 (3)C16—O4—Ca1i93.54 (17)
O5—C16—C15118.6 (3)Ca1—O4—Ca1i108.96 (8)
O4—C16—C15118.7 (3)C16—O5—Ca1iv157.43 (19)
O5—C16—Ca1i61.88 (15)C16—O5—Ca1i92.60 (17)
O4—C16—Ca1i60.85 (14)Ca1iv—O5—Ca1i109.02 (8)
C15—C16—Ca1i177.18 (19)C9—O6—C15116.8 (3)
O5ii—Ca1—O1W86.07 (8)Ca1—O1W—H2W112 (3)
O5ii—Ca1—O2W78.00 (8)Ca1—O1W—H1W117 (3)
O1W—Ca1—O2W98.71 (9)H2W—O1W—H1W103.9 (16)
O5ii—Ca1—O4150.41 (8)Ca1—O2W—H3W114 (3)
O1W—Ca1—O484.21 (8)Ca1—O2W—H4W116 (3)
O2W—Ca1—O475.96 (8)H3W—O2W—H4W103.2 (16)
O5ii—Ca1—O176.38 (8)H5W—O3W—H6W109.8 (17)
O1W—Ca1—O188.67 (8)
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, y−1, z; (iii) −x, y−1/2, −z+1/2; (iv) x, y+1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H6W···O2ii0.848 (10)2.176 (14)3.013 (4)169 (3)
O2W—H4W···O2iii0.823 (10)2.079 (16)2.866 (3)160 (4)
O2W—H3W···O1i0.822 (10)2.205 (18)2.986 (4)159 (4)
O1W—H1W···O3Wv0.823 (10)1.927 (11)2.745 (4)173 (4)
O3W—H5W···O10.850 (10)1.986 (12)2.830 (4)172 (5)
O1W—H2W···Cl40.818 (10)2.88 (2)3.530 (3)138 (3)
O1W—H2W···O60.818 (10)2.20 (2)2.938 (3)150 (4)
Symmetry codes: (ii) x, y−1, z; (iii) −x, y−1/2, −z+1/2; (i) −x, y+1/2, −z+1/2; (v) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H6W···O2i0.848 (10)2.176 (14)3.013 (4)169 (3)
O2W—H4W···O2ii0.823 (10)2.079 (16)2.866 (3)160 (4)
O2W—H3W···O1iii0.822 (10)2.205 (18)2.986 (4)159 (4)
O1W—H1W···O3Wiv0.823 (10)1.927 (11)2.745 (4)173 (4)
O3W—H5W···O10.850 (10)1.986 (12)2.830 (4)172 (5)
O1W—H2W···Cl40.818 (10)2.88 (2)3.530 (3)138 (3)
O1W—H2W···O60.818 (10)2.20 (2)2.938 (3)150 (4)
Symmetry codes: (i) x, y−1, z; (ii) −x, y−1/2, −z+1/2; (iii) −x, y+1/2, −z+1/2; (iv) −x, −y+1, −z+1.
references
References top

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc, Madison, Wisconsin, USA.

Hao, X.-M., Gu, C.-S., Song, W.-D., Ma, D.-Y. & Liu, Z.-Y. (2006). Acta Cryst. E62, m2618–m2620.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Song, W.-D. & Xi, D.-L. (2006). Acta Cryst. E62, m2594–m2596.