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

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

doi:10.1107/S1600536808009379

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page m654

doi:10.1107/S1600536808009379

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

Wen-Dong Song,^a ^* Xiang-Hu Huang,^b Jian-Bin Yan ^a and De-Yun Ma ^c

^aCollege of Science, Guang Dong Ocean University, Zhanjiang 524088, People's Republic of China, ^bCollege of Fisheries, Guang Dong Ocean University, Zhan Jiang 524088, People's Republic of China, and ^cCollege of Chemistry, South China University of Technology, Guangzhou 510640, People's Republic of China
^*Correspondence e-mail: songwd60@126.com

(Received 18 February 2008; accepted 6 April 2008; online 10 April 2008)

In the title coordination polymer, {[Ca(C₈H₅Cl₂O₃)₂(H₂O)₂]·H₂O}_n, the Ca^II 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.

Related literature

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

Experimental

Crystal data

[Ca(C₈H₅Cl₂O₃)₂(H₂O)₂]·H₂O
M_r = 534.17
Monoclinic, P 2₁ /c
a = 17.8354 (7) Å
b = 6.8077 (3) Å
c = 18.5276 (8) Å
β = 101.297 (3)°
V = 2206.00 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 296 (2) K
0.30 × 0.26 × 0.23 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.790, T_max = 0.840
15522 measured reflections
5049 independent reflections
2962 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.158
S = 1.00
5049 reflections
289 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3W—H6W⋯O2ⁱ	0.848 (10)	2.176 (14)	3.013 (4)	169 (3)
O2W—H4W⋯O2ⁱⁱ	0.823 (10)	2.079 (16)	2.866 (3)	160 (4)
O2W—H3W⋯O1ⁱⁱⁱ	0.822 (10)	2.205 (18)	2.986 (4)	159 (4)
O1W—H1W⋯O3W^iv	0.823 (10)	1.927 (11)	2.745 (4)	173 (4)
O3W—H5W⋯O1	0.850 (10)	1.986 (12)	2.830 (4)	172 (5)
O1W—H2W⋯Cl4	0.818 (10)	2.88 (2)	3.530 (3)	138 (3)
O1W—H2W⋯O6	0.818 (10)	2.20 (2)	2.938 (3)	150 (4)
Symmetry codes: (i) x, y-1, z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808009379/zl2102sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808009379/zl2102Isup2.hkl

checkCIF report

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 Ca^II 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.

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

	Fig. 1. The structure of (I), showing the atomic numbering scheme. Non-H atoms are shown as 30% probability displacement ellipsoids.
	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]·H₂O	F(000) = 1088
M_r = 534.17	D_x = 1.608 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5837 reflections
a = 17.8354 (7) Å	θ = 2.8–27.9°
b = 6.8077 (3) Å	µ = 0.81 mm⁻¹
c = 18.5276 (8) Å	T = 296 K
β = 101.297 (3)°	Block, colorless
V = 2206.00 (16) Å³	0.30 × 0.26 × 0.23 mm
Z = 4

Data collection top

Bruker APEXII area-detector diffractometer	5049 independent reflections
Radiation source: fine-focus sealed tube	2962 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→23
T_min = 0.790, T_max = 0.840	k = −8→8
15522 measured reflections	l = −23→24

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0794P)²] where P = (F_o² + 2F_c²)/3
5049 reflections	(Δ/σ)_max < 0.001
289 parameters	Δρ_max = 0.55 e Å⁻³
9 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

[Ca(C₈H₅Cl₂O₃)₂(H₂O)₂]·H₂O	V = 2206.00 (16) Å³
M_r = 534.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.8354 (7) Å	µ = 0.81 mm⁻¹
b = 6.8077 (3) Å	T = 296 K
c = 18.5276 (8) Å	0.30 × 0.26 × 0.23 mm
β = 101.297 (3)°

Data collection top

Bruker APEXII area-detector diffractometer	5049 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2962 reflections with I > 2σ(I)
T_min = 0.790, T_max = 0.840	R_int = 0.047
15522 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	9 restraints
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.55 e Å⁻³
5049 reflections	Δρ_min = −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

	x	y	z	U_iso*/U_eq
C1	0.10806 (18)	0.6762 (5)	0.41264 (16)	0.0380 (7)
C2	0.18125 (18)	0.6618 (5)	0.46951 (19)	0.0450 (8)
H2A	0.1707	0.6023	0.5140	0.054*
H2B	0.2175	0.5790	0.4510	0.054*
C3	0.28244 (17)	0.8609 (6)	0.53280 (18)	0.0448 (9)
C4	0.3216 (2)	1.0370 (6)	0.5327 (2)	0.0570 (10)
C5	0.3898 (2)	1.0689 (7)	0.5798 (3)	0.0700 (13)
H5	0.4156	1.1874	0.5791	0.084*
C6	0.4196 (2)	0.9231 (7)	0.6281 (2)	0.0621 (11)
C7	0.3831 (2)	0.7454 (7)	0.6279 (2)	0.0622 (11)
H7	0.4046	0.6463	0.6600	0.075*
C8	0.31519 (19)	0.7145 (6)	0.5804 (2)	0.0555 (10)
H8	0.2908	0.5937	0.5801	0.067*
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	−0.2156	1.3243	0.2373	0.063*
C11	−0.3083 (2)	1.2475 (7)	0.1617 (2)	0.0632 (11)
H11	−0.3112	1.3622	0.1340	0.076*
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	−0.3919	0.8289	0.1668	0.077*
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	−0.1135	1.1485	0.4023	0.048*
H15B	−0.1637	1.3001	0.3502	0.048*
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)
Cl1	0.28379 (8)	1.21602 (17)	0.46954 (10)	0.1105 (6)
Cl2	0.50445 (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)
O1	0.07745 (13)	0.5164 (3)	0.39084 (12)	0.0501 (6)
O2	0.08134 (12)	0.8394 (3)	0.38986 (12)	0.0456 (6)
O3	0.21318 (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*
O3W	0.0390 (2)	0.1918 (4)	0.47185 (15)	0.0702 (8)
H5W	0.047 (3)	0.286 (3)	0.444 (2)	0.105*
H6W	0.049 (3)	0.084 (3)	0.453 (2)	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0464 (17)	0.033 (2)	0.0330 (15)	−0.0011 (16)	0.0041 (13)	0.0020 (17)
C2	0.0487 (18)	0.035 (2)	0.0459 (17)	0.0030 (16)	−0.0045 (14)	−0.0007 (18)
C3	0.0376 (16)	0.045 (2)	0.0480 (18)	0.0036 (16)	−0.0011 (14)	−0.0061 (18)
C4	0.051 (2)	0.038 (2)	0.075 (2)	0.0067 (18)	−0.0046 (18)	−0.008 (2)
C5	0.047 (2)	0.053 (3)	0.103 (3)	−0.003 (2)	−0.005 (2)	−0.016 (3)
C6	0.0421 (19)	0.069 (3)	0.068 (2)	0.007 (2)	−0.0073 (17)	−0.020 (3)
C7	0.056 (2)	0.070 (3)	0.055 (2)	0.013 (2)	−0.0043 (18)	0.003 (2)
C8	0.0472 (19)	0.059 (3)	0.056 (2)	−0.0014 (19)	−0.0016 (16)	0.005 (2)
C9	0.0363 (15)	0.039 (2)	0.0495 (18)	0.0025 (15)	0.0130 (14)	−0.0018 (18)
C10	0.0451 (18)	0.045 (2)	0.067 (2)	0.0010 (18)	0.0072 (17)	0.009 (2)
C11	0.051 (2)	0.067 (3)	0.070 (3)	0.010 (2)	0.0087 (19)	0.017 (2)
C12	0.044 (2)	0.083 (3)	0.067 (2)	0.002 (2)	0.0049 (18)	0.000 (3)
C13	0.050 (2)	0.075 (3)	0.066 (2)	−0.015 (2)	0.0083 (18)	−0.014 (3)
C14	0.0439 (18)	0.045 (2)	0.058 (2)	−0.0077 (17)	0.0157 (16)	−0.007 (2)
C15	0.0465 (17)	0.0297 (19)	0.0453 (17)	−0.0031 (15)	0.0128 (14)	−0.0073 (17)
C16	0.0321 (13)	0.0212 (17)	0.0317 (14)	−0.0017 (13)	0.0012 (11)	−0.0023 (15)
Ca1	0.0361 (3)	0.0204 (3)	0.0360 (3)	−0.0013 (3)	0.0055 (2)	−0.0010 (3)
Cl1	0.0981 (9)	0.0400 (7)	0.1650 (15)	−0.0089 (7)	−0.0439 (10)	0.0245 (8)
Cl2	0.0585 (6)	0.1143 (12)	0.1209 (11)	0.0061 (7)	−0.0348 (6)	−0.0308 (10)
Cl3	0.0697 (7)	0.1599 (15)	0.0775 (8)	0.0059 (8)	−0.0140 (6)	0.0030 (9)
Cl4	0.0734 (6)	0.0479 (7)	0.0945 (8)	−0.0211 (5)	0.0145 (6)	0.0040 (6)
O1	0.0637 (14)	0.0287 (14)	0.0493 (13)	−0.0065 (12)	−0.0102 (11)	−0.0002 (12)
O2	0.0485 (12)	0.0296 (14)	0.0523 (13)	−0.0008 (11)	−0.0060 (10)	0.0041 (12)
O3	0.0491 (13)	0.0330 (14)	0.0660 (15)	0.0001 (11)	−0.0159 (11)	0.0012 (13)
O4	0.0465 (11)	0.0192 (12)	0.0479 (12)	0.0012 (10)	0.0163 (10)	−0.0007 (11)
O5	0.0455 (11)	0.0198 (12)	0.0528 (13)	−0.0056 (10)	0.0143 (10)	−0.0036 (11)
O6	0.0399 (11)	0.0360 (14)	0.0535 (13)	−0.0074 (11)	0.0121 (10)	0.0018 (12)
O1W	0.0600 (15)	0.0416 (16)	0.0490 (13)	0.0065 (13)	0.0161 (11)	0.0002 (13)
O2W	0.0533 (13)	0.0359 (15)	0.0495 (13)	0.0035 (13)	−0.0031 (11)	−0.0039 (12)
O3W	0.109 (2)	0.0463 (18)	0.0554 (16)	−0.0093 (19)	0.0159 (15)	−0.0003 (15)

Geometric parameters (Å, º) top

C1—O1	1.248 (4)	C14—Cl4	1.732 (4)
C1—O2	1.250 (4)	C15—O6	1.424 (4)
C1—C2	1.512 (4)	C15—C16	1.520 (4)
C2—O3	1.417 (4)	C15—H15A	0.9700
C2—H2A	0.9700	C15—H15B	0.9700
C2—H2B	0.9700	C16—O5	1.246 (3)
C3—O3	1.367 (4)	C16—O4	1.251 (3)
C3—C8	1.382 (5)	C16—Ca1ⁱ	2.888 (3)
C3—C4	1.387 (5)	Ca1—O5ⁱⁱ	2.379 (2)
C4—C5	1.370 (5)	Ca1—O1W	2.397 (2)
C4—Cl1	1.732 (4)	Ca1—O2W	2.398 (2)
C5—C6	1.370 (6)	Ca1—O4	2.405 (2)
C5—H5	0.9300	Ca1—O1	2.485 (2)
C6—C7	1.373 (6)	Ca1—O4ⁱⁱⁱ	2.527 (2)
C6—Cl2	1.745 (4)	Ca1—O2	2.536 (2)
C7—C8	1.367 (5)	Ca1—O5ⁱⁱⁱ	2.550 (2)
C7—H7	0.9300	Ca1—C16ⁱⁱⁱ	2.888 (3)
C8—H8	0.9300	Ca1—Ca1ⁱⁱⁱ	4.0148 (6)
C9—O6	1.372 (4)	Ca1—Ca1ⁱ	4.0148 (6)
C9—C10	1.379 (5)	O4—Ca1ⁱ	2.527 (2)
C9—C14	1.392 (5)	O5—Ca1^iv	2.379 (2)
C10—C11	1.386 (5)	O5—Ca1ⁱ	2.550 (2)
C10—H10	0.9300	O1W—H2W	0.818 (10)
C11—C12	1.364 (6)	O1W—H1W	0.823 (10)
C11—H11	0.9300	O2W—H3W	0.822 (10)
C12—C13	1.379 (6)	O2W—H4W	0.823 (10)
C12—Cl3	1.739 (4)	O3W—H5W	0.850 (10)
C13—C14	1.379 (5)	O3W—H6W	0.848 (10)
C13—H13	0.9300

O1—C1—O2	123.5 (3)	O2W—Ca1—O1	152.75 (8)
O1—C1—C2	115.6 (3)	O4—Ca1—O1	131.10 (8)
O2—C1—C2	120.9 (3)	O5ⁱⁱ—Ca1—O4ⁱⁱⁱ	71.29 (7)
O3—C2—C1	110.2 (3)	O1W—Ca1—O4ⁱⁱⁱ	155.21 (8)
O3—C2—H2A	109.6	O2W—Ca1—O4ⁱⁱⁱ	86.63 (8)
C1—C2—H2A	109.6	O4—Ca1—O4ⁱⁱⁱ	120.50 (6)
O3—C2—H2B	109.6	O1—Ca1—O4ⁱⁱⁱ	76.53 (8)
C1—C2—H2B	109.6	O5ⁱⁱ—Ca1—O2	128.21 (8)
H2A—C2—H2B	108.1	O1W—Ca1—O2	88.91 (8)
O3—C3—C8	126.0 (3)	O2W—Ca1—O2	153.37 (8)
O3—C3—C4	115.7 (3)	O4—Ca1—O2	79.51 (7)
C8—C3—C4	118.3 (3)	O1—Ca1—O2	51.97 (7)
C5—C4—C3	121.4 (4)	O4ⁱⁱⁱ—Ca1—O2	97.10 (7)
C5—C4—Cl1	119.9 (3)	O5ⁱⁱ—Ca1—O5ⁱⁱⁱ	120.33 (6)
C3—C4—Cl1	118.7 (3)	O1W—Ca1—O5ⁱⁱⁱ	153.23 (8)
C4—C5—C6	118.9 (4)	O2W—Ca1—O5ⁱⁱⁱ	83.90 (8)
C4—C5—H5	120.6	O4—Ca1—O5ⁱⁱⁱ	70.50 (7)
C6—C5—H5	120.6	O1—Ca1—O5ⁱⁱⁱ	101.18 (8)
C5—C6—C7	120.9 (3)	O4ⁱⁱⁱ—Ca1—O5ⁱⁱⁱ	51.11 (7)
C5—C6—Cl2	119.0 (4)	O2—Ca1—O5ⁱⁱⁱ	78.24 (7)
C7—C6—Cl2	120.1 (3)	O5ⁱⁱ—Ca1—C16ⁱⁱⁱ	96.11 (8)
C8—C7—C6	119.8 (4)	O1W—Ca1—C16ⁱⁱⁱ	175.59 (8)
C8—C7—H7	120.1	O2W—Ca1—C16ⁱⁱⁱ	85.51 (8)
C6—C7—H7	120.1	O4—Ca1—C16ⁱⁱⁱ	95.63 (8)
C7—C8—C3	120.7 (4)	O1—Ca1—C16ⁱⁱⁱ	88.12 (8)
C7—C8—H8	119.7	O4ⁱⁱⁱ—Ca1—C16ⁱⁱⁱ	25.61 (7)
C3—C8—H8	119.7	O2—Ca1—C16ⁱⁱⁱ	86.73 (8)
O6—C9—C10	125.0 (3)	O5ⁱⁱⁱ—Ca1—C16ⁱⁱⁱ	25.52 (7)
O6—C9—C14	116.4 (3)	O5ⁱⁱ—Ca1—Ca1ⁱⁱⁱ	36.91 (5)
C10—C9—C14	118.6 (3)	O1W—Ca1—Ca1ⁱⁱⁱ	122.70 (6)
C9—C10—C11	120.6 (4)	O2W—Ca1—Ca1ⁱⁱⁱ	78.57 (6)
C9—C10—H10	119.7	O4—Ca1—Ca1ⁱⁱⁱ	145.47 (6)
C11—C10—H10	119.7	O1—Ca1—Ca1ⁱⁱⁱ	75.42 (6)
C12—C11—C10	119.6 (4)	O4ⁱⁱⁱ—Ca1—Ca1ⁱⁱⁱ	34.50 (5)
C12—C11—H11	120.2	O2—Ca1—Ca1ⁱⁱⁱ	118.48 (6)
C10—C11—H11	120.2	O5ⁱⁱⁱ—Ca1—Ca1ⁱⁱⁱ	84.01 (5)
C11—C12—C13	121.1 (4)	C16ⁱⁱⁱ—Ca1—Ca1ⁱⁱⁱ	59.25 (7)
C11—C12—Cl3	120.2 (4)	O5ⁱⁱ—Ca1—Ca1ⁱ	148.24 (6)
C13—C12—Cl3	118.7 (3)	O1W—Ca1—Ca1ⁱ	119.82 (6)
C14—C13—C12	119.0 (4)	O2W—Ca1—Ca1ⁱ	79.94 (6)
C14—C13—H13	120.5	O4—Ca1—Ca1ⁱ	36.54 (5)
C12—C13—H13	120.5	O1—Ca1—Ca1ⁱ	118.95 (6)
C13—C14—C9	121.0 (4)	O4ⁱⁱⁱ—Ca1—Ca1ⁱ	84.92 (5)
C13—C14—Cl4	119.4 (3)	O2—Ca1—Ca1ⁱ	74.18 (5)
C9—C14—Cl4	119.6 (3)	O5ⁱⁱⁱ—Ca1—Ca1ⁱ	34.07 (5)
O6—C15—C16	111.8 (2)	C16ⁱⁱⁱ—Ca1—Ca1ⁱ	59.49 (7)
O6—C15—H15A	109.3	Ca1ⁱⁱⁱ—Ca1—Ca1ⁱ	115.95 (3)
C16—C15—H15A	109.3	C1—O1—Ca1	93.37 (19)
O6—C15—H15B	109.3	C1—O2—Ca1	90.98 (19)
C16—C15—H15B	109.3	C3—O3—C2	117.1 (3)
H15A—C15—H15B	107.9	C16—O4—Ca1	150.93 (19)
O5—C16—O4	122.7 (3)	C16—O4—Ca1ⁱ	93.54 (17)
O5—C16—C15	118.6 (3)	Ca1—O4—Ca1ⁱ	108.96 (8)
O4—C16—C15	118.7 (3)	C16—O5—Ca1^iv	157.43 (19)
O5—C16—Ca1ⁱ	61.88 (15)	C16—O5—Ca1ⁱ	92.60 (17)
O4—C16—Ca1ⁱ	60.85 (14)	Ca1^iv—O5—Ca1ⁱ	109.02 (8)
C15—C16—Ca1ⁱ	177.18 (19)	C9—O6—C15	116.8 (3)
O5ⁱⁱ—Ca1—O1W	86.07 (8)	Ca1—O1W—H2W	112 (3)
O5ⁱⁱ—Ca1—O2W	78.00 (8)	Ca1—O1W—H1W	117 (3)
O1W—Ca1—O2W	98.71 (9)	H2W—O1W—H1W	103.9 (16)
O5ⁱⁱ—Ca1—O4	150.41 (8)	Ca1—O2W—H3W	114 (3)
O1W—Ca1—O4	84.21 (8)	Ca1—O2W—H4W	116 (3)
O2W—Ca1—O4	75.96 (8)	H3W—O2W—H4W	103.2 (16)
O5ⁱⁱ—Ca1—O1	76.38 (8)	H5W—O3W—H6W	109.8 (17)
O1W—Ca1—O1	88.67 (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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H6W···O2ⁱⁱ	0.85 (1)	2.18 (1)	3.013 (4)	169 (3)
O2W—H4W···O2ⁱⁱⁱ	0.82 (1)	2.08 (2)	2.866 (3)	160 (4)
O2W—H3W···O1ⁱ	0.82 (1)	2.21 (2)	2.986 (4)	159 (4)
O1W—H1W···O3W^v	0.82 (1)	1.93 (1)	2.745 (4)	173 (4)
O3W—H5W···O1	0.85 (1)	1.99 (1)	2.830 (4)	172 (5)
O1W—H2W···Cl4	0.82 (1)	2.88 (2)	3.530 (3)	138 (3)
O1W—H2W···O6	0.82 (1)	2.20 (2)	2.938 (3)	150 (4)

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

Experimental details

Crystal data
Chemical formula	[Ca(C₈H₅Cl₂O₃)₂(H₂O)₂]·H₂O
M_r	534.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	17.8354 (7), 6.8077 (3), 18.5276 (8)
β (°)	101.297 (3)
V (Å³)	2206.00 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.30 × 0.26 × 0.23

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.790, 0.840
No. of measured, independent and observed [I > 2σ(I)] reflections	15522, 5049, 2962
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.158, 1.00
No. of reflections	5049
No. of parameters	289
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.60

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H6W···O2ⁱ	0.848 (10)	2.176 (14)	3.013 (4)	169 (3)
O2W—H4W···O2ⁱⁱ	0.823 (10)	2.079 (16)	2.866 (3)	160 (4)
O2W—H3W···O1ⁱⁱⁱ	0.822 (10)	2.205 (18)	2.986 (4)	159 (4)
O1W—H1W···O3W^iv	0.823 (10)	1.927 (11)	2.745 (4)	173 (4)
O3W—H5W···O1	0.850 (10)	1.986 (12)	2.830 (4)	172 (5)
O1W—H2W···Cl4	0.818 (10)	2.88 (2)	3.530 (3)	138 (3)
O1W—H2W···O6	0.818 (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.

Acknowledgements

The authors acknowledge Guang Dong Ocean University for supporting this work.

References

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc, Madison, Wisconsin, USA. Google Scholar
Hao, X.-M., Gu, C.-S., Song, W.-D., Ma, D.-Y. & Liu, Z.-Y. (2006). Acta Cryst. E62, m2618–m2620. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, W.-D. & Xi, D.-L. (2006). Acta Cryst. E62, m2594–m2596. Web of Science CSD CrossRef IUCr Journals Google Scholar