Poly[[diaqua-(μ(2)-1,4-dioxane-κO:O')(μ(2)-2,3,5,6-tetra-fluoro-benzene-1,4-dicarboxyl-ato-κO:O)copper(II)] 1,4-dioxane disolvate dihydrate].

In the title complex, {[Cu(C(8)F(4)O(4))(C(4)H(8)O(2))(H(2)O)(2)]·2C(4)H(8)O(2)·2H(2)O}(n), the Cu(II) ion is six-coordinated by two oxygen donors from two trans 2,3,5,6-tetra-fluoro-1,4-dicarboxyl-ate (BDC-F(4)) ligands, two O atoms from two chair 1,4-dioxane ligands and two O atoms from two terminal water mol-ecules, adopting a distorted octa-hedral coordinated geometry. Each BDC-F(4) anion bridges two Cu(II) ions in a bis-monodentate fashion, forming a [Cu(BDC-F(4))](n) chain. These chains are further linked by bridging 1,4-dioxane ligands, generating a two-dimensional net with approximately recta-ngular grids of 11.253 × 7.654 Å. Such adjacent parallel layers are connected by O-H⋯O hydrogen bonds between guest water mol-ecules and the uncoordinated carboxyl-ate O atoms and coordinated water mol-ecules into the final three-dimensional supra-molecular network.

Related literature

For the solvent template effect of 1,4-dioxane in the construction of coordination polymers, see: Chen et al. (2008 ▶); He et al. (2009 ▶).

Experimental

Crystal data

[Cu(C8F4O4)(C4H8O2)(H2O)2]·2C4H8O2·2H2O

M = 636.00

Monoclinic,

a = 7.654 (2) Å

b = 11.253 (3) Å

c = 16.126 (4) Å

β = 99.634 (6)°

V = 1369.4 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.89 mm−1

T = 297 K

0.20 × 0.15 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.842, T max = 0.901

7646 measured reflections

2536 independent reflections

2011 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.182

S = 1.07

2536 reflections

173 parameters

H-atom parameters constrained

Δρmax = 0.77 e Å−3

Δρmin = −0.47 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2 and SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 2005 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009755/jj2078sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009755/jj2078Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C8F4O4)(C4H8O2)(H2O)2]·2C4H8O2·2H2O	F(000) = 658
Mr = 636.00	Dx = 1.543 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3648 reflections
a = 7.654 (2) Å	θ = 2.6–29.9°
b = 11.253 (3) Å	µ = 0.89 mm−1
c = 16.126 (4) Å	T = 297 K
β = 99.634 (6)°	Block, blue
V = 1369.4 (6) Å3	0.20 × 0.15 × 0.12 mm
Z = 2

Bruker APEXII CCD diffractometer	2536 independent reflections
Radiation source: fine-focus sealed tube	2011 reflections with I > 2σ(I)
graphite	Rint = 0.030
φ and ω scans	θmax = 25.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→9
Tmin = 0.842, Tmax = 0.901	k = −11→13
7646 measured reflections	l = −19→19

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.182	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.1255P)2 + 0.7817P] where P = (Fo2 + 2Fc2)/3
2536 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.77 e Å−3
0 restraints	Δρmin = −0.47 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cu1	0.5000	0.0000	0.0000	0.0256 (3)
O1	0.4795 (5)	0.2295 (2)	−0.12878 (17)	0.0582 (9)
O2	0.4927 (3)	0.1749 (2)	0.00527 (13)	0.0332 (6)
O3	0.1848 (4)	−0.0053 (3)	0.0096 (3)	0.0592 (10)
O4	0.5645 (4)	0.00298 (18)	0.12299 (16)	0.0356 (6)
H4A	0.5557	−0.0669	0.1362	0.053*
H4B	0.5186	0.0562	0.1466	0.053*
O5	−0.0024 (8)	0.7388 (5)	0.2701 (5)	0.135 (2)
O6	0.2054 (7)	0.9379 (4)	0.3007 (4)	0.1177 (19)
O7	0.4024 (5)	0.1145 (4)	0.2350 (2)	0.0845 (13)
H7C	0.3248	0.0770	0.2530	0.127*
H7D	0.4640	0.1633	0.2643	0.127*
C1	0.4872 (4)	0.2499 (3)	−0.0530 (2)	0.0317 (8)
C2	0.4925 (4)	0.3790 (3)	−0.0259 (2)	0.0314 (7)
C3	0.3590 (5)	0.4308 (3)	0.0086 (3)	0.0442 (10)
C4	0.6337 (5)	0.4519 (4)	−0.0345 (3)	0.0431 (9)
C5	0.1002 (7)	0.0757 (7)	0.0515 (6)	0.111 (3)
H5A	0.1186	0.0516	0.1101	0.133*
H5B	0.1612	0.1508	0.0492	0.133*
C6	0.0753 (7)	−0.0976 (6)	−0.0285 (6)	0.101 (3)
H6A	0.1210	−0.1224	−0.0784	0.121*
H6B	0.0881	−0.1645	0.0099	0.121*
C7	0.1634 (10)	0.7455 (7)	0.2473 (5)	0.109 (2)*
H7A	0.1508	0.7722	0.1894	0.131*
H7B	0.2155	0.6667	0.2503	0.131*
C8	0.2799 (8)	0.8240 (5)	0.2992 (4)	0.0816 (16)
H8A	0.3044	0.7925	0.3560	0.098*
H8B	0.3912	0.8293	0.2782	0.098*
C9	0.0421 (9)	0.9318 (7)	0.3302 (6)	0.110 (3)
H9A	−0.0091	1.0105	0.3307	0.132*
H9B	0.0606	0.9009	0.3872	0.132*
C10	−0.0808 (8)	0.8519 (9)	0.2736 (5)	0.111 (3)
H10A	−0.1918	0.8443	0.2946	0.133*
H10B	−0.1058	0.8859	0.2176	0.133*
F1	0.2156 (4)	0.3659 (2)	0.0169 (3)	0.0886 (12)
F2	0.7708 (4)	0.4067 (2)	−0.0662 (2)	0.0849 (12)

	U11	U22	U33	U12	U13	U23
Cu1	0.0368 (4)	0.0138 (4)	0.0265 (4)	0.0004 (2)	0.0061 (2)	−0.00102 (18)
O1	0.118 (3)	0.0239 (14)	0.0345 (15)	0.0042 (15)	0.0166 (16)	0.0019 (11)
O2	0.0513 (15)	0.0138 (12)	0.0359 (13)	0.0002 (9)	0.0113 (11)	−0.0005 (9)
O3	0.0333 (14)	0.057 (2)	0.087 (3)	−0.0027 (12)	0.0096 (15)	−0.0362 (16)
O4	0.0545 (16)	0.0235 (14)	0.0279 (13)	0.0028 (10)	0.0050 (11)	−0.0025 (8)
O5	0.122 (5)	0.088 (4)	0.175 (6)	−0.026 (4)	−0.030 (4)	0.009 (4)
O6	0.107 (3)	0.071 (3)	0.193 (6)	−0.016 (3)	0.076 (4)	−0.010 (3)
O7	0.100 (3)	0.085 (3)	0.081 (2)	−0.040 (2)	0.052 (2)	−0.047 (2)
C1	0.0404 (18)	0.0200 (18)	0.0345 (19)	0.0026 (13)	0.0053 (14)	0.0001 (13)
C2	0.045 (2)	0.0178 (16)	0.0322 (17)	0.0039 (14)	0.0096 (14)	0.0022 (15)
C3	0.047 (2)	0.025 (2)	0.067 (3)	−0.0066 (15)	0.027 (2)	−0.0025 (17)
C4	0.049 (2)	0.0226 (19)	0.064 (3)	0.0014 (16)	0.0288 (19)	−0.0039 (18)
C5	0.048 (3)	0.108 (5)	0.175 (7)	−0.011 (3)	0.018 (4)	−0.102 (5)
C6	0.044 (3)	0.075 (4)	0.179 (7)	−0.001 (3)	0.006 (3)	−0.077 (4)
C8	0.080 (4)	0.080 (4)	0.085 (4)	0.009 (3)	0.016 (3)	−0.005 (3)
C9	0.093 (5)	0.090 (5)	0.159 (8)	0.012 (4)	0.053 (5)	−0.018 (5)
C10	0.061 (3)	0.154 (8)	0.112 (6)	0.011 (4)	−0.004 (3)	0.021 (6)
F1	0.0747 (18)	0.0350 (15)	0.175 (4)	−0.0207 (14)	0.075 (2)	−0.0258 (18)
F2	0.0752 (19)	0.0419 (15)	0.157 (3)	−0.0095 (13)	0.076 (2)	−0.0325 (17)

Cu1—O4	1.962 (3)	C3—F1	1.344 (4)
Cu1—O4i	1.962 (3)	C3—C4ii	1.382 (6)
Cu1—O2i	1.971 (3)	C4—F2	1.343 (4)
Cu1—O2	1.971 (3)	C4—C3ii	1.382 (6)
Cu1—O3	2.444 (3)	C5—C6iii	1.355 (8)
O1—C1	1.234 (4)	C5—H5A	0.9700
O2—C1	1.259 (4)	C5—H5B	0.9700
O3—C5	1.361 (6)	C6—C5iii	1.355 (8)
O3—C6	1.409 (6)	C6—H6A	0.9700
O4—H4A	0.8203	C6—H6B	0.9700
O4—H4B	0.8202	C7—C8	1.424 (9)
O5—C7	1.381 (9)	C7—H7A	0.9700
O5—C10	1.412 (9)	C7—H7B	0.9700
O6—C8	1.405 (7)	C8—H8A	0.9700
O6—C9	1.411 (8)	C8—H8B	0.9700
O7—H7C	0.8202	C9—C10	1.496 (11)
O7—H7D	0.8203	C9—H9A	0.9700
C1—C2	1.515 (5)	C9—H9B	0.9700
C2—C3	1.372 (5)	C10—H10A	0.9700
C2—C4	1.382 (5)	C10—H10B	0.9700
O4—Cu1—O4i	180.0	O3—C5—H5A	107.0
O4—Cu1—O2i	93.24 (8)	C6iii—C5—H5B	107.0
O4i—Cu1—O2i	86.76 (8)	O3—C5—H5B	107.0
O4—Cu1—O2	86.76 (8)	H5A—C5—H5B	106.8
O4i—Cu1—O2	93.24 (8)	C5iii—C6—O3	118.4 (5)
O2i—Cu1—O2	180.0	C5iii—C6—H6A	107.7
O4—Cu1—O3	91.16 (13)	O3—C6—H6A	107.7
O4i—Cu1—O3	88.85 (13)	C5iii—C6—H6B	107.7
O2i—Cu1—O3	90.79 (9)	O3—C6—H6B	107.7
O2—Cu1—O3	89.21 (9)	H6A—C6—H6B	107.1
C1—O2—Cu1	129.4 (2)	O5—C7—C8	112.9 (6)
C5—O3—C6	114.3 (4)	O5—C7—H7A	109.0
C5—O3—Cu1	124.9 (3)	C8—C7—H7A	109.0
C6—O3—Cu1	120.7 (3)	O5—C7—H7B	109.0
Cu1—O4—H4A	103.2	C8—C7—H7B	109.0
Cu1—O4—H4B	115.3	H7A—C7—H7B	107.8
H4A—O4—H4B	121.3	O6—C8—C7	111.1 (6)
C7—O5—C10	112.2 (6)	O6—C8—H8A	109.4
C8—O6—C9	110.2 (5)	C7—C8—H8A	109.4
H7C—O7—H7D	121.4	O6—C8—H8B	109.4
O1—C1—O2	127.2 (3)	C7—C8—H8B	109.4
O1—C1—C2	117.3 (3)	H8A—C8—H8B	108.0
O2—C1—C2	115.5 (3)	O6—C9—C10	109.0 (6)
C3—C2—C4	115.8 (3)	O6—C9—H9A	109.9
C3—C2—C1	122.6 (3)	C10—C9—H9A	109.9
C4—C2—C1	121.6 (3)	O6—C9—H9B	109.9
F1—C3—C2	119.0 (3)	C10—C9—H9B	109.9
F1—C3—C4ii	118.7 (3)	H9A—C9—H9B	108.3
C2—C3—C4ii	122.2 (3)	O5—C10—C9	109.7 (5)
F2—C4—C3ii	118.9 (3)	O5—C10—H10A	109.7
F2—C4—C2	119.1 (3)	C9—C10—H10A	109.7
C3ii—C4—C2	122.0 (3)	O5—C10—H10B	109.7
C6iii—C5—O3	121.3 (5)	C9—C10—H10B	109.7
C6iii—C5—H5A	107.0	H10A—C10—H10B	108.2
O4—Cu1—O2—C1	166.7 (3)	C1—C2—C3—F1	−1.6 (6)
O4i—Cu1—O2—C1	−13.3 (3)	C4—C2—C3—C4ii	−1.1 (7)
O3—Cu1—O2—C1	−102.1 (3)	C1—C2—C3—C4ii	178.9 (4)
O4—Cu1—O3—C5	55.5 (6)	C3—C2—C4—F2	178.8 (4)
O4i—Cu1—O3—C5	−124.5 (6)	C1—C2—C4—F2	−1.2 (6)
O2i—Cu1—O3—C5	148.8 (6)	C3—C2—C4—C3ii	1.1 (7)
O2—Cu1—O3—C5	−31.2 (6)	C1—C2—C4—C3ii	−178.9 (4)
O4—Cu1—O3—C6	−123.5 (5)	C6—O3—C5—C6iii	−27.8 (12)
O4i—Cu1—O3—C6	56.5 (5)	Cu1—O3—C5—C6iii	153.1 (6)
O2i—Cu1—O3—C6	−30.2 (5)	C5—O3—C6—C5iii	26.9 (12)
O2—Cu1—O3—C6	149.8 (5)	Cu1—O3—C6—C5iii	−154.0 (6)
Cu1—O2—C1—O1	2.5 (6)	C10—O5—C7—C8	54.0 (9)
Cu1—O2—C1—C2	−176.9 (2)	C9—O6—C8—C7	58.4 (8)
O1—C1—C2—C3	115.0 (4)	O5—C7—C8—O6	−55.3 (9)
O2—C1—C2—C3	−65.5 (5)	C8—O6—C9—C10	−59.1 (9)
O1—C1—C2—C4	−65.0 (5)	C7—O5—C10—C9	−54.3 (9)
O2—C1—C2—C4	114.5 (4)	O6—C9—C10—O5	57.0 (10)
C4—C2—C3—F1	178.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···O7	0.82	1.92	2.670 (5)	152
C5—H5B···F1	0.97	2.53	3.453 (8)	160
O4—H4A···O1i	0.82	1.85	2.641 (3)	162
O7—H7C···O6iv	0.82	2.03	2.807 (7)	158
O7—H7D···O1v	0.82	2.09	2.797 (5)	144

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4B⋯O7	0.82	1.92	2.670 (5)	152
O4—H4A⋯O1i	0.82	1.85	2.641 (3)	162
O7—H7C⋯O6ii	0.82	2.03	2.807 (7)	158
O7—H7D⋯O1iii	0.82	2.09	2.797 (5)	144

Symmetry codes: (i) ; (ii) ; (iii) .