Poly[[(methanol)(μ(4)-2,4,5,6-tetra-fluoro-benzene-1,3-dicarboxyl-ato)copper(II)] methanol monosolvate].

In the title compound, {[Cu(C(8)F(4)O(4))(CH(3)OH)]·CH(3)OH}(n), two Cu(II) atoms are bridged by four carboxyl-ate groups, forming the well known paddle-wheel secondary building unit (SBU) with axial methanol ligands. In each ligand, the dihedral angles between the benzene ring and the two carboxyl-ate groups are 80.43 (17) and 62.5 (4)°. Within each SBU, the four carboxyl-ate groups come from four symmetry-equivalent tetra-fluoro-isophthalate ligands. Each tetra-fluoro-isophthalate group connects two SBUs, forming a layered structure . In the crystal, O-H⋯O hydrogen bonds involving the free and ligated methanol mol-ecules link the mol-ecules into a three-dimensional supra-molecular network.

Related literature

For background to coordination polymers, see: Kim et al. (2001 ▶); Kitagawa et al. (2004 ▶). For applications of coordination polymers, see: Wang et al. (2009 ▶); Dincă & Long (2008 ▶); Furukawa et al. (2008 ▶). For information on fluorinated coordination polymers, see: Yang et al. (2007 ▶); Hulvey et al. (2009 ▶).

Experimental

Crystal data

[Cu(C8F4O4)(CH4O)]·CH4O

M = 363.70

Monoclinic,

a = 8.6542 (7) Å

b = 12.1882 (10) Å

c = 12.4272 (10) Å

β = 98.390 (1)°

V = 1296.78 (18) Å3

Z = 4

Mo Kα radiation

μ = 1.76 mm−1

T = 200 K

0.34 × 0.22 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.621, T max = 0.715

8122 measured reflections

2575 independent reflections

2365 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.092

S = 1.07

2575 reflections

196 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.05 e Å−3

Δρmin = −0.40 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812020740/pk2400sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020740/pk2400Isup2.hkl

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

[Cu(C8F4O4)(CH4O)]·CH4O	F(000) = 724
Mr = 363.70	Dx = 1.863 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2575 reflections
a = 8.6542 (7) Å	θ = 2.4–26.1°
b = 12.1882 (10) Å	µ = 1.76 mm−1
c = 12.4272 (10) Å	T = 200 K
β = 98.390 (1)°	Block, green
V = 1296.78 (18) Å3	0.34 × 0.22 × 0.19 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	2575 independent reflections
Radiation source: fine-focus sealed tube	2365 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
Detector resolution: 9.00 pixels mm-1	θmax = 26.1°, θmin = 2.4°
φ and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→14
Tmin = 0.621, Tmax = 0.715	l = −13→15
8122 measured reflections

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0551P)2 + 1.2274P] where P = (Fo2 + 2Fc2)/3
2575 reflections	(Δ/σ)max = 0.001
196 parameters	Δρmax = 1.05 e Å−3
1 restraint	Δρmin = −0.40 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	0.86874 (3)	0.96498 (2)	0.53265 (2)	0.01964 (12)
C1	0.8110 (3)	1.2979 (2)	0.4412 (2)	0.0263 (5)
C2	0.7454 (3)	1.32560 (19)	0.33704 (19)	0.0244 (5)
C3	0.6682 (3)	1.4235 (2)	0.30967 (19)	0.0253 (5)
C4	0.6579 (4)	1.4958 (2)	0.3942 (2)	0.0364 (7)
C5	0.7222 (5)	1.4715 (2)	0.4996 (2)	0.0471 (9)
C6	0.7980 (4)	1.3732 (2)	0.5220 (2)	0.0412 (7)
C7	0.8867 (3)	1.18712 (19)	0.46554 (18)	0.0237 (5)
C8	0.6012 (3)	1.45109 (18)	0.1942 (2)	0.0239 (5)
C9	0.6040 (4)	0.8097 (3)	0.5897 (3)	0.0528 (9)
H9A	0.5000	0.8111	0.6079	0.079*
H9B	0.6736	0.7776	0.6485	0.079*
H9C	0.6053	0.7668	0.5250	0.079*
C10	0.0958 (4)	0.3426 (3)	0.2112 (3)	0.0545 (9)
H10A	0.2061	0.3549	0.2157	0.082*
H10B	0.0624	0.2914	0.1538	0.082*
H10C	0.0735	0.3132	0.2790	0.082*
F1	0.7529 (2)	1.25055 (12)	0.25928 (11)	0.0331 (4)
F2	0.5866 (3)	1.59239 (14)	0.37550 (13)	0.0523 (5)
F3	0.7098 (4)	1.54384 (16)	0.57961 (16)	0.0796 (9)
F4	0.8600 (3)	1.35034 (16)	0.62475 (14)	0.0636 (6)
O1	0.8026 (2)	1.11737 (14)	0.50171 (15)	0.0307 (4)
O2	1.0228 (2)	1.17630 (14)	0.44677 (15)	0.0313 (4)
O3	0.4671 (2)	1.48965 (17)	0.17844 (14)	0.0319 (4)
O4	0.6883 (2)	1.43243 (16)	0.12365 (13)	0.0285 (4)
O5	0.6524 (2)	0.91720 (17)	0.57154 (19)	0.0400 (5)
H5	0.601 (4)	0.960 (2)	0.606 (3)	0.057 (12)*
O6	0.0148 (3)	0.4435 (2)	0.1894 (2)	0.0569 (7)
H6	−0.0781	0.4313	0.1697	0.085*

	U11	U22	U33	U12	U13	U23
Cu1	0.02543 (18)	0.01590 (18)	0.01669 (18)	−0.00318 (10)	0.00001 (11)	0.00040 (10)
C1	0.0362 (13)	0.0189 (11)	0.0219 (12)	0.0017 (10)	−0.0022 (10)	0.0017 (9)
C2	0.0350 (13)	0.0201 (11)	0.0173 (11)	0.0010 (10)	0.0014 (9)	−0.0004 (9)
C3	0.0351 (13)	0.0206 (11)	0.0183 (11)	0.0019 (10)	−0.0023 (9)	0.0010 (9)
C4	0.0620 (19)	0.0204 (13)	0.0239 (13)	0.0141 (13)	−0.0028 (12)	0.0015 (10)
C5	0.088 (3)	0.0274 (15)	0.0208 (14)	0.0171 (14)	−0.0073 (15)	−0.0089 (10)
C6	0.073 (2)	0.0284 (14)	0.0171 (12)	0.0104 (14)	−0.0107 (12)	0.0024 (11)
C7	0.0353 (13)	0.0181 (11)	0.0155 (11)	0.0014 (9)	−0.0037 (9)	0.0005 (9)
C8	0.0335 (13)	0.0162 (11)	0.0200 (12)	0.0003 (9)	−0.0022 (10)	−0.0006 (9)
C9	0.0485 (19)	0.0407 (18)	0.070 (2)	−0.0086 (14)	0.0117 (17)	0.0131 (16)
C10	0.0519 (19)	0.061 (2)	0.049 (2)	−0.0095 (17)	0.0024 (15)	0.0140 (17)
F1	0.0550 (10)	0.0226 (7)	0.0197 (7)	0.0083 (6)	−0.0017 (6)	−0.0035 (6)
F2	0.0966 (15)	0.0268 (8)	0.0287 (9)	0.0282 (9)	−0.0068 (9)	−0.0013 (7)
F3	0.166 (3)	0.0405 (12)	0.0247 (10)	0.0440 (13)	−0.0131 (12)	−0.0126 (8)
F4	0.1242 (19)	0.0373 (10)	0.0196 (8)	0.0251 (11)	−0.0217 (9)	−0.0025 (7)
O1	0.0374 (10)	0.0191 (8)	0.0356 (10)	0.0020 (7)	0.0055 (8)	0.0043 (7)
O2	0.0369 (10)	0.0207 (8)	0.0359 (10)	0.0013 (7)	0.0046 (8)	0.0085 (7)
O3	0.0376 (10)	0.0376 (10)	0.0192 (9)	0.0111 (8)	0.0001 (7)	0.0032 (8)
O4	0.0319 (9)	0.0330 (9)	0.0190 (8)	0.0050 (8)	−0.0016 (7)	0.0054 (7)
O5	0.0375 (11)	0.0297 (10)	0.0566 (13)	−0.0091 (8)	0.0192 (10)	−0.0092 (9)
O6	0.0374 (12)	0.0643 (15)	0.0666 (17)	−0.0080 (11)	−0.0002 (11)	0.0208 (13)

Cu1—O2i	1.9600 (18)	C7—O2	1.241 (3)
Cu1—O1	1.9650 (18)	C7—O1	1.245 (3)
Cu1—O3ii	1.9656 (18)	C8—O3	1.240 (3)
Cu1—O4iii	1.9734 (17)	C8—O4	1.258 (3)
Cu1—O5	2.0834 (19)	C9—O5	1.404 (4)
Cu1—Cu1i	2.6622 (6)	C9—H9A	0.9600
C1—C6	1.377 (4)	C9—H9B	0.9600
C1—C2	1.378 (3)	C9—H9C	0.9600
C1—C7	1.512 (3)	C10—O6	1.422 (5)
C2—F1	1.339 (3)	C10—H10A	0.9600
C2—C3	1.385 (3)	C10—H10B	0.9600
C3—C4	1.384 (4)	C10—H10C	0.9600
C3—C8	1.505 (3)	O2—Cu1i	1.9600 (18)
C4—F2	1.334 (3)	O3—Cu1iv	1.9656 (18)
C4—C5	1.379 (4)	O4—Cu1v	1.9733 (17)
C5—F3	1.344 (3)	O5—H5	0.842 (10)
C5—C6	1.375 (4)	O6—H6	0.8200
C6—F4	1.340 (3)
O2i—Cu1—O1	167.50 (8)	F4—C6—C5	119.1 (3)
O2i—Cu1—O3ii	89.55 (8)	F4—C6—C1	119.5 (2)
O1—Cu1—O3ii	89.38 (8)	C5—C6—C1	121.4 (2)
O2i—Cu1—O4iii	89.89 (8)	O2—C7—O1	128.0 (2)
O1—Cu1—O4iii	88.48 (8)	O2—C7—C1	116.9 (2)
O3ii—Cu1—O4iii	167.51 (8)	O1—C7—C1	115.0 (2)
O2i—Cu1—O5	98.84 (8)	O3—C8—O4	126.9 (2)
O1—Cu1—O5	93.64 (8)	O3—C8—C3	117.2 (2)
O3ii—Cu1—O5	98.51 (8)	O4—C8—C3	115.9 (2)
O4iii—Cu1—O5	93.91 (8)	O5—C9—H9A	109.5
O2i—Cu1—Cu1i	84.70 (5)	O5—C9—H9B	109.5
O1—Cu1—Cu1i	82.79 (6)	H9A—C9—H9B	109.5
O3ii—Cu1—Cu1i	85.21 (6)	O5—C9—H9C	109.5
O4iii—Cu1—Cu1i	82.31 (5)	H9A—C9—H9C	109.5
O5—Cu1—Cu1i	174.85 (7)	H9B—C9—H9C	109.5
C6—C1—C2	117.1 (2)	O6—C10—H10A	109.5
C6—C1—C7	121.9 (2)	O6—C10—H10B	109.5
C2—C1—C7	120.9 (2)	H10A—C10—H10B	109.5
F1—C2—C1	117.0 (2)	O6—C10—H10C	109.5
F1—C2—C3	118.9 (2)	H10A—C10—H10C	109.5
C1—C2—C3	124.0 (2)	H10B—C10—H10C	109.5
C4—C3—C2	116.4 (2)	C7—O1—Cu1	123.16 (17)
C4—C3—C8	121.5 (2)	C7—O2—Cu1i	121.24 (15)
C2—C3—C8	122.1 (2)	C8—O3—Cu1iv	121.44 (17)
F2—C4—C5	117.8 (2)	C8—O4—Cu1v	124.10 (16)
F2—C4—C3	120.6 (2)	C9—O5—Cu1	126.70 (19)
C5—C4—C3	121.5 (2)	C9—O5—H5	108 (3)
F3—C5—C6	120.6 (3)	Cu1—O5—H5	120 (3)
F3—C5—C4	119.8 (3)	C10—O6—H6	109.5
C6—C5—C4	119.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O6vi	0.84 (1)	1.80 (1)	2.637 (3)	173 (4)
O6—H6···O4vii	0.82	2.02	2.828 (3)	169

Table 1

Selected bond lengths (Å)

Cu1—O2i	1.9600 (18)
Cu1—O1	1.9650 (18)
Cu1—O3ii	1.9656 (18)
Cu1—O4iii	1.9734 (17)
Cu1—O5	2.0834 (19)

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

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O6iv	0.84 (1)	1.80 (1)	2.637 (3)	173 (4)
O6—H6⋯O4v	0.82	2.02	2.828 (3)	169

Symmetry codes: (iv) ; (v) .