catena-Poly[[[di­pyridine­copper(II)]-μ-2,3,5,6-tetra­methyl­benzene-1,4-di­carboxyl­ato] monohydrate]

In the title complex, {[Cu(C₁₂H₁₂O₄)(C₅H₅N)₂]·H₂O}_n, the Cu^II ion lies on an inversion center and is coordinated by two O atoms from two 2,3,5,6-tetra­methyl­benzene-1,4-dicarboxyl­ate (TBDC) ligands and two N atoms from two pyridine ligands in a slightly distorted square-planar environment. The TBDC ligands act as bridging ligands, forming chains along [110]. These chains are further linked into a two-dimensional network via inter­molecular O—H⋯O hydrogen bonds. The solvent water mol­ecule lies on a twofold rotation axis.

Related literature

For related structures, see: Chun et al. (2005); Diniz et al. (2002).

Experimental

Crystal data

• [Cu(C₁₂H₁₂O₄)(C₅H₅N)₂]·H₂O

• M_r = 459.98

• Monoclinic, C 2/c

• a = 13.3280 (8) Å

• b = 17.1434 (11) Å

• c = 10.7390 (7) Å

• β = 108.481 (1)°

• V = 2327.2 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.97 mm⁻¹

• T = 298 K

• 0.15 × 0.10 × 0.08 mm

Data collection

• Bruker SMART CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T_min = 0.868, T_max = 0.926

• 6747 measured reflections

• 2594 independent reflections

• 2283 reflections with I > 2σ(I)

• R_int = 0.017

Refinement

• R[F² > 2σ(F²)] = 0.029

• wR(F²) = 0.086

• S = 1.06

• 2594 reflections

• 142 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.34 e Å⁻³

• Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O01—H1A⋯O1	0.92 (3)	1.93 (3)	2.854 (2)	173 (3)

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL.

Supporting information

S1. Comment

The title compound (I), was designed as a ligand for preparing MOF materials and its single-crystal is presented herein. Some crystal structures containing TBDC and 1,2,4,5-benzenetetracarboxylate as ligands have already appeared in the literature (Chun et al., 2005; Diniz et al., 2002). The asymmetric unit (labeled in Fig. 1) contains one half copper ion, one pyridine ligand, one half solvent water molecule and half of a TBDC ligand (Fig 1.). The Cu^II ion lies on an inversion center and is coordinated by two oxygen atoms from two TBDC ligands and two nitrogen atoms from two pyridine ligands in a slightly distorted square-planar environment. The TBDC ligands act as bridiging to form one-dimensional chains along [110] (Fig 2.). These chains are further linked into a two-dimensional network via intermolecular O-H···O hydrogen bonds (Fig. 3).

Related literature

For related structures, see: Chun et al. (2005); Diniz et al. (2002).

S2. Experimental

A mixture of Cu(NO₃)₂(20 mg, 0.08 mmol),H₂TBDC (10 mg,0.05 mmol) and two drops of pyridine was suspended in 15 ml water and heated in a teflon-lined steel bomb at 100 centigrade degree for 3 days. The block blue crystals of the title compound were obtained, washed with water and dried in the air.

S3. Refinement

H atoms bonded to C atoms were placed in calculated positions with C-H = 0.93-0.96Šand included in the refinement with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl H atoms. The unique H atom of the water molecule was refined indpendently with an isotropic displacement parameter. Since our goal was to prepare a porous material the solvent accessible voids of 138.00ų present in the structure might be expected.

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. View of the coordination around the Cu^II ion in the title compound. Probabilty ellipsoids are drawn at the 50% level. Only the atoms of the asymmetric unit are labeled.
	Fig. 2. Part of the one-dimensional chain of the title compound.
	Fig. 3. Part of the crystal structure of the title compound with hydrogen bonds shown as dashed lines. Only H atoms involved in hydrogen bonds are showm.

catena-Poly[[[dipyridinecopper(II)]-µ-2,3,5,6-tetramethylbenzene- 1,4-dicarboxylato] monohydrate]

Crystal data

[Cu(C12H12O4)(C5H5N)2]·H2O	F(000) = 956
Mr = 459.98	Dx = 1.313 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3713 reflections
a = 13.3280 (8) Å	θ = 2.4–27.5°
b = 17.1434 (11) Å	µ = 0.97 mm^−1
c = 10.7390 (7) Å	T = 298 K
β = 108.481 (1)°	Block, blue
V = 2327.2 (3) Å^3	0.15 × 0.10 × 0.08 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	2594 independent reflections
Radiation source: fine-focus sealed tube	2283 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ϕ and ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADBAS; Sheldrick, 1996)	h = −17→10
Tmin = 0.868, Tmax = 0.926	k = −19→21
6747 measured reflections	l = −10→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0467P)^2 + 1.775P] where P = (Fo^2 + 2Fc^2)/3
2594 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.0000	0.0000	0.0000	0.02763 (11)
O2	0.07772 (9)	0.07930 (7)	−0.06903 (12)	0.0326 (3)
N1	−0.12716 (11)	0.06855 (8)	−0.04454 (14)	0.0313 (3)
O1	0.10913 (11)	0.10867 (8)	0.14011 (13)	0.0418 (3)
C1	0.12054 (13)	0.12134 (9)	0.03160 (17)	0.0294 (3)
C2	0.18792 (13)	0.18884 (9)	0.01433 (16)	0.0289 (3)
C3	0.13967 (13)	0.25988 (10)	−0.03235 (17)	0.0312 (4)
C5	0.29738 (13)	0.17762 (10)	0.04732 (17)	0.0315 (4)
C11	−0.17376 (16)	0.08364 (12)	0.0463 (2)	0.0416 (4)
H11	−0.1455	0.0619	0.1294	0.050*
C7	−0.16747 (16)	0.10076 (13)	−0.1635 (2)	0.0451 (5)
H7	−0.1352	0.0910	−0.2270	0.054*
C4	0.02162 (15)	0.26957 (12)	−0.0624 (2)	0.0474 (5)
H4A	−0.0085	0.2213	−0.0462	0.071*
H4B	−0.0097	0.2840	−0.1528	0.071*
H4C	0.0081	0.3096	−0.0073	0.071*
C6	0.34512 (16)	0.09915 (12)	0.0956 (3)	0.0512 (5)
H6A	0.2904	0.0640	0.1001	0.077*
H6B	0.3961	0.1048	0.1813	0.077*
H6C	0.3793	0.0788	0.0361	0.077*
C9	−0.3036 (2)	0.16249 (18)	−0.1002 (3)	0.0691 (7)
H9	−0.3636	0.1938	−0.1193	0.083*
C10	−0.2619 (2)	0.13013 (15)	0.0210 (3)	0.0598 (6)
H10	−0.2928	0.1394	0.0861	0.072*
C8	−0.2556 (2)	0.14817 (16)	−0.1942 (2)	0.0634 (7)
H8	−0.2823	0.1702	−0.2774	0.076*
O01	0.0000	0.21858 (15)	0.2500	0.0601 (6)
H1A	0.040 (2)	0.1861 (19)	0.216 (3)	0.094 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02676 (16)	0.02207 (16)	0.03625 (18)	−0.00754 (10)	0.01309 (12)	0.00071 (10)
O2	0.0348 (6)	0.0276 (6)	0.0381 (7)	−0.0120 (5)	0.0153 (5)	−0.0013 (5)
N1	0.0316 (7)	0.0265 (7)	0.0372 (8)	−0.0057 (6)	0.0128 (6)	−0.0004 (6)
O1	0.0521 (8)	0.0389 (7)	0.0396 (7)	−0.0136 (6)	0.0222 (6)	0.0006 (6)
C1	0.0286 (8)	0.0235 (8)	0.0385 (9)	−0.0048 (6)	0.0140 (7)	0.0024 (6)
C2	0.0308 (8)	0.0242 (8)	0.0332 (8)	−0.0089 (6)	0.0121 (6)	−0.0012 (6)
C3	0.0280 (8)	0.0278 (8)	0.0382 (9)	−0.0059 (6)	0.0113 (7)	0.0009 (7)
C5	0.0307 (8)	0.0245 (8)	0.0400 (9)	−0.0049 (6)	0.0120 (7)	0.0023 (7)
C11	0.0478 (11)	0.0397 (10)	0.0400 (10)	0.0014 (8)	0.0180 (8)	0.0000 (8)
C7	0.0462 (11)	0.0508 (12)	0.0397 (10)	0.0010 (9)	0.0154 (8)	0.0041 (9)
C4	0.0315 (9)	0.0413 (11)	0.0705 (14)	−0.0024 (8)	0.0178 (9)	0.0140 (10)
C6	0.0395 (10)	0.0303 (10)	0.0824 (16)	−0.0018 (8)	0.0175 (10)	0.0143 (10)
C9	0.0547 (14)	0.0729 (18)	0.0800 (18)	0.0285 (13)	0.0219 (13)	0.0116 (14)
C10	0.0622 (14)	0.0614 (15)	0.0669 (15)	0.0164 (12)	0.0364 (12)	0.0021 (12)
C8	0.0574 (14)	0.0753 (17)	0.0524 (13)	0.0182 (12)	0.0102 (11)	0.0181 (12)
O01	0.0687 (16)	0.0490 (14)	0.0683 (15)	0.000	0.0296 (13)	0.000

Geometric parameters (Å, º)

Cu1—O2	1.9894 (11)	C11—H11	0.9300
Cu1—O2^i	1.9894 (11)	C7—C8	1.380 (3)
Cu1—N1	1.9920 (15)	C7—H7	0.9300
Cu1—N1^i	1.9921 (15)	C4—H4A	0.9600
O2—C1	1.273 (2)	C4—H4B	0.9600
N1—C11	1.337 (2)	C4—H4C	0.9600
N1—C7	1.338 (3)	C6—H6A	0.9600
O1—C1	1.241 (2)	C6—H6B	0.9600
C1—C2	1.512 (2)	C6—H6C	0.9600
C2—C3	1.394 (2)	C9—C10	1.361 (4)
C2—C5	1.401 (2)	C9—C8	1.377 (4)
C3—C5^ii	1.401 (2)	C9—H9	0.9300
C3—C4	1.512 (2)	C10—H10	0.9300
C5—C3^ii	1.401 (2)	C8—H8	0.9300
C5—C6	1.508 (3)	O01—H1A	0.92 (3)
C11—C10	1.374 (3)
O2—Cu1—O2^i	180.00 (6)	N1—C7—C8	121.7 (2)
O2—Cu1—N1	90.64 (5)	N1—C7—H7	119.1
O2^i—Cu1—N1	89.36 (5)	C8—C7—H7	119.1
O2—Cu1—N1^i	89.36 (5)	C3—C4—H4A	109.5
O2^i—Cu1—N1^i	90.65 (5)	C3—C4—H4B	109.5
N1—Cu1—N1^i	180.0	H4A—C4—H4B	109.5
C1—O2—Cu1	102.52 (10)	C3—C4—H4C	109.5
C11—N1—C7	118.53 (17)	H4A—C4—H4C	109.5
C11—N1—Cu1	119.71 (13)	H4B—C4—H4C	109.5
C7—N1—Cu1	121.76 (13)	C5—C6—H6A	109.5
O1—C1—O2	122.84 (15)	C5—C6—H6B	109.5
O1—C1—C2	120.22 (15)	H6A—C6—H6B	109.5
O2—C1—C2	116.93 (14)	C5—C6—H6C	109.5
C3—C2—C5	122.37 (14)	H6A—C6—H6C	109.5
C3—C2—C1	119.25 (14)	H6B—C6—H6C	109.5
C5—C2—C1	118.37 (15)	C10—C9—C8	119.0 (2)
C2—C3—C5^ii	118.98 (15)	C10—C9—H9	120.5
C2—C3—C4	120.19 (15)	C8—C9—H9	120.5
C5^ii—C3—C4	120.80 (16)	C9—C10—C11	119.3 (2)
C2—C5—C3^ii	118.64 (15)	C9—C10—H10	120.4
C2—C5—C6	120.10 (15)	C11—C10—H10	120.4
C3^ii—C5—C6	121.25 (16)	C9—C8—C7	119.2 (2)
N1—C11—C10	122.3 (2)	C9—C8—H8	120.4
N1—C11—H11	118.9	C7—C8—H8	120.4
C10—C11—H11	118.9
O2^i—Cu1—O2—C1	93.10 (11)	C1—C2—C3—C5^ii	179.58 (16)
N1—Cu1—O2—C1	89.16 (11)	C5—C2—C3—C4	−178.05 (18)
N1^i—Cu1—O2—C1	−90.84 (11)	C3—C2—C5—C3^ii	−0.2 (3)
O2—Cu1—N1—C11	−129.39 (14)	C1—C2—C5—C3^ii	−179.59 (16)
O2^i—Cu1—N1—C11	50.61 (14)	C3—C2—C5—C6	−179.15 (18)
O2—Cu1—N1—C7	50.15 (15)	C1—C2—C5—C6	1.5 (3)
O2^i—Cu1—N1—C7	−129.85 (15)	C7—N1—C11—C10	0.8 (3)
Cu1—O2—C1—O1	−0.1 (2)	Cu1—N1—C11—C10	−179.66 (18)
Cu1—O2—C1—C2	179.68 (12)	C11—N1—C7—C8	−0.5 (3)
O1—C1—C2—C3	−94.9 (2)	Cu1—N1—C7—C8	179.92 (18)
O2—C1—C2—C3	85.3 (2)	C8—C9—C10—C11	−0.5 (4)
O1—C1—C2—C5	84.5 (2)	N1—C11—C10—C9	−0.3 (4)
O2—C1—C2—C5	−95.3 (2)	C10—C9—C8—C7	0.7 (4)
C5—C2—C3—C5^ii	0.2 (3)	N1—C7—C8—C9	−0.2 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O01—H1A···O1	0.92 (3)	1.93 (3)	2.854 (2)	173 (3)