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

Hu, X.

doi:10.1107/S1600536810036913

metal-organic compounds

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doi:10.1107/S1600536810036913

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

Xiaoqin Hu ^a ^*

^aDepartment of Chemistry, North University of China, Taiyuan, Shanxi 030051, People's Republic of China
^*Correspondence e-mail: hxqyxt8888@163.com

(Received 24 July 2010; accepted 15 September 2010; online 25 September 2010)

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) Å³
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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036913/lh5099sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810036913/lh5099Isup2.hkl

checkCIF report

Comment top

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 top

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

Experimental top

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.

Computing details top

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 top

	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] top

Crystal data top

[Cu(C₁₂H₁₂O₄)(C₅H₅N)₂]·H₂O	F(000) = 956
M_r = 459.98	D_x = 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) Å³	0.15 × 0.10 × 0.08 mm
Z = 4

Data collection top

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

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0467P)² + 1.775P] where P = (F_o² + 2F_c²)/3
2594 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Cu(C₁₂H₁₂O₄)(C₅H₅N)₂]·H₂O	V = 2327.2 (3) Å³
M_r = 459.98	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 13.3280 (8) Å	µ = 0.97 mm⁻¹
b = 17.1434 (11) Å	T = 298 K
c = 10.7390 (7) Å	0.15 × 0.10 × 0.08 mm
β = 108.481 (1)°

Data collection top

Bruker SMART CCD diffractometer	2594 independent reflections
Absorption correction: multi-scan (SADBAS; Sheldrick, 1996)	2283 reflections with I > 2σ(I)
T_min = 0.868, T_max = 0.926	R_int = 0.017
6747 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.34 e Å⁻³
2594 reflections	Δρ_min = −0.31 e Å⁻³
142 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
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

Cu1—O2	1.9894 (11)	C11—H11	0.9300
Cu1—O2ⁱ	1.9894 (11)	C7—C8	1.380 (3)
Cu1—N1	1.9920 (15)	C7—H7	0.9300
Cu1—N1ⁱ	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—C5ⁱⁱ	1.401 (2)	C9—H9	0.9300
C3—C4	1.512 (2)	C10—H10	0.9300
C5—C3ⁱⁱ	1.401 (2)	C8—H8	0.9300
C5—C6	1.508 (3)	O01—H1A	0.92 (3)
C11—C10	1.374 (3)

O2—Cu1—O2ⁱ	180.00 (6)	N1—C7—C8	121.7 (2)
O2—Cu1—N1	90.64 (5)	N1—C7—H7	119.1
O2ⁱ—Cu1—N1	89.36 (5)	C8—C7—H7	119.1
O2—Cu1—N1ⁱ	89.36 (5)	C3—C4—H4A	109.5
O2ⁱ—Cu1—N1ⁱ	90.65 (5)	C3—C4—H4B	109.5
N1—Cu1—N1ⁱ	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—C5ⁱⁱ	118.98 (15)	C10—C9—H9	120.5
C2—C3—C4	120.19 (15)	C8—C9—H9	120.5
C5ⁱⁱ—C3—C4	120.80 (16)	C9—C10—C11	119.3 (2)
C2—C5—C3ⁱⁱ	118.64 (15)	C9—C10—H10	120.4
C2—C5—C6	120.10 (15)	C11—C10—H10	120.4
C3ⁱⁱ—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

O2ⁱ—Cu1—O2—C1	93.10 (11)	C1—C2—C3—C5ⁱⁱ	179.58 (16)
N1—Cu1—O2—C1	89.16 (11)	C5—C2—C3—C4	−178.05 (18)
N1ⁱ—Cu1—O2—C1	−90.84 (11)	C3—C2—C5—C3ⁱⁱ	−0.2 (3)
O2—Cu1—N1—C11	−129.39 (14)	C1—C2—C5—C3ⁱⁱ	−179.59 (16)
O2ⁱ—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)
O2ⁱ—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—C5ⁱⁱ	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) top

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)

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₁₂O₄)(C₅H₅N)₂]·H₂O
M_r	459.98
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	13.3280 (8), 17.1434 (11), 10.7390 (7)
β (°)	108.481 (1)
V (Å³)	2327.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.15 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADBAS; Sheldrick, 1996)
T_min, T_max	0.868, 0.926
No. of measured, independent and observed [I > 2σ(I)] reflections	6747, 2594, 2283
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.086, 1.06
No. of reflections	2594
No. of parameters	142
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.31

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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)

Acknowledgements

The author is grateful for funding support from the Natural Science Foundation of Shanxi Province (2007011033).

References

Bruker (2007). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chun, H., Dybtsev, D. N., Kim, H. & Kim, K. (2005). Chem. Eur. J. 11, 3521–3529. Web of Science CSD CrossRef PubMed CAS Google Scholar
Diniz, R., de Abreu, H. A., de Almeida, W. B., Sansiviero, M. T. C. & Fernandes, N. G. (2002). Eur. J. Inorg. Chem. pp. 1115–1123. CrossRef 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
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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