catena-Poly[[diaqua­copper(II)]-μ-hy­drox­ido-κ2O:O-μ-[4-(4H-1,2,4-triazol-4-yl)benzoato]-κ2N1:N2]

Shi, H.; Gao, F.; Qi, J.

doi:10.1107/S1600536811032624

metal-organic compounds

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Volume 67| Part 9| September 2011| Pages m1255-m1256

doi:10.1107/S1600536811032624

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catena-Poly[[diaquacopper(II)]-μ-hydroxido-κ²O:O-μ-[4-(4H-1,2,4-triazol-4-yl)benzoato]-κ²N¹:N²]

Haochen Shi,^a,^b ^* Feng Gao ^b and Jingang Qi ^b

^aCollege of Physics, Jilin University, Changchun 130012, People's Republic of China, and ^bDepartment of Physics Education, Changchun Normal University, Changchun 130032, People's Republic of China
^*Correspondence e-mail: chemshihc@163.com

(Received 7 August 2011; accepted 11 August 2011; online 17 August 2011)

The title compound, [Cu(C₉H₆N₃O₂)(OH)(H₂O)₂]_n, adopts a chain motif along [010] in which the Cu^II atoms are bridged by hydroxy groups and 4-(1,2,4-triazol-4-yl)benzoate (tab) ligands. The Cu^II atom lies on an inversion center and is six-coordinated by two N atoms from two tab ligands, two hydroxy groups and two water molecules, giving a distorted octahedral geometry. The hydroxy group and the tab ligand are located on a mirror plane. One of the water H atoms is disordered over two positions with equal occupancy factors. Intermolecular O—H⋯O hydrogen bonds extend the chains into a layer parallel to (100) and C—H⋯O hydrogen bonds connect the layers into a three-dimensional network.

Related literature

For general background to the applications of coordination polymers, see: Aghabozorg et al. (2008 ); Liu et al. (2010 ); Wang et al. (2009 ); Zhang et al. (2004 ). For a related structure, see: Lin et al. (2011 ).

Experimental

Crystal data

[Cu(C₉H₆N₃O₂)(OH)(H₂O)₂]
M_r = 304.75
Monoclinic, P 2₁ /m
a = 6.787 (5) Å
b = 6.758 (5) Å
c = 12.036 (5) Å
β = 102.919 (5)°
V = 538.1 (6) Å³
Z = 2
Mo Kα radiation
μ = 2.05 mm⁻¹
T = 293 K
0.21 × 0.19 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.64, T_max = 0.75
3021 measured reflections
1165 independent reflections
1010 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.083
S = 1.12
1165 reflections
111 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H9⋯O2ⁱ	0.84 (3)	2.07 (3)	2.907 (4)	172 (3)
O4—H10A⋯O2ⁱⁱ	0.83 (3)	1.94 (3)	2.746 (3)	164 (3)
O4—H10⋯O4ⁱⁱⁱ	0.85 (6)	1.94 (6)	2.762 (4)	165 (6)
O4—H10′⋯O4^iv	0.85 (2)	1.93 (2)	2.759 (4)	165 (7)
C6—H6⋯O1^v	0.93	2.44	3.172 (5)	135
C8—H8⋯O1^vi	0.93	2.23	3.052 (4)	147
Symmetry codes: (i) x, y, z+1; (ii) $[-x, y-{\script{1\over 2}}, -z-1]$ ; (iii) -x-1, -y, -z; (iv) $[x, -y+{\script{1\over 2}}, z]$ ; (v) x-1, y, z; (vi) $[-x+1, y-{\script{1\over 2}}, -z-1]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: 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; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811032624/hy2457sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811032624/hy2457Isup2.hkl

checkCIF report

Comment top

Coordination polymers are currently of great interest due to structural versatility, unique properties and potential applications in catalysis, gas storage and in molecular-based magnetic materials (Liu et al., 2010; Zhang et al., 2004). Heterocyclic carboxylates have often been used as mono-, bi- or multidentate ligands to bind transition metal centers, leading to the formation of moderately robust metal–organic coordination frameworks (Aghabozorg et al., 2008; Wang et al., 2009). In this contribution, we selected 4-(1,2,4-triazol-4-yl)benzoic acid (Htab) as an organic carboxylate ligand, generating a coordination polymer, [Cu(C₉H₆N₃O₂)(H₂O)₂(OH)], which is reported here.

The title compound adopts a chain motif, in which the hydroxy groups and tab ligands as bridges to connect adjacent octahedrally coordinated Cu^II atoms (Fig. 1). The Cu^II atom lies on an inversion center and is six-coordinated by two N atoms from two tab ligands, two O atoms from hydroxy groups and two water molecules, giving a distorted octahedral geometry. The Cu—O and Cu—N bond lengths and the O—Cu—O, O—Cu—N and N—Cu—N bond angles are in the normal range (Lin et al., 2011). The hydroxy group and the tab ligand are located on a mirro plane. One of the water H atoms is disordered over two positions with equal occupancy factors. Intermolecular O—H···O hydrogen bonds extend the chains into a layer parallel to (1 0 0). C—H···O hydrogen bonds connect the layers into a three-dimensional network (Fig. 2).

Related literature top

For general background to the applications of coordination polymers, see: Aghabozorg et al. (2008); Liu et al. (2010); Wang et al. (2009); Zhang et al. (2004). For a related structure, see: Lin et al. (2011).

Experimental top

The synthesis was performed under hydrothermal conditions. A mixture of CuCl₂.2H₂O (0.2 mmol, 0.034 g), 4-(1,2,4-triazol-4-yl)benzoic acid (0.2 mmol, 0.038 g), NaOH (0.2 mmol, 0.008 g) and H₂O (15 ml) in a 25 ml stainless steel reactor with a Teflon liner was heated from 293 to 433 K and a constant temperature was maintained at 433 K for 96 h. After the mixture was cooled to 293 K, blue crystals of the title compound were obtained from the reaction.

Computing details top

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

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. One H atom of water molecule (O4) is disordered over two positions with equal occupancy factors. [Symmetry codes: (i) -x, -y, -z; (ii) x, 1/2 - y, z; (iii) -x, y - 1/2, -z; (iv) x, y - 1/2, z; (v) x, y + 1/2, z.]
	Fig. 2. View of the three-dimensional structure of the title compound, built by hydrogen bonds (dashed lines).

catena-Poly[[diaquacopper(II)]-µ-hydroxido-κ²O:O- µ-[4-(4H-1,2,4-triazol-4-yl)benzoato]- κ²N¹:N²] top

Crystal data top

[Cu(C₉H₆N₃O₂)(OH)(H₂O)₂]	F(000) = 310
M_r = 304.75	D_x = 1.881 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1165 reflections
a = 6.787 (5) Å	θ = 1.0–26.1°
b = 6.758 (5) Å	µ = 2.05 mm⁻¹
c = 12.036 (5) Å	T = 293 K
β = 102.919 (5)°	Block, blue
V = 538.1 (6) Å³	0.21 × 0.19 × 0.15 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1165 independent reflections
Radiation source: fine-focus sealed tube	1010 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 26.1°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→8
T_min = 0.64, T_max = 0.75	k = −7→8
3021 measured reflections	l = −14→12

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0403P)² + 0.5502P] where P = (F_o² + 2F_c²)/3
1165 reflections	(Δ/σ)_max < 0.001
111 parameters	Δρ_max = 0.45 e Å⁻³
4 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Cu(C₉H₆N₃O₂)(OH)(H₂O)₂]	V = 538.1 (6) Å³
M_r = 304.75	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 6.787 (5) Å	µ = 2.05 mm⁻¹
b = 6.758 (5) Å	T = 293 K
c = 12.036 (5) Å	0.21 × 0.19 × 0.15 mm
β = 102.919 (5)°

Data collection top

Bruker APEXII CCD diffractometer	1165 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1010 reflections with I > 2σ(I)
T_min = 0.64, T_max = 0.75	R_int = 0.022
3021 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	4 restraints
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.45 e Å⁻³
1165 reflections	Δρ_min = −0.37 e Å⁻³
111 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.2717 (6)	0.2500	−0.3753 (3)	0.0147 (7)
C2	0.4779 (6)	0.2500	−0.3610 (3)	0.0185 (8)
H2	0.5611	0.2500	−0.2882	0.022*
C3	0.5609 (6)	0.2500	−0.4564 (3)	0.0176 (8)
H3	0.7006	0.2500	−0.4473	0.021*
C4	0.4374 (5)	0.2500	−0.5653 (3)	0.0135 (7)
C5	0.2310 (6)	0.2500	−0.5770 (3)	0.0264 (10)
H5	0.1474	0.2500	−0.6496	0.032*
C6	0.1448 (6)	0.2500	−0.4827 (3)	0.0279 (10)
H6	0.0052	0.2500	−0.4915	0.033*
C7	0.5284 (6)	0.2500	−0.6686 (3)	0.0148 (7)
C8	0.1359 (4)	0.0900 (4)	−0.2195 (2)	0.0174 (6)
H8	0.1530	−0.0410	−0.2390	0.021*
N1	0.1836 (5)	0.2500	−0.2760 (2)	0.0151 (7)
N2	0.0624 (3)	0.1479 (3)	−0.13349 (17)	0.0150 (5)
O1	0.7151 (4)	0.2500	−0.6538 (2)	0.0184 (6)
O2	0.4060 (4)	0.2500	−0.7656 (2)	0.0260 (7)
Cu1	0.0000	0.0000	0.0000	0.01409 (17)
O3	0.0096 (4)	0.2500	0.0802 (2)	0.0145 (5)
O4	−0.3805 (3)	0.0459 (3)	−0.07541 (19)	0.0254 (5)
H9	0.118 (4)	0.2500	0.130 (3)	0.038*
H10A	−0.413 (5)	−0.040 (4)	−0.126 (2)	0.038*
H10	−0.471 (8)	0.017 (11)	−0.040 (6)	0.038*	0.50
H10'	−0.372 (10)	0.169 (2)	−0.086 (6)	0.038*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0200 (19)	0.0156 (18)	0.0121 (18)	0.000	0.0112 (15)	0.000
C2	0.0175 (19)	0.026 (2)	0.0116 (18)	0.000	0.0030 (15)	0.000
C3	0.0141 (18)	0.023 (2)	0.0166 (18)	0.000	0.0064 (15)	0.000
C4	0.0189 (18)	0.0116 (17)	0.0118 (18)	0.000	0.0071 (15)	0.000
C5	0.019 (2)	0.053 (3)	0.0076 (18)	0.000	0.0021 (15)	0.000
C6	0.0142 (19)	0.051 (3)	0.020 (2)	0.000	0.0059 (16)	0.000
C7	0.0224 (19)	0.0125 (18)	0.0121 (18)	0.000	0.0092 (15)	0.000
C8	0.0221 (13)	0.0154 (13)	0.0172 (13)	0.0008 (11)	0.0096 (11)	−0.0004 (11)
N1	0.0174 (16)	0.0186 (16)	0.0121 (15)	0.000	0.0090 (12)	0.000
N2	0.0193 (11)	0.0134 (11)	0.0140 (10)	0.0011 (9)	0.0073 (9)	0.0003 (9)
O1	0.0196 (14)	0.0210 (14)	0.0178 (14)	0.000	0.0110 (11)	0.000
O2	0.0230 (15)	0.0456 (19)	0.0098 (13)	0.000	0.0046 (11)	0.000
Cu1	0.0197 (3)	0.0131 (3)	0.0117 (2)	0.00017 (17)	0.00825 (18)	0.00091 (17)
O3	0.0205 (14)	0.0146 (13)	0.0095 (12)	0.000	0.0056 (10)	0.000
O4	0.0300 (11)	0.0221 (11)	0.0270 (11)	−0.0001 (10)	0.0124 (9)	−0.0014 (9)

Geometric parameters (Å, º) top

C1—C2	1.371 (5)	C7—O2	1.272 (4)
C1—C6	1.383 (5)	C8—N2	1.306 (3)
C1—N1	1.452 (4)	C8—N1	1.354 (3)
C2—C3	1.388 (5)	C8—H8	0.9300
C2—H2	0.9300	N2—N2ⁱ	1.381 (4)
C3—C4	1.389 (5)	Cu1—O3	1.9397 (16)
C3—H3	0.9300	Cu1—N2ⁱⁱ	2.016 (2)
C4—C5	1.376 (6)	Cu1—O4	2.558 (3)
C4—C7	1.508 (5)	O3—H9	0.839 (10)
C5—C6	1.388 (5)	O4—H10A	0.836 (10)
C5—H5	0.9300	O4—H10	0.846 (10)
C6—H6	0.9300	O4—H10'	0.844 (10)
C7—O1	1.239 (5)

C2—C1—C6	121.5 (3)	N2—C8—N1	109.6 (2)
C2—C1—N1	119.5 (3)	N2—C8—H8	125.2
C6—C1—N1	119.0 (3)	N1—C8—H8	125.2
C1—C2—C3	119.2 (3)	C8—N1—C8ⁱ	105.9 (3)
C1—C2—H2	120.4	C8—N1—C1	127.03 (15)
C3—C2—H2	120.4	C8ⁱ—N1—C1	127.03 (15)
C2—C3—C4	120.6 (3)	C8—N2—N2ⁱ	107.42 (16)
C2—C3—H3	119.7	C8—N2—Cu1	132.01 (19)
C4—C3—H3	119.7	N2ⁱ—N2—Cu1	119.72 (6)
C5—C4—C3	118.9 (3)	O3—Cu1—N2	88.58 (10)
C5—C4—C7	120.7 (3)	O3—Cu1—N2ⁱⁱ	91.42 (10)
C3—C4—C7	120.4 (3)	N2—Cu1—N2ⁱⁱ	180.00 (11)
C4—C5—C6	121.4 (4)	O3—Cu1—O4	89.42 (9)
C4—C5—H5	119.3	O3—Cu1—O4ⁱⁱ	90.58 (9)
C6—C5—H5	119.3	N2—Cu1—O4ⁱⁱ	88.14 (8)
C1—C6—C5	118.4 (4)	O4—Cu1—N2	91.86 (8)
C1—C6—H6	120.8	Cu1—O3—Cu1ⁱⁱⁱ	121.15 (13)
C5—C6—H6	120.8	Cu1—O3—H9	106.6 (15)
O1—C7—O2	124.7 (3)	H10A—O4—H10	96 (5)
O1—C7—C4	118.4 (3)	H10A—O4—H10'	126 (5)
O2—C7—C4	116.9 (3)	H10—O4—H10'	113 (7)

N2—C8—N1—C8ⁱ	0.2 (4)	N1—C8—N2—Cu1	−169.2 (2)
N2—C8—N1—C1	179.1 (3)	C8—N2—Cu1—O3ⁱⁱ	−20.5 (3)
C2—C1—N1—C8	−89.3 (3)	N2ⁱ—N2—Cu1—O3ⁱⁱ	171.53 (8)
C6—C1—N1—C8	90.7 (3)	C8—N2—Cu1—O3	159.5 (3)
C2—C1—N1—C8ⁱ	89.3 (3)	N2ⁱ—N2—Cu1—O3	−8.47 (8)
C6—C1—N1—C8ⁱ	−90.7 (3)	N2—Cu1—O3—Cu1ⁱⁱⁱ	15.10 (15)
N1—C8—N2—N2ⁱ	−0.2 (2)	N2ⁱⁱ—Cu1—O3—Cu1ⁱⁱⁱ	−164.90 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H9···O2^iv	0.84 (3)	2.07 (3)	2.907 (4)	172 (3)
O4—H10A···O2^v	0.83 (3)	1.94 (3)	2.746 (3)	164 (3)
O4—H10···O4^vi	0.85 (6)	1.94 (6)	2.762 (4)	165 (6)
O4—H10′···O4ⁱ	0.85 (2)	1.93 (2)	2.759 (4)	165 (7)
C6—H6···O1^vii	0.93	2.44	3.172 (5)	135
C8—H8···O1^viii	0.93	2.23	3.052 (4)	147

Symmetry codes: (i) x, −y+1/2, z; (iv) x, y, z+1; (v) −x, y−1/2, −z−1; (vi) −x−1, −y, −z; (vii) x−1, y, z; (viii) −x+1, y−1/2, −z−1.

Experimental details

Crystal data
Chemical formula	[Cu(C₉H₆N₃O₂)(OH)(H₂O)₂]
M_r	304.75
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	293
a, b, c (Å)	6.787 (5), 6.758 (5), 12.036 (5)
β (°)	102.919 (5)
V (Å³)	538.1 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.05
Crystal size (mm)	0.21 × 0.19 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.64, 0.75
No. of measured, independent and observed [I > 2σ(I)] reflections	3021, 1165, 1010
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.083, 1.12
No. of reflections	1165
No. of parameters	111
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.37

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H9···O2ⁱ	0.84 (3)	2.07 (3)	2.907 (4)	172 (3)
O4—H10A···O2ⁱⁱ	0.83 (3)	1.94 (3)	2.746 (3)	164 (3)
O4—H10···O4ⁱⁱⁱ	0.85 (6)	1.94 (6)	2.762 (4)	165 (6)
O4—H10'···O4^iv	0.85 (2)	1.93 (2)	2.759 (4)	165 (7)
C6—H6···O1^v	0.93	2.44	3.172 (5)	135
C8—H8···O1^vi	0.93	2.23	3.052 (4)	147

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

Acknowledgements

The authors thank Jilin University for supporting this work.

References

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