catena-Poly[[[4,6-bis­(2-pyrid­yl)-1,3,5-triazin-2-olato]copper(II)]-μ-chlorido]

Cao, M.-L.

doi:10.1107/S1600536811016989

metal-organic compounds

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doi:10.1107/S1600536811016989

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catena-Poly[[[4,6-bis(2-pyridyl)-1,3,5-triazin-2-olato]copper(II)]-μ-chlorido]

Man-Li Cao ^a ^*

^aDepartment of Chemistry, Guangdong University of Education, Guangzhou 510303, People's Republic of China
^*Correspondence e-mail: caoml@mail3.sysu.edu.cn

(Received 12 March 2011; accepted 5 May 2011; online 11 May 2011)

The title compound, [Cu(C₁₃H₈N₅O)Cl]_n, has a chain structure parallel to [100] with Cu²⁺ cations in a trigonal–bipyramidal coordination environment. The ligand adopts a tridentate tripyridyl coordination mode and a chloride ion acts as a bridge. The chains are linked via weak C—H⋯O and C—H⋯Cl hydrogen bonds into a three-dimensional supramolecular network.

Related literature

For background to rigid multidentate polypyridyl ligands containing a triazine ring as a bridge, see: Zhou, Li, Zheng et al. (2006 ); Zhou, Li, Wu et al. (2006 ). For the synthesis of the ligand, see: Wieprecht et al. (2005 ). For complexes based on the ligand, see: Cao et al. (2008 , 2009 ).

Experimental

Crystal data

[Cu(C₁₃H₈N₅O)Cl]
M_r = 349.23
Monoclinic, P 2₁ /m
a = 3.7687 (13) Å
b = 13.698 (5) Å
c = 11.852 (4) Å
β = 92.851 (6)°
V = 611.1 (4) Å³
Z = 2
Mo Kα radiation
μ = 2.01 mm⁻¹
T = 293 K
0.09 × 0.09 × 0.07 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.840, T_max = 0.872
3063 measured reflections
1109 independent reflections
952 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.085
S = 1.03
1109 reflections
103 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O1ⁱ	0.96	2.37	3.145 (2)	138
C2—H2A⋯Cl1ⁱⁱ	0.96	2.89	3.836 (3)	170
Symmetry codes: (i) $[-x+2, y+{\script{3\over 2}}, -z]$ ; (ii) $[-x, y+{\script{3\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811016989/aa2005sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811016989/aa2005Isup2.hkl

checkCIF report

Comment top

The rigid multidentate polypyridyl ligands containing a triazine ring as a bridge have attracted greatly our attention due to their coordination diversity (Zhou, Li, Zheng et al., 2006; Zhou, Li, Wu et al. 2006). Although coordination chemistry of the symmetrical ligands like TPT has been well explored, the observations on the asymmetric ligands containing triazine ring are still rare. As a contribution to the synthesis and structural studies of coordination abilities of 4,6-bis(2-pyridyl)-1,3,5-triazin-2-ol ligand (Wieprecht et al., 2005; Cao et al., 2008, 2009), I present here the crystal structure of the title compound (Fig. 1)- a new copper(II) complex with the ligand. Within the title compound, the copper(II) center is five-coordinated respectively by three N atoms [the distances of Cu—N are in the range of 1.896 (2) - 2.049 (2) Å] from the ligand and two Cl atoms [the bond lengths of Cu—Cl are 2.224 (1) Å and 2.778 (2) Å]. The complex is a chain structure, in which the ligand adopts a tridentate tripyridyl coordination mode and the chloride ion acts as a bridge (Fig. 2). The chains are linked via weak hydrogen bondings of C—H···O and C—H···Cl into a three-dimensional supramolecular network.

Related literature top

For background to rigid multidentate polypyridyl ligands containing a triazine ring as a bridge, see: Zhou, Li, Zheng et al. (2006); Zhou, Li, Wu et al. (2006). For the synthesis of the ligand, see: Wieprecht et al. (2005). For complexes based on the ligand, see: Cao et al. (2008, and 2009).

Experimental top

The ligand 4,6-bis(2-pyridyl)-1,3,5-triazin-2-ol was prepared according to previously reported procedures (Wieprecht et al., 2005), yield 56%. The ligand (0.125 g, 0.5 mmol), CuCl₂(0.07 g, 0.5 mmol), 7 ml distilled water and 7 ml ethanol were put into a 25 ml Teflon-lined Parr. The mixture was heated to 100 °C for 48 h, and then cooled to room temperature at a rate of 5 °C/h. The obtained mixture was filtered and green crystals were obtained. Yield: 0.108 g, 62% (base on the ligand). Anal. Calcd. for C₁₃H₈ClCuN₅O (%): C 44.71, H 2.31, N 20.05; Found(%): C 44.52, H 2.43, N 19.91

Computing details top

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i): x, 0.5 - y, z; (ii): 1 + x, y, z].
	Fig. 2. The chain structure in the title compound, H atoms are omitted for clarity. [Symmetry codes: (i): x, 0.5 - y, z; (ii): 1 + x, y, z; (iii): 1 + x, 0.5 - y, z; (iv): 2 + x, y, z; (v): 2 + x, 0.5 - y, z; (vi): 3 + x, y, z].

catena-Poly[[4,6-bis(2-pyridyl)-1,3,5-triazin-2-olato]copper(II)]- µ-chlorido] top

Crystal data top

[Cu(C₁₃H₈N₅O)Cl]	F(000) = 350
M_r = 349.23	D_x = 1.898 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1109 reflections
a = 3.7687 (13) Å	θ = 2.3–25.0°
b = 13.698 (5) Å	µ = 2.01 mm⁻¹
c = 11.852 (4) Å	T = 293 K
β = 92.851 (6)°	Block, green
V = 611.1 (4) Å³	0.09 × 0.09 × 0.07 mm
Z = 2

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1109 independent reflections
Radiation source: fine-focus sealed tube	952 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→4
T_min = 0.840, T_max = 0.872	k = −16→16
3063 measured reflections	l = −14→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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0528P)²] where P = (F_o² + 2F_c²)/3
1109 reflections	(Δ/σ)_max < 0.001
103 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Cu(C₁₃H₈N₅O)Cl]	V = 611.1 (4) Å³
M_r = 349.23	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 3.7687 (13) Å	µ = 2.01 mm⁻¹
b = 13.698 (5) Å	T = 293 K
c = 11.852 (4) Å	0.09 × 0.09 × 0.07 mm
β = 92.851 (6)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1109 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	952 reflections with I > 2σ(I)
T_min = 0.840, T_max = 0.872	R_int = 0.030
3063 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.03	Δρ_max = 0.49 e Å⁻³
1109 reflections	Δρ_min = −0.27 e Å⁻³
103 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	0.39787 (13)	0.2500	0.32504 (4)	0.0267 (2)
Cl1	0.0169 (3)	0.2500	0.46244 (8)	0.0325 (3)
O1	1.0547 (10)	0.2500	−0.1071 (3)	0.0457 (9)
N1	0.4310 (6)	0.39688 (17)	0.29470 (19)	0.0252 (5)
N2	0.6066 (9)	0.2500	0.1827 (3)	0.0288 (8)
N3	0.8356 (7)	0.33967 (17)	0.03443 (19)	0.0295 (6)
C1	0.3326 (8)	0.4686 (2)	0.3618 (3)	0.0294 (7)
H1A	0.2282	0.4523	0.4316	0.035*
C2	0.3786 (8)	0.5661 (2)	0.3345 (2)	0.0353 (8)
H2A	0.3090	0.6168	0.3849	0.042*
C3	0.5252 (9)	0.5888 (2)	0.2342 (3)	0.0357 (8)
H3A	0.5538	0.6559	0.2130	0.043*
C4	0.6294 (8)	0.5153 (2)	0.1635 (2)	0.0304 (7)
H4A	0.7350	0.5298	0.0934	0.036*
C5	0.5795 (7)	0.4205 (2)	0.1963 (2)	0.0249 (7)
C6	0.6831 (8)	0.3335 (2)	0.1299 (2)	0.0249 (6)
C7	0.9152 (11)	0.2500	−0.0159 (3)	0.0308 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0324 (3)	0.0226 (3)	0.0256 (3)	0.000	0.0083 (2)	0.000
Cl1	0.0327 (6)	0.0348 (6)	0.0312 (6)	0.000	0.0117 (4)	0.000
O1	0.063 (2)	0.0376 (19)	0.0392 (19)	0.000	0.0247 (16)	0.000
N1	0.0264 (14)	0.0236 (13)	0.0257 (12)	−0.0008 (10)	0.0025 (10)	0.0006 (10)
N2	0.042 (2)	0.0183 (18)	0.0272 (19)	0.000	0.0114 (16)	0.000
N3	0.0319 (15)	0.0318 (15)	0.0254 (13)	−0.0008 (11)	0.0069 (11)	0.0019 (10)
C1	0.0306 (17)	0.0287 (17)	0.0290 (15)	0.0014 (13)	0.0031 (12)	−0.0039 (12)
C2	0.0368 (19)	0.0290 (17)	0.0400 (19)	0.0052 (14)	0.0000 (15)	−0.0083 (14)
C3	0.039 (2)	0.0246 (17)	0.0434 (19)	−0.0013 (13)	−0.0019 (15)	0.0045 (13)
C4	0.0325 (18)	0.0238 (16)	0.0347 (17)	−0.0035 (13)	0.0011 (14)	0.0032 (12)
C5	0.0224 (16)	0.0266 (16)	0.0255 (15)	0.0002 (12)	−0.0012 (12)	0.0005 (11)
C6	0.0222 (15)	0.0254 (16)	0.0268 (15)	−0.0009 (12)	−0.0020 (12)	0.0016 (12)
C7	0.030 (2)	0.038 (3)	0.024 (2)	0.000	0.0038 (18)	0.000

Geometric parameters (Å, º) top

Cu1—N2	1.896 (3)	N3—C7	1.405 (3)
Cu1—N1ⁱ	2.049 (2)	C1—C2	1.387 (4)
Cu1—N1	2.049 (2)	C1—H1A	0.9602
Cu1—Cl1	2.2239 (12)	C2—C3	1.371 (4)
Cu1—Cl1ⁱⁱ	2.778 (2)	C2—H2A	0.9602
O1—C7	1.225 (5)	C3—C4	1.380 (4)
N1—C1	1.329 (4)	C3—H3A	0.9603
N1—C5	1.358 (4)	C4—C5	1.371 (4)
N2—C6ⁱ	1.343 (3)	C4—H4A	0.9602
N2—C6	1.343 (3)	C5—C6	1.491 (4)
N3—C6	1.297 (4)	C7—N3ⁱ	1.405 (3)

N2—Cu1—N1ⁱ	79.18 (7)	C3—C2—C1	118.8 (3)
N2—Cu1—N1	79.18 (7)	C3—C2—H2A	120.6
N1ⁱ—Cu1—N1	158.25 (13)	C1—C2—H2A	120.6
N2—Cu1—Cl1	164.32 (11)	C2—C3—C4	120.0 (3)
N1ⁱ—Cu1—Cl1	100.12 (7)	C2—C3—H3A	120.0
N1—Cu1—Cl1	100.12 (7)	C4—C3—H3A	120.0
Cl1ⁱⁱ—Cu1—Cl1	100.12 (7)	C5—C4—C3	118.2 (3)
Cl1ⁱⁱ—Cu1—N1	100.12 (7)	C5—C4—H4A	120.6
Cl1ⁱⁱ—Cu1—N2	100.12 (7)	C3—C4—H4A	121.2
C1—N1—C5	118.5 (3)	N1—C5—C4	122.5 (3)
C1—N1—Cu1	126.9 (2)	N1—C5—C6	113.1 (2)
C5—N1—Cu1	114.60 (19)	C4—C5—C6	124.3 (3)
C6ⁱ—N2—C6	116.9 (3)	N3—C6—N2	125.2 (3)
C6ⁱ—N2—Cu1	121.53 (17)	N3—C6—C5	123.2 (2)
C6—N2—Cu1	121.53 (17)	N2—C6—C5	111.5 (3)
C6—N3—C7	115.3 (2)	O1—C7—N3	119.01 (17)
N1—C1—C2	122.1 (3)	O1—C7—N3ⁱ	119.01 (17)
N1—C1—H1A	118.8	N3—C7—N3ⁱ	122.0 (3)
C2—C1—H1A	119.1

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O1ⁱⁱⁱ	0.96	2.37	3.145 (2)	138
C2—H2A···Cl1^iv	0.96	2.89	3.836 (3)	170

Symmetry codes: (iii) −x+2, y+3/2, −z; (iv) −x, y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₃H₈N₅O)Cl]
M_r	349.23
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	293
a, b, c (Å)	3.7687 (13), 13.698 (5), 11.852 (4)
β (°)	92.851 (6)
V (Å³)	611.1 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.01
Crystal size (mm)	0.09 × 0.09 × 0.07

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.840, 0.872
No. of measured, independent and observed [I > 2σ(I)] reflections	3063, 1109, 952
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.085, 1.03
No. of reflections	1109
No. of parameters	103
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.27

Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O1ⁱ	0.96	2.366	3.145 (2)	138
C2—H2A···Cl1ⁱⁱ	0.96	2.89	3.836 (3)	170

Symmetry codes: (i) −x+2, y+3/2, −z; (ii) −x, y+3/2, −z+1.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 21001031) and the Special Research Fund for PhD of Guangdong University of Education (grant No. 10ARF05).

References

Bruker (2005). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cao, M.-L., Hao, H.-G., Zhang, W.-X. & Ye, B.-H. (2008). Inorg. Chem. 47, 8126–8133 Web of Science CrossRef PubMed CAS Google Scholar
Cao, M.-L., Wu, J.-J., Mo, H.-J. & Ye, B.-H. (2009). J. Am. Chem. Soc. 131, 3458–3459 Web of Science CrossRef PubMed CAS 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
Wieprecht, T., Dubs, M.-J. & Schlingloff, G. (2005). Int. Patent WO 2005105303. Google Scholar
Zhou, X.-P., Li, D., Wu, T. & Zhang, X. (2006). Discuss. Faraday Soc. p. 2435. Google Scholar
Zhou, X.-P., Li, D., Zheng, S.-L., Zhang, X. & Wu, T. (2006). Inorg. Chem. 45, 7119–7125. Web of Science CSD CrossRef PubMed CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page m739

doi:10.1107/S1600536811016989

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		EndNote
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		Refer
		Medline
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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

catena-Poly[[[4,6-bis­­(2-pyrid­yl)-1,3,5-triazin-2-olato]copper(II)]-μ-chlorido]

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

catena-Poly[[[4,6-bis(2-pyridyl)-1,3,5-triazin-2-olato]copper(II)]-μ-chlorido]