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

Abstract

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,

• a = 3.7687 (13) Å

• b = 13.698 (5) Å

• c = 11.852 (4) Å

• β = 92.851 (6)°

• V = 611.1 (4) ų

• 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[F ² > 2σ(F ²)] = 0.033

• wR(F ²) = 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

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.

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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

Refinement

All H atoms were calculated geometrically and treated as riding with C—H = 0.96 Å and U_iso(H) = 1.2 U_eq(C).

Figures

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].

Crystal data

[Cu(C13H8N5O)Cl]	F(000) = 350
Mr = 349.23	Dx = 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

Bruker SMART APEX CCD area-detector diffractometer	1109 independent reflections
Radiation source: fine-focus sealed tube	952 reflections with I > 2σ(I)
graphite	Rint = 0.030
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→4
Tmin = 0.840, Tmax = 0.872	k = −16→16
3063 measured reflections	l = −14→13

Refinement

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(Fo2) + (0.0528P)2] where P = (Fo2 + 2Fc2)/3
1109 reflections	(Δ/σ)max < 0.001
103 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.27 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	0.39787 (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 (Ų)

	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, °)

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, °)

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···Cl1iv	0.96	2.89	3.836 (3)	170

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