catena-Poly[[(1,10-phenanthroline-κ2N,N′)copper(I)]-μ-thio­cyanato-κ2N:S]

Li, H.; Zhang, S.G.

doi:10.1107/S1600536810035002

metal-organic compounds

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Volume 66| Part 10| October 2010| Page m1216

doi:10.1107/S1600536810035002

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catena-Poly[[(1,10-phenanthroline-κ²N,N′)copper(I)]-μ-thiocyanato-κ²N:S]

Hong Li ^a ^* and Shi Guo Zhang ^a

^aBinzhou Key Laboratory of Material Chemistry, Department of Chemistry and Chemical Engineering, Binzhou University, Binzhou 256603, People's Republic of China
^*Correspondence e-mail: honglizhang1968@yahoo.cn

(Received 16 August 2010; accepted 31 August 2010; online 8 September 2010)

In the title complex, [Cu(NCS)(C₁₂H₈N₂)]_n, the Cu^I ion is in a distorted tetrahedral CuN₃S coordination geometry. The thiocyanate ligand acts as bridging ligand, forming chains along [100]. A crystallographic mirror plane runs through the Cu^I ion, the thiocyanate ligand and the middle of the phenanthroline ligand.

Related literature

For related structures, see: Shi et al. (2006 ); Tadashi et al. (1990 ).

Experimental

Crystal data

[Cu(NCS)(C₁₂H₈N₂)]
M_r = 301.82
Orthorhombic, P n m a
a = 7.9744 (15) Å
b = 11.948 (2) Å
c = 12.956 (2) Å
V = 1234.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.92 mm⁻¹
T = 298 K
0.23 × 0.15 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.667, T_max = 0.762
6226 measured reflections
1421 independent reflections
1146 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.080
S = 1.03
1421 reflections
89 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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 I, global. DOI: 10.1107/S1600536810035002/lh5123sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810035002/lh5123Isup2.hkl

checkCIF report

Comment top

1,10-phenanthroline and thiocyanate anions play an important role in modern coordination chemistry and many complexes have been published with them as ligands (e.g. Shi et al., 2006; Tadashi et al. (1990). We originally tried to prepare a new divalent Cu(II) complex with these two ligands, but the title monovalent Cu(I) complex was fortuitously obtained. Herein we report its crystal structure.

Fig. 1 shows part of the title complex. The Cu^I ion is coordinated by three N atoms and one S atom, and is in a distorted tetrahedral coordination environment. The thiocyanate ligand acts as bridging forming a 1-D chain with a Cu···Cu distance of 5.9960 (9) Å.

Related literature top

For related structures, see: Shi et al. (2006); Tadashi et al. (1990).

Experimental top

A 5 ml H₂O solution of Cu(ClO₄)₂6H₂O (0.2000 g, 0.54 mmol) was added to a 10 ml methanol solution of 1,10-phenanthroline (0.1070 g, 0.54 mmol), and the mixture was stirred for a few minutes, then a 5 ml H₂O solution of NaNCS (0.0875 g, 1.08 mmol) was added dropwise and the mixture was stirred for a few minutes and then placed in a Teflon-lined autoclave and heated at 433K for 144 h at autogenous pressure. After the contents of the autoclave were cooled to room temperature, the red single crystals were obtained.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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. Part of the 1-D chain of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [symmetry codes: (i): x, -y + 3/2, z; (ii): x - 1/2, y, -z + 3/2; (iii): x + 1/2, y, -z + 3/2]

catena-Poly[[(1,10-phenanthroline-κ²N,N')copper(I)]- µ-thiocyanato-κ²N:S] top

Crystal data top

[Cu(NCS)(C₁₂H₈N₂)]	F(000) = 608
M_r = 301.82	D_x = 1.624 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 2278 reflections
a = 7.9744 (15) Å	θ = 2.3–27.9°
b = 11.948 (2) Å	µ = 1.92 mm⁻¹
c = 12.956 (2) Å	T = 298 K
V = 1234.4 (4) Å³	Block, red
Z = 4	0.23 × 0.15 × 0.15 mm

Data collection top

Bruker SMART APEX CCD diffractometer	1421 independent reflections
Radiation source: fine-focus sealed tube	1146 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
T_min = 0.667, T_max = 0.762	k = −15→15
6226 measured reflections	l = −5→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0508P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
1421 reflections	Δρ_max = 0.29 e Å⁻³
89 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0039 (10)

Crystal data top

[Cu(NCS)(C₁₂H₈N₂)]	V = 1234.4 (4) Å³
M_r = 301.82	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 7.9744 (15) Å	µ = 1.92 mm⁻¹
b = 11.948 (2) Å	T = 298 K
c = 12.956 (2) Å	0.23 × 0.15 × 0.15 mm

Data collection top

Bruker SMART APEX CCD diffractometer	1421 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1146 reflections with I > 2σ(I)
T_min = 0.667, T_max = 0.762	R_int = 0.028
6226 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.03	Δρ_max = 0.29 e Å⁻³
1421 reflections	Δρ_min = −0.28 e Å⁻³
89 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
C1	0.13936 (17)	0.68993 (15)	1.13076 (12)	0.0406 (4)
C2	0.1011 (2)	0.63175 (18)	1.22243 (13)	0.0543 (5)
C3	0.0628 (3)	0.69444 (18)	1.31338 (13)	0.0712 (6)
H3	0.0372	0.6565	1.3740	0.085*
C4	0.1051 (2)	0.51479 (18)	1.21873 (16)	0.0669 (6)
H4	0.0792	0.4731	1.2772	0.080*
C5	0.1468 (2)	0.46262 (19)	1.12958 (17)	0.0648 (6)
H5	0.1491	0.3849	1.1262	0.078*
C6	0.1862 (2)	0.52657 (16)	1.04275 (16)	0.0528 (5)
H6	0.2175	0.4895	0.9826	0.063*
C7	0.5834 (3)	0.7500	0.79202 (17)	0.0436 (5)
Cu1	0.23713 (4)	0.7500	0.92283 (2)	0.04865 (16)
N1	0.6286 (2)	0.7500	0.70801 (14)	0.0487 (5)
N2	0.18111 (17)	0.63783 (12)	1.04164 (11)	0.0412 (3)
S1	0.52660 (9)	0.7500	0.91372 (4)	0.0702 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0342 (8)	0.0577 (10)	0.0300 (8)	−0.0010 (7)	0.0005 (6)	0.0033 (7)
C2	0.0467 (10)	0.0768 (13)	0.0392 (9)	−0.0047 (9)	0.0023 (8)	0.0131 (9)
C3	0.0708 (12)	0.1093 (18)	0.0335 (9)	−0.0073 (11)	0.0146 (9)	0.0111 (9)
C4	0.0664 (14)	0.0748 (15)	0.0593 (13)	−0.0081 (10)	−0.0013 (10)	0.0283 (11)
C5	0.0638 (13)	0.0510 (11)	0.0796 (16)	−0.0007 (10)	−0.0080 (12)	0.0169 (11)
C6	0.0548 (11)	0.0519 (11)	0.0517 (11)	0.0028 (9)	−0.0052 (9)	−0.0009 (9)
C7	0.0417 (12)	0.0567 (15)	0.0323 (12)	0.000	−0.0043 (10)	0.000
Cu1	0.0589 (3)	0.0631 (3)	0.0240 (2)	0.000	0.00043 (12)	0.000
N1	0.0563 (13)	0.0619 (13)	0.0278 (9)	0.000	0.0038 (9)	0.000
N2	0.0423 (7)	0.0469 (8)	0.0345 (7)	0.0000 (6)	−0.0012 (6)	0.0021 (6)
S1	0.0499 (4)	0.1360 (8)	0.0245 (3)	0.000	0.0024 (3)	0.000

Geometric parameters (Å, º) top

C1—N2	1.353 (2)	C5—H5	0.9300
C1—C2	1.410 (2)	C6—N2	1.330 (2)
C1—C1ⁱ	1.435 (4)	C6—H6	0.9300
C2—C4	1.399 (3)	C7—N1	1.147 (3)
C2—C3	1.429 (2)	C7—S1	1.640 (2)
C3—C3ⁱ	1.328 (4)	Cu1—N1ⁱⁱ	1.9033 (19)
C3—H3	0.9300	Cu1—N2ⁱ	2.0893 (14)
C4—C5	1.354 (3)	Cu1—N2	2.0893 (14)
C4—H4	0.9300	Cu1—S1	2.3113 (9)
C5—C6	1.396 (3)	N1—Cu1ⁱⁱⁱ	1.9033 (19)

N2—C1—C2	123.04 (17)	N2—C6—C5	123.3 (2)
N2—C1—C1ⁱ	117.39 (9)	N2—C6—H6	118.4
C2—C1—C1ⁱ	119.55 (11)	C5—C6—H6	118.4
C4—C2—C1	117.32 (19)	N1—C7—S1	177.7 (2)
C4—C2—C3	123.83 (19)	N1ⁱⁱ—Cu1—N2ⁱ	123.98 (6)
C1—C2—C3	118.84 (18)	N1ⁱⁱ—Cu1—N2	123.98 (6)
C3ⁱ—C3—C2	121.60 (11)	N2ⁱ—Cu1—N2	79.80 (8)
C3ⁱ—C3—H3	119.2	N1ⁱⁱ—Cu1—S1	114.12 (6)
C2—C3—H3	119.2	N2ⁱ—Cu1—S1	104.55 (4)
C5—C4—C2	119.65 (19)	N2—Cu1—S1	104.55 (4)
C5—C4—H4	120.2	C7—N1—Cu1ⁱⁱⁱ	171.3 (2)
C2—C4—H4	120.2	C6—N2—C1	117.26 (16)
C4—C5—C6	119.4 (2)	C6—N2—Cu1	129.99 (13)
C4—C5—H5	120.3	C1—N2—Cu1	112.71 (11)
C6—C5—H5	120.3	C7—S1—Cu1	108.96 (9)

N2—C1—C2—C4	−0.9 (2)	C1ⁱ—C1—N2—C6	177.93 (12)
C1ⁱ—C1—C2—C4	−179.14 (12)	C2—C1—N2—Cu1	−178.16 (12)
N2—C1—C2—C3	178.35 (16)	C1ⁱ—C1—N2—Cu1	0.08 (11)
C1ⁱ—C1—C2—C3	0.1 (2)	N1ⁱⁱ—Cu1—N2—C6	58.10 (18)
C4—C2—C3—C3ⁱ	179.09 (13)	N2ⁱ—Cu1—N2—C6	−177.60 (14)
C1—C2—C3—C3ⁱ	−0.2 (2)	S1—Cu1—N2—C6	−75.07 (16)
C1—C2—C4—C5	0.9 (3)	N1ⁱⁱ—Cu1—N2—C1	−124.40 (10)
C3—C2—C4—C5	−178.38 (19)	N2ⁱ—Cu1—N2—C1	−0.09 (13)
C2—C4—C5—C6	0.4 (3)	S1—Cu1—N2—C1	102.44 (10)
C4—C5—C6—N2	−1.7 (3)	N1—C7—S1—Cu1	180.00 (2)
S1—C7—N1—Cu1ⁱⁱⁱ	0.00 (2)	N1ⁱⁱ—Cu1—S1—C7	0.0
C5—C6—N2—C1	1.7 (3)	N2ⁱ—Cu1—S1—C7	−138.50 (4)
C5—C6—N2—Cu1	179.08 (13)	N2—Cu1—S1—C7	138.50 (4)
C2—C1—N2—C6	−0.3 (2)

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

Experimental details

Crystal data
Chemical formula	[Cu(NCS)(C₁₂H₈N₂)]
M_r	301.82
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	7.9744 (15), 11.948 (2), 12.956 (2)
V (Å³)	1234.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.92
Crystal size (mm)	0.23 × 0.15 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.667, 0.762
No. of measured, independent and observed [I > 2σ(I)] reflections	6226, 1421, 1146
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.080, 1.03
No. of reflections	1421
No. of parameters	89
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.28

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Natural Science Foundation of Shandong Province of China (grant No. ZR2009BL002).

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. 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
Shi, J. M., Sun, Y. M., Liu, Z., Liu, L. D., Shi, W. & Cheng, P. (2006). Dalton Trans. pp. 376–380. CSD CrossRef PubMed Google Scholar
Tadashi, T., Naofumi, W., Michio, N., Yoneichiro, M., Mitsuo, M., Shigeru, O. & Yoshihiko, S. (1990). Bull. Chem. Soc. Jpn, 63, 364–369. Google Scholar