A second polymorph of catena-poly[[(1,10-phenanthroline-κ²N,N′)copper(II)]-di-μ-thio­cyanato-κ²N:S;κ²S:N]

In the title coordination polymer, [Cu(NCS)₂(C₁₂H₈N₂)]_n, the Cu^II atom is situated on a twofold rotation axis and is coordinated by two N atoms from the bidentate 1,10-phenanthroline ligand and four thio­cyanate groups to confer a CuN₄S₂ octa­hedral geometry and resulting in a layer structure extending parallel to (100).

Related literature

For the first polymorph of this composition, see: Breneman & Parker (1993). For related structures, see: Kulkarni et al. (2002); Morpurgo et al. (1984).

Experimental

Crystal data

• [Cu(NCS)₂(C₁₂H₈N₂)]

• M_r = 359.90

• Monoclinic, C 2/c

• a = 14.0353 (13) Å

• b = 10.3081 (9) Å

• c = 10.2670 (9) Å

• β = 111.034 (2)°

• V = 1386.4 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 1.87 mm⁻¹

• T = 294 K

• 0.25 × 0.22 × 0.15 mm

Data collection

• Bruker SMART diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T_min = 0.633, T_max = 0.755

• 3938 measured reflections

• 1362 independent reflections

• 1254 reflections with I > 2σ(I)

• R_int = 0.015

Refinement

• R[F² > 2σ(F²)] = 0.027

• wR(F²) = 0.076

• S = 1.08

• 1362 reflections

• 97 parameters

• H-atom parameters constrained

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.31 e Å⁻³

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); 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

S1. Comment

Phenanthroline and its derivatives have been achieving rapidly increasing attention not only for their potential application as functional materials, but aslo from their intriguing variety of architectures and topologies. 1, 10-Phenanthroline, as one kind of those ligand, has usually been used to construct a great variety of structurally interesting entities, such as monomers(Breneman et al. 1993), ploymers(Kulkarni et al. 2002; Morpurgo et al. 1984).

The structure of the title compound (I) is illustrated in Fig. 1. the Cu^II atom is coordinated by two N atoms from1, 10-Phenanthroline ligand, as well as by the two N atoms and two S atoms from four thiocyanate groups to confer a distorted octahedral coordination at the metal centre. Two S atoms occupy the axial position, showing weak interaction of Cu1—S1 bond [2.952 (3)], which give rise to one-dimensional chain along (100), the crystal packing is stabilized by the intermolecular π-π stacking interaction(Fig. 2).

In contrast to the first polymorph of this composition in which the distance of Cu—S bonds are longer [3.163 (2) Å], and the S—Cu—S' angles are nearly linear [170.86 (6)°]. The S—Cu—N angles in reported complex vary from 73.8 (1) to 99.1 (1)°, which make the octahedral geometry of this compound more disordered than the title compoud.

Related literature

For related structures, see: Breneman et al. (1993); Kulkarni et al. (2002); Morpurgo et al. (1984).

S2. Experimental

The mixture of CuSCN (0.0244 g, 0.2 mmol), 1, 10-Phenanthroline (0.0132 g, 0.1 mmol), were placed and sealed in a 10 ml Teflon-lined stainless steel reactor and heated to 160 °C for 72 h, then cooled down to room temperature at a rate of 5 °C/ 60 min. Single crystals suitable for X-ray diffraction were obtained in the form of black bars in ca 35% yield.

The web of checkcif show one Alert level B(Hirshfeld Test Diff S1 – C7..8.52 su), we think this is the result of the sightly distorted S atom of the thiocyanate group for his weak interaction to the Cu atom.

S3. Refinement

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93?Å(aromatic) and Uĩso(H) = 1.2Ueq(C)

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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

	Fig. 1. The coordination environment of the title compound
	Fig. 2. The crystal packing of the title compound

catena-Poly[[(1,10-phenanthroline-κ²N,N')copper(II)]- di-µ-thiocyanato-κ²N:S;κ²S:N]

Crystal data

[Cu(NCS)2(C12H8N2)]	F(000) = 724
Mr = 359.90	Dx = 1.724 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -c 2yc	Cell parameters from 1647 reflections
a = 14.0353 (13) Å	θ = 2.5–27.8°
b = 10.3081 (9) Å	µ = 1.87 mm^−1
c = 10.2670 (9) Å	T = 294 K
β = 111.034 (2)°	Block, black
V = 1386.4 (2) Å^3	0.25 × 0.22 × 0.15 mm
Z = 4

Data collection

Bruker SMART diffractometer	1362 independent reflections
Radiation source: fine-focus sealed tube	1254 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
ϕ and ω scans	θmax = 26.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.633, Tmax = 0.755	k = −12→5
3938 measured reflections	l = −12→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0475P)^2 + 0.5818P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
1362 reflections	Δρmax = 0.33 e Å^−3
97 parameters	Δρmin = −0.31 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0008 (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	0.5000	0.62211 (3)	0.2500	0.03359 (15)
N2	0.43016 (13)	0.49319 (16)	0.32227 (17)	0.0407 (4)
N1	0.56960 (11)	0.77181 (16)	0.19112 (15)	0.0330 (3)
C7	0.39033 (14)	0.43783 (18)	0.38718 (19)	0.0324 (4)
C6	0.53802 (14)	0.88917 (17)	0.21873 (19)	0.0326 (4)
C1	0.64028 (15)	0.7684 (2)	0.1322 (2)	0.0426 (5)
H1	0.6632	0.6884	0.1136	0.051*
C4	0.57499 (16)	1.0064 (2)	0.1877 (2)	0.0415 (5)
C3	0.64909 (17)	0.9994 (2)	0.1252 (2)	0.0488 (6)
H3	0.6761	1.0749	0.1027	0.059*
C2	0.68083 (19)	0.8814 (2)	0.0979 (3)	0.0507 (6)
H2	0.7296	0.8759	0.0562	0.061*
S1	0.33300 (4)	0.36018 (5)	0.47588 (6)	0.04095 (18)
C5	0.5358 (2)	1.12518 (19)	0.2202 (3)	0.0548 (6)
H5	0.5599	1.2038	0.1999	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0418 (2)	0.0268 (2)	0.0433 (2)	0.000	0.02887 (17)	0.000
N2	0.0479 (10)	0.0375 (9)	0.0432 (9)	−0.0075 (8)	0.0242 (8)	0.0008 (7)
N1	0.0348 (8)	0.0338 (8)	0.0351 (8)	−0.0009 (6)	0.0182 (6)	0.0016 (6)
C7	0.0353 (9)	0.0279 (9)	0.0358 (9)	−0.0008 (8)	0.0148 (8)	−0.0027 (7)
C6	0.0359 (10)	0.0312 (9)	0.0302 (9)	−0.0021 (7)	0.0111 (8)	0.0015 (7)
C1	0.0424 (10)	0.0461 (12)	0.0487 (11)	−0.0017 (9)	0.0280 (9)	0.0019 (9)
C4	0.0451 (11)	0.0366 (11)	0.0391 (10)	−0.0057 (9)	0.0107 (9)	0.0052 (8)
C3	0.0515 (12)	0.0467 (13)	0.0501 (12)	−0.0150 (10)	0.0206 (10)	0.0097 (10)
C2	0.0481 (12)	0.0637 (16)	0.0498 (13)	−0.0116 (10)	0.0293 (11)	0.0039 (10)
S1	0.0430 (3)	0.0442 (3)	0.0433 (3)	−0.0070 (2)	0.0249 (2)	0.0026 (2)
C5	0.0705 (17)	0.0301 (11)	0.0589 (15)	−0.0062 (9)	0.0174 (12)	0.0025 (9)

Geometric parameters (Å, º)

Cu1—N2	1.9492 (16)	C1—C2	1.397 (3)
Cu1—N2^i	1.9492 (16)	C1—H1	0.9300
Cu1—N1	2.0310 (15)	C4—C3	1.406 (3)
Cu1—N1^i	2.0310 (15)	C4—C5	1.430 (3)
N2—C7	1.162 (3)	C3—C2	1.359 (3)
N1—C1	1.335 (2)	C3—H3	0.9300
N1—C6	1.353 (2)	C2—H2	0.9300
C7—S1	1.6259 (19)	C5—C5^i	1.351 (6)
C6—C4	1.397 (3)	C5—H5	0.9300
C6—C6^i	1.430 (4)
N2—Cu1—N2^i	94.04 (10)	N1—C1—H1	119.0
N2—Cu1—N1	173.03 (6)	C2—C1—H1	119.0
N2^i—Cu1—N1	92.49 (7)	C6—C4—C3	117.1 (2)
N2—Cu1—N1^i	92.49 (7)	C6—C4—C5	118.8 (2)
N2^i—Cu1—N1^i	173.03 (6)	C3—C4—C5	124.1 (2)
N1—Cu1—N1^i	81.10 (9)	C2—C3—C4	119.4 (2)
C7—N2—Cu1	164.69 (16)	C2—C3—H3	120.3
C1—N1—C6	118.10 (17)	C4—C3—H3	120.3
C1—N1—Cu1	129.05 (15)	C3—C2—C1	120.1 (2)
C6—N1—Cu1	112.85 (12)	C3—C2—H2	120.0
N2—C7—S1	179.12 (18)	C1—C2—H2	120.0
N1—C6—C4	123.34 (18)	C5^i—C5—C4	121.13 (13)
N1—C6—C6^i	116.59 (10)	C5^i—C5—H5	119.4
C4—C6—C6^i	120.07 (12)	C4—C5—H5	119.4
N1—C1—C2	121.9 (2)

Symmetry code: (i) −x+1, y, −z+1/2.