Poly[μ-4,4′-bipyridine-κ²N:N′-μ-thio­cyanato-κ²N:S-copper(I)]

In the crystal structure of the title compound, [Cu(NCS)(C₁₀H₈N₂)]_n, the Cu^I atom is coordinated by two N atoms from two symmetry-related 4,4′-bipyridine (bipy) ligands and one N and one S atom from two symmetry-related thio­cyanate ligands in a distorted tetra­hedral environment. The thio­cyanate ligands bridge the Cu^I atoms into a zigzag [CuSCN]_n chain running parallel to the a axis. These chains are further connected through two bipy ligands that bridge the Cu^I centers to generate a two-dimensional brick-like network. The pyridyl planes of the ligands exhibit a dihedral angle of 37.35 (12)°.

Key indicators

• Single-crystal X-ray study
• T = 170 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.090
• Data-to-parameter ratio = 20.0

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   170.000
            Value of melting point given =     0.000
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S11    --  C11     ..       6.01 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    --  S11_b   ..       7.74 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    --  N2_d    ..       7.49 su
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.11 Ratio

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In our ongoing investigation on the synthesis, structures and properties of new coordination polymers based on metal halides as well as pseudohalides and N-donor ligands, we have startet systematic investigation on their thermal behavior because we have demonstrated that new ligand deficient coordination polymers can be conveniently prepared by thermal decompisition of suitable ligand rich precursor compounds (Näther, Wriedt & Jeß, 2003; Näther & Jeß, 2006; Bhosekar et al. 2007). If the ligand rich precursor compounds contain besides the N-donor ligands paramagnetic metal atoms and small magnetically active ligands like SCN^-, ligand deficient compounds with briding SCN^- ligands are obtained, which show cooperative magnetic phenomena at lower temperatures (Näther & Greve, 2003). During these investigations we have reacted copper(II)chloride and potassium thiocyanate with bipy. In this reaction the diamagnetic copper(I) title compound has been formed by accident.

The coordination properties of bipy enables a series of different coordination modes, because it can connect two different metal cations. In addition, typical Cu—S—C angles in CuSCN polymers are in the range of 100–106° (Healy et al. 1984) and this should enable the construction of stairlike single or double [Cu(SCN)] chains in 1:1 and 2:1 complexes, whose Cu atoms can then be connected by linear spacer ligands into sheets (Näther & Jeß, 2001; Näther et al. 2002; Näther, Greve & Jeß, 2003).

The 1:1 title compound [CuSCN(bipy)]_n, whose structure (Fig. 1) represents a two-dimensional CuSCN coordination polymer, contains single [CuSCN] ribbons (Fig. 2) as a characteristic motif. Copper(i) thiocyanato compounds with pyrazine (Goher & Mautner, 1999), methylpyrazine (Teichert & Sheldrick, 1999) and 1,2-bis(4-pyridyl)ethane (Wang et al. 1999) as ligand show a similar topology. Within each layer the metal ions are bridged by two µ₂(N,N')-bipy ligands and two µ(N,S)-thiocyanato groups. Thus, each copper(i) atom is tetrahedrally coordinated. The angels arround the copper(i) atoms range between 97.36 (9) and 115.22 (7)° and the Cu—SCN and Cu—NCS distances amount to 2.2755 (8) and 1.966 (2) Å, respectively. The Cu—N_bipy distances ranges from 2.080 (2) to 2.122 (2) Å (Tab. 1). The layers can be described as formed by two types of perpendicular zigzag like chains crossing at the copper(i) centers. Chains of the first type run along the c-axis and have bipy as a bridging ligand, while the second type extend along the a-axis containing bridging thiocyanate ligands. The intralayer Cu···Cu distances are 5.7942 (2) and 11.2037 (3) Å for Cu—NCS—Cu and Cu—bipy—Cu, respectively. The packing of the crystal structure is achieved by stacking the two-dimensional layers along the b-axis in corrugated sheets (Fig. 3) with an interlayer stacking distance between the centroides of the sixmembered rings of 4.237 (2) Å.

Related literature

For related structures, see: Goher & Mautner (1999); Teichert & Sheldrick (1999); Wang et al. (1999). For related chemistry, see: Bhosekar et al. (2007); Healy et al. (1984); Näther & Greve (2003); Näther & Jeß (2001, 2006); Näther et al. (2002); Näther, Greve & Jeß (2003); Näther, Wriedt & Jeß (2003).

S2. Experimental

CuCl₂ and bipy was obtained from Alfa Aesar, KSCN and methanol was obtained from Fluka. 0.1 mmol (13.4 mg) CuCl₂, 0.2 mmol (19.4 mg) KSCN, 0.6 mmol (93.7 mg) and 1 ml of methanol were transfered in a test-tube, which was closed and heated to 120 °C for three days. On cooling orange block-shaped single crystals of the title compound were obtained.

S3. Refinement

All H atoms were located in difference map but were positioned with idealized geometry and were refined isotropic with U_eq(H) = 1.2 U_eq(C) of the parent atom using a riding model with C—H = 0.95 Å.

Computing details

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. Crystal structure of the title compund with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: i = x, -y + 1/2, z - 1/2; ii = x - 1/2, y, -z + 1/2; iii = x + 1/2, y, -z + 1/2.]
	Fig. 2. Crystal structure of the title compound with view along the b axis.
	Fig. 3. Crystal structure of the title compound with view along the a axis.

Poly[µ-4,4'-bipyridine-κ²N:N'-µ-thiocyanato-κ²N:S- copper(I)]

Crystal data

[Cu(NCS)(C10H8N2)]	Dx = 1.713 Mg m^−3
Mr = 277.80	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 23129 reflections
a = 11.4340 (4) Å	θ = 1.7–29.7°
b = 12.2530 (5) Å	µ = 2.19 mm^−1
c = 15.3806 (6) Å	T = 170 K
V = 2154.83 (14) Å^3	Block, orange
Z = 8	0.12 × 0.08 × 0.05 mm
F(000) = 1120

Data collection

Stoe IPDS-II diffractometer	2915 independent reflections
Radiation source: fine-focus sealed tube	2567 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ω scans	θmax = 29.3°, θmin = 2.7°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −15→15
Tmin = 0.817, Tmax = 0.901	k = −16→16
23916 measured reflections	l = −21→20

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)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0317P)^2 + 1.4342P] where P = (Fo^2 + 2Fc^2)/3
S = 1.24	(Δ/σ)max = 0.001
2915 reflections	Δρmax = 0.32 e Å^−3
146 parameters	Δρmin = −0.43 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: 0.0015 (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	0.44386 (3)	0.58247 (3)	0.28065 (2)	0.03676 (11)
N1	0.42996 (19)	0.45592 (18)	0.37017 (14)	0.0353 (5)
N2	0.4249 (2)	0.01317 (17)	0.66651 (14)	0.0361 (5)
C1	0.3680 (2)	0.4601 (2)	0.44384 (17)	0.0385 (6)
H1	0.3252	0.5247	0.4561	0.046*
C2	0.3631 (2)	0.3757 (2)	0.50299 (17)	0.0388 (6)
H2	0.3176	0.3825	0.5544	0.047*
C3	0.4252 (2)	0.2806 (2)	0.48664 (16)	0.0325 (5)
C4	0.4902 (2)	0.2762 (2)	0.41074 (17)	0.0372 (5)
H4	0.5350	0.2132	0.3972	0.045*
C5	0.4892 (2)	0.3641 (2)	0.35506 (17)	0.0387 (6)
H5	0.5332	0.3591	0.3028	0.046*
C6	0.4236 (2)	0.18673 (19)	0.54777 (15)	0.0314 (5)
C7	0.3241 (2)	0.1573 (2)	0.59312 (19)	0.0404 (6)
H7	0.2532	0.1963	0.5845	0.048*
C8	0.3280 (2)	0.0711 (2)	0.65107 (18)	0.0414 (6)
H8	0.2585	0.0521	0.6813	0.050*
C9	0.5207 (2)	0.0408 (2)	0.62150 (17)	0.0389 (6)
H9	0.5902	−0.0001	0.6308	0.047*
C10	0.5238 (2)	0.1255 (2)	0.56241 (17)	0.0375 (6)
H10	0.5939	0.1417	0.5320	0.045*
N11	0.6066 (2)	0.6321 (2)	0.26898 (16)	0.0419 (5)
C11	0.6915 (2)	0.6652 (2)	0.23866 (16)	0.0342 (5)
S11	0.81061 (6)	0.71667 (6)	0.19394 (5)	0.04387 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03545 (17)	0.03621 (17)	0.03862 (17)	−0.00274 (13)	0.00331 (14)	0.00139 (13)
N1	0.0374 (11)	0.0341 (10)	0.0342 (11)	−0.0018 (9)	0.0027 (9)	0.0024 (9)
N2	0.0416 (12)	0.0339 (10)	0.0329 (11)	−0.0005 (9)	0.0020 (9)	0.0028 (8)
C1	0.0445 (15)	0.0336 (12)	0.0375 (13)	0.0026 (11)	0.0052 (11)	−0.0007 (11)
C2	0.0459 (15)	0.0372 (13)	0.0334 (12)	0.0005 (11)	0.0078 (11)	0.0011 (11)
C3	0.0352 (12)	0.0322 (11)	0.0302 (11)	−0.0046 (9)	−0.0020 (9)	0.0001 (9)
C4	0.0419 (14)	0.0338 (12)	0.0359 (13)	0.0039 (11)	0.0027 (11)	0.0004 (10)
C5	0.0430 (14)	0.0406 (13)	0.0323 (12)	0.0017 (11)	0.0053 (11)	0.0022 (11)
C6	0.0386 (13)	0.0275 (10)	0.0281 (11)	−0.0027 (9)	−0.0021 (9)	−0.0015 (9)
C7	0.0374 (14)	0.0366 (13)	0.0472 (15)	0.0009 (11)	0.0032 (11)	0.0052 (11)
C8	0.0385 (14)	0.0411 (14)	0.0446 (14)	−0.0020 (11)	0.0043 (11)	0.0049 (12)
C9	0.0397 (13)	0.0404 (13)	0.0366 (13)	0.0038 (11)	0.0004 (11)	0.0035 (11)
C10	0.0375 (13)	0.0418 (14)	0.0332 (12)	−0.0012 (11)	0.0027 (10)	0.0030 (11)
N11	0.0348 (12)	0.0455 (13)	0.0455 (13)	−0.0060 (10)	−0.0005 (10)	−0.0006 (10)
C11	0.0322 (12)	0.0330 (12)	0.0374 (13)	0.0021 (10)	−0.0057 (10)	−0.0006 (10)
S11	0.0321 (3)	0.0384 (3)	0.0611 (4)	−0.0008 (3)	0.0043 (3)	0.0118 (3)

Geometric parameters (Å, º)

Cu1—N11	1.966 (2)	C4—C5	1.376 (4)
Cu1—N1	2.080 (2)	C4—H4	0.9500
Cu1—N2^i	2.122 (2)	C5—H5	0.9500
Cu1—S11^ii	2.2755 (8)	C6—C7	1.382 (4)
N1—C5	1.333 (3)	C6—C10	1.388 (4)
N1—C1	1.337 (3)	C7—C8	1.383 (4)
N2—C8	1.336 (4)	C7—H7	0.9500
N2—C9	1.339 (3)	C8—H8	0.9500
N2—Cu1^iii	2.122 (2)	C9—C10	1.380 (4)
C1—C2	1.379 (4)	C9—H9	0.9500
C1—H1	0.9500	C10—H10	0.9500
C2—C3	1.388 (4)	N11—C11	1.151 (3)
C2—H2	0.9500	C11—S11	1.651 (3)
C3—C4	1.385 (4)	S11—Cu1^iv	2.2755 (8)
C3—C6	1.485 (3)
N11—Cu1—N1	111.31 (9)	C3—C4—H4	120.3
N11—Cu1—N2^i	101.07 (9)	N1—C5—C4	123.8 (2)
N1—Cu1—N2^i	97.36 (9)	N1—C5—H5	118.1
N11—Cu1—S11^ii	115.22 (7)	C4—C5—H5	118.1
N1—Cu1—S11^ii	111.96 (6)	C7—C6—C10	117.2 (2)
N2^i—Cu1—S11^ii	118.21 (6)	C7—C6—C3	122.1 (2)
C5—N1—C1	116.7 (2)	C10—C6—C3	120.7 (2)
C5—N1—Cu1	118.34 (17)	C6—C7—C8	119.8 (3)
C1—N1—Cu1	124.96 (18)	C6—C7—H7	120.1
C8—N2—C9	116.8 (2)	C8—C7—H7	120.1
C8—N2—Cu1^iii	121.67 (18)	N2—C8—C7	123.2 (3)
C9—N2—Cu1^iii	118.92 (18)	N2—C8—H8	118.4
N1—C1—C2	123.5 (3)	C7—C8—H8	118.4
N1—C1—H1	118.2	N2—C9—C10	123.5 (3)
C2—C1—H1	118.2	N2—C9—H9	118.3
C1—C2—C3	119.3 (2)	C10—C9—H9	118.3
C1—C2—H2	120.4	C9—C10—C6	119.5 (2)
C3—C2—H2	120.4	C9—C10—H10	120.3
C4—C3—C2	117.4 (2)	C6—C10—H10	120.3
C4—C3—C6	120.7 (2)	C11—N11—Cu1	160.8 (2)
C2—C3—C6	121.9 (2)	N11—C11—S11	177.9 (2)
C5—C4—C3	119.4 (2)	C11—S11—Cu1^iv	101.83 (9)
C5—C4—H4	120.3

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