catena-Poly[[(5-phenyl-2,2′-bipyridine-κ2N,N′)copper(I)]-μ-thio­cyanido-κ2N:S]

Cui, S.; Zuo, M.; Zhang, J.; Zhao, Y.; Wang, H.

doi:10.1107/S1600536812000682

catena-Poly[[(5-phenyl-2,2′-bipyridine-κ²N,N′)copper(I)]-μ-thiocyanido-κ²N:S]

S. Cui, M. Zuo, J. Zhang, Y. Zhao and H. Wang

The title compound, [Cu(NCS)(C₁₆H₁₂N₂)]_n, was synthesised under hydrothermal conditions. The Cu^I ion shows distorted tetrahedral geometry being coordinated by two N atoms from a 5-phenyl-2,2′-bipyridine ligand and by the N and S atoms from two different thiocyanate anions. The Cu^I ions are bridged by thiocyanide groups, forming a one-dimensional coordination polymer along the b axis. The crystal packing is through van der Waals contacts and C—H

π interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812000682/kp2379sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536812000682/kp2379Isup2.hkl Contains datablock I

CCDC reference: 705191

checkCIF report

Key indicators

Single-crystal X-ray study
T = 153 K
Mean (C-C) = 0.004 Å
R factor = 0.035
wR factor = 0.091
Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    --  S1      ..       13.4 su

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     --  C1      ..        6.1 su
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1    --  N3      ..        7.1 su

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   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
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Comment top

The title compound [Cu(SCN)(5-ph-2,2'-bpy)]_n(I), was synthesised under hydrothermal conditions. In the complex, the Cu^I ion shows distorted tetrahedral geometry coordinated by two N atoms from a 5-ph-2,2,-bpy ligand, N and S atoms from the different thiocyanate anions (Fig.1 and Table 1). The Cu^Iions are bridged by thiocyanide groups to form a one-dimensional coordination polymeric along the b axis (Fig. 2). Crystal packing is through van der Waals contacts and C-H···π interaction [C17-H···Cg(C12→C17)symmetry operation: 1/2+x,3/2-y,1-z with geometric parameters H···Cg of 2.92 Å, C17···Cg of 3.757 (3) Å, and C17-H···Cg of 150 °].

Related literature top

For applications of coordination metal complexes, see: Kong et al. (2008); Ohba et al. (2008). For related compounds, see Chen et al. (2009); Cui et al. (2011); Zhang et al. (2008).

Experimental top

A mixture of Cu(Ac)₂ (0.086 g, 0.64 mmol), 5-ph-2,2'-bpy (0.0231 g, 0.1 mmol), KSCN (0.059 g, 0.6 mmol), and water (8 mL) was added to a 15-mL Teflon-lined autoclave and heated at 443 K for 3 d. The autoclave was then cooled to room temperature. Red block crystals of (I) deposited on the wall of container were collected and air-dried.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Complex (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small of arbitrary radii.
	Fig. 2. A perspective view of polymer chain of complex (I).

catena-Poly[[(5-phenyl-2,2'-bipyridine- κ²N,N')copper(I)]-µ-thiocyanido-κ²N:S] top

Crystal data top

[Cu(NCS)(C₁₆H₁₂N₂)]	F(000) = 1440
M_r = 353.90	D_x = 1.584 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 15488 reflections
a = 7.7978 (9) Å	θ = 2.3–26.0°
b = 10.7744 (12) Å	µ = 1.61 mm⁻¹
c = 35.325 (4) Å	T = 153 K
V = 2967.8 (6) Å³	Block, red
Z = 8	0.42 × 0.09 × 0.06 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	2932 independent reflections
Radiation source: fine-focus sealed tube	2212 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 9 pixels mm^-1	θ_max = 26.0°, θ_min = 2.3°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −13→10
T_min = 0.840, T_max = 0.914	l = −43→35
15488 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0444P)² + 0.9913P] where P = (F_o² + 2F_c²)/3
2932 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

[Cu(NCS)(C₁₆H₁₂N₂)]	V = 2967.8 (6) Å³
M_r = 353.90	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.7978 (9) Å	µ = 1.61 mm⁻¹
b = 10.7744 (12) Å	T = 153 K
c = 35.325 (4) Å	0.42 × 0.09 × 0.06 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	2932 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2212 reflections with I > 2σ(I)
T_min = 0.840, T_max = 0.914	R_int = 0.033
15488 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.03	Δρ_max = 0.32 e Å⁻³
2932 reflections	Δρ_min = −0.20 e Å⁻³
199 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	1.11691 (4)	0.67597 (3)	0.345104 (9)	0.04739 (14)
S1	1.40271 (9)	0.61263 (7)	0.34368 (3)	0.0578 (2)
N1	1.1156 (3)	0.8538 (2)	0.34377 (6)	0.0470 (6)
C1	1.3879 (3)	0.4601 (3)	0.34412 (7)	0.0402 (6)
N3	0.9620 (3)	0.59247 (18)	0.38739 (6)	0.0373 (5)
C12	0.8393 (3)	0.6026 (2)	0.49059 (6)	0.0325 (5)
C7	0.8656 (3)	0.4982 (2)	0.37430 (7)	0.0351 (5)
C10	0.8445 (3)	0.5642 (2)	0.45016 (6)	0.0327 (5)
N2	0.9760 (3)	0.5504 (2)	0.31300 (6)	0.0460 (5)
C6	0.8833 (3)	0.4689 (2)	0.33359 (7)	0.0378 (6)
C8	0.7568 (3)	0.4343 (3)	0.39843 (7)	0.0457 (6)
H8	0.6907	0.3691	0.3893	0.055*
C15	0.8303 (4)	0.6706 (3)	0.56739 (7)	0.0461 (7)
H15	0.8272	0.6938	0.5927	0.055*
C11	0.9497 (3)	0.6232 (2)	0.42376 (7)	0.0381 (6)
H11	1.0163	0.6891	0.4323	0.046*
C17	0.9373 (3)	0.7005 (2)	0.50432 (7)	0.0423 (6)
H17	1.0077	0.7444	0.4878	0.051*
C16	0.9318 (3)	0.7338 (3)	0.54203 (8)	0.0471 (7)
H16	0.9979	0.8002	0.5504	0.057*
C14	0.7336 (3)	0.5726 (3)	0.55461 (7)	0.0465 (6)
H14	0.6649	0.5287	0.5714	0.056*
C9	0.7469 (3)	0.4675 (2)	0.43580 (7)	0.0451 (6)
H9	0.6733	0.4244	0.4518	0.054*
C5	0.8093 (4)	0.3650 (3)	0.31698 (8)	0.0490 (7)
H5	0.7476	0.3088	0.3316	0.059*
C13	0.7381 (3)	0.5388 (2)	0.51663 (7)	0.0426 (6)
H13	0.6720	0.4722	0.5084	0.051*
C3	0.9202 (4)	0.4297 (3)	0.25767 (9)	0.0643 (9)
H3	0.9332	0.4194	0.2317	0.077*
C4	0.8281 (4)	0.3458 (3)	0.27870 (9)	0.0621 (9)
H4	0.7789	0.2768	0.2672	0.074*
C2	0.9924 (4)	0.5287 (3)	0.27587 (8)	0.0607 (8)
H2	1.0568	0.5844	0.2616	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0601 (2)	0.0344 (2)	0.0477 (2)	−0.00445 (15)	0.00674 (16)	0.00251 (14)
S1	0.0532 (4)	0.0325 (4)	0.0878 (6)	−0.0041 (3)	0.0084 (4)	−0.0025 (4)
N1	0.0582 (15)	0.0369 (13)	0.0459 (14)	0.0008 (11)	−0.0004 (11)	0.0028 (10)
C1	0.0414 (14)	0.0413 (16)	0.0378 (14)	−0.0003 (11)	0.0025 (11)	−0.0002 (11)
N3	0.0432 (11)	0.0341 (11)	0.0346 (11)	−0.0032 (9)	0.0032 (9)	0.0012 (9)
C12	0.0312 (12)	0.0312 (12)	0.0349 (13)	0.0072 (10)	0.0011 (10)	0.0035 (10)
C7	0.0361 (12)	0.0336 (13)	0.0357 (13)	0.0044 (11)	−0.0020 (10)	0.0018 (10)
C10	0.0323 (12)	0.0324 (12)	0.0334 (13)	0.0048 (10)	−0.0004 (10)	0.0035 (10)
N2	0.0554 (13)	0.0483 (13)	0.0344 (12)	−0.0005 (11)	−0.0003 (10)	0.0018 (10)
C6	0.0387 (13)	0.0382 (14)	0.0365 (13)	0.0040 (11)	−0.0043 (11)	−0.0002 (11)
C8	0.0485 (15)	0.0470 (15)	0.0415 (14)	−0.0155 (13)	−0.0023 (12)	−0.0002 (12)
C15	0.0520 (15)	0.0526 (17)	0.0337 (14)	0.0146 (14)	0.0011 (12)	−0.0028 (12)
C11	0.0446 (14)	0.0335 (13)	0.0364 (14)	−0.0058 (11)	0.0010 (11)	−0.0011 (11)
C17	0.0482 (14)	0.0396 (15)	0.0392 (14)	−0.0019 (12)	0.0032 (11)	0.0023 (12)
C16	0.0535 (16)	0.0406 (15)	0.0473 (16)	0.0018 (13)	−0.0021 (12)	−0.0062 (12)
C14	0.0467 (15)	0.0547 (17)	0.0381 (14)	0.0032 (14)	0.0070 (12)	0.0049 (13)
C9	0.0443 (14)	0.0525 (16)	0.0386 (14)	−0.0143 (13)	0.0010 (12)	0.0051 (12)
C5	0.0486 (15)	0.0484 (16)	0.0501 (17)	−0.0032 (13)	−0.0006 (13)	−0.0068 (13)
C13	0.0436 (14)	0.0425 (15)	0.0416 (14)	−0.0008 (12)	0.0026 (12)	0.0012 (11)
C3	0.076 (2)	0.080 (2)	0.0370 (16)	0.0006 (19)	−0.0013 (15)	−0.0126 (16)
C4	0.0609 (18)	0.066 (2)	0.059 (2)	0.0003 (16)	−0.0046 (16)	−0.0277 (16)
C2	0.074 (2)	0.071 (2)	0.0367 (16)	−0.0054 (17)	0.0034 (14)	0.0021 (14)

Geometric parameters (Å, º) top

Cu1—N1	1.917 (2)	C8—H8	0.9300
Cu1—N2	2.079 (2)	C15—C14	1.374 (4)
Cu1—N3	2.121 (2)	C15—C16	1.376 (4)
Cu1—S1	2.3313 (9)	C15—H15	0.9300
S1—C1	1.648 (3)	C11—H11	0.9300
N1—C1ⁱ	1.145 (4)	C17—C16	1.380 (4)
C1—N1ⁱⁱ	1.145 (4)	C17—H17	0.9300
N3—C11	1.330 (3)	C16—H16	0.9300
N3—C7	1.346 (3)	C14—C13	1.390 (3)
C12—C17	1.390 (3)	C14—H14	0.9300
C12—C13	1.393 (3)	C9—H9	0.9300
C12—C10	1.487 (3)	C5—C4	1.376 (4)
C7—C8	1.385 (3)	C5—H5	0.9300
C7—C6	1.479 (3)	C13—H13	0.9300
C10—C9	1.386 (3)	C3—C2	1.367 (4)
C10—C11	1.395 (3)	C3—C4	1.373 (5)
N2—C2	1.339 (3)	C3—H3	0.9300
N2—C6	1.350 (3)	C4—H4	0.9300
C6—C5	1.390 (4)	C2—H2	0.9300
C8—C9	1.370 (4)

N1—Cu1—N2	129.35 (9)	C16—C15—H15	120.6
N1—Cu1—N3	115.99 (9)	N3—C11—C10	125.1 (2)
N2—Cu1—N3	78.88 (8)	N3—C11—H11	117.5
N1—Cu1—S1	107.29 (7)	C10—C11—H11	117.5
N2—Cu1—S1	107.64 (7)	C16—C17—C12	121.1 (2)
N3—Cu1—S1	115.82 (6)	C16—C17—H17	119.4
C1—S1—Cu1	102.99 (9)	C12—C17—H17	119.4
C1ⁱ—N1—Cu1	177.7 (2)	C15—C16—C17	121.2 (3)
N1ⁱⁱ—C1—S1	177.1 (2)	C15—C16—H16	119.4
C11—N3—C7	118.7 (2)	C17—C16—H16	119.4
C11—N3—Cu1	127.99 (17)	C15—C14—C13	120.3 (2)
C7—N3—Cu1	113.34 (15)	C15—C14—H14	119.8
C17—C12—C13	117.1 (2)	C13—C14—H14	119.8
C17—C12—C10	122.1 (2)	C8—C9—C10	121.2 (2)
C13—C12—C10	120.8 (2)	C8—C9—H9	119.4
N3—C7—C8	120.3 (2)	C10—C9—H9	119.4
N3—C7—C6	116.3 (2)	C4—C5—C6	119.4 (3)
C8—C7—C6	123.3 (2)	C4—C5—H5	120.3
C9—C10—C11	114.9 (2)	C6—C5—H5	120.3
C9—C10—C12	123.0 (2)	C14—C13—C12	121.5 (2)
C11—C10—C12	122.1 (2)	C14—C13—H13	119.3
C2—N2—C6	117.8 (2)	C12—C13—H13	119.3
C2—N2—Cu1	126.7 (2)	C2—C3—C4	118.3 (3)
C6—N2—Cu1	114.36 (17)	C2—C3—H3	120.8
N2—C6—C5	121.3 (2)	C4—C3—H3	120.8
N2—C6—C7	115.8 (2)	C3—C4—C5	119.3 (3)
C5—C6—C7	122.9 (2)	C3—C4—H4	120.4
C9—C8—C7	119.9 (2)	C5—C4—H4	120.4
C9—C8—H8	120.1	N2—C2—C3	123.9 (3)
C7—C8—H8	120.1	N2—C2—H2	118.1
C14—C15—C16	118.8 (2)	C3—C2—H2	118.1
C14—C15—H15	120.6

N1—Cu1—S1—C1	−178.99 (11)	C8—C7—C6—N2	171.1 (2)
N2—Cu1—S1—C1	−36.25 (11)	N3—C7—C6—C5	171.7 (2)
N3—Cu1—S1—C1	49.68 (11)	C8—C7—C6—C5	−8.5 (4)
N1—Cu1—N3—C11	−45.7 (2)	N3—C7—C8—C9	0.2 (4)
N2—Cu1—N3—C11	−174.2 (2)	C6—C7—C8—C9	−179.6 (2)
S1—Cu1—N3—C11	81.5 (2)	C7—N3—C11—C10	0.6 (4)
N1—Cu1—N3—C7	133.67 (16)	Cu1—N3—C11—C10	179.92 (18)
N2—Cu1—N3—C7	5.13 (16)	C9—C10—C11—N3	−0.7 (4)
S1—Cu1—N3—C7	−99.22 (16)	C12—C10—C11—N3	179.1 (2)
C11—N3—C7—C8	−0.3 (3)	C13—C12—C17—C16	−1.0 (4)
Cu1—N3—C7—C8	−179.74 (18)	C10—C12—C17—C16	−179.3 (2)
C11—N3—C7—C6	179.4 (2)	C14—C15—C16—C17	0.2 (4)
Cu1—N3—C7—C6	0.0 (3)	C12—C17—C16—C15	0.5 (4)
C17—C12—C10—C9	−179.4 (2)	C16—C15—C14—C13	−0.4 (4)
C13—C12—C10—C9	2.2 (3)	C7—C8—C9—C10	−0.2 (4)
C17—C12—C10—C11	0.9 (3)	C11—C10—C9—C8	0.4 (4)
C13—C12—C10—C11	−177.5 (2)	C12—C10—C9—C8	−179.3 (2)
N1—Cu1—N2—C2	68.4 (3)	N2—C6—C5—C4	−1.2 (4)
N3—Cu1—N2—C2	−176.9 (3)	C7—C6—C5—C4	178.4 (3)
S1—Cu1—N2—C2	−63.2 (2)	C15—C14—C13—C12	−0.1 (4)
N1—Cu1—N2—C6	−124.53 (18)	C17—C12—C13—C14	0.7 (4)
N3—Cu1—N2—C6	−9.93 (18)	C10—C12—C13—C14	179.2 (2)
S1—Cu1—N2—C6	103.86 (17)	C2—C3—C4—C5	1.0 (5)
C2—N2—C6—C5	0.9 (4)	C6—C5—C4—C3	0.2 (5)
Cu1—N2—C6—C5	−167.4 (2)	C6—N2—C2—C3	0.4 (5)
C2—N2—C6—C7	−178.8 (2)	Cu1—N2—C2—C3	167.1 (2)
Cu1—N2—C6—C7	13.0 (3)	C4—C3—C2—N2	−1.4 (5)
N3—C7—C6—N2	−8.7 (3)

Symmetry codes: (i) −x+5/2, y+1/2, z; (ii) −x+5/2, y−1/2, z.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C12–C17 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···Cgⁱⁱⁱ	0.93	2.92	3.757 (3)	150

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

Experimental details

Crystal data
Chemical formula	[Cu(NCS)(C₁₆H₁₂N₂)]
M_r	353.90
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	153
a, b, c (Å)	7.7978 (9), 10.7744 (12), 35.325 (4)
V (Å³)	2967.8 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.61
Crystal size (mm)	0.42 × 0.09 × 0.06

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.840, 0.914
No. of measured, independent and observed [I > 2σ(I)] reflections	15488, 2932, 2212
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.091, 1.03
No. of reflections	2932
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.20

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N1	1.917 (2)	Cu1—N3	2.121 (2)
Cu1—N2	2.079 (2)	Cu1—S1	2.3313 (9)