catena-Poly[{μ-cyanido-bis­[(4,4′-dimethyl-2,2′-bipyridine-κ2N,N′)copper(I)]}-μ-cyanido-copper(I)-μ-cyanido]

Lin, S.-H.; Yang, Y.-Y.; Ng, S.W.

doi:10.1107/S1600536808022964

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page m1076

doi:10.1107/S1600536808022964

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catena-Poly[{μ-cyanido-bis[(4,4′-dimethyl-2,2′-bipyridine-κ²N,N′)copper(I)]}-μ-cyanido-copper(I)-μ-cyanido]

Shi-Hong Lin,^a Ying-Yi Yang ^a and Seik Weng Ng ^b ^*

^aDepartment of Chemistry, Shantou University, Shantou, Guangdong 515063, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 10 July 2008; accepted 22 July 2008; online 26 July 2008)

In the title compound, [Cu₃(CN)₃(C₁₂H₁₂N₂)₂], two 2,2′-bipyridine N,N′-chelated Cu^I atoms are linked by a cyanide bridge that lies about a center of inversion; the Cu^I atom exists in a tetrahedral coordination geometry. This dinuclear entity is linked to another Cu^I atom that lies on a twofold rotation axis by another cyanide bridge, these bridges giving rise to the formation of a linear chain motif.

Related literature

Some copper(I) cyanide adducts with 2,2′-bipyridine-like ligands that adopt chain structures in which the cyanide group functions as a bridge are triscyano-bis(2,2′-biquinoline)tricopper (Chesnut et al., 2001 ; Dessy et al., 1985 ), tetrakiscyano(2,2′-biquinoline)tetracopper (Chesnut & Zubieta, 1998 ) and biscyano-(4,4′-diphenyl-2,2′-bipyridine)dicopper (Chesnut et al., 2001).

Experimental

Crystal data

[Cu₃(CN)₃(C₁₂H₁₂N₂)₂]
M_r = 637.15
Monoclinic, C 2/c
a = 10.7196 (7) Å
b = 12.3700 (9) Å
c = 20.9182 (14) Å
β = 100.146 (1)°
V = 2730.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.34 mm⁻¹
T = 295 (2) K
0.30 × 0.20 × 0.16 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.540, T_max = 0.705
8685 measured reflections
3125 independent reflections
2491 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.110
S = 1.03
3125 reflections
170 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808022964/rk2103sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808022964/rk2103Isup2.hkl

checkCIF report

Comment top

The cyanide group functions as a bridging group in a number of copper(I) adducts of 2,2'-bipyridine type of N-heterocycles. Those who crystal structure have been described include the triscyano-bis(2,2'-biquinoline)tricopper (Chesnut et al., 2001; Dessy et al., 1985), tetrakiscyano(2,2'-biquinoline)tetracopper (Chesnut & Zubieta, 1998) and biscyano-(4,4'-diphenyl-2,2'-bipyridine)dicopper (Chesnut et al., 2001).

The copper(I) cyanide adduct with 4,4'-dimethyl-2,2'-biyridine (Scheme 1, Fig. 1) adopts a similar chain motif. Two N-heterocycle-chelated copper(I) atoms are linked by a cyanide bridge that lies about a center-of-inversion; the copper(I) atom exists in a tetrahedral coordination geometry. This dinuclear entity is linked to copper(I) atom that lies on a twofold rotation axis by another cyanide bridge.

Related literature top

Some copper(I) cyanide adducts with 2,2'-bipyridine-like ligands that adopt chain structures in which the cyanide group functions as a bridge are triscyano-bis(2,2'-biquinoline)tricopper (Chesnut et al., 2001; Dessy et al., 1985), tetrakiscyano(2,2'-biquinoline)tetracopper (Chesnut & Zubieta, 1998) and biscyano-(4,4'-diphenyl-2,2'-bipyridine)dicopper (Chesnut et al., 2001).

Experimental top

4,4'-Dimethyl-2,2'-bipyridine (0.055 g, 0.3 mmol), cuprous cyanide (0.009 g, 0.1 mmol) and acetonitrile (8 ml) were placed in a 15-ml, teflon-lined autoclave. It was heated at 453 K for 72 hours, then was cooled to 333 K at a rate of 5 K per hour and then kept at this temperature for a further 10 hours before being cooled to room temperature. Red prisms were in 50% yield based on the N-heterocycle.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of a portion of the linear chain motif; probability levels are set at 50%.

catena-Poly[{µ-cyanido-bis[(4,4'-dimethyl-2,2'-bipyridine- κ²N,N')copper(I)]}-µ-cyanido-copper(I)-µ-cyanido] top

Crystal data top

[Cu₃(CN)₃(C₁₂H₁₂N₂)₂]	F(000) = 1288
M_r = 637.15	D_x = 1.550 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2750 reflections
a = 10.7196 (7) Å	θ = 2.5–27.0°
b = 12.3700 (9) Å	µ = 2.34 mm⁻¹
c = 20.9182 (14) Å	T = 295 K
β = 100.146 (1)°	Block, red
V = 2730.4 (3) Å³	0.30 × 0.20 × 0.16 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	3125 independent reflections
Radiation source: fine-focus sealed tube	2491 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.540, T_max = 0.705	k = −16→15
8685 measured reflections	l = −16→27

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.065P)² + 0.8323P] where P = (F_o² + 2F_c²)/3
3125 reflections	(Δ/σ)_max = 0.001
170 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

[Cu₃(CN)₃(C₁₂H₁₂N₂)₂]	V = 2730.4 (3) Å³
M_r = 637.15	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 10.7196 (7) Å	µ = 2.34 mm⁻¹
b = 12.3700 (9) Å	T = 295 K
c = 20.9182 (14) Å	0.30 × 0.20 × 0.16 mm
β = 100.146 (1)°

Data collection top

Bruker SMART APEX diffractometer	3125 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2491 reflections with I > 2σ(I)
T_min = 0.540, T_max = 0.705	R_int = 0.024
8685 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.03	Δρ_max = 0.53 e Å⁻³
3125 reflections	Δρ_min = −0.22 e Å⁻³
170 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.74268 (3)	0.41078 (2)	0.072850 (16)	0.04716 (14)
Cu2	0.5000	0.41827 (4)	0.2500	0.05469 (16)
N1	0.75592 (19)	0.54384 (16)	0.01065 (10)	0.0420 (5)
N2	0.92273 (18)	0.47469 (15)	0.11124 (9)	0.0406 (4)
N3	0.6442 (3)	0.41773 (18)	0.14085 (14)	0.0519 (6)	0.50
N4	0.5915 (2)	0.4184 (2)	0.18400 (12)	0.0502 (6)	0.50
N5	0.7489 (2)	0.28632 (17)	0.01721 (11)	0.0487 (6)	0.50
C3'	0.6442 (3)	0.41773 (18)	0.14085 (14)	0.0519 (6)	0.50
C4'	0.5915 (2)	0.4184 (2)	0.18400 (12)	0.0502 (6)	0.50
C5'	0.7489 (2)	0.28632 (17)	0.01721 (11)	0.0487 (6)	0.50
C1	0.6717 (3)	0.5725 (2)	−0.04135 (14)	0.0531 (6)
H1	0.5932	0.5384	−0.0485	0.064*
C2	0.6951 (3)	0.6501 (2)	−0.08494 (13)	0.0562 (7)
H2	0.6325	0.6680	−0.1200	0.067*
C3	0.8105 (3)	0.7011 (2)	−0.07670 (12)	0.0493 (6)
C4	0.8992 (2)	0.67121 (18)	−0.02273 (12)	0.0450 (6)
H4	0.9791	0.7030	−0.0154	0.054*
C5	0.8687 (2)	0.59363 (16)	0.02044 (12)	0.0385 (5)
C6	0.8409 (4)	0.7858 (2)	−0.12307 (15)	0.0699 (9)
H6A	0.8117	0.7623	−0.1669	0.105*
H6B	0.9309	0.7970	−0.1164	0.105*
H6C	0.7997	0.8523	−0.1156	0.105*
C7	0.9594 (2)	0.56084 (18)	0.07973 (11)	0.0391 (5)
C8	1.0699 (2)	0.61388 (19)	0.10154 (13)	0.0461 (6)
H8	1.0910	0.6739	0.0789	0.055*
C9	1.1516 (3)	0.5801 (2)	0.15691 (14)	0.0523 (6)
C10	1.1131 (3)	0.4918 (2)	0.18924 (14)	0.0559 (7)
H10	1.1634	0.4661	0.2270	0.067*
C11	1.0006 (3)	0.4430 (2)	0.16498 (13)	0.0516 (6)
H11	0.9766	0.3837	0.1873	0.062*
C12	1.2752 (3)	0.6366 (3)	0.18039 (18)	0.0781 (10)
H12A	1.3038	0.6203	0.2255	0.117*
H12B	1.2635	0.7133	0.1751	0.117*
H12C	1.3372	0.6125	0.1556	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0535 (2)	0.0446 (2)	0.0483 (2)	−0.01261 (12)	0.02281 (16)	−0.00397 (12)
Cu2	0.0494 (3)	0.0793 (4)	0.0406 (3)	0.000	0.0223 (2)	0.000
N1	0.0483 (11)	0.0401 (10)	0.0402 (12)	−0.0070 (8)	0.0149 (9)	−0.0055 (8)
N2	0.0469 (10)	0.0416 (10)	0.0376 (11)	−0.0031 (8)	0.0193 (9)	0.0007 (8)
N3	0.0530 (13)	0.0527 (14)	0.0522 (15)	−0.0098 (10)	0.0152 (12)	−0.0068 (10)
N4	0.0469 (13)	0.0700 (16)	0.0387 (13)	−0.0049 (10)	0.0214 (11)	−0.0049 (10)
N5	0.0560 (13)	0.0453 (12)	0.0514 (15)	−0.0154 (10)	0.0281 (11)	−0.0066 (9)
C3'	0.0530 (13)	0.0527 (14)	0.0522 (15)	−0.0098 (10)	0.0152 (12)	−0.0068 (10)
C4'	0.0469 (13)	0.0700 (16)	0.0387 (13)	−0.0049 (10)	0.0214 (11)	−0.0049 (10)
C5'	0.0560 (13)	0.0453 (12)	0.0514 (15)	−0.0154 (10)	0.0281 (11)	−0.0066 (9)
C1	0.0539 (15)	0.0559 (15)	0.0491 (16)	−0.0090 (12)	0.0082 (13)	−0.0071 (12)
C2	0.0655 (16)	0.0599 (16)	0.0415 (15)	0.0020 (13)	0.0047 (13)	0.0003 (12)
C3	0.0678 (16)	0.0432 (12)	0.0409 (14)	0.0022 (12)	0.0206 (13)	0.0002 (10)
C4	0.0525 (14)	0.0423 (13)	0.0451 (14)	−0.0055 (10)	0.0221 (11)	−0.0005 (10)
C5	0.0457 (12)	0.0370 (11)	0.0365 (13)	−0.0020 (9)	0.0175 (10)	−0.0035 (9)
C6	0.098 (2)	0.0630 (18)	0.0550 (19)	0.0058 (16)	0.0312 (17)	0.0142 (14)
C7	0.0456 (13)	0.0367 (11)	0.0400 (13)	−0.0031 (9)	0.0216 (11)	−0.0021 (9)
C8	0.0501 (14)	0.0424 (12)	0.0482 (15)	−0.0047 (10)	0.0153 (12)	0.0046 (10)
C9	0.0506 (14)	0.0537 (15)	0.0530 (17)	−0.0049 (11)	0.0103 (12)	−0.0013 (11)
C10	0.0554 (15)	0.0640 (17)	0.0473 (16)	0.0013 (13)	0.0066 (12)	0.0101 (13)
C11	0.0628 (16)	0.0484 (13)	0.0474 (15)	−0.0050 (12)	0.0201 (13)	0.0069 (12)
C12	0.0605 (18)	0.080 (2)	0.086 (2)	−0.0172 (16)	−0.0074 (17)	0.0093 (19)

Geometric parameters (Å, º) top

Cu1—N1	2.118 (2)	C4—C5	1.395 (3)
Cu1—N2	2.109 (2)	C4—H4	0.9300
Cu1—N3	1.917 (3)	C5—C7	1.491 (3)
Cu1—N5	1.938 (2)	C6—H6A	0.9600
Cu2—N4	1.829 (2)	C6—H6B	0.9600
Cu2—N4ⁱ	1.829 (2)	C6—H6C	0.9600
N1—C1	1.333 (3)	C7—C8	1.361 (4)
N1—C5	1.340 (3)	C8—C9	1.388 (4)
N2—C11	1.336 (3)	C8—H8	0.9300
N2—C7	1.347 (3)	C9—C10	1.385 (4)
N3—N4	1.146 (4)	C9—C12	1.502 (4)
N5—C5'ⁱⁱ	1.154 (4)	C10—C11	1.364 (4)
C1—C2	1.377 (4)	C10—H10	0.9300
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.372 (4)	C12—H12A	0.9600
C2—H2	0.9300	C12—H12B	0.9600
C3—C4	1.392 (4)	C12—H12C	0.9600
C3—C6	1.503 (4)

N3—Cu1—N5	124.25 (9)	N1—C5—C4	121.7 (2)
N3—Cu1—N2	106.70 (9)	N1—C5—C7	116.1 (2)
N5—Cu1—N2	113.61 (9)	C4—C5—C7	122.2 (2)
N3—Cu1—N1	121.75 (9)	C3—C6—H6A	109.5
N5—Cu1—N1	103.61 (9)	C3—C6—H6B	109.5
N2—Cu1—N1	77.69 (7)	H6A—C6—H6B	109.5
N4—Cu2—C4'ⁱ	179.88 (15)	C3—C6—H6C	109.5
C4'ⁱ—Cu2—N4ⁱ	0.00 (12)	H6A—C6—H6C	109.5
C1—N1—C5	117.7 (2)	H6B—C6—H6C	109.5
C1—N1—Cu1	126.79 (17)	N2—C7—C8	121.9 (2)
C5—N1—Cu1	114.80 (16)	N2—C7—C5	114.8 (2)
C11—N2—C7	116.8 (2)	C8—C7—C5	123.3 (2)
C11—N2—Cu1	127.21 (16)	C7—C8—C9	121.3 (2)
C7—N2—Cu1	115.86 (16)	C7—C8—H8	119.4
N4—N3—Cu1	175.6 (3)	C9—C8—H8	119.4
N3—N4—Cu2	177.1 (3)	C10—C9—C8	116.5 (2)
C5'ⁱⁱ—N5—Cu1	178.3 (3)	C10—C9—C12	121.9 (3)
N5ⁱⁱ—N5—Cu1	178.3 (3)	C8—C9—C12	121.6 (3)
N1—C1—C2	123.4 (2)	C11—C10—C9	119.2 (3)
N1—C1—H1	118.3	C11—C10—H10	120.4
C2—C1—H1	118.3	C9—C10—H10	120.4
C3—C2—C1	120.2 (3)	N2—C11—C10	124.3 (2)
C3—C2—H2	119.9	N2—C11—H11	117.8
C1—C2—H2	119.9	C10—C11—H11	117.8
C2—C3—C4	116.8 (2)	C9—C12—H12A	109.5
C2—C3—C6	122.2 (3)	C9—C12—H12B	109.5
C4—C3—C6	120.9 (2)	H12A—C12—H12B	109.5
C3—C4—C5	120.2 (2)	C9—C12—H12C	109.5
C3—C4—H4	119.9	H12A—C12—H12C	109.5
C5—C4—H4	119.9	H12B—C12—H12C	109.5

N3—Cu1—N1—C1	−81.2 (2)	C1—N1—C5—C7	178.9 (2)
N5—Cu1—N1—C1	64.9 (2)	Cu1—N1—C5—C7	−9.9 (2)
N2—Cu1—N1—C1	176.6 (2)	C3—C4—C5—N1	1.8 (3)
N3—Cu1—N1—C5	108.54 (18)	C3—C4—C5—C7	−178.5 (2)
N5—Cu1—N1—C5	−105.30 (17)	C11—N2—C7—C8	−0.4 (3)
N2—Cu1—N1—C5	6.36 (15)	Cu1—N2—C7—C8	176.04 (18)
N3—Cu1—N2—C11	54.7 (2)	C11—N2—C7—C5	−179.5 (2)
N5—Cu1—N2—C11	−85.9 (2)	Cu1—N2—C7—C5	−3.0 (2)
N1—Cu1—N2—C11	174.5 (2)	N1—C5—C7—N2	8.7 (3)
N3—Cu1—N2—C7	−121.34 (17)	C4—C5—C7—N2	−171.0 (2)
N5—Cu1—N2—C7	98.09 (17)	N1—C5—C7—C8	−170.4 (2)
N1—Cu1—N2—C7	−1.55 (15)	C4—C5—C7—C8	10.0 (4)
C5—N1—C1—C2	0.0 (4)	N2—C7—C8—C9	1.3 (4)
Cu1—N1—C1—C2	−170.0 (2)	C5—C7—C8—C9	−179.7 (2)
N1—C1—C2—C3	1.1 (4)	C7—C8—C9—C10	−1.5 (4)
C1—C2—C3—C4	−0.7 (4)	C7—C8—C9—C12	178.5 (3)
C1—C2—C3—C6	179.7 (3)	C8—C9—C10—C11	1.0 (4)
C2—C3—C4—C5	−0.7 (4)	C12—C9—C10—C11	−179.1 (3)
C6—C3—C4—C5	179.0 (2)	C7—N2—C11—C10	−0.2 (4)
C1—N1—C5—C4	−1.4 (3)	Cu1—N2—C11—C10	−176.2 (2)
Cu1—N1—C5—C4	169.76 (17)	C9—C10—C11—N2	−0.1 (5)

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

Experimental details

Crystal data
Chemical formula	[Cu₃(CN)₃(C₁₂H₁₂N₂)₂]
M_r	637.15
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	10.7196 (7), 12.3700 (9), 20.9182 (14)
β (°)	100.146 (1)
V (Å³)	2730.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.34
Crystal size (mm)	0.30 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.540, 0.705
No. of measured, independent and observed [I > 2σ(I)] reflections	8685, 3125, 2491
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.110, 1.03
No. of reflections	3125
No. of parameters	170
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.22

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Acknowledgements

The authors thank Shantou University and the University of Malaya for supporting this study.

References

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