catena-Poly[{μ-cyanido-bis­[(4,4′-dimethyl-2,2′-bipyridine-κ² N,N′)copper(I)]}-μ-cyanido-copper(I)-μ-cyanido]

Abstract

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,

• a = 10.7196 (7) Å

• b = 12.3700 (9) Å

• c = 20.9182 (14) Å

• β = 100.146 (1)°

• V = 2730.4 (3) ų

• 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[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

The component atoms of the cyanide groups were each refined as a 50%:50% mixture of carbon and nitrogen. The pair of C/N atoms were restrained to the same site and also to have the same temperature factors. Hydrogen atoms were placed at calculated positions in the riding model approximation with C—H = 0.93–0.98 Å and U_iso(H) = 1.2–1.5U_eq(C).

Figures

Fig. 1.

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

Crystal data

[Cu3(CN)3(C12H12N2)2]	F000 = 1288
Mr = 637.15	Dx = 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 = 2.5–27.0º
b = 12.3700 (9) Å	µ = 2.34 mm−1
c = 20.9182 (14) Å	T = 295 (2) K
β = 100.146 (1)º	Block, red
V = 2730.4 (3) Å3	0.30 × 0.20 × 0.16 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer	3125 independent reflections
Radiation source: fine-focus sealed tube	2491 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.024
T = 295(2) K	θmax = 27.5º
φ and ω scans	θmin = 2.5º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.540, Tmax = 0.705	k = −16→15
8685 measured reflections	l = −16→27

Refinement

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)] = 0.038	H-atom parameters constrained
wR(F2) = 0.110	w = 1/[σ2(Fo2) + (0.065P)2 + 0.8323P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
3125 reflections	Δρmax = 0.53 e Å−3
170 parameters	Δρmin = −0.21 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	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, °)

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.