Poly[(2,2′-bipyrid­yl)-μ₃-cyanido-di-μ₂-cyanido-dicopper(I,II)]

The title compound, [Cu₂(CN)₃(C₁₀H₈N₂)]_n, crystallizes as a cyanido-bridged three-dimensional polymeric structure, where there coexist Cu^I and Cu^II ions along with μ₃- and μ₂-bridging cyanide groups. Each Cu^I ion is coordinated by four C atoms [Cu—C = 1.956 (3)–2.147 (3) Å] from two μ₃- and two μ₂-cyanide groups in a tetra­hedral environment. The Cu^II ion is coordinated by two N atoms from the 2,2′-bipyridyl ligand and three N atoms from one μ₃- and two μ₂-cyanide groups in a square-pyramidal geometry [Cu—N = 1.967 (3)–2.183 (3) Å]. The Cu^I ions are paired by two C atoms from two cyanide groups into a dinuclear unit with a short Cu^I...Cu^I distance of 2.5398 (8) Å. Each dinuclear unit links six Cu^II ions by four μ₂- and two μ₃-cyanide groups to form a 4,6-connected framework, with Cu^I...Cu^II separations ranging from 4.864 (4) to 5.252 (4) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.031
• wR factor = 0.081
• Data-to-parameter ratio = 15.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.76
PLAT320_ALERT_2_C Check Hybridisation of  C11    in Main Residue .          ?
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.16 Ratio

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.763
            Tmax scaled      0.763 Tmin scaled      0.723
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The crystal structures of some cyano-bridged Cu^I or Cu^II complexes with 2,2'-bipyridyl as co-ligand have been reported, such as catena-[(µ₂-cyano)-bis(2,2'-bipyridyl)-copper(I)] hexakis[(µ₂-cyano)-penta-copper(I)] (Chesnut & Zubieta, 1998); catena-[(µ₂-cyano)-(2,2'-bipyridyl)-copper(I)] (He et al., 2005, Mao et al., 2005) and catena-[(µ₂-cyano)-bis(2,2'-bipyridyl)-cyano-copper(II)] (Yan et al., 2006). In such complexes, one type of Cu ion either Cu^I or Cu^II appeared, and the cyano groups adopted only µ₂ bridging mode. Herein, we report a new three-dimensional polymeric Cu complex, C₁₃H₈Cu₂N₅ (I), in which there exist both Cu^I and Cu^II ions, and µ₃- and µ₂- coordination cyano groups.

As shown in Fig. 1, the Cu^I ion [Cu1] is coordinated to four C atoms from two µ₃- and two µ₂-cyano groups, respectively, in a tetrahedral environment. The Cu^II ion [Cu2] coordinates with two N atoms of one 2,2'-bipyridyl ligand, one µ₃- and two µ₂-cyano N atoms in a square-pyramidal geometry. In the structure, each two Cu^I atoms [Cu1 and Cu1A] are bridged by two µ₂-C atoms of µ₃- cyano groups to form a dinuclear unit with a Cu—Cu distance of 2.5398 (8) Å. Each such dinuclear unit is further linked to six Cu^II ions by four µ₂- and two µ₃-cyano groups, to give a 4,6-connected framework, with the Cu^I—Cu^II separations of 4.864 (4) Å for Cu1—Cu2, 4.963 (4) Å for Cu1B—Cu2, 5.010 (4) Å for Cu1C—Cu2 and 5.252 (4) Å for Cu1A—Cu2, corresponding to Fig. 1.

Related literature

For related crystal structures, see: Chesnut & Zubieta (1998); He et al. (2005); Mao et al. (2005); Yan et al. (2006).

S2. Experimental

CuCl₂.2H₂O (34 mg, 0.2 mmol), 2,2'-bipyridine (31 mg, 0.2 mmol) and cyanoacetic acid (51 mg, 0.6 mmol) were dissolved in ammonium hydroxide (20%, 10 ml). The solution was filtered and the filtrate was allowed to stand for about 30 days. Black crystals of (I) were isolated in about 20% yield with respect to Cu. The cyano groups and Cu^I ions in the product come from the in situ decomposition of cyanoacetic acid and the reduction of Cu^II ions, respectively.

S3. Refinement

H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 Å and U_iso(H) = 1.2 U_eq(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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures

Fig. 1. A portion of the polymeric network in (I), showing the atomic numbering and 30% probability displacement ellipsoids [symmetry codes: (A) -x, 1 - y, 1 - z; (B) 1/2 - x, 1/2 + y, 3/2 - z; (C) 1 - x, 1 - y, 1 - z].

Poly[(2,2'-bipyridyl)-µ₃-cyano-di-µ₂-cyano-dicopper(I,II)]

Crystal data

[Cu2(CN)3(C10H8N2)]	F(000) = 716
Mr = 361.32	Dx = 1.914 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 10053 reflections
a = 8.3009 (17) Å	θ = 3.1–27.5°
b = 13.972 (3) Å	µ = 3.39 mm^−1
c = 10.814 (2) Å	T = 293 K
β = 90.27 (3)°	Block, black
V = 1254.2 (4) Å^3	0.10 × 0.08 × 0.08 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2869 independent reflections
Radiation source: fine-focus sealed tube	2458 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ϕ and ω scan	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→10
Tmin = 0.948, Tmax = 1.000	k = −17→18
12108 measured reflections	l = −13→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0283P)^2 + 1.8789P] where P = (Fo^2 + 2Fc^2)/3
2869 reflections	(Δ/σ)max = 0.001
181 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.60 e Å^−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	0.07091 (5)	0.42052 (3)	0.51708 (3)	0.02646 (11)
Cu2	0.44880 (5)	0.61074 (3)	0.75886 (3)	0.02377 (11)
N1	0.3200 (3)	0.57131 (19)	0.9116 (2)	0.0273 (6)
N2	0.4729 (3)	0.46640 (18)	0.7511 (2)	0.0272 (6)
N3	0.2456 (4)	0.59756 (19)	0.6310 (3)	0.0322 (6)
C12	0.2496 (4)	0.3838 (2)	0.4065 (3)	0.0282 (7)
C13	0.0437 (4)	0.3177 (2)	0.6380 (3)	0.0293 (7)
C1	0.2443 (4)	0.6312 (3)	0.9891 (3)	0.0356 (8)
H1A	0.2484	0.6967	0.9738	0.043*
C2	0.1606 (4)	0.5987 (3)	1.0907 (3)	0.0402 (9)
H2A	0.1075	0.6415	1.1423	0.048*
C3	0.1570 (5)	0.5032 (3)	1.1144 (3)	0.0431 (9)
H3A	0.1024	0.4801	1.1830	0.052*
C4	0.2352 (5)	0.4403 (3)	1.0356 (3)	0.0401 (8)
H4A	0.2345	0.3749	1.0511	0.048*
C5	0.3145 (4)	0.4766 (2)	0.9334 (3)	0.0282 (7)
C6	0.3988 (4)	0.4166 (2)	0.8423 (3)	0.0269 (6)
C7	0.4030 (5)	0.3175 (2)	0.8446 (3)	0.0374 (8)
H7A	0.3535	0.2841	0.9083	0.045*
C8	0.4813 (5)	0.2692 (2)	0.7519 (4)	0.0428 (9)
H8A	0.4853	0.2027	0.7525	0.051*
C9	0.5534 (5)	0.3196 (3)	0.6583 (4)	0.0422 (9)
H9A	0.6056	0.2880	0.5944	0.051*
C10	0.5469 (5)	0.4182 (2)	0.6612 (3)	0.0382 (8)
H10A	0.5960	0.4525	0.5980	0.046*
C11	0.1443 (4)	0.5593 (2)	0.5813 (3)	0.0313 (7)
N4	0.3625 (4)	0.37243 (19)	0.3484 (3)	0.0338 (6)
N5	0.0438 (4)	0.2456 (2)	0.6877 (3)	0.0350 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0284 (2)	0.0192 (2)	0.0318 (2)	0.00216 (15)	0.00388 (15)	0.00332 (14)
Cu2	0.0269 (2)	0.01838 (19)	0.02610 (19)	−0.00175 (14)	0.00628 (14)	−0.00388 (13)
N1	0.0273 (14)	0.0282 (14)	0.0262 (13)	−0.0015 (11)	0.0030 (10)	−0.0018 (10)
N2	0.0318 (15)	0.0206 (13)	0.0292 (13)	−0.0009 (11)	0.0045 (11)	−0.0020 (10)
N3	0.0315 (15)	0.0267 (14)	0.0383 (15)	0.0014 (12)	−0.0078 (12)	−0.0078 (11)
C12	0.0302 (17)	0.0217 (15)	0.0329 (16)	−0.0012 (13)	0.0062 (13)	−0.0025 (12)
C13	0.0328 (18)	0.0245 (16)	0.0308 (16)	0.0033 (13)	0.0085 (13)	0.0019 (13)
C1	0.0350 (19)	0.0338 (19)	0.0380 (18)	0.0014 (15)	0.0076 (14)	−0.0052 (14)
C2	0.0316 (19)	0.058 (2)	0.0308 (17)	0.0021 (17)	0.0095 (14)	−0.0071 (16)
C3	0.037 (2)	0.062 (3)	0.0303 (18)	−0.0030 (18)	0.0115 (15)	0.0063 (16)
C4	0.041 (2)	0.042 (2)	0.0374 (19)	−0.0071 (16)	0.0013 (15)	0.0112 (15)
C5	0.0250 (16)	0.0316 (17)	0.0281 (16)	−0.0021 (13)	−0.0007 (12)	−0.0004 (12)
C6	0.0262 (16)	0.0259 (16)	0.0286 (15)	−0.0036 (12)	−0.0019 (12)	0.0006 (12)
C7	0.045 (2)	0.0251 (18)	0.0423 (19)	−0.0033 (15)	0.0011 (16)	0.0067 (14)
C8	0.055 (2)	0.0163 (16)	0.057 (2)	0.0014 (15)	−0.0017 (18)	−0.0020 (15)
C9	0.051 (2)	0.0264 (18)	0.049 (2)	0.0051 (16)	0.0104 (17)	−0.0089 (15)
C10	0.048 (2)	0.0252 (17)	0.0418 (19)	−0.0012 (15)	0.0150 (16)	−0.0041 (14)
C11	0.0291 (17)	0.0346 (18)	0.0302 (16)	−0.0008 (14)	0.0058 (13)	−0.0047 (13)
N4	0.0359 (16)	0.0244 (14)	0.0411 (16)	−0.0030 (12)	0.0109 (13)	−0.0021 (11)
N5	0.0423 (17)	0.0266 (15)	0.0361 (15)	0.0041 (12)	0.0131 (12)	0.0059 (11)

Geometric parameters (Å, º)

Cu1—C11^i	2.094 (4)	C2—C3	1.359 (6)
Cu1—C11	2.147 (3)	C2—H2A	0.9300
Cu1—C12	1.977 (3)	C3—C4	1.387 (5)
Cu1—C13	1.956 (3)	C3—H3A	0.9300
Cu1—Cu1^i	2.5398 (8)	C4—C5	1.385 (5)
Cu2—N1	2.047 (3)	C4—H4A	0.9300
Cu2—N2	2.028 (3)	C5—C6	1.473 (4)
Cu2—N3	2.183 (3)	C6—C7	1.385 (5)
Cu2—N4^ii	1.967 (3)	C7—C8	1.375 (5)
Cu2—N5^iii	1.972 (3)	C7—H7A	0.9300
N1—C1	1.343 (4)	C8—C9	1.373 (5)
N1—C5	1.344 (4)	C8—H8A	0.9300
N2—C10	1.335 (4)	C9—C10	1.379 (5)
N2—C6	1.357 (4)	C9—H9A	0.9300
N3—C11	1.131 (4)	C10—H10A	0.9300
C12—N4	1.143 (4)	C11—Cu1^i	2.094 (4)
C13—N5	1.142 (4)	N4—Cu2^ii	1.967 (3)
C1—C2	1.380 (5)	N5—Cu2^iv	1.972 (3)
C1—H1A	0.9300
C13—Cu1—C12	107.62 (13)	C2—C1—H1A	119.0
C13—Cu1—C11^i	109.73 (14)	C3—C2—C1	119.0 (3)
C12—Cu1—C11^i	111.61 (13)	C3—C2—H2A	120.5
C13—Cu1—C11	118.70 (13)	C1—C2—H2A	120.5
C12—Cu1—C11	102.58 (13)	C2—C3—C4	119.7 (3)
C11^i—Cu1—C11	106.44 (11)	C2—C3—H3A	120.2
C13—Cu1—Cu1^i	133.18 (10)	C4—C3—H3A	120.2
C12—Cu1—Cu1^i	119.19 (9)	C5—C4—C3	118.9 (3)
C11^i—Cu1—Cu1^i	54.18 (9)	C5—C4—H4A	120.5
C11—Cu1—Cu1^i	52.25 (10)	C3—C4—H4A	120.5
N4^ii—Cu2—N5^iii	92.00 (11)	N1—C5—C4	121.1 (3)
N4^ii—Cu2—N2	90.89 (11)	N1—C5—C6	115.2 (3)
N5^iii—Cu2—N2	163.61 (12)	C4—C5—C6	123.6 (3)
N4^ii—Cu2—N1	158.12 (12)	N2—C6—C7	121.0 (3)
N5^iii—Cu2—N1	92.08 (11)	N2—C6—C5	114.4 (3)
N2—Cu2—N1	79.50 (10)	C7—C6—C5	124.7 (3)
N4^ii—Cu2—N3	104.58 (12)	C8—C7—C6	119.3 (3)
N5^iii—Cu2—N3	106.79 (12)	C8—C7—H7A	120.3
N2—Cu2—N3	88.05 (11)	C6—C7—H7A	120.3
N1—Cu2—N3	94.78 (11)	C9—C8—C7	119.6 (3)
Cu1^i—C11—Cu1	73.56 (11)	C9—C8—H8A	120.2
C1—N1—C5	119.2 (3)	C7—C8—H8A	120.2
C1—N1—Cu2	125.7 (2)	C8—C9—C10	118.6 (3)
C5—N1—Cu2	115.1 (2)	C8—C9—H9A	120.7
C10—N2—C6	118.9 (3)	C10—C9—H9A	120.7
C10—N2—Cu2	125.3 (2)	N2—C10—C9	122.6 (3)
C6—N2—Cu2	115.8 (2)	N2—C10—H10A	118.7
C11—N3—Cu2	155.8 (3)	C9—C10—H10A	118.7
N4—C12—Cu1	171.4 (3)	N3—C11—Cu1^i	144.0 (3)
N5—C13—Cu1	164.3 (3)	N3—C11—Cu1	142.2 (3)
N1—C1—C2	122.0 (3)	C12—N4—Cu2^ii	164.9 (3)
N1—C1—H1A	119.0	C13—N5—Cu2^iv	168.8 (3)
N4^ii—Cu2—N1—C1	115.0 (4)	Cu2—N1—C5—C4	178.2 (3)
N5^iii—Cu2—N1—C1	14.4 (3)	C1—N1—C5—C6	179.1 (3)
N2—Cu2—N1—C1	−179.7 (3)	Cu2—N1—C5—C6	−1.4 (4)
N3—Cu2—N1—C1	−92.6 (3)	C3—C4—C5—N1	1.7 (5)
N4^ii—Cu2—N1—C5	−64.5 (4)	C3—C4—C5—C6	−178.8 (3)
N5^iii—Cu2—N1—C5	−165.1 (2)	C10—N2—C6—C7	1.7 (5)
N2—Cu2—N1—C5	0.7 (2)	Cu2—N2—C6—C7	178.2 (3)
N3—Cu2—N1—C5	87.8 (2)	C10—N2—C6—C5	−177.3 (3)
N4^ii—Cu2—N2—C10	−23.5 (3)	Cu2—N2—C6—C5	−0.8 (3)
N5^iii—Cu2—N2—C10	−123.7 (4)	N1—C5—C6—N2	1.4 (4)
N1—Cu2—N2—C10	176.3 (3)	C4—C5—C6—N2	−178.1 (3)
N3—Cu2—N2—C10	81.0 (3)	N1—C5—C6—C7	−177.5 (3)
N4^ii—Cu2—N2—C6	160.3 (2)	C4—C5—C6—C7	3.0 (5)
N5^iii—Cu2—N2—C6	60.2 (5)	N2—C6—C7—C8	−1.1 (5)
N1—Cu2—N2—C6	0.1 (2)	C5—C6—C7—C8	177.8 (3)
N3—Cu2—N2—C6	−95.1 (2)	C6—C7—C8—C9	−0.2 (6)
N4^ii—Cu2—N3—C11	110.5 (7)	C7—C8—C9—C10	0.8 (6)
N5^iii—Cu2—N3—C11	−152.8 (7)	C6—N2—C10—C9	−1.1 (6)
N2—Cu2—N3—C11	20.1 (7)	Cu2—N2—C10—C9	−177.1 (3)
N1—Cu2—N3—C11	−59.2 (7)	C8—C9—C10—N2	−0.2 (6)
C12—Cu1—C13—N5	−24.5 (12)	Cu2—N3—C11—Cu1^i	160.3 (4)
C11^i—Cu1—C13—N5	97.1 (12)	Cu2—N3—C11—Cu1	−28.0 (10)
C11—Cu1—C13—N5	−140.2 (12)	C13—Cu1—C11—N3	60.8 (5)
Cu1^i—Cu1—C13—N5	156.1 (11)	C12—Cu1—C11—N3	−57.6 (5)
C5—N1—C1—C2	−0.1 (5)	C11^i—Cu1—C11—N3	−175.0 (5)
Cu2—N1—C1—C2	−179.6 (3)	Cu1^i—Cu1—C11—N3	−175.0 (5)
N1—C1—C2—C3	1.2 (6)	C13—Cu1—C11—Cu1^i	−124.25 (13)
C1—C2—C3—C4	−0.8 (6)	C12—Cu1—C11—Cu1^i	117.34 (12)
C2—C3—C4—C5	−0.6 (6)	C11^i—Cu1—C11—Cu1^i	0.0
C1—N1—C5—C4	−1.4 (5)	Cu1—C13—N5—Cu2^iv	−16 (3)

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