Poly[dipyridine­copper(II)-μ-cyano-copper(II)-tri-μ-cyano]

The crystal structure of the title compound, [Cu(C₅H₅N)₂{Cu(CN)₄}]_n, comprises [Cu(py)₂]²⁺ (py is pyridine) and [Cu(CN)₄]²⁻ subunits which are connected through bridging cyano groups to form a three-dimensional network, with Cu atoms located on sites of symmetry 2/m and 222 for the cation and anion, respectively.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.030
• wR factor = 0.077
• Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 2000); molecular graphics: SHELXTL (Sheldrick, 1999) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.

Poly[µ-cyano-tetracyanodipyridinedicopper(II)]

Crystal data

[Cu2(CN)4(C5H5N)2]	F(000) = 776
Mr = 389.36	Dx = 1.569 Mg m^−3
Orthorhombic, Cccm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2 2 c	Cell parameters from 4561 reflections
a = 9.231 (3) Å	θ = 2.7–26.7°
b = 13.375 (4) Å	µ = 2.58 mm^−1
c = 13.354 (4) Å	T = 273 K
V = 1648.8 (9) Å^3	Block, yellow
Z = 4	0.40 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer	806 independent reflections
Radiation source: fine-focus sealed tube	726 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 25.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −11→10
Tmin = 0.404, Tmax = 0.595	k = −9→16
3933 measured reflections	l = −13→16

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0459P)^2 + 1.7229P] where P = (Fo^2 + 2Fc^2)/3
806 reflections	(Δ/σ)max < 0.001
56 parameters	Δρmax = 0.43 e Å^−3
1 restraint	Δρmin = −0.26 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	1.0000	0.5000	0.2500	0.0292 (2)
Cu2	1.2500	0.2500	0.5000	0.0316 (2)
N1	1.1774 (3)	0.3525 (2)	0.3873 (2)	0.0451 (7)
N2	1.0402 (4)	0.1821 (3)	0.5000	0.0439 (9)
C1	1.1191 (3)	0.4088 (2)	0.3368 (2)	0.0380 (7)
C2	0.9716 (4)	0.1615 (3)	0.4162 (3)	0.0664 (11)
H2	1.0179	0.1751	0.3559	0.080*
C3	0.8357 (5)	0.1211 (4)	0.4134 (4)	0.0894 (16)
H3	0.7909	0.1083	0.3524	0.107*
C4	0.7675 (7)	0.1001 (6)	0.5000	0.089 (2)
H4	0.6755	0.0717	0.5000	0.107*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0358 (4)	0.0257 (4)	0.0261 (4)	0.000	0.000	0.000
Cu2	0.0353 (4)	0.0312 (4)	0.0281 (4)	0.0042 (3)	0.000	0.000
N1	0.0521 (16)	0.0404 (15)	0.0426 (15)	0.0023 (13)	−0.0030 (12)	0.0074 (13)
N2	0.047 (2)	0.042 (2)	0.043 (2)	−0.0018 (18)	0.000	0.000
C1	0.0428 (16)	0.0374 (16)	0.0339 (15)	−0.0021 (14)	−0.0011 (13)	0.0023 (14)
C2	0.066 (2)	0.081 (3)	0.052 (2)	−0.016 (2)	−0.0049 (18)	−0.005 (2)
C3	0.081 (3)	0.106 (4)	0.081 (3)	−0.046 (3)	−0.022 (2)	−0.006 (3)
C4	0.067 (4)	0.092 (5)	0.108 (5)	−0.038 (4)	0.000	0.000

Geometric parameters (Å, º)

Cu1—C1^i	2.011 (3)	N1—C1	1.144 (4)
Cu1—C1^ii	2.011 (3)	N2—C2	1.315 (4)
Cu1—C1^iii	2.011 (3)	N2—C2^v	1.315 (4)
Cu1—C1	2.011 (3)	C2—C3	1.366 (6)
Cu2—N2^iv	2.139 (4)	C2—H2	0.9300
Cu2—N2	2.139 (4)	C3—C4	1.347 (6)
Cu2—N1^v	2.144 (3)	C3—H3	0.9300
Cu2—N1^vi	2.144 (3)	C4—C3^v	1.347 (6)
Cu2—N1	2.144 (3)	C4—H4	0.9300
Cu2—N1^iv	2.144 (3)
C1^i—Cu1—C1^ii	109.55 (17)	N1^v—Cu2—N1^iv	90.77 (14)
C1^i—Cu1—C1^iii	113.68 (17)	N1^vi—Cu2—N1^iv	89.23 (14)
C1^ii—Cu1—C1^iii	105.29 (17)	N1—Cu2—N1^iv	180.00 (10)
C1^i—Cu1—C1	105.29 (17)	C1—N1—Cu2	168.8 (3)
C1^ii—Cu1—C1	113.68 (17)	C2—N2—C2^v	116.7 (4)
C1^iii—Cu1—C1	109.55 (17)	C2—N2—Cu2	121.6 (2)
N2^iv—Cu2—N2	180.0	C2^v—N2—Cu2	121.6 (2)
N2^iv—Cu2—N1^v	90.67 (10)	N1—C1—Cu1	174.6 (3)
N2—Cu2—N1^v	89.33 (10)	N2—C2—C3	123.2 (4)
N2^iv—Cu2—N1^vi	89.33 (10)	N2—C2—H2	118.4
N2—Cu2—N1^vi	90.67 (10)	C3—C2—H2	118.4
N1^v—Cu2—N1^vi	180.0	C4—C3—C2	119.2 (5)
N2^iv—Cu2—N1	90.67 (10)	C4—C3—H3	120.4
N2—Cu2—N1	89.33 (10)	C2—C3—H3	120.4
N1^v—Cu2—N1	89.23 (14)	C3^v—C4—C3	118.4 (6)
N1^vi—Cu2—N1	90.77 (14)	C3^v—C4—H4	120.8
N2^iv—Cu2—N1^iv	89.33 (10)	C3—C4—H4	120.8
N2—Cu2—N1^iv	90.67 (10)
N2^iv—Cu2—N1—C1	−133.9 (14)	N1^v—Cu2—N2—C2^v	−44.4 (4)
N2—Cu2—N1—C1	46.1 (14)	N1^vi—Cu2—N2—C2^v	135.6 (4)
N1^v—Cu2—N1—C1	−43.2 (14)	N1—Cu2—N2—C2^v	−133.7 (4)
N1^vi—Cu2—N1—C1	136.8 (14)	N1^iv—Cu2—N2—C2^v	46.3 (4)
N1^v—Cu2—N2—C2	133.7 (4)	C2^v—N2—C2—C3	0.3 (8)
N1^vi—Cu2—N2—C2	−46.3 (4)	Cu2—N2—C2—C3	−177.9 (4)
N1—Cu2—N2—C2	44.4 (4)	N2—C2—C3—C4	−0.6 (9)
N1^iv—Cu2—N2—C2	−135.6 (4)	C2—C3—C4—C3^v	0.9 (12)

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