catena-Poly[[bis­(N-ethyl­ethylene­di­amine-κ2N,N′)copper(II)]-μ-cyanido-κ2N:C-[dicyanido-κ2C-palladium(II)]-μ-cyanido-κ2C:N]

Akitsu, T.; Endo, Y.

doi:10.1107/S160053680900885X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Pages m406-m407

doi:10.1107/S160053680900885X

Open

access

catena-Poly[[bis(N-ethylethylenediamine-κ²N,N′)copper(II)]-μ-cyanido-κ²N:C-[dicyanido-κ²C-palladium(II)]-μ-cyanido-κ²C:N]

Takashiro Akitsu ^a ^* and Yuki Endo ^a

^aDepartment of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
^*Correspondence e-mail: akitsu@rs.kagu.tus.ac.jp

(Received 9 March 2009; accepted 10 March 2009; online 19 March 2009)

The title compound, [CuPd(CN)₄(C₄H₁₂N₂)₂]_n, consists of one-dimensional chains. The Cu and Pd atoms are both located on centers of symmetry in an alternating array of [Cu(N-Eten)₂]²⁺ (N-Eten = N-ethylethylenediamine) and [Pd(CN)₄]²⁻ units. The Pd—C distances of 1.991 (3) and 1.992 (3) Å are intermediate values compared with the analogous Ni^II and Pt^II complexes [Akitsu & Einaga (2007 ). Inorg. Chim. Acta, 360, 497–505]. Due to Jahn–Teller effects, the axial Cu—N bond distance of 2.548 (2) Å is noticeably longer than the equatorial distances [Cu—NH₂ = 2.007 (2) and Cu—NHC₂H₅ = 2.050 (2) Å]. There are interchain hybrogen bonds, with N(—H)⋯N = 3.099(4) Å.

Related literature

For photo-functional cyanide-bridged complexes, see: Escax et al. (2005 ). For Jahn–Teller switching, see: Falvello (1997 ). For the photo-induced and thermally accessible structural change of [Cu(en)₂](ClO₄)₂ (en = ethylenediamine), see: Akitsu & Einaga (2003 ). For various coordination polymers designed so far, see: Kuchár et al. (2003 , 2004 ); Petříček et al. (2005 ); Černák et al. (1998 ); Černák & Abboud (2002 ); Manna et al. (2007 ). Ni(en)₂M(CN)₄ affords slightly elongated or compressed octahedral coordination geometries for M = Ni^II or Pd^II, see: Černák et al. (1988 ). For related complexes, see: [Cu(en)₂][Ni(CN)₄] (Lokaj et al., 1991 ); [Cu(en)₂][Pd(CN)₄] (Černák et al., 2001 ); [Cu(en)₂][Pt(CN)₄] (Akitsu & Einaga, 2006a ). For isotypic structures, see: [Cu(N-Eten)₂][Ni(CN)₄] and [Cu(N-Eten)₂][Pt(CN)₄] (Akitsu & Einaga, 2007). For a related mononuclear complex, see: Grenthe et al. (1979 ). For the two-dimensional Cu^II–Co^III(CN)₆ complex, see: Akitsu & Einaga (2006b ). For tetragonal Jahn–Teller distortion, see: Hathaway & Billing (1970 ). For a mononuclear Cu^II complex without Jahn–Teller distortion, see: Zibaseresht & Hartshorn (2006 ).

Experimental

Crystal data

[CuPd(CN)₄(C₄H₁₂N₂)₂]
M_r = 450.33
Triclinic, $[P \overline 1]$
a = 7.360 (4) Å
b = 7.567 (4) Å
c = 9.061 (4) Å
α = 69.091 (5)°
β = 72.490 (6)°
γ = 89.680 (6)°
V = 446.6 (4) Å³
Z = 1
Mo Kα radiation
μ = 2.21 mm⁻¹
T = 296 K
0.20 × 0.15 × 0.10 mm

Data collection

Brruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.662, T_max = 0.806
2943 measured reflections
1934 independent reflections
1763 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.105
S = 0.85
1934 reflections
105 parameters
H-atom parameters constrained
Δρ_max = 1.24 e Å⁻³
Δρ_min = −1.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3C⋯N2ⁱ	0.90	2.26	3.099 (4)	156
Symmetry code: (i) x-1, y, z+1.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680900885X/bg2245sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680900885X/bg2245Isup2.hkl

checkCIF report

Comment top

Associated with certain photo-functional cyanide-bridged complexes, Escax et al. (2005) have focused on the importance that structural strain of the lattice weaken ligand field strength of cyanide ligands. Additionally, so called Jahn-Teller switching (Falvello, 1997) may be a new mechanism for structural and electronic states switching even for cyanide-bridged coordination polymers containing a Cu^II moiety. We have reported photo-induced and thermally accessible structural change of [Cu(en)₂](ClO₄)₂ (en = ethylenediamine; Akitsu & Einaga, 2003). Moreover, numerous coordination polymers, such as one-dimensional Cu^II—Ni(CN)₄ (Kuchár et al., 2003), Cd^II—Ni(CN)₄ (Petříček et al., 2005), Cu^II—Pd(CN)₄ (Kuchár et al., 2004), Cu^II—Ag₂(CN)₃ (Černák et al., 1998), two-dimensional Cu^I/Cu^II—Ni(CN)₄ (Černák et al., 2002), and cis and trans Cu^II—Pd(CN)₄ complexes (Manna et al., 2007) have been designed so far. Among them, it has been reported that Ni(en)₂M(CN)₄ affords slightly elongated or compressed octahedral coordination geometries for M = Ni^II or Pd^II, respectively (Černák et al., 1988). In this context, we are interested in isostructral complexes by element-substitution and their structural differences, for example, [Cu(en)₂][Ni(CN)₄] (Lokaj et al., 1991), [Cu(en)₂][Pd(CN)₄] (Černák et al., 2001), and [Cu(en)₂][Pt(CN)₄] (Akitsu & Einaga, 2006a). Because we have already reported [Cu(N-Eten)₂][Ni(CN)₄] and [Cu(N-Eten)₂][Pt(CN)₄] complexes (Akitsu & Einaga, 2007), we report herein [Cu(N-Eten)₂][Pd(CN)₄](I)in order to investigate stereochemical effects by ethyl groups as the second series.

Compound (I) consists of one-dimensional chains (Fig. 1). Both Cu and Pd atoms are located on centers of symmetry in the alternative array of [Cu(N-Eten)₂]²⁺ and [Pd(CN)₄]^2- moieties(Fig. 2). The Pd—C bond distances of (I) (Table 1) and the unit cell volume of (I) (446.6 (4) Å³) is middle value among the corresponding Ni^II (438.5 (5) Å³) and Pt^II (448.5 (3) Å³) complexes (Akitsu & Einaga, 2007). As for the [Cu(en)₂][M(CN)₄] series, similar features were also observed in Ni^II (333.9 (9) Å³) (Lokaj et al., 1991), Pd^II (347.63 (6) Å³) (Černák et al., 2001), and Pt^II (353.9 (4) Å³) (Akitsu & Einaga, 2006a), which are mainly attributed to gradual changes of ionic radii of Ni^II, Pd^II, and Pt^II ions.

The geometry of the [Cu(N-Eten)₂]²⁺ unit in (I) is similar to the related mononuclear (Grenthe et al., 1979) and two-dimensional Cu^II—Co^III(CN)₆ (Akitsu & Einaga, 2006b) complexes.

Due to Jahn–Teller effects the axial Cu—N bond distance of 2.548 (2) Å is sensibly longer than the equatorial ones, (NH₂) 2.007 (2) and (NHC₂H₅) 2.050 (2) Å. However, it should be noted that ethyl groups gave characteristic strain to the crystal lattice and deviate from clearly gradual structural changes of the [Cu(N-Eten)₂][M(CN)₄] series. The axial Cu1—N1 bond length of 2.548 (2) Å in (I) is comparable to the analogous Ni^II (2.554 (2) Å) and Pt^II (2.550 (3) Å) complexes (Akitsu & Einaga, 2007). The degree of tetragonal Jahn–Teller distortion of [Cu(N-Eten)₂]²⁺ moiety in (I) is T = 0.796 (mean T is the ratio of in-plane Cu—N bond lengths / axial Cu—N bond lengths; Hathaway & Billing, 1970). The T values are 0.796 and 0.797 for the analogous Ni^II and Pt^II complexes, respectively. On the other hand, as for [Cu(en)₂][M(CN)₄] series, the axial Cu—N bond lengths exhibited gradual changes for Ni^II(2.533 (4) Å, Lokaj et al., 1991), Pd^II (2.544 (2) Å, Černák et al., 2001), and Pt^II (2.562 (5) Å, Akitsu & Einaga, 2006a) complexes, respectively. Interestingly, absence of Jahn-Teller distortion is also reported for a certain mononuclear Cu^II complex (Zibaseresht & Hartshorn, 2006). In (I), there are N—H^···N hydrogen bonds (Table 2), though some H^···N distances are longer than the common values.

Related literature top

For photo-functional cyanide-bridged complexes, see: Escax et al. (2005). For Jahn–Teller switching, see: Falvello (1997). For the photo-induced and thermally accessible structural change of [Cu(en)₂](ClO₄)₂ (en = ethylenediamine), see: Akitsu & Einaga (2003). For various coordination polymers designed so far, see: Kuchár et al. (2003, 2004); Petříček et al. (2005); Černák et al. (1998); Černák & Abboud (2002); Manna et al. (2007). Ni(en)₂M(CN)₄ affords slightly elongated or compressed octahedral coordination geometries for M = Ni^II or Pd^II, see: Černák et al. (1988). For isostructural complexes, see: [Cu(en)₂][Ni(CN)₄] (Lokaj et al., 1991); [Cu(en)₂][Pd(CN)₄] (Černák et al., 2001); [Cu(en)₂][Pt(CN)₄] (Akitsu & Einaga, 2006a); [Cu(N-Eten)₂][Ni(CN)₄] and [Cu(N-Eten)₂][Pt(CN)₄] (Akitsu & Einaga, 2007). For a related mononuclear complex, see: Grenthe et al. (1979) and for the two-dimensional Cu^II–Co^III(CN)₆ complex, see: Akitsu & Einaga (2006b). For tetragonal Jahn–Teller distortion, see: Hathaway & Billing (1970). For a mononuclear Cu^II complex without Jahn–Teller distortion, see: Zibaseresht & Hartshorn (2006).

Experimental top

The compound (I) was obtained by slow diffusion of a methanol solution (36 ml) of [Cu(N-Eten)₂](NO₃)₂ (36.0 mg, 0.100 mmol) onto an aqueous solution (5 ml) of K₂[Pd(CN)₄] (29.0 mg, 0.100 mmol) at 298 K. After several days, blue single crystals of (I) were obtained from the surface (Yield: 34.4 mg, 76.6%). Anal. Calcd for C₁₂H₂₄CuN₈Pd: C 32.00, H 5.37, N 24.88%. Found: C 32.08, H 5.13, N 25.00%. IR (KBr, ν, cm^-1): 470, 665, 721, 981, 1068, 1096, 1156, 1377, 1464, 1591, 2129 and 2132 (cyanide), 2853, 2923, 2953, 3162, 3253, 3273, 3310, 3582. Electronic spectrum (diffuse reflectance): 18100 cm^-1 (F(R_d) 1.73) (d-d transition of distorted octahedral Cu^II ion). Weiss constant = -7.76 K (antiferromagnteic interaction). XPS Cu 2p_1/2 960, Cu Cu 2p_3/2 940 eV (Cu^II), Pd 3d_3/2 357, and Pd 3d_5/2 352 eV (Pd^II).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) -x, -y, 2 - z, (ii) 1 - x, 1 - y, 1 - z, (iii) x - 1, y - 1, z + 1.

catena-Poly[[bis(N-ethylethylenediamine- κ²N,N')copper(II)]-µ-cyanido-κ²N:C- [dicyanido-κ²C-palladium(II)]-µ-cyanido-κ²C:N] top

Crystal data top

[CuPd(CN)₄(C₄H₁₂N₂)₂]	Z = 1
M_r = 450.33	F(000) = 227
Triclinic, P1	D_x = 1.674 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.360 (4) Å	Cell parameters from 1805 reflections
b = 7.567 (4) Å	θ = 2.5–27.5°
c = 9.061 (4) Å	µ = 2.21 mm⁻¹
α = 69.091 (5)°	T = 296 K
β = 72.490 (6)°	Prismatic, blue violet
γ = 89.680 (6)°	0.20 × 0.15 × 0.10 mm
V = 446.6 (4) Å³

Data collection top

Brruker SMART CCD area-detector diffractometer	1934 independent reflections
Radiation source: fine-focus sealed tube	1763 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −8→9
T_min = 0.662, T_max = 0.806	k = −4→9
2943 measured reflections	l = −7→11

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)] = 0.034	Hydrogen site location: mixed
wR(F²) = 0.105	H-atom parameters constrained
S = 0.85	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
1934 reflections	(Δ/σ)_max < 0.001
105 parameters	Δρ_max = 1.24 e Å⁻³
0 restraints	Δρ_min = −1.28 e Å⁻³

Crystal data top

[CuPd(CN)₄(C₄H₁₂N₂)₂]	γ = 89.680 (6)°
M_r = 450.33	V = 446.6 (4) Å³
Triclinic, P1	Z = 1
a = 7.360 (4) Å	Mo Kα radiation
b = 7.567 (4) Å	µ = 2.21 mm⁻¹
c = 9.061 (4) Å	T = 296 K
α = 69.091 (5)°	0.20 × 0.15 × 0.10 mm
β = 72.490 (6)°

Data collection top

Brruker SMART CCD area-detector diffractometer	1934 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1763 reflections with I > 2σ(I)
T_min = 0.662, T_max = 0.806	R_int = 0.027
2943 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 0.85	Δρ_max = 1.24 e Å⁻³
1934 reflections	Δρ_min = −1.28 e Å⁻³
105 parameters

Special details top

Experimental. 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 > 2sigma(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.

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.

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

	x	y	z	U_iso*/U_eq
Pd1	0.5000	0.5000	0.5000	0.02494 (14)
Cu1	0.0000	0.0000	1.0000	0.02702 (16)
N1	0.3378 (3)	0.1070 (3)	0.7927 (3)	0.0451 (6)
N2	0.8047 (4)	0.3301 (4)	0.2789 (3)	0.0489 (6)
N3	−0.0787 (3)	0.2641 (3)	0.9459 (3)	0.0325 (5)
H3C	−0.1484	0.2798	1.0398	0.039*
H3D	0.0256	0.3510	0.8958	0.039*
N4	−0.0720 (3)	0.0022 (3)	0.7978 (2)	0.0302 (4)
H4C	0.0309	−0.0288	0.7299	0.036*
C1	0.4025 (3)	0.2473 (4)	0.6839 (3)	0.0323 (5)
C2	0.6910 (4)	0.3871 (3)	0.3619 (3)	0.0318 (5)
C3	−0.1934 (4)	0.2879 (4)	0.8339 (3)	0.0414 (6)
H3A	−0.2025	0.4219	0.7785	0.050*
H3B	−0.3220	0.2234	0.8969	0.050*
C4	−0.0960 (4)	0.2037 (4)	0.7076 (3)	0.0381 (6)
H4A	−0.1728	0.2089	0.6362	0.046*
H4B	0.0282	0.2754	0.6384	0.046*
C5	−0.2390 (4)	−0.1323 (4)	0.8340 (3)	0.0398 (6)
H5A	−0.3545	−0.0876	0.8880	0.048*
H5B	−0.2271	−0.2555	0.9118	0.048*
C6	−0.2605 (5)	−0.1566 (5)	0.6817 (5)	0.0580 (9)
H6A	−0.3726	−0.2434	0.7139	0.070*
H6B	−0.1493	−0.2063	0.6301	0.070*
H6C	−0.2732	−0.0355	0.6041	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.02339 (19)	0.0266 (2)	0.01896 (19)	0.00152 (13)	−0.00348 (13)	−0.00440 (13)
Cu1	0.0346 (3)	0.0233 (3)	0.0227 (3)	0.0049 (2)	−0.0126 (2)	−0.0053 (2)
N1	0.0370 (12)	0.0373 (13)	0.0405 (13)	−0.0009 (10)	−0.0029 (10)	0.0013 (10)
N2	0.0459 (14)	0.0506 (14)	0.0457 (14)	0.0090 (12)	−0.0039 (12)	−0.0219 (12)
N3	0.0380 (12)	0.0271 (10)	0.0255 (10)	0.0025 (9)	−0.0059 (9)	−0.0052 (8)
N4	0.0275 (10)	0.0363 (11)	0.0248 (10)	0.0044 (8)	−0.0080 (8)	−0.0096 (8)
C1	0.0256 (11)	0.0370 (13)	0.0289 (12)	0.0042 (10)	−0.0041 (9)	−0.0099 (10)
C2	0.0312 (12)	0.0311 (12)	0.0270 (12)	0.0027 (10)	−0.0049 (10)	−0.0074 (9)
C3	0.0406 (15)	0.0352 (13)	0.0427 (16)	0.0100 (12)	−0.0156 (12)	−0.0061 (11)
C4	0.0445 (15)	0.0374 (13)	0.0264 (12)	0.0022 (12)	−0.0167 (11)	−0.0004 (10)
C5	0.0377 (14)	0.0421 (15)	0.0399 (14)	0.0006 (12)	−0.0134 (12)	−0.0146 (12)
C6	0.066 (2)	0.058 (2)	0.074 (2)	0.0132 (17)	−0.0404 (19)	−0.0370 (18)

Geometric parameters (Å, º) top

Pd1—C2	1.991 (3)	N4—C5	1.479 (3)
Pd1—C2ⁱ	1.991 (3)	N4—C4	1.489 (3)
Pd1—C1ⁱ	1.992 (3)	N4—H4C	0.9100
Pd1—C1	1.992 (3)	C3—C4	1.500 (4)
Cu1—N1	2.548 (2)	C3—H3A	0.9700
Cu1—N3ⁱⁱ	2.007 (2)	C3—H3B	0.9700
Cu1—N3	2.007 (2)	C4—H4A	0.9700
Cu1—N4ⁱⁱ	2.050 (2)	C4—H4B	0.9700
Cu1—N4	2.050 (2)	C5—C6	1.508 (4)
N1—C1	1.141 (3)	C5—H5A	0.9700
N2—C2	1.140 (3)	C5—H5B	0.9700
N3—C3	1.470 (3)	C6—H6A	0.9600
N3—H3C	0.9000	C6—H6B	0.9600
N3—H3D	0.9000	C6—H6C	0.9600

C2—Pd1—C2ⁱ	180.000 (1)	N2—C2—Pd1	177.0 (2)
C2—Pd1—C1ⁱ	87.83 (10)	N3—C3—C4	107.8 (2)
C2ⁱ—Pd1—C1ⁱ	92.17 (10)	N3—C3—H3A	110.1
C2—Pd1—C1	92.17 (10)	C4—C3—H3A	110.1
C2ⁱ—Pd1—C1	87.83 (10)	N3—C3—H3B	110.1
C1ⁱ—Pd1—C1	179.999 (1)	C4—C3—H3B	110.1
N3ⁱⁱ—Cu1—N3	180.0	H3A—C3—H3B	108.5
N3ⁱⁱ—Cu1—N4ⁱⁱ	85.55 (9)	N4—C4—C3	108.5 (2)
N3—Cu1—N4ⁱⁱ	94.45 (9)	N4—C4—H4A	110.0
N3ⁱⁱ—Cu1—N4	94.45 (9)	C3—C4—H4A	110.0
N3—Cu1—N4	85.55 (9)	N4—C4—H4B	110.0
N4ⁱⁱ—Cu1—N4	180.0	C3—C4—H4B	110.0
C3—N3—Cu1	107.38 (16)	H4A—C4—H4B	108.4
C3—N3—H3C	110.2	N4—C5—C6	113.9 (2)
Cu1—N3—H3C	110.2	N4—C5—H5A	108.8
C3—N3—H3D	110.2	C6—C5—H5A	108.8
Cu1—N3—H3D	110.2	N4—C5—H5B	108.8
H3C—N3—H3D	108.5	C6—C5—H5B	108.8
C5—N4—C4	112.8 (2)	H5A—C5—H5B	107.7
C5—N4—Cu1	116.00 (15)	C5—C6—H6A	109.5
C4—N4—Cu1	105.94 (16)	C5—C6—H6B	109.5
C5—N4—H4C	107.2	H6A—C6—H6B	109.5
C4—N4—H4C	107.2	C5—C6—H6C	109.5
Cu1—N4—H4C	107.2	H6A—C6—H6C	109.5
N1—C1—Pd1	176.2 (2)	H6B—C6—H6C	109.5

N4ⁱⁱ—Cu1—N3—C3	−163.23 (16)	Cu1—N3—C3—C4	−42.9 (2)
N4—Cu1—N3—C3	16.78 (16)	C5—N4—C4—C3	88.7 (3)
N3ⁱⁱ—Cu1—N4—C5	66.55 (19)	Cu1—N4—C4—C3	−39.2 (2)
N3—Cu1—N4—C5	−113.45 (19)	N3—C3—C4—N4	55.7 (3)
N3ⁱⁱ—Cu1—N4—C4	−167.52 (16)	C4—N4—C5—C6	70.2 (3)
N3—Cu1—N4—C4	12.47 (16)	Cu1—N4—C5—C6	−167.4 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···N2ⁱⁱⁱ	0.90	2.26	3.099 (4)	156

Symmetry code: (iii) x−1, y, z+1.

Experimental details

Crystal data
Chemical formula	[CuPd(CN)₄(C₄H₁₂N₂)₂]
M_r	450.33
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.360 (4), 7.567 (4), 9.061 (4)
α, β, γ (°)	69.091 (5), 72.490 (6), 89.680 (6)
V (Å³)	446.6 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.21
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Brruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.662, 0.806
No. of measured, independent and observed [I > 2σ(I)] reflections	2943, 1934, 1763
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.105, 0.85
No. of reflections	1934
No. of parameters	105
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.24, −1.28

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···N2ⁱ	0.90	2.257	3.099 (4)	156

Symmetry code: (i) x−1, y, z+1.

Acknowledgements

The author thanks the Materials Design and Characterization Laboratory, Institute for Solid State Physics, University of Tokyo, for the SQUID facilities.

References

Akitsu, T. & Einaga, Y. (2003). Bull. Chem. Soc. Jpn, 77, 763–764. Web of Science CSD CrossRef Google Scholar
Akitsu, T. & Einaga, Y. (2006a). Acta Cryst. E62, m862–m864. Web of Science CSD CrossRef IUCr Journals Google Scholar
Akitsu, T. & Einaga, Y. (2006b). Acta Cryst. E62, m750–m752. Web of Science CSD CrossRef IUCr Journals Google Scholar
Akitsu, T. & Einaga, Y. (2007). Inorg. Chim. Acta, 360, 497–505. Web of Science CSD CrossRef CAS Google Scholar
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Černák, J. & Abboud, K. A. (2002). Acta Cryst. C58, m167–m170. Web of Science CSD CrossRef IUCr Journals Google Scholar
Černák, J., Chomič, J., Baloghová, D. & Dunaj-Jurčo, M. (1988). Acta Cryst. C44, 1902–1905. CSD CrossRef Web of Science IUCr Journals Google Scholar
Černák, J., Chomič, J., Gravereau, P., Orendacova, A., Orendac, M., Kovac, J., Feher, A. & Kappenstein, C. (1998). Inorg. Chim. Acta, 281, 134–140. Google Scholar
Černák, J., Skorsepa, J., Abboud, K. A., Meisel, M. W., Orendac, M., Orendacova, A. & Feher, A. (2001). Inorg. Chim. Acta, 326, 3–8. Google Scholar
Escax, V., Champion, G., Arrio, M.-A., Zacchigna, M., Cartier dit Moulin, C. & Bleuzen, A. (2005). Angew. Chem. Int. Ed. 44, 4798–4801. Web of Science CrossRef CAS Google Scholar
Falvello, L. R. (1997). J. Chem. Soc. Dalton Trans. pp. 4463–4475. Web of Science CrossRef Google Scholar
Grenthe, I., Paoletti, P., Sandstorm, M. & Glikberg, S. (1979). Inorg. Chem. 18, 2687–2692. CSD CrossRef CAS Web of Science Google Scholar
Hathaway, B. J. & Billing, D. E. (1970). Coord. Chem. Rev. 5, 143–207. CrossRef CAS Web of Science Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Kuchár, J., Černák, J. & Abboud, K. A. (2004). Acta Cryst. C60, m492–m494. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kuchár, J., Černák, J., Mayerova, Z., Kubacek, P. & Zak, Z. (2003). Solid State Phenom. 90–91, 323–328. Google Scholar
Lokaj, J., Gyerová, K., Sopková, A., Sivý, J., Kettmann, V. & Vrábel, V. (1991). Acta Cryst. C47, 2447–2448. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Manna, S. C., Ribas, J., Zangrando, E. & Chaudhuri, N. R. (2007). Polyhedron, 26, 3189–3198. Web of Science CSD CrossRef CAS Google Scholar
Petříček, V., Dušek, M. & Černák, J. (2005). Acta Cryst. B61, 280–286. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zibaseresht, R. & Hartshorn, R. M. (2006). Acta Cryst. E62, i19–i22. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.