catena-Poly­[[bis­(ethyl­enedi­amine-κ2N,N′)copper(II)]-μ3-1,2-dicyanoethylenedi­thiolato-κ4N:S,S′:N′-[(1,2-dicyanoethylenedithiolato-κ2S,S′)­cuprate(II)]]

Fu, A.-Y.; Wang, D.-Q.; Sun, D.-Z.

doi:10.1107/S1600536804027461

catena-Poly[[bis(ethylenediamine-κ²N,N′)copper(II)]-μ₃-1,2-dicyanoethylenedithiolato-κ⁴N:S,S′:N′-[(1,2-dicyanoethylenedithiolato-κ²S,S′)cuprate(II)]]

The title complex, [Cu₂(C₄N₂S₂)₂(C₂H₈N₂)₂]_n, consists of centrosymmetric [Cu(C₄N₂S₂)₂]²⁻ anions and [Cu(C₂H₈N₂)₂]²⁺ cations. The Cu^II atom in each anion shows a slightly distorted square-planar coordination, comprising four S-atom donors from two chelating 2,3-dimercaptobutenedinitrile ligands. The Cu^II atom in the cation is six-coordinated by four N-atom donors from two ethylenediamine ligands and two N-atom donors from 2,3-dimercaptobutenedinitrile, and has an elongated octahedral environment. The asymmetric unit contains one cation and two half-anions. The cations and anions are connected by Cu—N (nitrile) bonds to form a one-dimensional chain along the a axis. The crystal structure is stabilized by hydrogen bonds of the types N—H

N and N—H

S, forming a three-dimensional network.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804027461/cf6376sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536804027461/cf6376Isup2.hkl Contains datablock I

CCDC reference: 179811

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.006 Å
R factor = 0.036
wR factor = 0.071
Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.372     0.790
            Tmin and Tmax expected:      0.318     0.781
            RR =      1.156
            Please check that your absorption correction is appropriate.
PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large .......       1.15
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.80 Ratio
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors  for         S3
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors  for         N4
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors  for         N5
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors  for         N6
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C9     -   C10_b  ...       1.40 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.43 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C3     -   C4     ...       1.44 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C5     -   C6     ...       1.44 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C7     -   C8     ...       1.44 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       N8     -   H8B    ...          ?

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  11 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: SMART (Bruker,1997); cell refinement: SAINT (Bruker,1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

catena-Poly[[bis(ethylenediamine-κ²N,N')copper(II)]-µ₃– 2,3-dimercaptobutenedinitrile-κ⁴N:S,S':N'-[(2,3-dimercaptobutenedinitrile- κ⁴S,S',N,N')cuprate(II)]] top

Crystal data top

[Cu₂(C₄N₂S₂)₂(C₂H₈N₂)₂]	Z = 2
M_r = 527.65	F(000) = 532
Triclinic, P1	D_x = 1.689 Mg m⁻³
a = 9.535 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.720 (3) Å	Cell parameters from 1885 reflections
c = 11.955 (4) Å	θ = 2.2–24.8°
α = 96.928 (4)°	µ = 2.47 mm⁻¹
β = 95.608 (4)°	T = 293 K
γ = 107.680 (4)°	Plate, blue
V = 1037.3 (5) Å³	0.50 × 0.40 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3626 independent reflections
Radiation source: fine-focus sealed tube	2487 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
φ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −10→11
T_min = 0.372, T_max = 0.791	k = −11→9
5482 measured reflections	l = −11→14

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0236P)²] where P = (F_o² + 2F_c²)/3
3626 reflections	(Δ/σ)_max = 0.001
238 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	1.22885 (5)	0.87106 (5)	−0.12829 (4)	0.04358 (15)
Cu2	1.0000	1.0000	0.5000	0.04219 (19)
Cu3	0.5000	0.5000	0.0000	0.0497 (2)
N1	1.6528 (4)	1.1289 (5)	−0.3944 (3)	0.0732 (12)
N2	1.5642 (5)	0.6942 (5)	−0.4401 (4)	0.0978 (16)
N3	0.7695 (4)	0.6603 (4)	0.1219 (3)	0.0622 (11)
N4	1.0793 (4)	1.0153 (4)	0.3008 (3)	0.0635 (11)
N5	1.0966 (3)	0.8520 (4)	0.5366 (3)	0.0512 (9)
H5A	1.1681	0.8527	0.4925	0.061*
H5B	1.1391	0.8740	0.6099	0.061*
N6	1.1735 (3)	1.1766 (4)	0.5707 (3)	0.0533 (9)
H6A	1.2049	1.1670	0.6420	0.064*
H6B	1.2493	1.1850	0.5299	0.064*
N7	0.4058 (4)	0.6529 (3)	0.0364 (3)	0.0548 (9)
H7A	0.4766	0.7399	0.0605	0.066*
H7B	0.3504	0.6604	−0.0265	0.066*
N8	0.5737 (4)	0.5716 (4)	−0.1411 (3)	0.0588 (10)
H8A	0.5021	0.5937	−0.1829	0.071*
H8B	0.6534	0.6526	−0.1220	0.071*
S1	1.35850 (10)	1.05414 (11)	−0.21304 (8)	0.0436 (3)
S2	1.28599 (12)	0.70134 (11)	−0.24889 (9)	0.0498 (3)
S3	1.01584 (12)	0.71752 (13)	−0.09479 (9)	0.0629 (4)
S4	1.26910 (11)	1.00842 (12)	0.04549 (8)	0.0488 (3)
C1	1.5632 (5)	1.0533 (5)	−0.3526 (3)	0.0500 (11)
C2	1.4507 (4)	0.9637 (4)	−0.2978 (3)	0.0395 (10)
C3	1.4196 (4)	0.8168 (4)	−0.3133 (3)	0.0431 (10)
C4	1.4998 (5)	0.7493 (5)	−0.3860 (4)	0.0607 (12)
C5	0.8760 (5)	0.7224 (5)	0.0892 (3)	0.0489 (11)
C6	1.0056 (4)	0.7953 (4)	0.0405 (3)	0.0455 (10)
C7	1.1105 (4)	0.9172 (4)	0.0985 (3)	0.0411 (10)
C8	1.0918 (4)	0.9742 (4)	0.2108 (3)	0.0452 (10)
C9	0.9856 (7)	0.7092 (6)	0.5166 (5)	0.111 (2)
H9A	1.0334	0.6356	0.4997	0.133*
H9B	0.9414	0.6922	0.5855	0.133*
C10	1.1271 (6)	1.3068 (6)	0.5731 (5)	0.0983 (19)
H10A	1.0916	1.3256	0.6449	0.118*
H10B	1.2120	1.3904	0.5683	0.118*
C11	0.3113 (5)	0.6150 (5)	0.1257 (4)	0.0654 (13)
H11A	0.2143	0.5477	0.0921	0.078*
H11B	0.2977	0.7023	0.1651	0.078*
C12	0.6143 (5)	0.4544 (5)	−0.2074 (4)	0.0687 (14)
H12A	0.6811	0.4950	−0.2600	0.082*
H12B	0.5260	0.3821	−0.2510	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0466 (3)	0.0468 (3)	0.0371 (3)	0.0128 (2)	0.0116 (2)	0.0069 (2)
Cu2	0.0400 (4)	0.0404 (4)	0.0436 (4)	0.0106 (3)	0.0041 (3)	0.0041 (3)
Cu3	0.0571 (5)	0.0403 (5)	0.0500 (5)	0.0127 (4)	0.0045 (4)	0.0114 (3)
N1	0.062 (3)	0.081 (3)	0.077 (3)	0.012 (2)	0.034 (2)	0.021 (2)
N2	0.113 (4)	0.072 (3)	0.123 (4)	0.040 (3)	0.068 (3)	0.006 (3)
N3	0.055 (2)	0.056 (3)	0.072 (3)	0.007 (2)	0.027 (2)	0.012 (2)
N4	0.069 (2)	0.074 (3)	0.047 (2)	0.021 (2)	0.020 (2)	0.003 (2)
N5	0.051 (2)	0.057 (2)	0.047 (2)	0.0207 (19)	0.0073 (16)	0.0075 (17)
N6	0.048 (2)	0.058 (3)	0.042 (2)	0.0016 (19)	−0.0023 (16)	0.0111 (17)
N7	0.057 (2)	0.041 (2)	0.059 (2)	0.0105 (18)	−0.0060 (19)	0.0074 (17)
N8	0.059 (2)	0.051 (2)	0.065 (2)	0.0123 (19)	0.0068 (19)	0.0216 (19)
S1	0.0462 (6)	0.0407 (6)	0.0434 (6)	0.0121 (5)	0.0123 (5)	0.0047 (5)
S2	0.0618 (7)	0.0416 (7)	0.0478 (7)	0.0160 (6)	0.0155 (5)	0.0092 (5)
S3	0.0594 (7)	0.0613 (8)	0.0487 (7)	−0.0061 (6)	0.0190 (6)	−0.0079 (5)
S4	0.0466 (6)	0.0510 (7)	0.0403 (6)	0.0043 (5)	0.0105 (5)	0.0007 (5)
C1	0.052 (3)	0.055 (3)	0.043 (3)	0.018 (2)	0.008 (2)	0.002 (2)
C2	0.040 (2)	0.050 (3)	0.031 (2)	0.015 (2)	0.0065 (18)	0.0106 (18)
C3	0.047 (2)	0.048 (3)	0.038 (2)	0.019 (2)	0.0112 (19)	0.0069 (19)
C4	0.069 (3)	0.054 (3)	0.065 (3)	0.022 (3)	0.025 (3)	0.011 (2)
C5	0.052 (3)	0.048 (3)	0.044 (3)	0.013 (2)	0.008 (2)	0.003 (2)
C6	0.040 (2)	0.049 (3)	0.048 (3)	0.013 (2)	0.013 (2)	0.010 (2)
C7	0.043 (2)	0.047 (3)	0.035 (2)	0.016 (2)	0.0064 (19)	0.0097 (19)
C8	0.044 (2)	0.049 (3)	0.044 (3)	0.014 (2)	0.010 (2)	0.010 (2)
C9	0.128 (5)	0.048 (4)	0.145 (6)	0.028 (4)	−0.032 (5)	0.011 (4)
C10	0.117 (5)	0.050 (4)	0.105 (5)	0.015 (3)	−0.026 (4)	−0.010 (3)
C11	0.056 (3)	0.052 (3)	0.082 (4)	0.015 (2)	0.004 (3)	−0.006 (3)
C12	0.075 (3)	0.060 (3)	0.062 (3)	0.006 (3)	0.021 (3)	0.009 (3)

Geometric parameters (Å, º) top

Cu1—S3	2.2304 (13)	N7—H7A	0.900
Cu1—S1	2.2506 (12)	N7—H7B	0.900
Cu1—S4	2.2605 (12)	N8—C12	1.479 (5)
Cu1—S2	2.2854 (12)	N8—H8A	0.900
Cu2—N5ⁱ	1.997 (3)	N8—H8B	0.900
Cu2—N5	1.997 (3)	S1—C2	1.732 (4)
Cu2—N6ⁱ	2.013 (3)	S2—C3	1.735 (4)
Cu2—N6	2.013 (3)	S3—C6	1.726 (4)
Cu2—N4ⁱ	2.576 (3)	S4—C7	1.727 (4)
Cu2—N4	2.576 (3)	C1—C2	1.430 (5)
Cu3—N7ⁱⁱ	1.984 (3)	C2—C3	1.352 (5)
Cu3—N7	1.984 (3)	C3—C4	1.438 (5)
Cu3—N8ⁱⁱ	2.010 (3)	C5—C6	1.441 (5)
Cu3—N8	2.010 (3)	C6—C7	1.353 (5)
Cu3—N3ⁱⁱ	2.729 (3)	C7—C8	1.438 (5)
Cu3—N3	2.729 (3)	C9—C10ⁱ	1.401 (6)
N1—C1	1.145 (5)	C9—H9A	0.970
N2—C4	1.129 (5)	C9—H9B	0.970
N3—C5	1.145 (4)	C10—C9ⁱ	1.401 (6)
N4—C8	1.132 (4)	C10—H10A	0.970
N5—C9	1.444 (6)	C10—H10B	0.970
N5—H5A	0.900	C11—C12ⁱⁱ	1.492 (6)
N5—H5B	0.900	C11—H11A	0.970
N6—C10	1.461 (5)	C11—H11B	0.970
N6—H6A	0.900	C12—C11ⁱⁱ	1.492 (6)
N6—H6B	0.900	C12—H12A	0.970
N7—C11	1.473 (5)	C12—H12B	0.970

S3—Cu1—S1	152.00 (5)	C11—N7—H7B	109.7
S3—Cu1—S4	92.68 (4)	Cu3—N7—H7B	109.7
S1—Cu1—S4	95.17 (5)	H7A—N7—H7B	108.2
S3—Cu1—S2	95.40 (5)	C12—N8—Cu3	108.3 (3)
S1—Cu1—S2	91.57 (5)	C12—N8—H8A	110.0
S4—Cu1—S2	149.00 (5)	Cu3—N8—H8A	110.0
N5ⁱ—Cu2—N5	180.000 (1)	C12—N8—H8B	110.0
N5ⁱ—Cu2—N6ⁱ	96.05 (14)	Cu3—N8—H8B	110.0
N5—Cu2—N6ⁱ	83.95 (14)	H8A—N8—H8B	108.4
N5ⁱ—Cu2—N6	83.95 (14)	C2—S1—Cu1	100.69 (14)
N5—Cu2—N6	96.05 (14)	C3—S2—Cu1	99.70 (14)
N6ⁱ—Cu2—N6	180.0	C6—S3—Cu1	100.76 (13)
N5ⁱ—Cu2—N4ⁱ	95.69 (12)	C7—S4—Cu1	99.92 (13)
N5—Cu2—N4ⁱ	84.31 (12)	N1—C1—C2	177.8 (5)
N6ⁱ—Cu2—N4ⁱ	91.94 (12)	C3—C2—C1	120.7 (3)
N6—Cu2—N4ⁱ	88.06 (12)	C3—C2—S1	123.0 (3)
N5ⁱ—Cu2—N4	84.31 (12)	C1—C2—S1	116.2 (3)
N5—Cu2—N4	95.69 (12)	C2—C3—C4	119.9 (4)
N6ⁱ—Cu2—N4	88.06 (12)	C2—C3—S2	123.4 (3)
N6—Cu2—N4	91.94 (12)	C4—C3—S2	116.7 (3)
N4ⁱ—Cu2—N4	180.000 (1)	N2—C4—C3	177.6 (6)
N7ⁱⁱ—Cu3—N7	180.00 (19)	N3—C5—C6	176.2 (4)
N7ⁱⁱ—Cu3—N8ⁱⁱ	95.33 (14)	C7—C6—C5	121.2 (4)
N7—Cu3—N8ⁱⁱ	84.67 (14)	C7—C6—S3	123.2 (3)
N7ⁱⁱ—Cu3—N8	84.67 (14)	C5—C6—S3	115.6 (3)
N7—Cu3—N8	95.33 (14)	C6—C7—C8	119.1 (3)
N8ⁱⁱ—Cu3—N8	180.0 (2)	C6—C7—S4	123.4 (3)
N7ⁱⁱ—Cu3—N3ⁱⁱ	94.41 (12)	C8—C7—S4	117.5 (3)
N7—Cu3—N3ⁱⁱ	85.59 (12)	N4—C8—C7	177.3 (5)
N8ⁱⁱ—Cu3—N3ⁱⁱ	89.23 (12)	C10ⁱ—C9—N5	112.9 (5)
N8—Cu3—N3ⁱⁱ	90.77 (12)	C10ⁱ—C9—H9A	109.0
N7ⁱⁱ—Cu3—N3	85.59 (12)	N5—C9—H9A	109.0
N7—Cu3—N3	94.41 (12)	C10ⁱ—C9—H9B	109.0
N8ⁱⁱ—Cu3—N3	90.77 (12)	N5—C9—H9B	109.0
N8—Cu3—N3	89.23 (12)	H9A—C9—H9B	107.8
N3ⁱⁱ—Cu3—N3	180.00 (14)	C9ⁱ—C10—N6	111.8 (4)
C5—N3—Cu3	128.6 (3)	C9ⁱ—C10—H10A	109.2
C8—N4—Cu2	157.3 (3)	N6—C10—H10A	109.2
C9—N5—Cu2	109.1 (3)	C9ⁱ—C10—H10B	109.2
C9—N5—H5A	109.9	N6—C10—H10B	109.2
Cu2—N5—H5A	109.9	H10A—C10—H10B	107.9
C9—N5—H5B	109.9	N7—C11—C12ⁱⁱ	108.3 (3)
Cu2—N5—H5B	109.9	N7—C11—H11A	110.0
H5A—N5—H5B	108.3	C12ⁱⁱ—C11—H11A	110.0
C10—N6—Cu2	109.0 (3)	N7—C11—H11B	110.0
C10—N6—H6A	109.9	C12ⁱⁱ—C11—H11B	110.0
Cu2—N6—H6A	109.9	H11A—C11—H11B	108.4
C10—N6—H6B	109.9	N8—C12—C11ⁱⁱ	108.0 (4)
Cu2—N6—H6B	109.9	N8—C12—H12A	110.1
H6A—N6—H6B	108.3	C11ⁱⁱ—C12—H12A	110.1
C11—N7—Cu3	109.9 (3)	N8—C12—H12B	110.1
C11—N7—H7A	109.7	C11ⁱⁱ—C12—H12B	110.1
Cu3—N7—H7A	109.7	H12A—C12—H12B	108.4

N8—C12—C11ⁱⁱ—N7ⁱⁱ	50.4 (4)	N6—C10—C9ⁱ—N5ⁱ	41.7 (7)
N7—C11—C12ⁱⁱ—N8ⁱⁱ	−50.4 (4)	N5—C9—C10ⁱ—N6ⁱ	−41.7 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N1ⁱⁱⁱ	0.90	2.14	3.039 (5)	176
N5—H5B···S1^iv	0.90	2.82	3.632 (3)	151
N6—H6A···S1^iv	0.90	2.70	3.513 (3)	151
N6—H6B···N2ⁱⁱⁱ	0.90	2.26	3.098 (5)	155
N7—H7A···S1^v	0.90	2.54	3.369 (3)	154
N7—H7B···S2^vi	0.90	2.77	3.621 (4)	158
N8—H8A···S2^vi	0.90	2.67	3.547 (4)	163

Symmetry codes: (iii) −x+3, −y+2, −z; (iv) x, y, z+1; (v) −x+2, −y+2, −z; (vi) x−1, y, z.

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catena-Poly­[[bis­(ethyl­enedi­amine-κ2N,N′)copper(II)]-μ3-1,2-dicyanoethylenedi­thiolato-κ4N:S,S′:N′-[(1,2-dicyanoethylenedithiolato-κ2S,S′)­cuprate(II)]]

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catena-Poly[[bis(ethylenediamine-κ²N,N′)copper(II)]-μ₃-1,2-dicyanoethylenedithiolato-κ⁴N:S,S′:N′-[(1,2-dicyanoethylenedithiolato-κ²S,S′)cuprate(II)]]