Tris­(ethyl­enedi­amine-κ²N,N′)­zinc(II) bis(1,2-di­cyano­ethyl­enedi­thiol­ato-κ²S,S′)­nickelate(II)

The title complex, [Zn(C₂H₈N₂)₃][Ni(C₄N₂S₂)₂], contains a [Zn(C₂H₈N₂)₃]²⁺ complex cation with a distorted octahedral coordination of the Zn atom and an [Ni(C₄N₂S₂)₂]²⁻ anion with a slightly distorted square-planar geometry for the Ni^II atom. The cation occupies a special position on a twofold axis, whereas the anion lies about a crystallographic inversion centre.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.049
• wR factor = 0.070
• Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT411_ALERT_2_B Short Inter H...H Contact  H6A    ..  H6A     ..       2.08 Ang.

Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         49 Perc.
PLAT213_ALERT_2_C Atom C5      has ADP max/min Ratio .............       3.30 prolat
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors  for         C6
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors  for        Zn1
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          9
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.42 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C3     -   C4     ...       1.43 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3B    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H4A    ...          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3B    ..  N2      ..       2.70 Ang.

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   9 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

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Computing details

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.

Tris(ethylenediamine-κ²N,N')zinc(II) bis(1,2-dicyanoethylenedithiolato-κ²S,S')nickelate(II)

Crystal data

[Zn(C2H8N2)3][Ni(C4N2S2)2]	F(000) = 1200
Mr = 584.75	Dx = 1.621 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 843 reflections
a = 8.743 (1) Å	θ = 2.7–18.0°
b = 17.0087 (19) Å	µ = 2.16 mm^−1
c = 16.3138 (17) Å	T = 295 K
β = 98.982 (3)°	Block, red
V = 2396.2 (5) Å^3	0.30 × 0.23 × 0.12 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2120 independent reflections
Radiation source: fine-focus sealed tube	1039 reflections with I > 2σ(I)'
Graphite monochromator	Rint = 0.071
φ and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→10
Tmin = 0.558, Tmax = 0.774	k = −13→20
6159 measured reflections	l = −19→17

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.070	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0064P)^2] where P = (Fo^2 + 2Fc^2)/3
2120 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.48 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
Ni1	0.7500	0.7500	0.5000	0.0576 (4)
Zn1	0.0000	0.22079 (5)	0.7500	0.0548 (3)
N1	0.7019 (7)	0.4283 (3)	0.4520 (3)	0.090 (2)
N2	1.0222 (7)	0.4830 (3)	0.6567 (3)	0.091 (2)
N3	0.1813 (6)	0.3094 (3)	0.7627 (3)	0.0890 (18)
H3A	0.2566	0.2949	0.7340	0.107*
H3B	0.1422	0.3556	0.7423	0.107*
N4	0.0397 (6)	0.2323 (3)	0.8810 (2)	0.0727 (16)
H4A	−0.0511	0.2378	0.8998	0.087*
H4B	0.0867	0.1888	0.9041	0.087*
N5	0.1599 (6)	0.1226 (3)	0.7526 (3)	0.0779 (16)
H5A	0.2246	0.1307	0.7155	0.093*
H5B	0.2169	0.1185	0.8033	0.093*
S1	0.6627 (2)	0.64257 (9)	0.43791 (9)	0.0709 (6)
S2	0.89858 (19)	0.68561 (8)	0.59631 (9)	0.0672 (5)
C1	0.7322 (7)	0.4905 (4)	0.4740 (3)	0.0616 (19)
C2	0.7618 (7)	0.5701 (3)	0.4980 (3)	0.0593 (18)
C3	0.8637 (7)	0.5880 (3)	0.5668 (4)	0.0555 (17)
C4	0.9492 (8)	0.5290 (4)	0.6171 (4)	0.066 (2)
C5	0.2450 (8)	0.3180 (4)	0.8512 (5)	0.117 (3)
H5C	0.3351	0.2843	0.8645	0.140*
H5D	0.2779	0.3719	0.8622	0.140*
C6	0.1323 (9)	0.2974 (5)	0.9030 (4)	0.114 (3)
H6A	0.1868	0.2889	0.9588	0.137*
H6B	0.0648	0.3423	0.9052	0.137*
C7	0.0717 (6)	0.0501 (3)	0.7322 (5)	0.098 (3)
H7A	0.0472	0.0449	0.6723	0.118*
H7B	0.1345	0.0053	0.7532	0.118*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0620 (9)	0.0502 (7)	0.0632 (7)	−0.0074 (6)	0.0185 (6)	−0.0088 (6)
Zn1	0.0626 (8)	0.0494 (7)	0.0518 (7)	0.000	0.0064 (5)	0.000
N1	0.132 (6)	0.054 (4)	0.073 (4)	−0.012 (4)	−0.016 (3)	−0.001 (3)
N2	0.125 (6)	0.077 (5)	0.066 (4)	0.000 (4)	−0.003 (4)	−0.003 (3)
N3	0.086 (5)	0.082 (4)	0.096 (4)	−0.030 (3)	0.006 (3)	0.012 (3)
N4	0.085 (4)	0.070 (4)	0.060 (3)	0.007 (3)	0.004 (3)	−0.005 (3)
N5	0.084 (4)	0.082 (4)	0.066 (3)	0.012 (3)	0.007 (3)	0.001 (3)
S1	0.0791 (14)	0.0528 (11)	0.0772 (12)	−0.0034 (9)	0.0008 (10)	−0.0053 (9)
S2	0.0772 (14)	0.0513 (10)	0.0725 (11)	−0.0094 (9)	0.0102 (10)	−0.0092 (9)
C1	0.073 (5)	0.055 (5)	0.053 (4)	−0.007 (4)	−0.001 (3)	0.006 (4)
C2	0.084 (5)	0.044 (4)	0.050 (4)	−0.015 (4)	0.012 (4)	−0.008 (3)
C3	0.061 (5)	0.051 (4)	0.059 (4)	0.000 (3)	0.022 (3)	−0.003 (4)
C4	0.087 (6)	0.048 (5)	0.057 (5)	−0.012 (4)	−0.002 (4)	−0.007 (4)
C5	0.035 (5)	0.144 (7)	0.162 (8)	−0.017 (5)	−0.011 (5)	−0.088 (6)
C6	0.080	0.134 (7)	0.117 (6)	−0.025 (6)	−0.020 (6)	−0.025 (6)
C7	0.080	0.071 (4)	0.127 (7)	0.022 (4)	−0.033 (6)	−0.017 (5)

Geometric parameters (Å, º)

Ni1—S1^i	2.1693 (14)	N4—H4B	0.9000
Ni1—S1	2.1693 (14)	N5—C7	1.465 (6)
Ni1—S2	2.1722 (15)	N5—H5A	0.9000
Ni1—S2^i	2.1722 (14)	N5—H5B	0.9000
Ni1—N4^ii	3.437 (5)	S1—C2	1.722 (6)
Zn1—N4	2.120 (4)	S2—C3	1.742 (5)
Zn1—N4^iii	2.120 (4)	C1—C2	1.422 (7)
Zn1—N3	2.174 (4)	C2—C3	1.354 (6)
Zn1—N3^iii	2.174 (4)	C3—C4	1.431 (7)
Zn1—N5^iii	2.174 (4)	C5—C6	1.439 (9)
Zn1—N5	2.174 (4)	C5—H5C	0.9700
N1—C1	1.136 (6)	C5—H5D	0.9700
N2—C4	1.144 (6)	C6—H6A	0.9700
N3—C5	1.471 (6)	C6—H6B	0.9700
N3—H3A	0.9000	C7—C7^iii	1.463 (12)
N3—H3B	0.9000	C7—H7A	0.9700
N4—C6	1.385 (7)	C7—H7B	0.9700
N4—H4A	0.9000
S1^i—Ni1—S1	180.000 (1)	H4A—N4—H4B	108.2
S1^i—Ni1—S2	87.70 (6)	C7—N5—Zn1	109.2 (4)
S1—Ni1—S2	92.30 (5)	C7—N5—H5A	109.8
S1^i—Ni1—S2^i	92.30 (5)	Zn1—N5—H5A	109.8
S1—Ni1—S2^i	87.70 (6)	C7—N5—H5B	109.8
S2—Ni1—S2^i	180.000 (1)	Zn1—N5—H5B	109.8
S1^i—Ni1—N4^ii	87.32 (8)	H5A—N5—H5B	108.3
S1—Ni1—N4^ii	92.68 (8)	C2—S1—Ni1	103.2 (2)
S2—Ni1—N4^ii	92.43 (8)	C3—S2—Ni1	102.8 (2)
S2^i—Ni1—N4^ii	87.57 (8)	N1—C1—C2	176.4 (7)
N4—Zn1—N4^iii	169.4 (2)	C3—C2—C1	120.7 (5)
N4—Zn1—N3	80.66 (17)	C3—C2—S1	121.2 (5)
N4^iii—Zn1—N3	91.97 (17)	C1—C2—S1	118.0 (4)
N4—Zn1—N3^iii	91.97 (17)	C2—C3—C4	122.3 (5)
N4^iii—Zn1—N3^iii	80.66 (17)	C2—C3—S2	120.5 (5)
N3—Zn1—N3^iii	92.2 (3)	C4—C3—S2	117.1 (4)
N4—Zn1—N5^iii	95.38 (18)	N2—C4—C3	177.6 (8)
N4^iii—Zn1—N5^iii	92.74 (16)	C6—C5—N3	111.3 (6)
N3—Zn1—N5^iii	172.59 (18)	C6—C5—H5C	109.4
N3^iii—Zn1—N5^iii	94.23 (18)	N3—C5—H5C	109.4
N4—Zn1—N5	92.74 (16)	C6—C5—H5D	109.4
N4^iii—Zn1—N5	95.38 (18)	N3—C5—H5D	109.4
N3—Zn1—N5	94.23 (18)	H5C—C5—H5D	108.0
N3^iii—Zn1—N5	172.59 (18)	N4—C6—C5	117.9 (7)
N5^iii—Zn1—N5	79.6 (3)	N4—C6—H6A	107.8
C5—N3—Zn1	108.7 (4)	C5—C6—H6A	107.8
C5—N3—H3A	109.9	N4—C6—H6B	107.8
Zn1—N3—H3A	109.9	C5—C6—H6B	107.8
C5—N3—H3B	109.9	H6A—C6—H6B	107.2
Zn1—N3—H3B	109.9	C7^iii—C7—N5	111.3 (5)
H3A—N3—H3B	108.3	C7^iii—C7—H7A	109.4
C6—N4—Zn1	109.4 (4)	N5—C7—H7A	109.4
C6—N4—H4A	109.8	C7^iii—C7—H7B	109.4
Zn1—N4—H4A	109.8	N5—C7—H7B	109.4
C6—N4—H4B	109.8	H7A—C7—H7B	108.0
Zn1—N4—H4B	109.8
N3—C5—C6—N4	41.1 (10)	N5—C7—C7^iii—N5^iii	50.8 (10)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···N2^iv	0.90	2.70	3.590 (7)	171
N4—H4B···N1^v	0.90	2.31	3.208 (6)	175
N5—H5A···S2^vi	0.90	2.81	3.696 (5)	169
N5—H5B···N1^v	0.90	2.57	3.331 (6)	142

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