Tris­(ethyl­enedi­amine-κ²N,N′)­zinc(II) bis­[2,3-di­mercaptobutenedi­nitrile(2–)-κ²S,S′]­zincate(II)

The title complex, [Zn(C₂H₈N₂)₃][Zn(C₄N₂S₂)₂], exists as discrete ions, both of which lie on twofold rotation axes. The [Zn(C₂H₈N₂)₃]²⁺ cation exhibits a slightly distorted octahedral geometry. In the [Zn(C₄N₂S₂)₂]²⁻ anion, the Zn^II atom is surrounded by two chelating ligands in a distorted tetrahedral geometry. The crystal structure is stabilized by hydrogen bonds of the types N—H...N and N—H...S.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.011 Å
• R factor = 0.054
• wR factor = 0.138
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low    U(eq) as Compared to Neighbors  for        Zn2

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn2    -   N3      ..       5.10 su
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors  for         N3
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors  for         N5
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         11
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C5     -   C6     ...       1.42 Ang.
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C7     -   C7_b   ...       1.39 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C3     -   C4     ...       1.43 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H4B    ...          ?

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  10 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
   8 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, 1997a); 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[2,3-dimercaptobutenedinitrile(2-)-κ²S,S']zincate(II)

Crystal data

[Zn(C2H8N2)3][Zn(C4N2S2)2]	Dx = 1.573 Mg m^−3
Mr = 591.41	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 1781 reflections
a = 12.0231 (12) Å	θ = 2.6–20.7°
b = 14.269 (3) Å	µ = 2.28 mm^−1
c = 14.559 (3) Å	T = 296 K
V = 2497.8 (8) Å^3	Block, colourless
Z = 4	0.25 × 0.20 × 0.10 mm
F(000) = 1208

Data collection

Bruker SMART CCD area-detector diffractometer	2158 independent reflections
Radiation source: fine-focus sealed tube	1150 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→13
Tmin = 0.600, Tmax = 0.804	k = −16→16
12094 measured reflections	l = −16→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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0649P)^2] where P = (Fo^2 + 2Fc^2)/3
2158 reflections	(Δ/σ)max < 0.001
130 parameters	Δρmax = 0.75 e Å^−3
0 restraints	Δρmin = −0.75 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
Zn1	0.0000	0.46180 (7)	0.2500	0.0509 (3)
Zn2	0.0000	0.89594 (7)	0.2500	0.0523 (3)
N1	0.3136 (5)	0.5639 (5)	−0.0127 (4)	0.0827 (19)
N2	−0.1415 (6)	0.3519 (6)	0.5997 (5)	0.101 (2)
N3	0.1767 (5)	0.8768 (5)	0.2716 (4)	0.093 (2)
H3A	0.2132	0.9305	0.2599	0.112*
H3B	0.1899	0.8602	0.3302	0.112*
N4	0.0378 (5)	0.7939 (4)	0.1416 (4)	0.080
H4A	0.0193	0.7358	0.1602	0.096*
H4B	−0.0013	0.8073	0.0905	0.096*
N5	0.0037 (6)	1.0133 (5)	0.1537 (5)	0.0978 (19)
H5A	0.0721	1.0198	0.1294	0.117*
H5B	−0.0452	1.0040	0.1078	0.117*
S1	0.14412 (14)	0.55308 (11)	0.19266 (12)	0.0557 (5)
S2	0.01484 (14)	0.37256 (12)	0.38355 (12)	0.0592 (5)
C1	0.2399 (6)	0.5362 (5)	0.0298 (5)	0.0624 (17)
C2	0.1553 (5)	0.5005 (4)	0.0858 (4)	0.0507 (16)
C3	−0.1182 (6)	0.3874 (5)	0.5308 (6)	0.0695 (19)
C4	−0.0894 (5)	0.4265 (4)	0.4437 (4)	0.0532 (16)
C5	0.2151 (7)	0.8014 (5)	0.2078 (8)	0.096 (3)
H5C	0.2936	0.8103	0.1953	0.115*
H5D	0.2066	0.7412	0.2381	0.115*
C6	0.1564 (8)	0.7991 (6)	0.1228 (6)	0.097 (3)
H6A	0.1795	0.7450	0.0872	0.117*
H6B	0.1728	0.8551	0.0875	0.117*
C7	−0.0269 (7)	1.0982 (7)	0.2078 (6)	0.101 (3)
H7A	−0.0065	1.1540	0.1737	0.121*
H7B	−0.1068	1.0993	0.2174	0.121*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0512 (6)	0.0469 (6)	0.0547 (6)	0.000	0.0026 (5)	0.000
Zn2	0.0513 (6)	0.0516 (6)	0.0539 (6)	0.000	0.0026 (5)	0.000
N1	0.074 (4)	0.101 (5)	0.074 (4)	−0.003 (4)	0.008 (4)	0.010 (4)
N2	0.124 (6)	0.112 (6)	0.067 (5)	0.004 (5)	0.005 (4)	0.026 (4)
N3	0.079 (5)	0.109 (5)	0.092 (5)	0.016 (4)	0.005 (4)	−0.010 (4)
N4	0.080	0.080	0.080	−0.017 (3)	0.007 (4)	−0.017 (3)
N5	0.133 (6)	0.080	0.080	−0.003 (4)	0.000 (4)	0.016 (4)
S1	0.0602 (10)	0.0463 (9)	0.0605 (10)	−0.0064 (8)	0.0051 (9)	−0.0052 (9)
S2	0.0642 (11)	0.0506 (10)	0.0627 (10)	0.0050 (8)	−0.0061 (9)	0.0051 (8)
C1	0.061 (4)	0.076 (5)	0.050 (4)	0.006 (4)	−0.003 (4)	0.005 (4)
C2	0.049 (4)	0.050 (4)	0.054 (4)	0.008 (3)	−0.001 (3)	0.013 (3)
C3	0.070 (5)	0.064 (5)	0.074 (5)	−0.002 (4)	−0.008 (4)	0.000 (4)
C4	0.068 (4)	0.049 (4)	0.043 (4)	−0.006 (3)	−0.009 (3)	0.000 (3)
C5	0.083 (6)	0.055 (5)	0.149 (9)	0.003 (4)	0.051 (6)	−0.006 (5)
C6	0.138 (8)	0.065 (5)	0.089 (6)	−0.022 (5)	0.068 (6)	−0.019 (5)
C7	0.080	0.142 (8)	0.080	0.009 (5)	0.001 (5)	0.029 (6)

Geometric parameters (Å, º)

Zn1—S1^i	2.3229 (17)	N5—C7	1.491 (11)
Zn1—S1	2.3229 (17)	N5—H5A	0.9000
Zn1—S2^i	2.3311 (18)	N5—H5B	0.9000
Zn1—S2	2.3311 (18)	S1—C2	1.733 (6)
Zn2—N3^i	2.164 (6)	S2—C4	1.712 (7)
Zn2—N3	2.164 (6)	C1—C2	1.399 (9)
Zn2—N5^i	2.185 (6)	C2—C4^i	1.388 (8)
Zn2—N5	2.185 (6)	C3—C4	1.428 (11)
Zn2—N4	2.195 (6)	C4—C2^i	1.388 (8)
Zn2—N4^i	2.195 (6)	C5—C6	1.425 (11)
N1—C1	1.151 (8)	C5—H5C	0.9700
N2—C3	1.159 (9)	C5—H5D	0.9700
N3—C5	1.495 (10)	C6—H6A	0.9700
N3—H3A	0.9000	C6—H6B	0.9700
N3—H3B	0.9000	C7—C7^i	1.389 (16)
N4—C6	1.455 (9)	C7—H7A	0.9700
N4—H4A	0.9000	C7—H7B	0.9700
N4—H4B	0.9000
S1^i—Zn1—S1	111.79 (9)	C7—N5—H5A	110.5
S1^i—Zn1—S2^i	123.30 (6)	Zn2—N5—H5A	110.5
S1—Zn1—S2^i	93.65 (6)	C7—N5—H5B	110.5
S1^i—Zn1—S2	93.65 (6)	Zn2—N5—H5B	110.5
S1—Zn1—S2	123.30 (6)	H5A—N5—H5B	108.7
S2^i—Zn1—S2	113.78 (10)	C2—S1—Zn1	97.9 (2)
N3^i—Zn2—N3	165.5 (4)	C4—S2—Zn1	97.2 (2)
N3^i—Zn2—N5^i	99.8 (3)	N1—C1—C2	176.2 (7)
N3—Zn2—N5^i	91.4 (3)	C4^i—C2—C1	120.8 (6)
N3^i—Zn2—N5	91.4 (3)	C4^i—C2—S1	124.2 (5)
N3—Zn2—N5	99.8 (3)	C1—C2—S1	115.0 (5)
N5^i—Zn2—N5	79.9 (4)	N2—C3—C4	177.0 (8)
N3^i—Zn2—N4	90.9 (2)	C2^i—C4—C3	115.7 (6)
N3—Zn2—N4	79.5 (2)	C2^i—C4—S2	127.0 (5)
N5^i—Zn2—N4	167.0 (2)	C3—C4—S2	117.1 (5)
N5—Zn2—N4	92.5 (3)	C6—C5—N3	113.8 (7)
N3^i—Zn2—N4^i	79.5 (2)	C6—C5—H5C	108.8
N3—Zn2—N4^i	90.9 (2)	N3—C5—H5C	108.8
N5^i—Zn2—N4^i	92.5 (3)	C6—C5—H5D	108.8
N5—Zn2—N4^i	167.0 (2)	N3—C5—H5D	108.8
N4—Zn2—N4^i	96.9 (3)	H5C—C5—H5D	107.7
C5—N3—Zn2	107.7 (5)	C5—C6—N4	108.8 (6)
C5—N3—H3A	110.2	C5—C6—H6A	109.9
Zn2—N3—H3A	110.2	N4—C6—H6A	109.9
C5—N3—H3B	110.2	C5—C6—H6B	109.9
Zn2—N3—H3B	110.2	N4—C6—H6B	109.9
H3A—N3—H3B	108.5	H6A—C6—H6B	108.3
C6—N4—Zn2	107.7 (4)	C7^i—C7—N5	110.6 (6)
C6—N4—H4A	110.2	C7^i—C7—H7A	109.5
Zn2—N4—H4A	110.2	N5—C7—H7A	109.5
C6—N4—H4B	110.2	C7^i—C7—H7B	109.5
Zn2—N4—H4B	110.2	N5—C7—H7B	109.5
H4A—N4—H4B	108.5	H7A—C7—H7B	108.1
C7—N5—Zn2	106.2 (5)
N5—C7—C7^i—N5^i	−59.6 (14)	N3—C5—C6—N4	−53.6 (9)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5B···N1^ii	0.90	2.40	3.265 (10)	162
N5—H5A···N1^iii	0.90	2.56	3.348 (9)	146
N4—H4A···N2^iv	0.90	2.46	3.056 (9)	124
N3—H3B···N1^v	0.90	2.53	3.255 (9)	138
N3—H3A···S1^iii	0.90	2.64	3.505 (8)	162

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