The title complex, [Zn(C
2H
8N
2)
3][Zn(C
4N
2S
2)
2], exists as discrete ions, both of which lie on twofold rotation axes. The [Zn(C
2H
8N
2)
3]
2+ cation exhibits a slightly distorted octahedral geometry. In the [Zn(C
4N
2S
2)
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.
Supporting information
CCDC reference: 179808
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (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
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)
top
Crystal data top
[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) Å3 | Block, colourless |
Z = 4 | 0.25 × 0.20 × 0.10 mm |
F(000) = 1208 | |
Data collection top
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 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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0649P)2] where P = (Fo2 + 2Fc2)/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 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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Zn1—S1i | 2.3229 (17) | N5—C7 | 1.491 (11) |
Zn1—S1 | 2.3229 (17) | N5—H5A | 0.9000 |
Zn1—S2i | 2.3311 (18) | N5—H5B | 0.9000 |
Zn1—S2 | 2.3311 (18) | S1—C2 | 1.733 (6) |
Zn2—N3i | 2.164 (6) | S2—C4 | 1.712 (7) |
Zn2—N3 | 2.164 (6) | C1—C2 | 1.399 (9) |
Zn2—N5i | 2.185 (6) | C2—C4i | 1.388 (8) |
Zn2—N5 | 2.185 (6) | C3—C4 | 1.428 (11) |
Zn2—N4 | 2.195 (6) | C4—C2i | 1.388 (8) |
Zn2—N4i | 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—C7i | 1.389 (16) |
N4—C6 | 1.455 (9) | C7—H7A | 0.9700 |
N4—H4A | 0.9000 | C7—H7B | 0.9700 |
N4—H4B | 0.9000 | | |
| | | |
S1i—Zn1—S1 | 111.79 (9) | C7—N5—H5A | 110.5 |
S1i—Zn1—S2i | 123.30 (6) | Zn2—N5—H5A | 110.5 |
S1—Zn1—S2i | 93.65 (6) | C7—N5—H5B | 110.5 |
S1i—Zn1—S2 | 93.65 (6) | Zn2—N5—H5B | 110.5 |
S1—Zn1—S2 | 123.30 (6) | H5A—N5—H5B | 108.7 |
S2i—Zn1—S2 | 113.78 (10) | C2—S1—Zn1 | 97.9 (2) |
N3i—Zn2—N3 | 165.5 (4) | C4—S2—Zn1 | 97.2 (2) |
N3i—Zn2—N5i | 99.8 (3) | N1—C1—C2 | 176.2 (7) |
N3—Zn2—N5i | 91.4 (3) | C4i—C2—C1 | 120.8 (6) |
N3i—Zn2—N5 | 91.4 (3) | C4i—C2—S1 | 124.2 (5) |
N3—Zn2—N5 | 99.8 (3) | C1—C2—S1 | 115.0 (5) |
N5i—Zn2—N5 | 79.9 (4) | N2—C3—C4 | 177.0 (8) |
N3i—Zn2—N4 | 90.9 (2) | C2i—C4—C3 | 115.7 (6) |
N3—Zn2—N4 | 79.5 (2) | C2i—C4—S2 | 127.0 (5) |
N5i—Zn2—N4 | 167.0 (2) | C3—C4—S2 | 117.1 (5) |
N5—Zn2—N4 | 92.5 (3) | C6—C5—N3 | 113.8 (7) |
N3i—Zn2—N4i | 79.5 (2) | C6—C5—H5C | 108.8 |
N3—Zn2—N4i | 90.9 (2) | N3—C5—H5C | 108.8 |
N5i—Zn2—N4i | 92.5 (3) | C6—C5—H5D | 108.8 |
N5—Zn2—N4i | 167.0 (2) | N3—C5—H5D | 108.8 |
N4—Zn2—N4i | 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) | C7i—C7—N5 | 110.6 (6) |
C6—N4—H4A | 110.2 | C7i—C7—H7A | 109.5 |
Zn2—N4—H4A | 110.2 | N5—C7—H7A | 109.5 |
C6—N4—H4B | 110.2 | C7i—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—C7i—N5i | −59.6 (14) | N3—C5—C6—N4 | −53.6 (9) |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5B···N1ii | 0.90 | 2.40 | 3.265 (10) | 162 |
N5—H5A···N1iii | 0.90 | 2.56 | 3.348 (9) | 146 |
N4—H4A···N2iv | 0.90 | 2.46 | 3.056 (9) | 124 |
N3—H3B···N1v | 0.90 | 2.53 | 3.255 (9) | 138 |
N3—H3A···S1iii | 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. |