In the crystal structure of the title compound, [N,N′-bis(3-aminopropyl)ethylenediamine-κ4N,N′,N′′,N′′′][1,3,5-triazine-2,4,6(1H,3H,5H)-trithionato(2−)-κ2N,S]zinc(II) ethanol solvate, [Zn(C8H22N4)2(C3HN3S3)]·C2H6O, the ZnII atom is octahedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N-donor N,N′-bis(3-aminopropyl)ethylenediamine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a trithiocyanurate(2−) (ttcH2−) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.
Supporting information
CCDC reference: 229088
N,N'-Bis(3-aminopropyl)ethylenediamine (0.18 ml, 1 mmol) was added to an ethanolic solution (80 ml) of zinc acetate dihydrate (0.22 g, 1 mmol) with stirring at room temperature. Into this solution, the trisodium salt of trithiocyanuric acid nonahydrate (ttcNa3·9H2O) (0.4 g, 1 mmol), dissolved in water (5 ml), was added with stirring over a period of 30 min. The colour of the solution changed to light yellow and a small amount of white precipitate formed. The precipitate was filtered off and discarded and the filtrate was left to crystallize at room temperature. Light-yellow crystals of (I) were obtained after a week. These were filtered off, washed with a small amount of ethanol and dried in the air. Elemental analysis (EA1108 CHNS Analyzer, Fisons Instruments, Beverly, Massachusetts, USA), found: C 33.3, H 6.1, N 21.2, S 21.0%; calculated: C 33.9, H 6.3, N 21.3, S 20.9%.
H atoms attached to C and N atoms were positioned geometrically, with C—H distances of 0.99 Å and N—H distances in the range 0.88–0.93 Å, and with Uiso values derived from Ueq of the corresponding C or N atoms. The parameters of atom H1O attached to atom O1 were refined with the O···H distance restrained to 0.95 (2) Å.
Data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2002); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Johnson & Burnett, 1996); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
[
N,
N'-bis(3-aminopropyl)ethylenediamine-
κ4N,
N',
N'',
N'''][1,3,5-triazine- 2,4,6(1
H,3H,5
H)-trithione
κ2N,
S]zinc(II) ethanol solvate
top
Crystal data top
[Zn(C8H22N4)(C3HN3S3)]·C2H6O | Z = 2 |
Mr = 460.98 | F(000) = 484 |
Triclinic, P1 | Dx = 1.505 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0791 (14) Å | Cell parameters from 2410 reflections |
b = 11.0455 (15) Å | θ = 26.5–2.2° |
c = 11.3580 (11) Å | µ = 1.53 mm−1 |
α = 93.592 (10)° | T = 120 K |
β = 102.316 (11)° | Prism, light yellow |
γ = 112.167 (14)° | 0.40 × 0.40 × 0.40 mm |
V = 1017.6 (3) Å3 | |
Data collection top
Kuma KM4 with CCD area detector diffractometer | 4279 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.023 |
Enhance (Oxford Diffraction) monochromator | θmax = 28.4°, θmin = 2.5° |
Detector resolution: 16.3 pixels mm-1 | h = −11→11 |
rotation method, ω scan | k = −13→14 |
6681 measured reflections | l = −15→14 |
4458 independent reflections | |
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: difference Fourier map |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.055P)2 + 1.75P] where P = (Fo2 + 2Fc2)/3 |
4458 reflections | (Δ/σ)max = 0.001 |
230 parameters | Δρmax = 1.08 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
Crystal data top
[Zn(C8H22N4)(C3HN3S3)]·C2H6O | γ = 112.167 (14)° |
Mr = 460.98 | V = 1017.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.0791 (14) Å | Mo Kα radiation |
b = 11.0455 (15) Å | µ = 1.53 mm−1 |
c = 11.3580 (11) Å | T = 120 K |
α = 93.592 (10)° | 0.40 × 0.40 × 0.40 mm |
β = 102.316 (11)° | |
Data collection top
Kuma KM4 with CCD area detector diffractometer | 4279 reflections with I > 2σ(I) |
6681 measured reflections | Rint = 0.023 |
4458 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 1.08 e Å−3 |
4458 reflections | Δρmin = −0.66 e Å−3 |
230 parameters | |
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 | |
Zn | 0.44691 (3) | 0.21844 (2) | 0.69155 (2) | 0.01459 (9) | |
S1 | 0.31572 (7) | 0.06521 (5) | 0.48436 (5) | 0.01884 (13) | |
S2 | 0.85613 (7) | 0.50263 (6) | 0.62917 (5) | 0.02149 (13) | |
S3 | 0.73699 (7) | 0.20877 (6) | 0.20745 (5) | 0.02066 (13) | |
N1 | 0.2868 (2) | 0.11116 (19) | 0.79283 (18) | 0.0182 (4) | |
H1A | 0.2982 | 0.0324 | 0.7997 | 0.022* | |
H1B | 0.3198 | 0.1582 | 0.8703 | 0.022* | |
N2 | 0.3020 (2) | 0.3349 (2) | 0.63181 (18) | 0.0191 (4) | |
H2 | 0.3130 | 0.3494 | 0.5538 | 0.023* | |
N3 | 0.5945 (2) | 0.39975 (17) | 0.81964 (16) | 0.0143 (3) | |
H3 | 0.6691 | 0.4543 | 0.7811 | 0.017* | |
N4 | 0.6261 (2) | 0.14065 (18) | 0.75268 (18) | 0.0175 (4) | |
H4A | 0.5749 | 0.0499 | 0.7332 | 0.021* | |
H4B | 0.7032 | 0.1686 | 0.7083 | 0.021* | |
N5 | 0.5826 (2) | 0.28271 (18) | 0.54067 (17) | 0.0154 (4) | |
N6 | 0.5283 (2) | 0.14832 (18) | 0.34803 (17) | 0.0175 (4) | |
N7 | 0.7781 (2) | 0.33083 (18) | 0.42804 (17) | 0.0151 (3) | |
H7 | 0.8787 | 0.3775 | 0.4229 | 0.018* | |
C1 | 0.1092 (3) | 0.0811 (2) | 0.7426 (2) | 0.0252 (5) | |
H1C | 0.0463 | 0.0314 | 0.7978 | 0.030* | |
H1D | 0.0697 | 0.0236 | 0.6622 | 0.030* | |
C2 | 0.0754 (3) | 0.2048 (3) | 0.7274 (2) | 0.0253 (5) | |
H2A | −0.0434 | 0.1812 | 0.7189 | 0.030* | |
H2B | 0.1365 | 0.2702 | 0.8028 | 0.030* | |
C3 | 0.1217 (3) | 0.2701 (3) | 0.6193 (2) | 0.0258 (5) | |
H3A | 0.0709 | 0.2022 | 0.5450 | 0.031* | |
H3B | 0.0746 | 0.3373 | 0.6075 | 0.031* | |
C4 | 0.3832 (3) | 0.4676 (2) | 0.7085 (2) | 0.0225 (5) | |
H4C | 0.2985 | 0.5007 | 0.7185 | 0.027* | |
H4D | 0.4576 | 0.5300 | 0.6669 | 0.027* | |
C5 | 0.4817 (3) | 0.4636 (2) | 0.8340 (2) | 0.0187 (4) | |
H5A | 0.5455 | 0.5548 | 0.8790 | 0.022* | |
H5B | 0.4059 | 0.4134 | 0.8815 | 0.022* | |
C6 | 0.6916 (3) | 0.3923 (2) | 0.9390 (2) | 0.0176 (4) | |
H6A | 0.6155 | 0.3446 | 0.9873 | 0.021* | |
H6B | 0.7587 | 0.4831 | 0.9839 | 0.021* | |
C7 | 0.8049 (3) | 0.3221 (2) | 0.9270 (2) | 0.0193 (4) | |
H7A | 0.8832 | 0.3374 | 1.0073 | 0.023* | |
H7B | 0.8697 | 0.3622 | 0.8690 | 0.023* | |
C8 | 0.7150 (3) | 0.1731 (2) | 0.8832 (2) | 0.0203 (4) | |
H8A | 0.7957 | 0.1319 | 0.8968 | 0.024* | |
H8B | 0.6356 | 0.1348 | 0.9322 | 0.024* | |
C9 | 0.4900 (3) | 0.1734 (2) | 0.4534 (2) | 0.0161 (4) | |
C10 | 0.6752 (3) | 0.2278 (2) | 0.33580 (19) | 0.0151 (4) | |
C11 | 0.7298 (3) | 0.3637 (2) | 0.5281 (2) | 0.0153 (4) | |
O1 | 0.3590 (2) | 0.1850 (2) | 1.06990 (17) | 0.0285 (4) | |
C13 | 0.1115 (4) | 0.2027 (4) | 1.0840 (4) | 0.0501 (9) | |
H13A | 0.1484 | 0.2842 | 1.0485 | 0.075* | |
H13B | 0.0469 | 0.2107 | 1.1408 | 0.075* | |
H13C | 0.0432 | 0.1276 | 1.0188 | 0.075* | |
C12 | 0.2555 (4) | 0.1812 (3) | 1.1500 (3) | 0.0422 (8) | |
H12A | 0.3175 | 0.2509 | 1.2223 | 0.051* | |
H12B | 0.2192 | 0.0942 | 1.1783 | 0.051* | |
H1O | 0.451 (4) | 0.180 (4) | 1.121 (3) | 0.060 (12)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn | 0.01375 (14) | 0.01480 (14) | 0.01548 (15) | 0.00543 (10) | 0.00536 (10) | 0.00039 (9) |
S1 | 0.0150 (3) | 0.0170 (3) | 0.0197 (3) | −0.0001 (2) | 0.0081 (2) | −0.00146 (19) |
S2 | 0.0195 (3) | 0.0182 (3) | 0.0190 (3) | −0.0028 (2) | 0.0102 (2) | −0.0027 (2) |
S3 | 0.0265 (3) | 0.0195 (3) | 0.0181 (3) | 0.0076 (2) | 0.0133 (2) | 0.0026 (2) |
N1 | 0.0157 (9) | 0.0164 (9) | 0.0210 (10) | 0.0037 (7) | 0.0066 (7) | 0.0023 (7) |
N2 | 0.0191 (9) | 0.0228 (9) | 0.0182 (9) | 0.0102 (8) | 0.0069 (7) | 0.0041 (7) |
N3 | 0.0151 (8) | 0.0133 (8) | 0.0157 (9) | 0.0051 (7) | 0.0072 (7) | 0.0032 (6) |
N4 | 0.0169 (9) | 0.0157 (8) | 0.0210 (10) | 0.0069 (7) | 0.0070 (7) | 0.0009 (7) |
N5 | 0.0152 (9) | 0.0144 (8) | 0.0159 (9) | 0.0031 (7) | 0.0077 (7) | 0.0017 (7) |
N6 | 0.0195 (9) | 0.0153 (8) | 0.0173 (9) | 0.0048 (7) | 0.0083 (7) | 0.0008 (7) |
N7 | 0.0141 (8) | 0.0150 (8) | 0.0162 (9) | 0.0035 (7) | 0.0081 (7) | 0.0035 (7) |
C1 | 0.0142 (10) | 0.0241 (11) | 0.0331 (13) | 0.0019 (9) | 0.0087 (9) | 0.0046 (10) |
C2 | 0.0157 (10) | 0.0292 (12) | 0.0314 (13) | 0.0084 (9) | 0.0087 (9) | 0.0030 (10) |
C3 | 0.0171 (11) | 0.0332 (13) | 0.0276 (13) | 0.0127 (10) | 0.0023 (9) | 0.0034 (10) |
C4 | 0.0275 (12) | 0.0177 (10) | 0.0259 (12) | 0.0124 (9) | 0.0075 (10) | 0.0058 (9) |
C5 | 0.0218 (11) | 0.0165 (10) | 0.0204 (11) | 0.0094 (8) | 0.0083 (9) | 0.0018 (8) |
C6 | 0.0179 (10) | 0.0155 (10) | 0.0170 (10) | 0.0042 (8) | 0.0045 (8) | 0.0003 (8) |
C7 | 0.0165 (10) | 0.0193 (10) | 0.0195 (11) | 0.0053 (8) | 0.0031 (8) | 0.0013 (8) |
C8 | 0.0228 (11) | 0.0170 (10) | 0.0211 (11) | 0.0089 (9) | 0.0043 (9) | 0.0022 (8) |
C9 | 0.0147 (10) | 0.0147 (9) | 0.0187 (10) | 0.0049 (8) | 0.0063 (8) | 0.0022 (8) |
C10 | 0.0195 (10) | 0.0138 (9) | 0.0153 (10) | 0.0077 (8) | 0.0084 (8) | 0.0046 (7) |
C11 | 0.0158 (10) | 0.0144 (9) | 0.0167 (10) | 0.0050 (8) | 0.0081 (8) | 0.0044 (7) |
O1 | 0.0236 (9) | 0.0372 (10) | 0.0262 (9) | 0.0132 (8) | 0.0078 (7) | 0.0035 (8) |
C13 | 0.0412 (18) | 0.056 (2) | 0.069 (2) | 0.0266 (16) | 0.0271 (17) | 0.0318 (19) |
C12 | 0.0389 (17) | 0.0464 (18) | 0.057 (2) | 0.0230 (14) | 0.0272 (15) | 0.0307 (16) |
Geometric parameters (Å, º) top
Zn—N1 | 2.104 (2) | C1—H1C | 0.9900 |
Zn—N4 | 2.1249 (19) | C1—H1D | 0.9900 |
Zn—N3 | 2.1682 (19) | C2—C3 | 1.520 (4) |
Zn—N2 | 2.2031 (19) | C2—H2A | 0.9900 |
Zn—N5 | 2.3132 (18) | C2—H2B | 0.9900 |
Zn—S1 | 2.5700 (7) | C3—H3A | 0.9900 |
S1—C9 | 1.708 (2) | C3—H3B | 0.9900 |
S2—C11 | 1.697 (2) | C4—C5 | 1.525 (3) |
S3—C10 | 1.698 (2) | C4—H4C | 0.9900 |
N1—C1 | 1.488 (3) | C4—H4D | 0.9900 |
N1—H1A | 0.9200 | C5—H5A | 0.9900 |
N1—H1B | 0.9200 | C5—H5B | 0.9900 |
N2—C4 | 1.484 (3) | C6—C7 | 1.526 (3) |
N2—C3 | 1.488 (3) | C6—H6A | 0.9900 |
N2—H2 | 0.9300 | C6—H6B | 0.9900 |
N3—C5 | 1.475 (3) | C7—C8 | 1.527 (3) |
N3—C6 | 1.476 (3) | C7—H7A | 0.9900 |
N3—H3 | 0.9300 | C7—H7B | 0.9900 |
N4—C8 | 1.477 (3) | C8—H8A | 0.9900 |
N4—H4A | 0.9200 | C8—H8B | 0.9900 |
N4—H4B | 0.9200 | O1—C12 | 1.432 (4) |
N5—C11 | 1.343 (3) | O1—H1O | 0.93 (4) |
N5—C9 | 1.370 (3) | C13—C12 | 1.472 (5) |
N6—C10 | 1.334 (3) | C13—H13A | 0.9800 |
N6—C9 | 1.355 (3) | C13—H13B | 0.9800 |
N7—C11 | 1.377 (3) | C13—H13C | 0.9800 |
N7—C10 | 1.377 (3) | C12—H12A | 0.9900 |
N7—H7 | 0.8800 | C12—H12B | 0.9900 |
C1—C2 | 1.521 (4) | | |
| | | |
N1—Zn—N4 | 94.66 (8) | N2—C3—C2 | 114.4 (2) |
N1—Zn—N3 | 100.92 (7) | N2—C3—H3A | 108.6 |
N4—Zn—N3 | 90.46 (7) | C2—C3—H3A | 108.6 |
N1—Zn—N2 | 93.77 (8) | N2—C3—H3B | 108.6 |
N4—Zn—N2 | 169.06 (8) | C2—C3—H3B | 108.6 |
N3—Zn—N2 | 81.09 (7) | H3A—C3—H3B | 107.6 |
N1—Zn—N5 | 163.89 (7) | N2—C4—C5 | 111.68 (18) |
N4—Zn—N5 | 84.67 (7) | N2—C4—H4C | 109.3 |
N3—Zn—N5 | 95.18 (7) | C5—C4—H4C | 109.3 |
N2—Zn—N5 | 89.15 (7) | N2—C4—H4D | 109.3 |
N1—Zn—S1 | 99.81 (6) | C5—C4—H4D | 109.3 |
N4—Zn—S1 | 95.51 (5) | H4C—C4—H4D | 107.9 |
N3—Zn—S1 | 157.87 (5) | N3—C5—C4 | 109.54 (18) |
N2—Zn—S1 | 89.91 (6) | N3—C5—H5A | 109.8 |
N5—Zn—S1 | 64.32 (5) | C4—C5—H5A | 109.8 |
C9—S1—Zn | 80.99 (8) | N3—C5—H5B | 109.8 |
C1—N1—Zn | 116.11 (15) | C4—C5—H5B | 109.8 |
C1—N1—H1A | 108.3 | H5A—C5—H5B | 108.2 |
Zn—N1—H1A | 108.3 | N3—C6—C7 | 112.71 (18) |
C1—N1—H1B | 108.3 | N3—C6—H6A | 109.1 |
Zn—N1—H1B | 108.3 | C7—C6—H6A | 109.1 |
H1A—N1—H1B | 107.4 | N3—C6—H6B | 109.1 |
C4—N2—C3 | 113.98 (19) | C7—C6—H6B | 109.1 |
C4—N2—Zn | 108.50 (14) | H6A—C6—H6B | 107.8 |
C3—N2—Zn | 116.68 (15) | C6—C7—C8 | 114.09 (19) |
C4—N2—H2 | 105.6 | C6—C7—H7A | 108.7 |
C3—N2—H2 | 105.6 | C8—C7—H7A | 108.7 |
Zn—N2—H2 | 105.6 | C6—C7—H7B | 108.7 |
C5—N3—C6 | 111.55 (17) | C8—C7—H7B | 108.7 |
C5—N3—Zn | 105.99 (13) | H7A—C7—H7B | 107.6 |
C6—N3—Zn | 118.77 (13) | N4—C8—C7 | 112.60 (19) |
C5—N3—H3 | 106.6 | N4—C8—H8A | 109.1 |
C6—N3—H3 | 106.6 | C7—C8—H8A | 109.1 |
Zn—N3—H3 | 106.6 | N4—C8—H8B | 109.1 |
C8—N4—Zn | 118.67 (14) | C7—C8—H8B | 109.1 |
C8—N4—H4A | 107.6 | H8A—C8—H8B | 107.8 |
Zn—N4—H4A | 107.6 | N6—C9—N5 | 124.5 (2) |
C8—N4—H4B | 107.6 | N6—C9—S1 | 120.12 (16) |
Zn—N4—H4B | 107.6 | N5—C9—S1 | 115.42 (16) |
H4A—N4—H4B | 107.1 | N6—C10—N7 | 119.33 (19) |
C11—N5—C9 | 118.13 (19) | N6—C10—S3 | 121.87 (17) |
C11—N5—Zn | 140.07 (15) | N7—C10—S3 | 118.77 (17) |
C9—N5—Zn | 98.37 (13) | N5—C11—N7 | 117.62 (19) |
C10—N6—C9 | 117.14 (19) | N5—C11—S2 | 122.90 (17) |
C11—N7—C10 | 122.54 (18) | N7—C11—S2 | 119.48 (16) |
C11—N7—H7 | 118.7 | C12—O1—H1O | 103 (3) |
C10—N7—H7 | 118.7 | C12—C13—H13A | 109.5 |
N1—C1—C2 | 112.9 (2) | C12—C13—H13B | 109.5 |
N1—C1—H1C | 109.0 | H13A—C13—H13B | 109.5 |
C2—C1—H1C | 109.0 | C12—C13—H13C | 109.5 |
N1—C1—H1D | 109.0 | H13A—C13—H13C | 109.5 |
C2—C1—H1D | 109.0 | H13B—C13—H13C | 109.5 |
H1C—C1—H1D | 107.8 | O1—C12—C13 | 109.1 (3) |
C3—C2—C1 | 115.1 (2) | O1—C12—H12A | 109.9 |
C3—C2—H2A | 108.5 | C13—C12—H12A | 109.9 |
C1—C2—H2A | 108.5 | O1—C12—H12B | 109.9 |
C3—C2—H2B | 108.5 | C13—C12—H12B | 109.9 |
C1—C2—H2B | 108.5 | H12A—C12—H12B | 108.3 |
H2A—C2—H2B | 107.5 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O1 | 0.92 | 2.20 | 3.065 (3) | 156 |
N1—H1A···S3i | 0.92 | 2.55 | 3.458 (2) | 167 |
N3—H3···S2 | 0.93 | 2.61 | 3.475 (2) | 154 |
N4—H4A···N6i | 0.92 | 2.09 | 2.991 (3) | 167 |
N7—H7···S2ii | 0.88 | 2.49 | 3.361 (2) | 170 |
O1—H1O···S3iii | 0.93 (4) | 2.46 (4) | 3.357 (2) | 161 (3) |
O1—H1O···N6iii | 0.93 (4) | 2.61 (3) | 3.326 (3) | 135 (3) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x, y, z+1. |
Experimental details
Crystal data |
Chemical formula | [Zn(C8H22N4)(C3HN3S3)]·C2H6O |
Mr | 460.98 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 9.0791 (14), 11.0455 (15), 11.3580 (11) |
α, β, γ (°) | 93.592 (10), 102.316 (11), 112.167 (14) |
V (Å3) | 1017.6 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.53 |
Crystal size (mm) | 0.40 × 0.40 × 0.40 |
|
Data collection |
Diffractometer | Kuma KM4 with CCD area detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6681, 4458, 4279 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.669 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.097, 1.01 |
No. of reflections | 4458 |
No. of parameters | 230 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.08, −0.66 |
Selected geometric parameters (Å, º) topZn—N1 | 2.104 (2) | Zn—S1 | 2.5700 (7) |
Zn—N4 | 2.1249 (19) | S1—C9 | 1.708 (2) |
Zn—N3 | 2.1682 (19) | S2—C11 | 1.697 (2) |
Zn—N2 | 2.2031 (19) | S3—C10 | 1.698 (2) |
Zn—N5 | 2.3132 (18) | | |
| | | |
N1—Zn—N4 | 94.66 (8) | N2—Zn—S1 | 89.91 (6) |
N1—Zn—N3 | 100.92 (7) | N5—Zn—S1 | 64.32 (5) |
N4—Zn—N3 | 90.46 (7) | C9—S1—Zn | 80.99 (8) |
N1—Zn—N2 | 93.77 (8) | C1—N1—Zn | 116.11 (15) |
N4—Zn—N2 | 169.06 (8) | N6—C9—N5 | 124.5 (2) |
N3—Zn—N2 | 81.09 (7) | N6—C9—S1 | 120.12 (16) |
N1—Zn—N5 | 163.89 (7) | N5—C9—S1 | 115.42 (16) |
N4—Zn—N5 | 84.67 (7) | N6—C10—N7 | 119.33 (19) |
N3—Zn—N5 | 95.18 (7) | N6—C10—S3 | 121.87 (17) |
N2—Zn—N5 | 89.15 (7) | N7—C10—S3 | 118.77 (17) |
N1—Zn—S1 | 99.81 (6) | N5—C11—N7 | 117.62 (19) |
N4—Zn—S1 | 95.51 (5) | N5—C11—S2 | 122.90 (17) |
N3—Zn—S1 | 157.87 (5) | N7—C11—S2 | 119.48 (16) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O1 | 0.92 | 2.20 | 3.065 (3) | 156 |
N1—H1A···S3i | 0.92 | 2.55 | 3.458 (2) | 167 |
N3—H3···S2 | 0.93 | 2.61 | 3.475 (2) | 154 |
N4—H4A···N6i | 0.92 | 2.09 | 2.991 (3) | 167 |
N7—H7···S2ii | 0.88 | 2.49 | 3.361 (2) | 170 |
O1—H1O···S3iii | 0.93 (4) | 2.46 (4) | 3.357 (2) | 161 (3) |
O1—H1O···N6iii | 0.93 (4) | 2.61 (3) | 3.326 (3) | 135 (3) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x, y, z+1. |
Trithiocyanuric acid (2,4,6-trimercaptotriazine, ttcH3) and its trisodium salt have a very wide range of applications, e.g. they can be used as precipitating agents for heavy metals (Henke et al., 2000; Matlock et al., 2001, 2002). The acid also shows antitoxoplasmal activity and is more effective than the presently used drugs 5-fluorouracil and emimicin (Iltzsch & Tankersley, 1994). The formation of metal complexes with trithiocyanuric acid depends strongly on the pH value. At pH below 5, only ttcH3 exists, which is insoluble in water, while ttcH2−, ttcH2− and ttc3− anions are formed if the pH is increased. In connection with the extent of ttcH3 deprotonation, the manner of coordination of the anion to the metal centre can be different and transition metal complexes with various nuclearities can be formed. These complexes can be mononuclear (Mahon et al., 2003; Zhao et al., 2000; Kopel et al., 1998, 2001, 2003; Kopel, Trávníček, Panchártková et al., 1999; Kopel, Trávníček, Kvítek et al., 1999), binuclear (Yamanari et al., 1993), trinuclear (Ainscough et al., 1993; Hunks et al., 1999; Haiduc et al., 2001; Cecconi et al., 2002) or even polynuclear (Chan et al., 1996; Tzeng et al., 1997; Aoki, Shiro & Kimura, 2002; Aoki, Zulkefeli et al., 2002). Here, we report the preparation and crystal structure of the title mononuclear [Zn(bapen)(ttcH)]·EtOH complex, (I) [bapen is N,N'-bis(3-aminopropyl)ethylenediamine]. \sch
The structure of the title ZnII complex, (I), is very similar to that previously reported for [Ni(bapen)(ttcH)]·2H2O, (II) (Kopel, Trávníček, Kvítek et al., 1999). Complex (II) is octahedral, with Ni—N(bapen) bond lengths in the range 2.08–2.12 Å, while the Ni—N and Ni—S (ttcH2−) distances are 2.143 and 2.521 Å, respectively. These interatomic parameters differ significantly from those found for (I). It is necessary to emphasize that the structure of (I) represents the first known example of a mononuclear ZnII complex with a coordinated trithiocyanurate dianion. If we compare (I) with known ZnII trithiocyanurate clusters (Aoki, Shiro & Kimura, 2002; Aoki, Zulkefeli et al., 2002), we can note that the higher nuclearity of the latter complexes was caused by the total deprotonation of ttcH3 as well as by the use of suitable bridging ligands. To prevent the formation of a polynuclear complex, we have used the bapen ligand for the synthesis of (I).
The crystal structure of (I) consists of [Zn(bapen)(ttcH)] and ethanol molecules (Fig. 1). The ZnII ion in the complex adopts a substantially distorted octahedral geometry, defined by the four N atoms of the bapen ligand and two S and N atoms of the ttcH2− anion in a cis configuration. The bapen ligand is bonded as a tetradentate N-donor ligand and forms with the Zn atom a five-membered (ring B) and two six-membered (ring A, containing atoms N1 and N2, and ring C, containing atoms N4 and N3) rings. The Zn—N distances in these rings (2.10–2.20 Å) are comparable with the average length (2.16 Å) of this bond in related complexes in the Cambridge Structural Database (Version 5.24.3; Allen, 2002). The five-membered ring B is twisted and both six-membered rings A and C are in chair conformations. The Cremer-Pople puckering parameters (Cremer & Pople, 1975) are Q = 0.563 (3) Å, θ = 161.5 (2)° and ϕ2 = −18.8 (8)° for ring A, Q = 0.575 (3) Å, θ = 165.1 (2)° and ϕ2 = −5.7 (9)° for ring C, and q2 = 0.458 (2) Å and ϕ2 = −64.8 (3)° for ring B.
The coordination of the ttcH2− anion to Zn in (I) differs significantly from the recently reported polynuclear ZnII trithiocyanurate structure (Aoki, Zulkefeli et al., 2002). While two distinct average values for the Zn—S (2.30 and 2.88 Å) and Zn—N (3.06 and 2.07 Å) bond distances for two different Zn-ttc coordination modes in Aoki's structure show the coordination of ttc through either S or N atoms, the intermediate values of the Zn—S (2.570 Å) and Zn—N (2.313 Å) bond distances in (I) indicate that the ttcH2− is chelated as a bidentate ligand.
In the crystal lattice of (I), Zn complex molecules and molecules of ethanol are linked by a network of hydrogen bonds (Table 2). The shortest one (N—H.·N 2.09 Å) connects atoms N4 and N6i from inversion-related molecules [symmetry code: (i) 1 − x, −y, 1 − z].