Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009088/na1492sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009088/na1492Isup2.hkl |
CCDC reference: 174791
The title complex, [Ni(dien)2](ats)Cl·H2O, was prepared by mixing nickel(II) chloride hexahydrate (1 mmol), diethylenetriamine (2 mmol) and 5-amino-1,3,4-thiadiazole-2-sulfonamide (2 mmol) in ethanol (50 ml), at room temperature. Single crystals were obtained after one month from the resulting pale purple solution.
All hydrogen atoms were localized geometrically and refined as riding, except H331 and the water H atoms that were located in subsequent difference Fourier maps. These atoms were refined.
Data collection: CAD-4 Software (Enraf-Nonius, 1997); cell refinement: CAD-4 Software; data reduction: Process in Omolen (Nonius, 1997); program(s) used to solve structure: DIRDIF (Beurskens, 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
[Ni(C4H13N3)2](C2H3N4O2S2)Cl·H2O | F(000) = 1024 |
Mr = 497.73 | Dx = 1.567 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.378 (6) Å | Cell parameters from 25 reflections |
b = 11.099 (10) Å | θ = 1.8–25.0° |
c = 23.042 (12) Å | µ = 1.28 mm−1 |
β = 99.44 (5)° | T = 293 K |
V = 2114 (3) Å3 | Prismatic, red |
Z = 4 | 0.15 × 0.10 × 0.10 mm |
Enraf-Nonius Cad-4 difractometer diffractometer | 2685 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.8° |
Graphite monochromator | h = 0→9 |
ω–2θ scans | k = 0→13 |
Absorption correction: ψ scan (North et al., 1968) | l = −27→26 |
Tmin = 0.774, Tmax = 0.880 | 60 standard reflections every 1000 reflections |
3706 measured reflections | intensity decay: 0.1% |
3706 independent reflections |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.149 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0531P)2 + 4.4405P] where P = (Fo2 + 2Fc2)/3 |
3706 reflections | (Δ/σ)max = 0.042 |
264 parameters | Δρmax = 0.67 e Å−3 |
6 restraints | Δρmin = −0.50 e Å−3 |
[Ni(C4H13N3)2](C2H3N4O2S2)Cl·H2O | V = 2114 (3) Å3 |
Mr = 497.73 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.378 (6) Å | µ = 1.28 mm−1 |
b = 11.099 (10) Å | T = 293 K |
c = 23.042 (12) Å | 0.15 × 0.10 × 0.10 mm |
β = 99.44 (5)° |
Enraf-Nonius Cad-4 difractometer diffractometer | 3706 independent reflections |
Absorption correction: ψ scan (North et al., 1968) | 2685 reflections with I > 2σ(I) |
Tmin = 0.774, Tmax = 0.880 | 60 standard reflections every 1000 reflections |
3706 measured reflections | intensity decay: 0.1% |
R[F2 > 2σ(F2)] = 0.059 | 6 restraints |
wR(F2) = 0.149 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | Δρmax = 0.67 e Å−3 |
3706 reflections | Δρmin = −0.50 e Å−3 |
264 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ni | 0.40181 (9) | 0.30325 (7) | 0.84560 (3) | 0.0268 (3) | |
N11 | 0.1522 (7) | 0.3011 (6) | 0.8507 (3) | 0.0459 (15) | |
H11A | 0.1285 | 0.3586 | 0.8755 | 0.071 (10)* | |
H11B | 0.0929 | 0.3141 | 0.8150 | 0.071 (10)* | |
N12 | 0.4079 (6) | 0.1676 (5) | 0.9112 (2) | 0.0336 (13) | |
H12 | 0.4530 | 0.0995 | 0.8990 | 0.028 (12)* | |
N13 | 0.4679 (7) | 0.4136 (5) | 0.9208 (2) | 0.0423 (15) | |
H13A | 0.5670 | 0.4448 | 0.9206 | 0.071 (10)* | |
H13B | 0.3974 | 0.4751 | 0.9199 | 0.075 (11)* | |
C11 | 0.1176 (10) | 0.1805 (9) | 0.8727 (4) | 0.070 (3) | |
H111 | 0.0134 | 0.1822 | 0.8859 | 0.076 (7)* | |
H112 | 0.1109 | 0.1229 | 0.8408 | 0.076 (7)* | |
C12 | 0.2413 (9) | 0.1408 (8) | 0.9213 (4) | 0.056 (2) | |
H121 | 0.2307 | 0.0546 | 0.9267 | 0.076 (7)* | |
H122 | 0.2232 | 0.1802 | 0.9572 | 0.076 (7)* | |
C13 | 0.5105 (9) | 0.2139 (7) | 0.9640 (3) | 0.0487 (19) | |
H131 | 0.6232 | 0.2085 | 0.9593 | 0.076 (7)* | |
H132 | 0.4956 | 0.1653 | 0.9977 | 0.076 (7)* | |
C14 | 0.4681 (10) | 0.3432 (7) | 0.9744 (3) | 0.052 (2) | |
H141 | 0.3621 | 0.3470 | 0.9861 | 0.076 (7)* | |
H142 | 0.5463 | 0.3766 | 1.0060 | 0.076 (7)* | |
N21 | 0.3750 (7) | 0.1739 (4) | 0.7766 (2) | 0.0336 (13) | |
H21A | 0.3576 | 0.1007 | 0.7913 | 0.071 (10)* | |
H21B | 0.2885 | 0.1929 | 0.7496 | 0.071 (10)* | |
N22 | 0.6447 (6) | 0.3024 (5) | 0.8293 (3) | 0.0367 (13) | |
H22 | 0.7122 | 0.2965 | 0.8644 | 0.028 (12)* | |
N23 | 0.3840 (7) | 0.4509 (5) | 0.7883 (3) | 0.0417 (15) | |
H23A | 0.2967 | 0.4417 | 0.7602 | 0.071 (10)* | |
H23B | 0.3703 | 0.5186 | 0.8084 | 0.071 (10)* | |
C21 | 0.5194 (9) | 0.1697 (6) | 0.7487 (3) | 0.0458 (19) | |
H211 | 0.5104 | 0.2292 | 0.7175 | 0.076 (7)* | |
H212 | 0.5284 | 0.0908 | 0.7313 | 0.076 (7)* | |
C22 | 0.6688 (9) | 0.1947 (7) | 0.7935 (4) | 0.0478 (19) | |
H221 | 0.6925 | 0.1254 | 0.8191 | 0.076 (7)* | |
H222 | 0.7605 | 0.2079 | 0.7734 | 0.076 (7)* | |
C23 | 0.6735 (9) | 0.4190 (7) | 0.8024 (4) | 0.050 (2) | |
H231 | 0.7637 | 0.4110 | 0.7811 | 0.076 (7)* | |
H232 | 0.7030 | 0.4783 | 0.8332 | 0.076 (7)* | |
C24 | 0.5278 (11) | 0.4632 (7) | 0.7609 (3) | 0.059 (2) | |
H241 | 0.5427 | 0.5471 | 0.7512 | 0.076 (7)* | |
H242 | 0.5147 | 0.4168 | 0.7248 | 0.076 (7)* | |
S3 | 0.4583 (2) | −0.16955 (14) | 0.82795 (7) | 0.0355 (4) | |
O31 | 0.3478 (6) | −0.0730 (5) | 0.8377 (3) | 0.0607 (16) | |
O32 | 0.5118 (7) | −0.1628 (7) | 0.7720 (2) | 0.083 (2) | |
N33 | 0.4032 (8) | −0.2958 (5) | 0.8401 (3) | 0.0537 (18) | |
H331 | 0.346 (17) | −0.274 (15) | 0.875 (5) | 0.23 (8)* | |
C41 | 0.6403 (7) | −0.1369 (5) | 0.8782 (3) | 0.0297 (14) | |
S4 | 0.7967 (2) | −0.23924 (15) | 0.88958 (8) | 0.0420 (5) | |
N41 | 0.6663 (7) | −0.0382 (5) | 0.9071 (2) | 0.0358 (13) | |
N42 | 0.8190 (6) | −0.0338 (5) | 0.9405 (2) | 0.0365 (13) | |
C42 | 0.9014 (8) | −0.1323 (6) | 0.9360 (3) | 0.0334 (15) | |
N5 | 1.0510 (7) | −0.1509 (5) | 0.9644 (3) | 0.0522 (18) | |
H51 | 1.0990 | −0.0962 | 0.9874 | 0.062 (18)* | |
H52 | 1.0997 | −0.2176 | 0.9599 | 0.062 (18)* | |
Cl | 0.1326 (2) | 0.58261 (17) | 0.91968 (9) | 0.0515 (5) | |
O6 | 0.8403 (9) | 0.4150 (7) | 0.9406 (3) | 0.085 (2) | |
H61 | 0.943 (7) | 0.444 (11) | 0.935 (6) | 0.14 (3)* | |
H62 | 0.847 (15) | 0.437 (11) | 0.9807 (18) | 0.14 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0324 (5) | 0.0197 (4) | 0.0267 (4) | 0.0026 (3) | 0.0000 (3) | −0.0042 (3) |
N11 | 0.034 (3) | 0.057 (4) | 0.045 (4) | 0.005 (3) | 0.001 (3) | −0.008 (3) |
N12 | 0.044 (3) | 0.030 (3) | 0.027 (3) | 0.002 (2) | 0.006 (2) | −0.003 (2) |
N13 | 0.046 (3) | 0.036 (3) | 0.042 (3) | 0.007 (3) | −0.003 (3) | −0.016 (3) |
C11 | 0.054 (5) | 0.087 (7) | 0.072 (6) | −0.024 (5) | 0.015 (5) | 0.003 (6) |
C12 | 0.055 (5) | 0.062 (5) | 0.051 (5) | −0.004 (4) | 0.013 (4) | 0.009 (4) |
C13 | 0.056 (5) | 0.055 (5) | 0.032 (4) | 0.009 (4) | −0.002 (3) | −0.003 (4) |
C14 | 0.064 (5) | 0.054 (5) | 0.036 (4) | 0.009 (4) | 0.000 (4) | −0.019 (4) |
N21 | 0.046 (3) | 0.026 (3) | 0.027 (3) | −0.001 (2) | 0.003 (2) | −0.003 (2) |
N22 | 0.032 (3) | 0.035 (3) | 0.042 (3) | 0.004 (2) | 0.002 (2) | 0.004 (3) |
N23 | 0.052 (4) | 0.027 (3) | 0.041 (3) | 0.000 (3) | −0.011 (3) | 0.005 (3) |
C21 | 0.067 (5) | 0.035 (4) | 0.041 (4) | 0.000 (3) | 0.025 (4) | −0.015 (3) |
C22 | 0.050 (4) | 0.039 (4) | 0.058 (5) | 0.008 (3) | 0.020 (4) | 0.002 (4) |
C23 | 0.051 (5) | 0.044 (4) | 0.058 (5) | −0.016 (4) | 0.016 (4) | 0.003 (4) |
C24 | 0.095 (7) | 0.038 (4) | 0.042 (5) | 0.000 (4) | 0.006 (4) | 0.016 (4) |
S3 | 0.0405 (9) | 0.0345 (9) | 0.0289 (8) | 0.0026 (7) | 0.0022 (7) | 0.0010 (7) |
O31 | 0.061 (3) | 0.047 (3) | 0.066 (4) | 0.013 (3) | −0.014 (3) | −0.002 (3) |
O32 | 0.069 (4) | 0.148 (7) | 0.031 (3) | −0.032 (4) | 0.004 (3) | 0.002 (4) |
N33 | 0.066 (4) | 0.030 (3) | 0.059 (4) | −0.004 (3) | −0.010 (4) | −0.009 (3) |
C41 | 0.037 (4) | 0.024 (3) | 0.029 (3) | −0.001 (3) | 0.004 (3) | 0.000 (3) |
S4 | 0.0468 (10) | 0.0301 (9) | 0.0444 (10) | 0.0071 (8) | −0.0067 (8) | −0.0144 (8) |
N41 | 0.047 (3) | 0.027 (3) | 0.031 (3) | 0.002 (2) | −0.001 (2) | −0.007 (2) |
N42 | 0.041 (3) | 0.025 (3) | 0.040 (3) | 0.003 (2) | −0.004 (3) | −0.010 (2) |
C42 | 0.036 (4) | 0.032 (4) | 0.031 (3) | 0.001 (3) | 0.001 (3) | −0.007 (3) |
N5 | 0.048 (4) | 0.036 (3) | 0.064 (4) | 0.011 (3) | −0.017 (3) | −0.022 (3) |
Cl | 0.0525 (11) | 0.0430 (10) | 0.0589 (12) | 0.0088 (9) | 0.0091 (9) | −0.0080 (9) |
O6 | 0.081 (5) | 0.108 (6) | 0.060 (4) | −0.041 (4) | −0.008 (4) | 0.001 (4) |
Ni—N23 | 2.094 (5) | N22—H22 | 0.9100 |
Ni—N11 | 2.114 (6) | N23—C24 | 1.455 (13) |
Ni—N13 | 2.123 (5) | N23—H23A | 0.9000 |
Ni—N21 | 2.126 (5) | N23—H23B | 0.9000 |
Ni—N22 | 2.129 (6) | C21—C22 | 1.514 (12) |
Ni—N12 | 2.129 (5) | C21—H211 | 0.9700 |
N11—C11 | 1.474 (10) | C21—H212 | 0.9700 |
N11—H11A | 0.9000 | C22—H221 | 0.9700 |
N11—H11B | 0.9000 | C22—H222 | 0.9700 |
N12—C13 | 1.461 (9) | C23—C24 | 1.506 (12) |
N12—C12 | 1.484 (13) | C23—H231 | 0.9700 |
N12—H12 | 0.9100 | C23—H232 | 0.9700 |
N13—C14 | 1.465 (10) | C24—H241 | 0.9700 |
N13—H13A | 0.9000 | C24—H242 | 0.9700 |
N13—H13B | 0.9000 | S3—O32 | 1.432 (6) |
C11—C12 | 1.463 (12) | S3—O31 | 1.459 (7) |
C11—H111 | 0.9700 | S3—N33 | 1.513 (7) |
C11—H112 | 0.9700 | S3—C41 | 1.792 (10) |
C12—H121 | 0.9700 | N33—H331 | 1.03 (13) |
C12—H122 | 0.9700 | C41—N41 | 1.283 (8) |
C13—C14 | 1.507 (10) | C41—S4 | 1.723 (9) |
C13—H131 | 0.9700 | S4—C42 | 1.738 (7) |
C13—H132 | 0.9700 | N41—N42 | 1.383 (11) |
C14—H141 | 0.9700 | N42—C42 | 1.304 (8) |
C14—H142 | 0.9700 | C42—N5 | 1.333 (11) |
N21—C21 | 1.463 (12) | N5—H51 | 0.8600 |
N21—H21A | 0.9000 | N5—H52 | 0.8600 |
N21—H21B | 0.9000 | O6—H61 | 0.95 (8) |
N22—C23 | 1.472 (8) | O6—H62 | 0.95 (6) |
N22—C22 | 1.484 (9) | ||
N23—Ni—N11 | 94.2 (2) | C21—N21—H21B | 109.5 |
N23—Ni—N13 | 92.6 (2) | Ni—N21—H21B | 109.5 |
N11—Ni—N13 | 95.0 (2) | H21A—N21—H21B | 108.1 |
N23—Ni—N21 | 94.0 (2) | C23—N22—C22 | 115.3 (6) |
N11—Ni—N21 | 93.0 (2) | C23—N22—Ni | 107.3 (4) |
N13—Ni—N21 | 169.2 (2) | C22—N22—Ni | 108.4 (4) |
N23—Ni—N22 | 82.2 (2) | C23—N22—H22 | 109.0 |
N11—Ni—N22 | 173.1 (3) | C22—N22—H22 | 109.0 |
N13—Ni—N22 | 91.0 (2) | Ni—N22—H22 | 109.0 |
N21—Ni—N22 | 81.5 (2) | C24—N23—Ni | 111.6 (4) |
N23—Ni—N12 | 172.9 (2) | C24—N23—H23A | 109.4 |
N11—Ni—N12 | 82.0 (2) | Ni—N23—H23A | 109.4 |
N13—Ni—N12 | 81.8 (2) | C24—N23—H23B | 109.4 |
N21—Ni—N12 | 92.2 (2) | Ni—N23—H23B | 109.4 |
N22—Ni—N12 | 102.1 (2) | H23A—N23—H23B | 108.0 |
C11—N11—Ni | 106.2 (4) | N21—C21—C22 | 110.4 (6) |
C11—N11—H11A | 110.5 | N21—C21—H211 | 109.6 |
Ni—N11—H11A | 110.5 | C22—C21—H211 | 109.6 |
C11—N11—H11B | 110.5 | N21—C21—H212 | 109.6 |
Ni—N11—H11B | 110.5 | C22—C21—H212 | 109.6 |
H11A—N11—H11B | 108.7 | H211—C21—H212 | 108.1 |
C13—N12—C12 | 112.7 (6) | N22—C22—C21 | 111.3 (5) |
C13—N12—Ni | 106.3 (4) | N22—C22—H221 | 109.4 |
C12—N12—Ni | 109.6 (4) | C21—C22—H221 | 109.4 |
C13—N12—H12 | 109.4 | N22—C22—H222 | 109.4 |
C12—N12—H12 | 109.4 | C21—C22—H222 | 109.4 |
Ni—N12—H12 | 109.4 | H221—C22—H222 | 108.0 |
C14—N13—Ni | 110.1 (4) | N22—C23—C24 | 112.9 (6) |
C14—N13—H13A | 109.6 | N22—C23—H231 | 109.0 |
Ni—N13—H13A | 109.6 | C24—C23—H231 | 109.0 |
C14—N13—H13B | 109.6 | N22—C23—H232 | 109.0 |
Ni—N13—H13B | 109.6 | C24—C23—H232 | 109.0 |
H13A—N13—H13B | 108.1 | H231—C23—H232 | 107.8 |
C12—C11—N11 | 113.0 (7) | N23—C24—C23 | 110.3 (7) |
C12—C11—H111 | 109.0 | N23—C24—H241 | 109.6 |
N11—C11—H111 | 109.0 | C23—C24—H241 | 109.6 |
C12—C11—H112 | 109.0 | N23—C24—H242 | 109.6 |
N11—C11—H112 | 109.0 | C23—C24—H242 | 109.6 |
H111—C11—H112 | 107.8 | H241—C24—H242 | 108.1 |
C11—C12—N12 | 112.8 (7) | O32—S3—O31 | 113.2 (4) |
C11—C12—H121 | 109.0 | O32—S3—N33 | 111.5 (4) |
N12—C12—H121 | 109.0 | O31—S3—N33 | 115.5 (5) |
C11—C12—H122 | 109.0 | O32—S3—C41 | 102.2 (3) |
N12—C12—H122 | 109.0 | O31—S3—C41 | 104.2 (3) |
H121—C12—H122 | 107.8 | N33—S3—C41 | 108.8 (3) |
N12—C13—C14 | 110.8 (5) | S3—N33—H331 | 100 (10) |
N12—C13—H131 | 109.5 | N41—C41—S4 | 114.7 (5) |
C14—C13—H131 | 109.5 | N41—C41—S3 | 124.1 (4) |
N12—C13—H132 | 109.5 | S4—C41—S3 | 120.7 (3) |
C14—C13—H132 | 109.5 | C41—S4—C42 | 86.7 (4) |
H131—C13—H132 | 108.1 | C41—N41—N42 | 112.9 (5) |
N13—C14—C13 | 109.9 (5) | C42—N42—N41 | 111.9 (5) |
N13—C14—H141 | 109.7 | N42—C42—N5 | 123.7 (6) |
C13—C14—H141 | 109.7 | N42—C42—S4 | 113.8 (5) |
N13—C14—H142 | 109.7 | N5—C42—S4 | 122.5 (5) |
C13—C14—H142 | 109.7 | C42—N5—H51 | 120.0 |
H141—C14—H142 | 108.2 | C42—N5—H52 | 120.0 |
C21—N21—Ni | 110.6 (4) | H51—N5—H52 | 120.0 |
C21—N21—H21A | 109.5 | H61—O6—H62 | 106 (8) |
Ni—N21—H21A | 109.5 | ||
N23—Ni—N11—C11 | 161.6 (5) | N12—Ni—N22—C23 | −159.1 (5) |
N13—Ni—N11—C11 | −105.8 (5) | N23—Ni—N22—C22 | −109.9 (4) |
N21—Ni—N11—C11 | 66.9 (5) | N13—Ni—N22—C22 | 157.2 (5) |
N12—Ni—N11—C11 | −24.8 (4) | N21—Ni—N22—C22 | −15.1 (5) |
N11—Ni—N12—C13 | −117.9 (5) | N12—Ni—N22—C22 | 75.5 (5) |
N13—Ni—N12—C13 | −21.6 (4) | N11—Ni—N23—C24 | −164.8 (4) |
N21—Ni—N12—C13 | 149.4 (4) | N13—Ni—N23—C24 | 100.0 (5) |
N22—Ni—N12—C13 | 67.4 (5) | N21—Ni—N23—C24 | −71.5 (5) |
N11—Ni—N12—C12 | 4.1 (4) | N22—Ni—N23—C24 | 9.7 (4) |
N13—Ni—N12—C12 | 100.4 (4) | Ni—N21—C21—C22 | 33.5 (6) |
N21—Ni—N12—C12 | −88.6 (4) | C23—N22—C22—C21 | −83.0 (7) |
N22—Ni—N12—C12 | −170.7 (4) | Ni—N22—C22—C21 | 36.9 (6) |
N23—Ni—N13—C14 | 170.9 (4) | N21—C21—C22—N22 | −47.5 (7) |
N11—Ni—N13—C14 | 76.4 (4) | C22—N22—C23—C24 | 84.0 (7) |
N21—Ni—N13—C14 | −61.0 (13) | Ni—N22—C23—C24 | −37.2 (8) |
N22—Ni—N13—C14 | −106.5 (4) | Ni—N23—C24—C23 | −31.7 (7) |
N12—Ni—N13—C14 | −4.7 (4) | N22—C23—C24—N23 | 46.2 (8) |
Ni—N11—C11—C12 | 43.5 (8) | O32—S3—C41—N41 | 108.1 (6) |
N11—C11—C12—N12 | −42.4 (9) | O31—S3—C41—N41 | −10.3 (6) |
C13—N12—C12—C11 | 137.6 (7) | N33—S3—C41—N41 | −133.6 (6) |
Ni—N12—C12—C11 | 18.5 (8) | O32—S3—C41—S4 | −70.5 (5) |
C12—N12—C13—C14 | −75.1 (7) | O31—S3—C41—S4 | 171.1 (3) |
Ni—N12—C13—C14 | 44.9 (6) | N33—S3—C41—S4 | 47.2 (5) |
Ni—N13—C14—C13 | 30.0 (7) | N41—C41—S4—C42 | −1.3 (5) |
N12—C13—C14—N13 | −51.2 (8) | S3—C41—S4—C42 | 177.4 (4) |
N23—Ni—N21—C21 | 71.4 (4) | S4—C41—N41—N42 | 1.6 (6) |
N11—Ni—N21—C21 | 165.9 (4) | S3—C41—N41—N42 | −177.1 (4) |
N13—Ni—N21—C21 | −56.6 (12) | C41—N41—N42—C42 | −0.9 (7) |
N22—Ni—N21—C21 | −10.5 (4) | N41—N42—C42—N5 | −178.8 (6) |
N12—Ni—N21—C21 | −112.1 (4) | N41—N42—C42—S4 | −0.1 (6) |
N23—Ni—N22—C23 | 15.1 (5) | C41—S4—C42—N42 | 0.8 (5) |
N13—Ni—N22—C23 | −77.4 (5) | C41—S4—C42—N5 | 179.5 (6) |
N21—Ni—N22—C23 | 110.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···Cl | 0.90 | 2.68 | 3.521 (7) | 155 |
N12—H12···O31 | 0.91 | 2.46 | 3.158 (8) | 134 |
N12—H12···N41 | 0.91 | 2.33 | 3.16 (1) | 150 |
N13—H13A···O6 | 0.90 | 2.29 | 3.08 (2) | 146 |
N13—H13B···Cl | 0.90 | 2.52 | 3.374 (7) | 159 |
N21—H21A···O31 | 0.90 | 2.21 | 3.108 (8) | 171 |
N22—H22···O6 | 0.91 | 2.31 | 3.08 (1) | 141 |
N23—H23A···O31i | 0.90 | 2.38 | 3.23 (1) | 156 |
N21—H21B···N33i | 0.90 | 2.40 | 3.28 (1) | 162 |
N11—H11B···O32i | 0.90 | 2.07 | 2.964 (9) | 171 |
N21—H21B···S3i | 0.90 | 2.93 | 3.796 (7) | 162 |
N23—H23A···S3i | 0.90 | 2.96 | 3.83 (1) | 161 |
O6—H62···Clii | 0.95 (6) | 2.28 (5) | 3.190 (8) | 160 (10) |
N23—H23B···N33iii | 0.90 | 2.19 | 3.048 (9) | 160 |
N5—H51···N42iv | 0.86 | 2.22 | 3.066 (9) | 166 |
N5—H52···Clv | 0.86 | 2.44 | 3.242 (7) | 156 |
O6—H61···Clvi | 0.95 (7) | 2.28 (7) | 3.174 (8) | 157 (10) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1, −y+1, −z+2; (iii) x, y+1, z; (iv) −x+2, −y, −z+2; (v) x+1, y−1, z; (vi) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C4H13N3)2](C2H3N4O2S2)Cl·H2O |
Mr | 497.73 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.378 (6), 11.099 (10), 23.042 (12) |
β (°) | 99.44 (5) |
V (Å3) | 2114 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.28 |
Crystal size (mm) | 0.15 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Enraf-Nonius Cad-4 difractometer diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.774, 0.880 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3706, 3706, 2685 |
Rint | ? |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.149, 1.15 |
No. of reflections | 3706 |
No. of parameters | 264 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.67, −0.50 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1997), CAD-4 Software, Process in Omolen (Nonius, 1997), DIRDIF (Beurskens, 1992), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Ni—N23 | 2.094 (5) | S3—O31 | 1.459 (7) |
Ni—N11 | 2.114 (6) | S3—N33 | 1.513 (7) |
Ni—N13 | 2.123 (5) | S3—C41 | 1.792 (10) |
Ni—N21 | 2.126 (5) | C41—S4 | 1.723 (9) |
Ni—N22 | 2.129 (6) | N41—N42 | 1.383 (11) |
Ni—N12 | 2.129 (5) | N42—C42 | 1.304 (8) |
S3—O32 | 1.432 (6) | ||
N23—Ni—N11 | 94.2 (2) | N23—Ni—N12 | 172.9 (2) |
N23—Ni—N13 | 92.6 (2) | N11—Ni—N12 | 82.0 (2) |
N11—Ni—N13 | 95.0 (2) | N13—Ni—N12 | 81.8 (2) |
N23—Ni—N21 | 94.0 (2) | N21—Ni—N12 | 92.2 (2) |
N11—Ni—N21 | 93.0 (2) | N22—Ni—N12 | 102.1 (2) |
N13—Ni—N21 | 169.2 (2) | N41—C41—S4 | 114.7 (5) |
N23—Ni—N22 | 82.2 (2) | C41—S4—C42 | 86.7 (4) |
N11—Ni—N22 | 173.1 (3) | C41—N41—N42 | 112.9 (5) |
N13—Ni—N22 | 91.0 (2) | C42—N42—N41 | 111.9 (5) |
N21—Ni—N22 | 81.5 (2) | N42—C42—S4 | 113.8 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···Cl | 0.90 | 2.68 | 3.521 (7) | 155 |
N12—H12···O31 | 0.91 | 2.46 | 3.158 (8) | 134 |
N12—H12···N41 | 0.91 | 2.33 | 3.16 (1) | 150 |
N13—H13A···O6 | 0.90 | 2.29 | 3.08 (2) | 146 |
N13—H13B···Cl | 0.90 | 2.52 | 3.374 (7) | 159 |
N21—H21A···O31 | 0.90 | 2.21 | 3.108 (8) | 171 |
N22—H22···O6 | 0.91 | 2.31 | 3.08 (1) | 141 |
N23—H23A···O31i | 0.90 | 2.38 | 3.23 (1) | 156 |
N21—H21B···N33i | 0.90 | 2.40 | 3.28 (1) | 162 |
N11—H11B···O32i | 0.90 | 2.07 | 2.964 (9) | 171 |
N21—H21B···S3i | 0.90 | 2.93 | 3.796 (7) | 162 |
N23—H23A···S3i | 0.90 | 2.96 | 3.83 (1) | 161 |
O6—H62···Clii | 0.95 (6) | 2.28 (5) | 3.190 (8) | 160 (10) |
N23—H23B···N33iii | 0.90 | 2.19 | 3.048 (9) | 160 |
N5—H51···N42iv | 0.86 | 2.22 | 3.066 (9) | 166 |
N5—H52···Clv | 0.86 | 2.44 | 3.242 (7) | 156 |
O6—H61···Clvi | 0.95 (7) | 2.28 (7) | 3.174 (8) | 157 (10) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1, −y+1, −z+2; (iii) x, y+1, z; (iv) −x+2, −y, −z+2; (v) x+1, y−1, z; (vi) x+1, y, z. |
N-S | S═O | S═O | S-C | |
Hats | 1.569 | 1.427 | 1.432 | 1.767 |
Ats-1 counter-ion [Ni(dien)](ats)(Cl).H2O | 1.528 | 1.434 | 1.453 | 1.785 |
Ats-1 monodentate ligand [Zn(ats)(NH2)].H2O | 1.542 | 1.435 | 1.444 | 1.774 |
Ats-1 bridging ligand [Zn(ats)(NH2)].H2O | 1.544 | 1.437 | 1.438 | 1.787 |
Heterocyclic sulfonamides constitute an important group of carbonic anhydrase inhibitors. The inhibition of this enzyme by sulfonamide drugs finds clinical application in the treatment of glaucoma, epilepsy and other disorders. Acetazolamide (5-acetamido-1,3,4-thiadiazole-2-sulfonamide) has shown to be one of the most potent inhibitors (Evelhoch et al., 1981). The search for new sulfonamides with major pharmacological potency, low toxicity and few side effects still continues (Jallon, 1997). Hats (5-amino-1,3,4- thiadiazole-2-sulfonamide), an acetazolamide analogue, has shown to be more potent than acetazolamide as anticonvulsant in mice, although its low inhibition ability on carbonic anhydrase (Chufán, Pedregosa, Baldini & Bruno-Blanch et al., 1999).
The knowledge of the interactions of sulfonamides with carbonic anhydrase (or its structural models) is of great pharmacological and therapeutic interest. Thus, metallic complexes with Hats were synthesized and some crystal structures were determined (Chufán et al., 1997; Borja et al., 1998; Chufán, 1999). The crystal structure of [Zn(ats)2(NH3)]·H2O in which the sulfonamide presents two different coordination behaviours: as monodentate ligand through the N-sulfonamido atom and as a bridging ligand, linking the zinc ions through the N-sulfonamido and the N-thiadiazole atoms are reported (Borja et al., 1998). Recently, we have synthesized a new copper complex, [Cu(ats)2(dipn)] (dipn = dipropylenetriamine), where the sulfonamide also shows two coordination modes: as monodentate ligand in the same way that in the zinc(II) complex described above and as a bridging ligand, linking the copper ions through the O-sulfonamido and the N-sulfonamido atoms (Chufán, Pedregosa, Ferrer & Borrás et al., 1999).
In the present paper, we report the crystal structure of [Ni(dien)2](ats)(Cl)·H2O (dien = diethylenetriamine), (I), in which the sulfonamide behaves as a counter-ion instead of a ligand. It is noteworthy that this is the first reported metal complex structure where the Hats sulfonamide acts as a counter-ion. \sch
The main structural difference between the sulfonamidate anion and the free sulfonamide is the shortening of the N—S bond, see Table 1. This is due to deprotonation of the sulfonamido group and subsequent delocalization of the negative charge through the N—S bond. This phenomenon is also present in [Zn(ats)2(NH3)]·H2O, but in an attenuate way because of the N-sulfonamido atom being in a coordination site. The increasing of the (C—S) exocyclic bond is also attributed to electronic delocalization after deprotonation. These facts are evidence that structural properties are more affected by deprotonation than by coordination effects, as was concluded by vibrational spectroscopy for similar metal complexes (Chufán, Pedregosa, Ferrer & Borrás et al., 1999).
The coordination polyhedron consists of [Ni(dien)2]2+ unities, in which the diethylenetriamine coordinates to the metal center as a tridentate ligand in facial position. The NiII ions are linked to six N atoms, forming NiN6 cromophores with octahedral geometry. On the other hand, the comparison between the differences of the angles at Ni (see Table 1) are due to the spanning of the dimethylene groups.
The analogous complex [Cu(dipn)(ats)2] was synthesized with the same metal:triamine:sulfonamide molar ratio (1:2:2) and similar experimental conditions. The reason by which in the copper(II) complex the bis(triamine) is not formed, is related with the fact that the copper(II) ion is subject to Jahn-Teller effect whose typical distortion is an elongation along one fourfold axis, so that there is a planar array of four short Cu—L bonds and two trans long ones (Cotton & Wilkinson, 1988).