Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103008667/ob1117sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103008667/ob1117Isup2.hkl |
CCDC reference: 219544
The title compound, (I), was obtained by slow diffusion of two unperturbed solutions. The lower solution was an aqueous solution of nickel nitrate and sodium thiosulfate; the upper solution was a dmf solution of bbip, the main three components being in a 1:3:1 molar ratio. Crystal growth took place at the interface of the two solutions, giving rise to green prisms of (I) suitable for X-ray diffraction.
H atoms attached to C atoms were added at their expected positions and refined as riding. Methyl H atoms were also allowed to rotate. H atoms attached to the water molecule and to the protonated N atoms in bbip were found in the final? difference Fourier map and refined with restrained N—H, O—H [0.90 (3) Å] and H···H (.66× O—H) distances.
Data collection: SMART-NT (Bruker, 2001); cell refinement: SMART-NT (Bruker, 2001); data reduction: SAINT-NT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Ni(S2O3)(C21H13N5)(CH7NO)]·H2O | Z = 2 |
Mr = 573.29 | F(000) = 592 |
Triclinic, P1 | Dx = 1.615 Mg m−3 |
a = 9.3815 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.4096 (8) Å | Cell parameters from 78 reflections |
c = 15.1968 (13) Å | θ = 4.1–23.3° |
α = 72.124 (2)° | µ = 1.05 mm−1 |
β = 83.169 (2)° | T = 293 K |
γ = 67.423 (2)° | Prisms, green |
V = 1178.91 (17) Å3 | 0.35 × 0.25 × 0.16 mm |
CCD area detector diffractometer | 4505 independent reflections |
Radiation source: fine-focus sealed tube | 3230 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.4° |
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 2000) | h = −5→11 |
Tmin = 0.73, Tmax = 0.81 | k = −11→11 |
5399 measured reflections | l = −18→18 |
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)] = 0.039 | Hydrogen site location: mixed |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.87 | w = 1/[σ2(Fo2) + (0.061P)2] where P = (Fo2 + 2Fc2)/3 |
4505 reflections | (Δ/σ)max = 0.004 |
335 parameters | Δρmax = 0.41 e Å−3 |
3 restraints | Δρmin = −0.40 e Å−3 |
[Ni(S2O3)(C21H13N5)(CH7NO)]·H2O | γ = 67.423 (2)° |
Mr = 573.29 | V = 1178.91 (17) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.3815 (8) Å | Mo Kα radiation |
b = 9.4096 (8) Å | µ = 1.05 mm−1 |
c = 15.1968 (13) Å | T = 293 K |
α = 72.124 (2)° | 0.35 × 0.25 × 0.16 mm |
β = 83.169 (2)° |
CCD area detector diffractometer | 4505 independent reflections |
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 2000) | 3230 reflections with I > 2σ(I) |
Tmin = 0.73, Tmax = 0.81 | Rint = 0.038 |
5399 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 3 restraints |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.87 | Δρmax = 0.41 e Å−3 |
4505 reflections | Δρmin = −0.40 e Å−3 |
335 parameters |
x | y | z | Uiso*/Ueq | ||
Ni | 0.81382 (5) | 0.41298 (5) | 0.75171 (3) | 0.03156 (14) | |
S1 | 0.67156 (10) | 0.24134 (10) | 0.82124 (6) | 0.0395 (2) | |
S2 | 0.59107 (10) | 0.32539 (10) | 0.69089 (6) | 0.0373 (2) | |
O1 | 0.6588 (3) | 0.4507 (3) | 0.64681 (15) | 0.0410 (6) | |
O2 | 0.6527 (3) | 0.1985 (3) | 0.64375 (16) | 0.0477 (6) | |
O3 | 0.4248 (3) | 0.3918 (3) | 0.68928 (19) | 0.0591 (8) | |
N1 | 0.6766 (3) | 0.6399 (3) | 0.77208 (18) | 0.0342 (6) | |
N2 | 0.9151 (3) | 0.5638 (3) | 0.66603 (18) | 0.0332 (6) | |
N3 | 1.0022 (3) | 0.2564 (3) | 0.69552 (18) | 0.0352 (6) | |
N4 | 0.6359 (3) | 0.9005 (3) | 0.73352 (19) | 0.0401 (7) | |
H4A | 0.6468 (7) | 0.9948 (4) | 0.7073 (6) | 0.048* | |
N5 | 1.2094 (3) | 0.2289 (3) | 0.60459 (19) | 0.0405 (7) | |
H5A | 1.2831 (16) | 0.2513 (6) | 0.5667 (14) | 0.049* | |
C1 | 0.5572 (4) | 0.7105 (4) | 0.8261 (2) | 0.0335 (7) | |
C2 | 0.4685 (4) | 0.6459 (4) | 0.8934 (2) | 0.0387 (8) | |
H2A | 0.4847 | 0.5372 | 0.9096 | 0.046* | |
C3 | 0.3564 (4) | 0.7472 (5) | 0.9351 (3) | 0.0470 (9) | |
H3A | 0.2958 | 0.7063 | 0.9809 | 0.056* | |
C4 | 0.3303 (4) | 0.9105 (5) | 0.9107 (3) | 0.0530 (10) | |
H4B | 0.2520 | 0.9758 | 0.9403 | 0.064* | |
C5 | 0.4161 (4) | 0.9778 (4) | 0.8446 (3) | 0.0506 (10) | |
H5B | 0.3985 | 1.0868 | 0.8288 | 0.061* | |
C6 | 0.5304 (4) | 0.8754 (4) | 0.8024 (2) | 0.0375 (8) | |
C7 | 0.7187 (4) | 0.7573 (4) | 0.7187 (2) | 0.0357 (8) | |
C8 | 0.8480 (4) | 0.7220 (4) | 0.6545 (2) | 0.0346 (8) | |
C9 | 0.9030 (4) | 0.8290 (4) | 0.5898 (2) | 0.0436 (9) | |
H9A | 0.8554 | 0.9391 | 0.5814 | 0.052* | |
C10 | 1.0308 (4) | 0.7673 (4) | 0.5384 (2) | 0.0455 (9) | |
H10A | 1.0696 | 0.8368 | 0.4944 | 0.055* | |
C11 | 1.1016 (4) | 0.6040 (4) | 0.5513 (2) | 0.0430 (9) | |
H11A | 1.1893 | 0.5622 | 0.5179 | 0.052* | |
C12 | 1.0382 (4) | 0.5045 (4) | 0.6154 (2) | 0.0349 (8) | |
C13 | 1.0862 (4) | 0.3301 (4) | 0.6383 (2) | 0.0362 (8) | |
C14 | 1.2051 (4) | 0.0773 (4) | 0.6427 (2) | 0.0397 (8) | |
C15 | 1.3027 (4) | −0.0703 (4) | 0.6320 (3) | 0.0487 (10) | |
H15A | 1.3883 | −0.0809 | 0.5932 | 0.058* | |
C16 | 1.2653 (5) | −0.1998 (5) | 0.6821 (3) | 0.0540 (11) | |
H16A | 1.3278 | −0.3013 | 0.6773 | 0.065* | |
C17 | 1.1363 (5) | −0.1839 (4) | 0.7402 (3) | 0.0522 (10) | |
H17A | 1.1164 | −0.2754 | 0.7734 | 0.063* | |
C18 | 1.0381 (4) | −0.0373 (4) | 0.7495 (2) | 0.0445 (9) | |
H18A | 0.9513 | −0.0269 | 0.7873 | 0.053* | |
C19 | 1.0752 (4) | 0.0950 (4) | 0.6994 (2) | 0.0360 (8) | |
O1A | 0.9368 (3) | 0.3551 (3) | 0.87102 (16) | 0.0434 (6) | |
C1A | 1.0673 (4) | 0.3577 (4) | 0.8722 (2) | 0.0395 (8) | |
H1AA | 1.1115 | 0.3924 | 0.8156 | 0.047* | |
N1A | 1.1485 (3) | 0.3154 (4) | 0.9468 (2) | 0.0425 (7) | |
C2A | 1.2994 (5) | 0.3266 (6) | 0.9427 (3) | 0.0730 (14) | |
H2AA | 1.3259 | 0.3665 | 0.8794 | 0.110* | |
H2AB | 1.3749 | 0.2222 | 0.9694 | 0.110* | |
H2AC | 1.2970 | 0.3985 | 0.9765 | 0.110* | |
C3A | 1.0894 (5) | 0.2565 (6) | 1.0370 (3) | 0.0690 (13) | |
H3AA | 0.9894 | 0.2551 | 1.0307 | 0.103* | |
H3AB | 1.0811 | 0.3255 | 1.0741 | 0.103* | |
H3AC | 1.1584 | 0.1496 | 1.0663 | 0.103* | |
O1W | 0.4479 (3) | 0.2713 (3) | 0.49596 (17) | 0.0468 (6) | |
H1WA | 0.512 (3) | 0.262 (4) | 0.5367 (18) | 0.056* | |
H1WB | 0.434 (4) | 0.360 (3) | 0.4499 (16) | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0352 (3) | 0.0271 (2) | 0.0347 (2) | −0.01412 (18) | 0.00095 (18) | −0.00880 (18) |
S1 | 0.0454 (5) | 0.0378 (5) | 0.0384 (5) | −0.0217 (4) | 0.0030 (4) | −0.0079 (4) |
S2 | 0.0403 (5) | 0.0274 (4) | 0.0468 (5) | −0.0136 (4) | −0.0055 (4) | −0.0107 (4) |
O1 | 0.0553 (15) | 0.0304 (12) | 0.0398 (13) | −0.0221 (11) | −0.0101 (11) | −0.0015 (10) |
O2 | 0.0646 (17) | 0.0331 (13) | 0.0501 (15) | −0.0183 (12) | −0.0050 (12) | −0.0162 (12) |
O3 | 0.0355 (15) | 0.0576 (17) | 0.085 (2) | −0.0118 (13) | −0.0126 (13) | −0.0232 (15) |
N1 | 0.0371 (16) | 0.0263 (14) | 0.0400 (16) | −0.0127 (12) | 0.0006 (12) | −0.0095 (12) |
N2 | 0.0378 (16) | 0.0294 (14) | 0.0348 (15) | −0.0161 (12) | 0.0020 (12) | −0.0085 (12) |
N3 | 0.0376 (16) | 0.0291 (14) | 0.0375 (16) | −0.0130 (12) | 0.0029 (12) | −0.0079 (12) |
N4 | 0.0501 (18) | 0.0241 (14) | 0.0468 (18) | −0.0134 (13) | 0.0001 (14) | −0.0117 (13) |
N5 | 0.0390 (17) | 0.0444 (18) | 0.0418 (17) | −0.0169 (14) | 0.0098 (13) | −0.0189 (14) |
C1 | 0.0341 (18) | 0.0312 (17) | 0.0365 (18) | −0.0114 (14) | −0.0034 (14) | −0.0111 (15) |
C2 | 0.040 (2) | 0.040 (2) | 0.0387 (19) | −0.0177 (16) | −0.0018 (16) | −0.0099 (16) |
C3 | 0.041 (2) | 0.055 (2) | 0.047 (2) | −0.0201 (18) | 0.0066 (17) | −0.0166 (19) |
C4 | 0.046 (2) | 0.053 (2) | 0.059 (3) | −0.0090 (19) | 0.0053 (19) | −0.027 (2) |
C5 | 0.054 (2) | 0.035 (2) | 0.059 (3) | −0.0086 (18) | −0.001 (2) | −0.0179 (19) |
C6 | 0.039 (2) | 0.0340 (19) | 0.041 (2) | −0.0123 (15) | −0.0027 (16) | −0.0138 (16) |
C7 | 0.042 (2) | 0.0318 (18) | 0.0371 (19) | −0.0159 (15) | −0.0031 (15) | −0.0114 (15) |
C8 | 0.044 (2) | 0.0322 (18) | 0.0341 (18) | −0.0192 (15) | −0.0017 (15) | −0.0104 (15) |
C9 | 0.058 (2) | 0.0347 (19) | 0.042 (2) | −0.0257 (17) | −0.0005 (18) | −0.0060 (16) |
C10 | 0.056 (2) | 0.046 (2) | 0.041 (2) | −0.0334 (19) | 0.0045 (18) | −0.0062 (17) |
C11 | 0.044 (2) | 0.052 (2) | 0.041 (2) | −0.0268 (18) | 0.0071 (16) | −0.0154 (18) |
C12 | 0.039 (2) | 0.0352 (18) | 0.0348 (18) | −0.0179 (15) | 0.0019 (15) | −0.0114 (15) |
C13 | 0.037 (2) | 0.0394 (19) | 0.0357 (19) | −0.0160 (16) | 0.0046 (15) | −0.0151 (16) |
C14 | 0.041 (2) | 0.040 (2) | 0.040 (2) | −0.0115 (16) | −0.0029 (16) | −0.0158 (16) |
C15 | 0.041 (2) | 0.047 (2) | 0.058 (2) | −0.0033 (18) | −0.0061 (18) | −0.028 (2) |
C16 | 0.059 (3) | 0.038 (2) | 0.063 (3) | −0.0019 (19) | −0.018 (2) | −0.024 (2) |
C17 | 0.066 (3) | 0.033 (2) | 0.056 (2) | −0.0141 (19) | −0.012 (2) | −0.0107 (18) |
C18 | 0.052 (2) | 0.0345 (19) | 0.045 (2) | −0.0143 (17) | −0.0031 (17) | −0.0094 (17) |
C19 | 0.038 (2) | 0.0307 (18) | 0.0371 (19) | −0.0076 (15) | −0.0025 (15) | −0.0127 (15) |
O1A | 0.0386 (14) | 0.0494 (15) | 0.0442 (14) | −0.0167 (12) | −0.0060 (11) | −0.0131 (12) |
C1A | 0.047 (2) | 0.0357 (19) | 0.038 (2) | −0.0172 (17) | 0.0012 (16) | −0.0116 (16) |
N1A | 0.0374 (17) | 0.0534 (19) | 0.0412 (17) | −0.0190 (14) | −0.0032 (13) | −0.0156 (15) |
C2A | 0.050 (3) | 0.108 (4) | 0.077 (3) | −0.040 (3) | −0.006 (2) | −0.031 (3) |
C3A | 0.066 (3) | 0.098 (4) | 0.041 (2) | −0.033 (3) | −0.003 (2) | −0.013 (2) |
O1W | 0.0504 (17) | 0.0458 (15) | 0.0419 (15) | −0.0194 (13) | 0.0026 (12) | −0.0080 (12) |
Ni—N2 | 2.054 (3) | C7—C8 | 1.464 (4) |
Ni—O1A | 2.080 (2) | C8—C9 | 1.384 (4) |
Ni—N3 | 2.107 (3) | C9—C10 | 1.380 (5) |
Ni—N1 | 2.124 (3) | C9—H9A | 0.9300 |
Ni—O1 | 2.142 (2) | C10—C11 | 1.380 (5) |
Ni—S1 | 2.4037 (10) | C10—H10A | 0.9300 |
S1—S2 | 2.0137 (12) | C11—C12 | 1.382 (4) |
S2—O3 | 1.441 (2) | C11—H11A | 0.9300 |
S2—O2 | 1.473 (2) | C12—C13 | 1.462 (4) |
S2—O1 | 1.494 (2) | C14—C15 | 1.386 (5) |
N1—C7 | 1.320 (4) | C14—C19 | 1.391 (5) |
N1—C1 | 1.384 (4) | C15—C16 | 1.372 (5) |
N2—C8 | 1.338 (4) | C15—H15A | 0.9300 |
N2—C12 | 1.339 (4) | C16—C17 | 1.398 (5) |
N3—C13 | 1.321 (4) | C16—H16A | 0.9300 |
N3—C19 | 1.391 (4) | C17—C18 | 1.373 (5) |
N4—C7 | 1.345 (4) | C17—H17A | 0.9300 |
N4—C6 | 1.383 (4) | C18—C19 | 1.392 (5) |
N4—H4A | 0.894 (6) | C18—H18A | 0.9300 |
N5—C13 | 1.349 (4) | O1A—C1A | 1.236 (4) |
N5—C14 | 1.379 (4) | C1A—N1A | 1.312 (4) |
N5—H5A | 0.893 (18) | C1A—H1AA | 0.9300 |
C1—C2 | 1.383 (4) | N1A—C3A | 1.443 (5) |
C1—C6 | 1.407 (4) | N1A—C2A | 1.451 (4) |
C2—C3 | 1.363 (5) | C2A—H2AA | 0.9600 |
C2—H2A | 0.9300 | C2A—H2AB | 0.9600 |
C3—C4 | 1.394 (5) | C2A—H2AC | 0.9600 |
C3—H3A | 0.9300 | C3A—H3AA | 0.9600 |
C4—C5 | 1.366 (5) | C3A—H3AB | 0.9600 |
C4—H4B | 0.9300 | C3A—H3AC | 0.9600 |
C5—C6 | 1.383 (5) | O1W—H1WA | 0.88 (3) |
C5—H5B | 0.9300 | O1W—H1WB | 0.89 (3) |
N2—Ni—O1A | 97.71 (10) | N4—C7—C8 | 127.1 (3) |
N2—Ni—N3 | 77.01 (10) | N2—C8—C9 | 121.2 (3) |
O1A—Ni—N3 | 91.86 (10) | N2—C8—C7 | 110.8 (3) |
N2—Ni—N1 | 76.78 (10) | C9—C8—C7 | 128.1 (3) |
O1A—Ni—N1 | 89.61 (10) | C10—C9—C8 | 117.9 (3) |
N3—Ni—N1 | 153.71 (11) | C10—C9—H9A | 121.0 |
N2—Ni—O1 | 93.34 (9) | C8—C9—H9A | 121.0 |
O1A—Ni—O1 | 168.70 (9) | C11—C10—C9 | 121.0 (3) |
N3—Ni—O1 | 92.91 (9) | C11—C10—H10A | 119.5 |
N1—Ni—O1 | 90.65 (9) | C9—C10—H10A | 119.5 |
N2—Ni—S1 | 167.51 (8) | C10—C11—C12 | 117.9 (3) |
O1A—Ni—S1 | 94.58 (7) | C10—C11—H11A | 121.0 |
N3—Ni—S1 | 100.47 (8) | C12—C11—H11A | 121.0 |
N1—Ni—S1 | 105.58 (8) | N2—C12—C11 | 121.2 (3) |
O1—Ni—S1 | 74.48 (7) | N2—C12—C13 | 110.3 (3) |
S2—S1—Ni | 79.99 (4) | C11—C12—C13 | 128.5 (3) |
O3—S2—O2 | 111.37 (15) | N3—C13—N5 | 112.9 (3) |
O3—S2—O1 | 112.01 (15) | N3—C13—C12 | 120.0 (3) |
O2—S2—O1 | 108.68 (14) | N5—C13—C12 | 127.1 (3) |
O3—S2—S1 | 111.21 (12) | N5—C14—C15 | 131.1 (3) |
O2—S2—S1 | 110.54 (10) | N5—C14—C19 | 106.4 (3) |
O1—S2—S1 | 102.70 (10) | C15—C14—C19 | 122.5 (3) |
S2—O1—Ni | 101.97 (11) | C16—C15—C14 | 115.9 (4) |
C7—N1—C1 | 105.5 (3) | C16—C15—H15A | 122.0 |
C7—N1—Ni | 112.9 (2) | C14—C15—H15A | 122.0 |
C1—N1—Ni | 141.5 (2) | C15—C16—C17 | 122.1 (4) |
C8—N2—C12 | 120.7 (3) | C15—C16—H16A | 118.9 |
C8—N2—Ni | 119.4 (2) | C17—C16—H16A | 118.9 |
C12—N2—Ni | 119.5 (2) | C18—C17—C16 | 121.9 (4) |
C13—N3—C19 | 105.4 (3) | C18—C17—H17A | 119.0 |
C13—N3—Ni | 113.0 (2) | C16—C17—H17A | 119.0 |
C19—N3—Ni | 141.5 (2) | C17—C18—C19 | 116.5 (4) |
C7—N4—C6 | 106.8 (3) | C17—C18—H18A | 121.7 |
C7—N4—H4A | 128.6 (4) | C19—C18—H18A | 121.7 |
C6—N4—H4A | 124.5 (4) | N3—C19—C14 | 108.6 (3) |
C13—N5—C14 | 106.7 (3) | N3—C19—C18 | 130.4 (3) |
C13—N5—H5A | 128.4 (4) | C14—C19—C18 | 121.0 (3) |
C14—N5—H5A | 124.9 (4) | C1A—O1A—Ni | 124.7 (2) |
C2—C1—N1 | 131.0 (3) | O1A—C1A—N1A | 125.3 (3) |
C2—C1—C6 | 120.3 (3) | O1A—C1A—H1AA | 117.4 |
N1—C1—C6 | 108.7 (3) | N1A—C1A—H1AA | 117.4 |
C3—C2—C1 | 117.6 (3) | C1A—N1A—C3A | 120.6 (3) |
C3—C2—H2A | 121.2 | C1A—N1A—C2A | 122.0 (3) |
C1—C2—H2A | 121.2 | C3A—N1A—C2A | 117.4 (3) |
C2—C3—C4 | 121.6 (4) | N1A—C2A—H2AA | 109.5 |
C2—C3—H3A | 119.2 | N1A—C2A—H2AB | 109.5 |
C4—C3—H3A | 119.2 | H2AA—C2A—H2AB | 109.5 |
C5—C4—C3 | 122.1 (4) | N1A—C2A—H2AC | 109.5 |
C5—C4—H4B | 119.0 | H2AA—C2A—H2AC | 109.5 |
C3—C4—H4B | 119.0 | H2AB—C2A—H2AC | 109.5 |
C4—C5—C6 | 116.5 (4) | N1A—C3A—H3AA | 109.5 |
C4—C5—H5B | 121.7 | N1A—C3A—H3AB | 109.5 |
C6—C5—H5B | 121.7 | H3AA—C3A—H3AB | 109.5 |
C5—C6—N4 | 132.4 (3) | N1A—C3A—H3AC | 109.5 |
C5—C6—C1 | 121.9 (3) | H3AA—C3A—H3AC | 109.5 |
N4—C6—C1 | 105.7 (3) | H3AB—C3A—H3AC | 109.5 |
N1—C7—N4 | 113.2 (3) | H1WA—O1W—H1WB | 110 (2) |
N1—C7—C8 | 119.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2 | 0.88 (3) | 2.01 (3) | 2.877 (3) | 168 (3) |
O1W—H1WB···O1i | 0.89 (3) | 1.90 (3) | 2.752 (3) | 162 (3) |
N4—H4A···O2ii | 0.89 (1) | 1.88 (1) | 2.773 (4) | 174 (1) |
N5—H5A···O1Wiii | 0.89 (2) | 1.81 (2) | 2.700 (4) | 173 (1) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z; (iii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(S2O3)(C21H13N5)(CH7NO)]·H2O |
Mr | 573.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.3815 (8), 9.4096 (8), 15.1968 (13) |
α, β, γ (°) | 72.124 (2), 83.169 (2), 67.423 (2) |
V (Å3) | 1178.91 (17) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.05 |
Crystal size (mm) | 0.35 × 0.25 × 0.16 |
Data collection | |
Diffractometer | CCD area detector diffractometer |
Absorption correction | Part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 2000) |
Tmin, Tmax | 0.73, 0.81 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5399, 4505, 3230 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.109, 0.87 |
No. of reflections | 4505 |
No. of parameters | 335 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.41, −0.40 |
Computer programs: SMART-NT (Bruker, 2001), SAINT-NT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick, 1994).
Ni—N2 | 2.054 (3) | Ni—S1 | 2.4037 (10) |
Ni—O1A | 2.080 (2) | S1—S2 | 2.0137 (12) |
Ni—N3 | 2.107 (3) | S2—O3 | 1.441 (2) |
Ni—N1 | 2.124 (3) | S2—O2 | 1.473 (2) |
Ni—O1 | 2.142 (2) | S2—O1 | 1.494 (2) |
N2—Ni—O1A | 97.71 (10) | O1A—Ni—S1 | 94.58 (7) |
N2—Ni—N3 | 77.01 (10) | N3—Ni—S1 | 100.47 (8) |
O1A—Ni—N3 | 91.86 (10) | N1—Ni—S1 | 105.58 (8) |
N2—Ni—N1 | 76.78 (10) | O1—Ni—S1 | 74.48 (7) |
O1A—Ni—N1 | 89.61 (10) | O3—S2—O2 | 111.37 (15) |
N3—Ni—N1 | 153.71 (11) | O3—S2—O1 | 112.01 (15) |
N2—Ni—O1 | 93.34 (9) | O2—S2—O1 | 108.68 (14) |
O1A—Ni—O1 | 168.70 (9) | O3—S2—S1 | 111.21 (12) |
N3—Ni—O1 | 92.91 (9) | O2—S2—S1 | 110.54 (10) |
N1—Ni—O1 | 90.65 (9) | O1—S2—S1 | 102.70 (10) |
N2—Ni—S1 | 167.51 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2 | 0.88 (3) | 2.01 (3) | 2.877 (3) | 168 (3) |
O1W—H1WB···O1i | 0.89 (3) | 1.90 (3) | 2.752 (3) | 162 (3) |
N4—H4A···O2ii | 0.894 (6) | 1.882 (7) | 2.773 (4) | 174.0 (10) |
N5—H5A···O1Wiii | 0.893 (18) | 1.813 (17) | 2.700 (4) | 172.9 (11) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z; (iii) x+1, y, z. |
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The coordination properties of the thiosulfate group have been extensively studied by our group in connection with their relevance in the discussion of dπ-pπ bonding in sulfur oxoanions. The anion has proven to be a quite versatile ligand, since it contains atoms classified as both soft and hard bases (Pearson, 1973). This situation produces a variety of coordination modes, especially when the metal ion is intermediate between classes a and b in the aforementioned classification. One factor that seems to influence the manner in which the ligand coordinates is the geometry of the organic ligands present in the complex. In this context, we have found the reaction between Ni2+ and S2O32−, in the presence of polynitrogenated bases, to be a very prolific one, with a variety of compounds of varied characteristics being generated (Freire et al., 1999; Freire, Baggio, Mombru et al., 2000; Freire, Baggio, Mariezcurrena et al., 2000; Freire, Baggio, Suescun et al., 2000), including products that are the result of redox processes (Freire, Baggio & Baggio, 2001). In this paper, we report an X-ray structural study of the title compound, (I).
The structure of (I) is monomeric, with the nickel ion surrounded by three different ligands, viz. a tridentate bisbenzimidazolylpyridine molecule (bbip), a bidentate thiosulfate molecule (ths) and a monodentate dimethylformamide molecule (dmf). The result is a highly distorted octahedral environment for the cation, with adjacent coordination sites subtending angles as low as 76.78 (10)°, (expected 90°) and opposite centers 153.71 (11)° apart (expected 180°).
The bbip ligand does not depart from the geometry it usually presents when complexed to a cation: the unprotonated imidazolyl N atoms are cis to the pyridyl N atom, thus defining the tridentate bite. Because of the restraints imposed by this chelate character, the three coordinated N atoms in the ligand are constrained not to be equidistant from the cation, the central Ni—N2 bond being shorter [2.054 (3) Å versus 2.107 (3) Å and 2.124 (3) Å for the other two bonds]. In addition, the stress arising from coordination tends to distort the molecule into a concave shape, the lateral wings being bent with respect to the central ring by 6.1 (1)° and 6.8 (1)°, respectively.
The ths anion binds through the common (S,O) chelate mode; a search in the November 2002 release of the Cambridge Structural Database (CSD; Allen, 2002) showed 11 such coordinations of the anion out of the 49 entries in which it appears bound to a metal. In the present structure, the S1 atom occupies the remaining equatorial site, in the plane defined by bbip and opposite to the central (and shortest) Ni—N2 bond. This behaviour appears to be common in these type of compounds, as it has also been observed in Ni(tpy)(ths)(H2O) (Freire, Baggio, Goeta et al., 2001), which is the only other reported ths complex with a tridentate base.
The structure of the ths anion displays a variety of S—O bond lengths, which are inversely related to the degree of compromise in coordination of the corresponding O atoms. Thus atom O1, which bonds directly to nickel and is also involved in a medium-strength hydrogen bond, forms the longest (i.e. weakest) bond [S2—O1 = 1.494 (2) Å]. The intermediate bond length involves atom O2, which only takes part in hydrogen bonding [S2—O2 = 1.473 (2) Å. Finally, O3 (which is not involved in any other interaction) provides the shortest (i.e. strongest) bond [S2—O3 = 1.441 (2) Å]. This effect is accompanied by a reduction of the corresponding S—S—O angle, which is directly related to the S—O bond enlargement (Table 1). This behavior has been observed previously in a variety of sulfur oxoanions (Freire, Baggio, Mombru et al., 2000; Freire, Baggio, Mariezcurrena et al., 2000; Harvey et al., 2001, 2002).
A monodentate dmf molecule completes the coordination around the Ni atom. The ligand geometry is unexceptional, and although a wide range of C—N and C═O bond length values are reported in the literature, those in (I) [1.312 (4) Å and 1.236 (4) Å] are close to the mean values obtained from ca 950 cases found in the CSD, viz. 1.32 (5) Å and 1.23 (6) Å, respectively.
The water molecule and imidazolyl H atoms participate in strong hydrogen-bonding interactions (Table 2). The water molecule, acting as a donor, links two centrosymmetrically related molecules, thus forming a closed loop centered at (1/2,1/2,1/2). These groups, in turn, interact with their homologous groups in neighboring cells through the remaining hydrogen bonds, mediated by the imidazolyl H atoms. The result is the build up of broad two-dimensional structures along c, parallel to (001) and one unit cell wide. Sheets interact with each other in this direction through weaker C—H···O contacts and van der Waal's forces. The packing is such as to drive the aromatic groups away from each other, thus preventing any kind of π–π interaction between them.