The title complex, [Ni(C6H6N4S2)(C3H2O4)(H2O)2], has a distorted octahedral coordination geometry with the malonate dianion and diaminobithiazole chelating to the NiII atom in the equatorial plane, and two water molecules in the axial positions. Both the malonate and diaminobithiazole are planar, and are tilted out of the equatorial plane, with dihedral angles of 9.87 (5) and 11.65 (5)°, respectively.
Supporting information
CCDC reference: 239043
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.002 Å
- R factor = 0.024
- wR factor = 0.059
- Data-to-parameter ratio = 16.0
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni - N1 .. 6.33 su
PLAT322_ALERT_2_C Check Hybridisation of S1 in Main Residue . ?
PLAT322_ALERT_2_C Check Hybridisation of S2 in Main Residue . ?
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 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
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: PROCESS-AUTO (Rigaku Corporation, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku Corporation, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Crystal data top
[Ni(C6H6N4S2)(C3H2O4)(H2O)2] | F(000) = 1616 |
Mr = 395.06 | Dx = 1.872 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 22240 reflections |
a = 11.0826 (3) Å | θ = 2.4–25.5° |
b = 12.1879 (3) Å | µ = 1.72 mm−1 |
c = 20.7505 (5) Å | T = 296 K |
V = 2802.85 (12) Å3 | Prism, green |
Z = 8 | 0.34 × 0.32 × 0.24 mm |
Data collection top
Rigaku RAXIS-RAPID diffractometer | 3207 independent reflections |
Radiation source: fine-focus sealed tube | 2983 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.4°, θmin = 2.0° |
ω scans | h = −13→14 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −15→15 |
Tmin = 0.57, Tmax = 0.66 | l = −26→26 |
25652 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0275P)2 + 1.626P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
3207 reflections | Δρmax = 0.35 e Å−3 |
200 parameters | Δρmin = −0.32 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0057 (2) |
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 | |
Ni | 0.616061 (17) | 0.111305 (16) | 0.196716 (9) | 0.02183 (7) | |
S1 | 0.39416 (4) | 0.25537 (4) | 0.02758 (2) | 0.04072 (12) | |
S2 | 0.85593 (4) | −0.06153 (4) | 0.04664 (2) | 0.03830 (12) | |
O1 | 0.70536 (11) | 0.03453 (10) | 0.26728 (5) | 0.0324 (3) | |
O2 | 0.77401 (12) | 0.00514 (11) | 0.36483 (6) | 0.0386 (3) | |
O3 | 0.50515 (10) | 0.18304 (10) | 0.26022 (5) | 0.0320 (3) | |
O4 | 0.45240 (12) | 0.25488 (11) | 0.35341 (6) | 0.0380 (3) | |
O5 | 0.49697 (11) | −0.02570 (10) | 0.19092 (6) | 0.0329 (3) | |
O6 | 0.73349 (11) | 0.24476 (10) | 0.20980 (6) | 0.0337 (3) | |
N1 | 0.52995 (12) | 0.17718 (11) | 0.11638 (6) | 0.0256 (3) | |
N2 | 0.38621 (14) | 0.30151 (13) | 0.15571 (8) | 0.0407 (4) | |
N3 | 0.72090 (12) | 0.04556 (10) | 0.12433 (6) | 0.0238 (3) | |
N4 | 0.87995 (13) | −0.04735 (12) | 0.17625 (7) | 0.0322 (3) | |
C1 | 0.43803 (15) | 0.24375 (13) | 0.10759 (8) | 0.0304 (3) | |
C2 | 0.50783 (17) | 0.16631 (15) | 0.00569 (8) | 0.0359 (4) | |
H2 | 0.5242 | 0.1442 | −0.0363 | 0.043* | |
C3 | 0.56952 (15) | 0.13332 (13) | 0.05825 (8) | 0.0274 (3) | |
C4 | 0.67449 (14) | 0.06075 (13) | 0.06266 (7) | 0.0257 (3) | |
C5 | 0.73475 (17) | 0.00887 (15) | 0.01536 (8) | 0.0340 (4) | |
H5 | 0.7139 | 0.0108 | −0.0280 | 0.041* | |
C6 | 0.81786 (14) | −0.01612 (12) | 0.12310 (7) | 0.0251 (3) | |
C7 | 0.70499 (14) | 0.05370 (13) | 0.32639 (7) | 0.0244 (3) | |
C8 | 0.61903 (15) | 0.13594 (16) | 0.35683 (9) | 0.0355 (4) | |
H8A | 0.6690 | 0.1927 | 0.3759 | 0.043* | |
H8B | 0.5800 | 0.0982 | 0.3923 | 0.043* | |
C9 | 0.51934 (14) | 0.19486 (12) | 0.31992 (7) | 0.0250 (3) | |
H2A | 0.3970 | 0.2787 | 0.1944 | 0.050* | |
H2B | 0.3213 | 0.3393 | 0.1488 | 0.050* | |
H4A | 0.8607 | −0.0195 | 0.2108 | 0.050* | |
H4B | 0.9543 | −0.0740 | 0.1705 | 0.050* | |
H5A | 0.4289 | −0.0187 | 0.1720 | 0.050* | |
H5B | 0.5242 | −0.0895 | 0.1780 | 0.050* | |
H6A | 0.7043 | 0.3022 | 0.1984 | 0.050* | |
H6B | 0.7968 | 0.2498 | 0.1886 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni | 0.02345 (11) | 0.02362 (11) | 0.01843 (11) | 0.00394 (7) | −0.00040 (7) | 0.00033 (7) |
S1 | 0.0414 (2) | 0.0357 (2) | 0.0451 (3) | 0.00052 (18) | −0.0216 (2) | 0.00831 (19) |
S2 | 0.0411 (2) | 0.0438 (3) | 0.0300 (2) | 0.0092 (2) | 0.00877 (18) | −0.00787 (18) |
O1 | 0.0401 (6) | 0.0360 (6) | 0.0210 (5) | 0.0149 (5) | −0.0028 (5) | 0.0002 (4) |
O2 | 0.0391 (7) | 0.0524 (8) | 0.0243 (5) | 0.0116 (6) | −0.0047 (5) | 0.0045 (5) |
O3 | 0.0311 (6) | 0.0384 (6) | 0.0264 (6) | 0.0111 (5) | 0.0018 (5) | −0.0021 (5) |
O4 | 0.0383 (7) | 0.0417 (7) | 0.0340 (6) | 0.0107 (6) | 0.0039 (5) | −0.0100 (5) |
O5 | 0.0295 (6) | 0.0276 (6) | 0.0415 (7) | −0.0012 (5) | 0.0008 (5) | −0.0003 (5) |
O6 | 0.0286 (6) | 0.0275 (6) | 0.0450 (7) | 0.0007 (5) | −0.0026 (5) | −0.0004 (5) |
N1 | 0.0260 (6) | 0.0248 (6) | 0.0260 (6) | 0.0007 (5) | −0.0033 (5) | 0.0016 (5) |
N2 | 0.0355 (8) | 0.0388 (8) | 0.0477 (9) | 0.0138 (7) | −0.0069 (7) | −0.0045 (7) |
N3 | 0.0260 (6) | 0.0250 (6) | 0.0204 (6) | 0.0010 (5) | 0.0007 (5) | −0.0007 (5) |
N4 | 0.0306 (7) | 0.0344 (7) | 0.0316 (7) | 0.0091 (6) | −0.0020 (6) | −0.0039 (6) |
C1 | 0.0275 (8) | 0.0252 (7) | 0.0385 (8) | −0.0028 (6) | −0.0106 (7) | 0.0031 (7) |
C2 | 0.0432 (10) | 0.0368 (9) | 0.0277 (8) | −0.0030 (8) | −0.0102 (7) | 0.0039 (7) |
C3 | 0.0318 (8) | 0.0266 (7) | 0.0239 (7) | −0.0048 (6) | −0.0039 (6) | 0.0028 (6) |
C4 | 0.0295 (8) | 0.0276 (7) | 0.0201 (7) | −0.0041 (6) | −0.0003 (6) | 0.0017 (6) |
C5 | 0.0416 (10) | 0.0389 (9) | 0.0214 (7) | −0.0009 (7) | 0.0015 (7) | −0.0018 (7) |
C6 | 0.0267 (7) | 0.0238 (7) | 0.0249 (7) | −0.0016 (6) | 0.0036 (6) | −0.0025 (6) |
C7 | 0.0238 (7) | 0.0268 (7) | 0.0224 (7) | −0.0028 (6) | 0.0003 (6) | 0.0028 (6) |
C8 | 0.0298 (8) | 0.0478 (10) | 0.0289 (8) | 0.0062 (7) | −0.0040 (7) | −0.0110 (7) |
C9 | 0.0233 (7) | 0.0236 (7) | 0.0282 (7) | −0.0032 (6) | 0.0035 (6) | −0.0035 (6) |
Geometric parameters (Å, º) top
Ni—O1 | 1.9997 (11) | N1—C3 | 1.390 (2) |
Ni—O3 | 2.0029 (11) | N2—C1 | 1.350 (2) |
Ni—N3 | 2.0612 (12) | N2—H2A | 0.858 |
Ni—N1 | 2.0818 (13) | N2—H2B | 0.866 |
Ni—O6 | 2.1007 (12) | N3—C6 | 1.312 (2) |
Ni—O5 | 2.1318 (12) | N3—C4 | 1.3914 (19) |
S1—C2 | 1.724 (2) | N4—C6 | 1.355 (2) |
S1—C1 | 1.7357 (17) | N4—H4A | 0.821 |
S2—C5 | 1.7208 (19) | N4—H4B | 0.894 |
S2—C6 | 1.7326 (15) | C2—C3 | 1.348 (2) |
O1—C7 | 1.2487 (19) | C2—H2 | 0.9300 |
O2—C7 | 1.2536 (19) | C3—C4 | 1.464 (2) |
O3—C9 | 1.2572 (19) | C4—C5 | 1.345 (2) |
O4—C9 | 1.2523 (19) | C5—H5 | 0.9300 |
O5—H5A | 0.855 | C7—C8 | 1.520 (2) |
O5—H5B | 0.876 | C8—C9 | 1.524 (2) |
O6—H6A | 0.807 | C8—H8A | 0.9700 |
O6—H6B | 0.830 | C8—H8B | 0.9700 |
N1—C1 | 1.315 (2) | | |
| | | |
O1—Ni—O3 | 91.50 (5) | C6—N4—H4A | 117.55 |
O1—Ni—N3 | 94.17 (5) | C6—N4—H4B | 117.51 |
O3—Ni—N3 | 174.33 (5) | H4A—N4—H4B | 120.41 |
O1—Ni—N1 | 173.52 (5) | N1—C1—N2 | 123.27 (15) |
O3—Ni—N1 | 94.42 (5) | N1—C1—S1 | 113.58 (13) |
N3—Ni—N1 | 79.91 (5) | N2—C1—S1 | 123.08 (13) |
O1—Ni—O6 | 87.77 (5) | C3—C2—S1 | 110.19 (14) |
O3—Ni—O6 | 87.54 (5) | C3—C2—H2 | 124.9 |
N3—Ni—O6 | 92.63 (5) | S1—C2—H2 | 124.9 |
N1—Ni—O6 | 95.10 (5) | C2—C3—N1 | 115.29 (15) |
O1—Ni—O5 | 88.92 (5) | C2—C3—C4 | 129.31 (16) |
O3—Ni—O5 | 89.95 (5) | N1—C3—C4 | 115.37 (13) |
N3—Ni—O5 | 90.20 (5) | C5—C4—N3 | 115.15 (15) |
N1—Ni—O5 | 88.46 (5) | C5—C4—C3 | 129.25 (15) |
O6—Ni—O5 | 175.79 (5) | N3—C4—C3 | 115.57 (13) |
C2—S1—C1 | 89.77 (8) | C4—C5—S2 | 110.28 (12) |
C5—S2—C6 | 89.77 (8) | C4—C5—H5 | 124.9 |
C7—O1—Ni | 129.06 (10) | S2—C5—H5 | 124.9 |
C9—O3—Ni | 128.44 (10) | N3—C6—N4 | 124.16 (14) |
Ni—O5—H5A | 119.62 | N3—C6—S2 | 113.60 (12) |
Ni—O5—H5B | 119.95 | N4—C6—S2 | 122.14 (12) |
H5A—O5—H5B | 104.60 | O1—C7—O2 | 122.32 (15) |
Ni—O6—H6A | 112.68 | O1—C7—C8 | 122.24 (14) |
Ni—O6—H6B | 120.81 | O2—C7—C8 | 115.42 (14) |
H6A—O6—H6B | 96.85 | C7—C8—C9 | 123.79 (14) |
C1—N1—C3 | 111.16 (14) | C7—C8—H8A | 106.4 |
C1—N1—Ni | 134.77 (12) | C9—C8—H8A | 106.4 |
C3—N1—Ni | 113.70 (10) | C7—C8—H8B | 106.4 |
C1—N2—H2A | 117.64 | C9—C8—H8B | 106.4 |
C1—N2—H2B | 120.54 | H8A—C8—H8B | 106.5 |
H2A—N2—H2B | 116.29 | O4—C9—O3 | 122.66 (15) |
C6—N3—C4 | 111.18 (13) | O4—C9—C8 | 115.20 (14) |
C6—N3—Ni | 134.33 (11) | O3—C9—C8 | 122.13 (14) |
C4—N3—Ni | 114.21 (10) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3 | 0.86 | 2.16 | 2.920 (2) | 148 |
N2—H2B···O2i | 0.87 | 2.30 | 3.081 (2) | 150 |
N4—H4A···O1 | 0.82 | 2.18 | 2.8823 (18) | 143 |
N4—H4B···N2ii | 0.89 | 2.35 | 3.208 (2) | 161 |
O5—H5A···O2iii | 0.86 | 1.90 | 2.7541 (18) | 175 |
O5—H5B···O4iv | 0.88 | 2.02 | 2.8832 (18) | 167 |
O6—H6A···N4v | 0.81 | 2.11 | 2.9129 (19) | 175 |
O6—H6B···O4vi | 0.83 | 1.93 | 2.7607 (18) | 174 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+3/2, y−1/2, z; (iii) x−1/2, y, −z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) −x+3/2, y+1/2, z; (vi) x+1/2, y, −z+1/2. |