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The title compound, [Ni(C18H18N6O2S2)](ClO4)2·2CH4O, (I), has been prepared by the reaction of 2,2'-(ethylenedioxy)dibenzaldehyde bis(thiosemicarbazone), L, with nickel(II) perchlorate. The chemical structural unit, which is twice the asymmetric unit of (I), consists of one NiII ion, one ligand L, two methanol solvent molecules and two uncoordinated perchlorate anions. The Ni atom lies on a crystallographic twofold axis of rotation. The ligand L coordinates to the central Ni atom through two O atoms, two S atoms and two N atoms, giving a distorted octahedral environment. The S and O atoms occupy equatorial positions, and are nearly coplanar with the nickel, while the two N atoms occupy axial positions, with the N-Ni-N angle being 177.06 (18)°.
Supporting information
CCDC reference: 248744
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.052
- wR factor = 0.158
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level C
ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
Tmin and Tmax reported: 0.651 0.866
Tmin' and Tmax expected: 0.810 0.866
RR' = 0.804
Please check that your absorption correction is appropriate.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.80
PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ... 6018.00 Ang-3
PLAT244_ALERT_4_C Low Solvent U(eq) as Compared to Neighbors for Cl1
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 7
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 16
N1 -NI1 -N1 -C8 65.60 0.40 6.554 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 21
N1 -NI1 -N1 -N2 -119.80 0.30 6.554 1.555 1.555 1.555
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
8 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
3 ALERT type 3 Indicator that the structure quality may be low
3 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
[2,2'-(ethylenedioxy)dibenzaldehyde bis(thiosemicarbazone)]nickel(II)
diperchlorate methanol disolvate
top
Crystal data top
[Ni(C18H18N6O2S2)](ClO4)2·2CH4O | Dx = 1.625 Mg m−3 |
Mr = 736.20 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 934 reflections |
Hall symbol: -I 4ad | θ = 2.5–25.5° |
a = 13.586 (8) Å | µ = 1.03 mm−1 |
c = 32.60 (4) Å | T = 293 K |
V = 6018 (9) Å3 | Block, green |
Z = 8 | 0.20 × 0.18 × 0.14 mm |
F(000) = 3024 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3097 independent reflections |
Radiation source: fine-focus sealed tube | 2286 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
φ and ω scans | θmax = 26.5°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→16 |
Tmin = 0.651, Tmax = 0.866 | k = −16→17 |
17255 measured reflections | l = −40→35 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.158 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0804P)2 + 15.2797P] where P = (Fo2 + 2Fc2)/3 |
3097 reflections | (Δ/σ)max < 0.002 |
197 parameters | Δρmax = 0.70 e Å−3 |
0 restraints | Δρmin = −0.81 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 | |
Ni1 | 0.5000 | 0.2500 | 0.61515 (2) | 0.0280 (2) | |
S1 | 0.42768 (7) | 0.13687 (9) | 0.56983 (4) | 0.0416 (3) | |
O1 | 0.5256 (2) | 0.3430 (2) | 0.66764 (9) | 0.0349 (6) | |
N1 | 0.3632 (2) | 0.3108 (2) | 0.61675 (10) | 0.0299 (7) | |
N2 | 0.2887 (2) | 0.2576 (3) | 0.59843 (11) | 0.0355 (8) | |
N3 | 0.2353 (3) | 0.1289 (3) | 0.56052 (12) | 0.0476 (10) | |
H3A | 0.1763 | 0.1500 | 0.5642 | 0.057* | |
H3B | 0.2454 | 0.0765 | 0.5463 | 0.057* | |
C1 | 0.5388 (3) | 0.2899 (3) | 0.70612 (13) | 0.0402 (10) | |
H1A | 0.5298 | 0.3336 | 0.7293 | 0.048* | |
H1B | 0.6041 | 0.2614 | 0.7076 | 0.048* | |
C2 | 0.4913 (3) | 0.4393 (3) | 0.67024 (14) | 0.0388 (10) | |
C3 | 0.5450 (4) | 0.5081 (4) | 0.69168 (17) | 0.0524 (13) | |
H3 | 0.6030 | 0.4902 | 0.7048 | 0.063* | |
C4 | 0.5116 (5) | 0.6038 (4) | 0.6934 (2) | 0.0682 (17) | |
H4 | 0.5469 | 0.6503 | 0.7083 | 0.082* | |
C5 | 0.4275 (5) | 0.6312 (4) | 0.6736 (2) | 0.0737 (18) | |
H5 | 0.4071 | 0.6965 | 0.6743 | 0.088* | |
C6 | 0.3732 (4) | 0.5631 (3) | 0.65267 (18) | 0.0550 (13) | |
H6 | 0.3153 | 0.5823 | 0.6397 | 0.066* | |
C7 | 0.4038 (3) | 0.4648 (3) | 0.65059 (14) | 0.0392 (10) | |
C8 | 0.3386 (3) | 0.3965 (3) | 0.63031 (14) | 0.0375 (10) | |
H8 | 0.2736 | 0.4159 | 0.6267 | 0.045* | |
C9 | 0.3103 (3) | 0.1767 (3) | 0.57670 (12) | 0.0330 (9) | |
Cl1 | 0.84538 (9) | 0.32414 (8) | 0.68629 (4) | 0.0461 (3) | |
O2 | 0.9019 (5) | 0.3441 (4) | 0.6506 (2) | 0.122 (2) | |
O3 | 0.7598 (4) | 0.3809 (4) | 0.6790 (2) | 0.1092 (19) | |
O4 | 0.8219 (4) | 0.2239 (3) | 0.68696 (16) | 0.0860 (15) | |
O5 | 0.8919 (5) | 0.3602 (4) | 0.7211 (2) | 0.138 (3) | |
O6 | 0.7701 (4) | 0.5213 (3) | 0.75400 (15) | 0.0861 (15) | |
H6A | 0.7996 | 0.4736 | 0.7448 | 0.129* | |
C10 | 0.7975 (6) | 0.6057 (5) | 0.7324 (2) | 0.091 (2) | |
H10A | 0.7880 | 0.6626 | 0.7494 | 0.137* | |
H10B | 0.7579 | 0.6116 | 0.7082 | 0.137* | |
H10C | 0.8656 | 0.6010 | 0.7248 | 0.137* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0202 (4) | 0.0315 (4) | 0.0323 (4) | 0.0005 (3) | 0.000 | 0.000 |
S1 | 0.0264 (5) | 0.0499 (7) | 0.0485 (7) | 0.0009 (4) | −0.0012 (5) | −0.0175 (5) |
O1 | 0.0392 (16) | 0.0299 (14) | 0.0355 (15) | −0.0005 (12) | −0.0053 (12) | 0.0000 (12) |
N1 | 0.0231 (16) | 0.0336 (18) | 0.0329 (18) | −0.0024 (13) | −0.0007 (13) | 0.0010 (14) |
N2 | 0.0226 (16) | 0.044 (2) | 0.040 (2) | −0.0005 (14) | −0.0032 (14) | −0.0031 (16) |
N3 | 0.0282 (19) | 0.057 (2) | 0.057 (2) | −0.0068 (17) | −0.0055 (17) | −0.017 (2) |
C1 | 0.047 (3) | 0.040 (2) | 0.034 (2) | −0.004 (2) | −0.0085 (19) | 0.0015 (18) |
C2 | 0.039 (2) | 0.032 (2) | 0.046 (3) | −0.0054 (18) | 0.0053 (19) | 0.0001 (18) |
C3 | 0.053 (3) | 0.040 (3) | 0.064 (3) | −0.014 (2) | −0.006 (2) | −0.005 (2) |
C4 | 0.071 (4) | 0.039 (3) | 0.095 (5) | −0.019 (3) | −0.006 (3) | −0.015 (3) |
C5 | 0.082 (4) | 0.028 (3) | 0.112 (5) | −0.001 (3) | 0.002 (4) | −0.012 (3) |
C6 | 0.056 (3) | 0.037 (3) | 0.072 (4) | 0.007 (2) | −0.002 (3) | −0.001 (2) |
C7 | 0.039 (2) | 0.031 (2) | 0.047 (3) | −0.0001 (18) | 0.005 (2) | −0.0014 (19) |
C8 | 0.028 (2) | 0.041 (2) | 0.044 (2) | 0.0086 (18) | 0.0000 (18) | 0.0015 (19) |
C9 | 0.027 (2) | 0.040 (2) | 0.032 (2) | −0.0018 (17) | −0.0033 (16) | 0.0001 (17) |
Cl1 | 0.0498 (7) | 0.0334 (6) | 0.0551 (7) | −0.0033 (5) | 0.0020 (5) | −0.0015 (5) |
O2 | 0.165 (6) | 0.065 (3) | 0.137 (5) | −0.035 (3) | 0.086 (4) | −0.012 (3) |
O3 | 0.088 (4) | 0.075 (3) | 0.165 (5) | 0.022 (3) | −0.040 (4) | −0.022 (3) |
O4 | 0.100 (3) | 0.036 (2) | 0.121 (4) | −0.010 (2) | 0.013 (3) | 0.013 (2) |
O5 | 0.195 (7) | 0.099 (4) | 0.119 (5) | 0.015 (4) | −0.094 (5) | −0.016 (4) |
O6 | 0.109 (4) | 0.067 (3) | 0.082 (3) | −0.004 (3) | 0.049 (3) | −0.019 (2) |
C10 | 0.109 (6) | 0.086 (5) | 0.079 (5) | −0.014 (4) | 0.032 (4) | −0.001 (4) |
Geometric parameters (Å, º) top
Ni1—N1i | 2.034 (3) | C3—C4 | 1.378 (8) |
Ni1—N1 | 2.034 (3) | C3—H3 | 0.9300 |
Ni1—O1 | 2.156 (3) | C4—C5 | 1.366 (9) |
Ni1—O1i | 2.156 (3) | C4—H4 | 0.9300 |
Ni1—S1i | 2.3475 (18) | C5—C6 | 1.365 (8) |
Ni1—S1 | 2.3476 (18) | C5—H5 | 0.9300 |
S1—C9 | 1.699 (4) | C6—C7 | 1.401 (6) |
O1—C2 | 1.391 (5) | C6—H6 | 0.9300 |
O1—C1 | 1.459 (5) | C7—C8 | 1.442 (6) |
N1—C8 | 1.290 (5) | C8—H8 | 0.9300 |
N1—N2 | 1.380 (5) | Cl1—O5 | 1.389 (5) |
N2—C9 | 1.341 (5) | Cl1—O4 | 1.399 (4) |
N3—C9 | 1.318 (5) | Cl1—O3 | 1.415 (5) |
N3—H3A | 0.8600 | Cl1—O2 | 1.419 (5) |
N3—H3B | 0.8600 | O6—C10 | 1.396 (8) |
C1—C1i | 1.511 (9) | O6—H6A | 0.8200 |
C1—H1A | 0.9700 | C10—H10A | 0.9600 |
C1—H1B | 0.9700 | C10—H10B | 0.9600 |
C2—C3 | 1.376 (6) | C10—H10C | 0.9600 |
C2—C7 | 1.395 (6) | | |
| | | |
N1i—Ni1—N1 | 177.06 (18) | C2—C3—C4 | 119.2 (5) |
N1i—Ni1—O1 | 94.02 (12) | C2—C3—H3 | 120.4 |
N1—Ni1—O1 | 83.64 (12) | C4—C3—H3 | 120.4 |
N1i—Ni1—O1i | 83.64 (12) | C5—C4—C3 | 120.9 (5) |
N1—Ni1—O1i | 94.02 (12) | C5—C4—H4 | 119.6 |
O1—Ni1—O1i | 74.90 (16) | C3—C4—H4 | 119.6 |
N1i—Ni1—S1i | 84.24 (10) | C6—C5—C4 | 120.3 (5) |
N1—Ni1—S1i | 97.62 (10) | C6—C5—H5 | 119.9 |
O1—Ni1—S1i | 92.77 (11) | C4—C5—H5 | 119.9 |
O1i—Ni1—S1i | 162.01 (8) | C5—C6—C7 | 120.7 (5) |
N1i—Ni1—S1 | 97.62 (10) | C5—C6—H6 | 119.7 |
N1—Ni1—S1 | 84.24 (10) | C7—C6—H6 | 119.7 |
O1—Ni1—S1 | 162.01 (8) | C2—C7—C6 | 117.9 (4) |
O1i—Ni1—S1 | 92.77 (11) | C2—C7—C8 | 125.0 (4) |
S1i—Ni1—S1 | 101.98 (10) | C6—C7—C8 | 117.0 (4) |
C9—S1—Ni1 | 95.83 (14) | N1—C8—C7 | 125.4 (4) |
C2—O1—C1 | 117.0 (3) | N1—C8—H8 | 117.3 |
C2—O1—Ni1 | 123.1 (3) | C7—C8—H8 | 117.3 |
C1—O1—Ni1 | 114.4 (2) | N3—C9—N2 | 116.6 (4) |
C8—N1—N2 | 115.5 (3) | N3—C9—S1 | 121.1 (3) |
C8—N1—Ni1 | 127.7 (3) | N2—C9—S1 | 122.4 (3) |
N2—N1—Ni1 | 116.5 (2) | O5—Cl1—O4 | 115.7 (4) |
C9—N2—N1 | 119.9 (3) | O5—Cl1—O3 | 108.6 (4) |
C9—N3—H3A | 120.0 | O4—Cl1—O3 | 110.2 (3) |
C9—N3—H3B | 120.0 | O5—Cl1—O2 | 110.9 (5) |
H3A—N3—H3B | 120.0 | O4—Cl1—O2 | 108.8 (3) |
O1—C1—C1i | 105.6 (3) | O3—Cl1—O2 | 101.7 (4) |
O1—C1—H1A | 110.6 | C10—O6—H6A | 109.5 |
C1i—C1—H1A | 110.6 | O6—C10—H10A | 109.5 |
O1—C1—H1B | 110.6 | O6—C10—H10B | 109.5 |
C1i—C1—H1B | 110.6 | H10A—C10—H10B | 109.5 |
H1A—C1—H1B | 108.7 | O6—C10—H10C | 109.5 |
C3—C2—O1 | 119.5 (4) | H10A—C10—H10C | 109.5 |
C3—C2—C7 | 121.1 (4) | H10B—C10—H10C | 109.5 |
O1—C2—C7 | 119.4 (4) | | |
| | | |
N1i—Ni1—S1—C9 | 169.64 (17) | Ni1—N1—N2—C9 | −7.8 (5) |
N1—Ni1—S1—C9 | −8.07 (17) | C2—O1—C1—C1i | 111.8 (4) |
O1—Ni1—S1—C9 | 39.7 (3) | Ni1—O1—C1—C1i | −42.8 (5) |
O1i—Ni1—S1—C9 | 85.69 (16) | C1—O1—C2—C3 | 59.9 (5) |
S1i—Ni1—S1—C9 | −104.67 (15) | Ni1—O1—C2—C3 | −148.0 (4) |
N1i—Ni1—O1—C2 | 140.8 (3) | C1—O1—C2—C7 | −121.0 (4) |
N1—Ni1—O1—C2 | −41.0 (3) | Ni1—O1—C2—C7 | 31.2 (5) |
O1i—Ni1—O1—C2 | −136.9 (3) | O1—C2—C3—C4 | 178.7 (5) |
S1i—Ni1—O1—C2 | 56.4 (3) | C7—C2—C3—C4 | −0.5 (8) |
S1—Ni1—O1—C2 | −88.9 (4) | C2—C3—C4—C5 | −1.2 (9) |
N1i—Ni1—O1—C1 | −66.4 (3) | C3—C4—C5—C6 | 2.1 (10) |
N1—Ni1—O1—C1 | 111.8 (3) | C4—C5—C6—C7 | −1.2 (10) |
O1i—Ni1—O1—C1 | 15.9 (2) | C3—C2—C7—C6 | 1.3 (7) |
S1i—Ni1—O1—C1 | −150.8 (3) | O1—C2—C7—C6 | −177.8 (4) |
S1—Ni1—O1—C1 | 63.9 (4) | C3—C2—C7—C8 | −174.7 (5) |
N1i—Ni1—N1—C8 | 65.6 (4) | O1—C2—C7—C8 | 6.2 (7) |
O1—Ni1—N1—C8 | 28.3 (4) | C5—C6—C7—C2 | −0.5 (8) |
O1i—Ni1—N1—C8 | 102.6 (4) | C5—C6—C7—C8 | 175.8 (5) |
S1i—Ni1—N1—C8 | −63.6 (4) | N2—N1—C8—C7 | 179.8 (4) |
S1—Ni1—N1—C8 | −165.0 (4) | Ni1—N1—C8—C7 | −5.5 (7) |
N1i—Ni1—N1—N2 | −119.8 (3) | C2—C7—C8—N1 | −21.8 (7) |
O1—Ni1—N1—N2 | −157.0 (3) | C6—C7—C8—N1 | 162.2 (5) |
O1i—Ni1—N1—N2 | −82.7 (3) | N1—N2—C9—N3 | 179.1 (4) |
S1i—Ni1—N1—N2 | 111.0 (3) | N1—N2—C9—S1 | −1.2 (5) |
S1—Ni1—N1—N2 | 9.7 (3) | Ni1—S1—C9—N3 | −172.8 (4) |
C8—N1—N2—C9 | 167.5 (4) | Ni1—S1—C9—N2 | 7.5 (4) |
Symmetry code: (i) −x+1, −y+1/2, z. |
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