The crystal structure of the title compound, [Co(C
6H
6N
4S
2)
2Cl
2]·2H
2O, comprises an octahedral Co
II complex and water of crystallization. Two Cl atoms and two diaminobithiazole (DABT) ligands coordinate to the Co
II atom in a
cis configuration. The overlapped arrangement and the short separation of 3.46 (2) Å between parallel DABT rings suggest the existence of π–π stacking interactions. A short S
S contact of 3.1822 (17) Å is observed between DABT ligands.
Supporting information
CCDC reference: 225665
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.006 Å
- R factor = 0.047
- wR factor = 0.108
- Data-to-parameter ratio = 18.6
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor O2 - H2B ... ?
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.99
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3
H2 O
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
2 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
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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
[Co(C6H6N4S2)2Cl2]·2H2O | F(000) = 1140 |
Mr = 562.44 | Dx = 1.748 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 10880 reflections |
a = 10.8616 (12) Å | θ = 2.5–24.0° |
b = 13.6096 (15) Å | µ = 1.47 mm−1 |
c = 15.0657 (17) Å | T = 295 K |
β = 106.282 (12)° | Prism, pink |
V = 2137.7 (4) Å3 | 0.28 × 0.22 × 0.18 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD diffractometer | 4872 independent reflections |
Radiation source: fine-focus sealed tube | 2794 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
ω and φ scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −13→14 |
Tmin = 0.660, Tmax = 0.765 | k = −17→10 |
13046 measured reflections | l = −18→19 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 0.86 | w = 1/[σ2(Fo2) + (0.0453P)2] where P = (Fo2 + 2Fc2)/3 |
4872 reflections | (Δ/σ)max = 0.001 |
262 parameters | Δρmax = 0.88 e Å−3 |
0 restraints | Δρmin = −0.78 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 | |
Co | 0.78650 (5) | 0.34418 (4) | 0.23843 (4) | 0.02050 (15) | |
Cl1 | 0.60477 (9) | 0.24860 (7) | 0.13650 (6) | 0.0213 (2) | |
Cl2 | 0.92233 (9) | 0.30808 (7) | 0.13309 (6) | 0.0218 (2) | |
S1 | 0.58537 (11) | 0.62228 (8) | 0.07480 (8) | 0.0354 (3) | |
S2 | 0.53993 (11) | 0.41287 (8) | 0.44330 (8) | 0.0320 (3) | |
S3 | 1.12840 (11) | 0.52188 (9) | 0.44303 (8) | 0.0366 (3) | |
S4 | 0.98523 (11) | 0.06458 (8) | 0.39751 (8) | 0.0353 (3) | |
N1 | 0.6925 (3) | 0.4734 (2) | 0.1718 (2) | 0.0226 (7) | |
N2 | 0.6678 (3) | 0.3833 (2) | 0.3261 (2) | 0.0216 (7) | |
N3 | 0.9467 (3) | 0.4185 (2) | 0.3363 (2) | 0.0225 (7) | |
N4 | 0.8832 (3) | 0.2255 (2) | 0.3210 (2) | 0.0230 (8) | |
N5 | 0.7340 (3) | 0.4855 (2) | 0.0274 (2) | 0.0273 (8) | |
N6 | 0.6886 (3) | 0.2570 (2) | 0.4379 (2) | 0.0281 (8) | |
N7 | 0.9263 (3) | 0.5898 (3) | 0.3105 (2) | 0.0340 (9) | |
N8 | 0.7654 (4) | 0.0832 (3) | 0.2629 (3) | 0.0381 (9) | |
C1 | 0.6803 (4) | 0.5177 (3) | 0.0919 (3) | 0.0239 (9) | |
C2 | 0.5544 (4) | 0.6022 (3) | 0.1795 (3) | 0.0345 (11) | |
H2 | 0.5027 | 0.6419 | 0.2043 | 0.041* | |
C3 | 0.6156 (4) | 0.5209 (3) | 0.2202 (3) | 0.0241 (9) | |
C4 | 0.6049 (4) | 0.4720 (3) | 0.3036 (3) | 0.0244 (9) | |
C5 | 0.5343 (4) | 0.5001 (3) | 0.3597 (3) | 0.0322 (11) | |
H5 | 0.4887 | 0.5586 | 0.3540 | 0.039* | |
C6 | 0.6445 (4) | 0.3434 (3) | 0.3995 (3) | 0.0221 (9) | |
C7 | 0.9868 (4) | 0.5100 (3) | 0.3543 (3) | 0.0277 (10) | |
C8 | 1.1314 (4) | 0.3968 (3) | 0.4568 (3) | 0.0335 (11) | |
H8 | 1.1951 | 0.3629 | 0.5002 | 0.040* | |
C9 | 1.0305 (4) | 0.3540 (3) | 0.3972 (3) | 0.0250 (9) | |
C10 | 0.9974 (4) | 0.2501 (3) | 0.3872 (3) | 0.0250 (9) | |
C11 | 1.0635 (4) | 0.1744 (3) | 0.4345 (3) | 0.0357 (11) | |
H11 | 1.1407 | 0.1800 | 0.4806 | 0.043* | |
C12 | 0.8655 (4) | 0.1284 (3) | 0.3190 (3) | 0.0263 (10) | |
O1 | 0.3346 (3) | 0.3599 (2) | 0.1107 (2) | 0.0458 (9) | |
O2 | 1.2026 (3) | 0.3670 (2) | 0.2475 (2) | 0.0400 (8) | |
H1A | 0.4179 | 0.3294 | 0.1243 | 0.050* | |
H1B | 0.3203 | 0.3606 | 0.1702 | 0.050* | |
H2A | 1.1488 | 0.3274 | 0.2119 | 0.050* | |
H2B | 1.2363 | 0.3296 | 0.3022 | 0.050* | |
H5A | 0.7172 | 0.5133 | −0.0270 | 0.050* | |
H5B | 0.7959 | 0.4338 | 0.0449 | 0.050* | |
H6A | 0.6981 | 0.2469 | 0.5010 | 0.050* | |
H6B | 0.7591 | 0.2404 | 0.4211 | 0.050* | |
H7A | 0.9529 | 0.6565 | 0.3285 | 0.050* | |
H7B | 0.8553 | 0.5863 | 0.2555 | 0.050* | |
H8A | 0.7707 | 0.0175 | 0.2663 | 0.050* | |
H8B | 0.7072 | 0.1159 | 0.2179 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co | 0.0213 (3) | 0.0155 (3) | 0.0264 (3) | 0.0010 (2) | 0.0093 (2) | 0.0006 (2) |
Cl1 | 0.0218 (5) | 0.0167 (5) | 0.0260 (5) | −0.0009 (4) | 0.0074 (4) | −0.0016 (4) |
Cl2 | 0.0232 (5) | 0.0169 (5) | 0.0279 (5) | 0.0012 (4) | 0.0116 (4) | 0.0000 (4) |
S1 | 0.0389 (7) | 0.0308 (7) | 0.0408 (7) | 0.0133 (5) | 0.0182 (5) | 0.0153 (5) |
S2 | 0.0373 (7) | 0.0312 (7) | 0.0329 (6) | 0.0110 (5) | 0.0188 (5) | 0.0037 (5) |
S3 | 0.0306 (6) | 0.0384 (7) | 0.0392 (7) | −0.0104 (5) | 0.0070 (5) | −0.0105 (5) |
S4 | 0.0425 (7) | 0.0258 (7) | 0.0372 (7) | 0.0118 (5) | 0.0102 (5) | 0.0076 (5) |
N1 | 0.0244 (19) | 0.0170 (18) | 0.029 (2) | −0.0001 (14) | 0.0117 (15) | −0.0002 (14) |
N2 | 0.0242 (18) | 0.0162 (18) | 0.0265 (19) | 0.0036 (15) | 0.0106 (15) | 0.0016 (14) |
N3 | 0.0230 (18) | 0.022 (2) | 0.0233 (18) | 0.0005 (15) | 0.0078 (14) | −0.0018 (14) |
N4 | 0.0183 (18) | 0.023 (2) | 0.030 (2) | 0.0050 (15) | 0.0104 (15) | 0.0025 (15) |
N5 | 0.030 (2) | 0.026 (2) | 0.028 (2) | 0.0033 (16) | 0.0107 (16) | 0.0061 (15) |
N6 | 0.034 (2) | 0.022 (2) | 0.033 (2) | 0.0063 (16) | 0.0168 (16) | 0.0027 (15) |
N7 | 0.041 (2) | 0.018 (2) | 0.040 (2) | −0.0052 (17) | 0.0064 (18) | −0.0030 (16) |
N8 | 0.037 (2) | 0.022 (2) | 0.051 (3) | 0.0023 (17) | 0.0040 (19) | 0.0021 (17) |
C1 | 0.026 (2) | 0.019 (2) | 0.028 (2) | −0.0025 (18) | 0.0074 (18) | 0.0013 (17) |
C2 | 0.041 (3) | 0.028 (3) | 0.040 (3) | 0.013 (2) | 0.020 (2) | 0.006 (2) |
C3 | 0.024 (2) | 0.021 (2) | 0.030 (2) | 0.0018 (18) | 0.0107 (18) | 0.0010 (18) |
C4 | 0.024 (2) | 0.022 (2) | 0.027 (2) | 0.0016 (18) | 0.0070 (18) | 0.0002 (17) |
C5 | 0.040 (3) | 0.026 (3) | 0.035 (3) | 0.017 (2) | 0.017 (2) | 0.0068 (19) |
C6 | 0.023 (2) | 0.020 (2) | 0.027 (2) | 0.0010 (18) | 0.0119 (17) | −0.0020 (17) |
C7 | 0.029 (2) | 0.030 (3) | 0.030 (2) | −0.007 (2) | 0.0169 (19) | −0.0053 (19) |
C8 | 0.024 (2) | 0.039 (3) | 0.036 (3) | −0.002 (2) | 0.006 (2) | −0.002 (2) |
C9 | 0.023 (2) | 0.030 (3) | 0.024 (2) | 0.0019 (19) | 0.0093 (18) | −0.0032 (18) |
C10 | 0.025 (2) | 0.026 (2) | 0.028 (2) | 0.0059 (19) | 0.0131 (18) | 0.0020 (18) |
C11 | 0.036 (3) | 0.035 (3) | 0.034 (3) | 0.010 (2) | 0.007 (2) | 0.001 (2) |
C12 | 0.027 (2) | 0.023 (2) | 0.033 (2) | 0.0046 (19) | 0.0159 (19) | 0.0038 (18) |
O1 | 0.0392 (19) | 0.062 (2) | 0.040 (2) | 0.0137 (17) | 0.0172 (15) | 0.0166 (16) |
O2 | 0.0408 (19) | 0.035 (2) | 0.048 (2) | −0.0045 (15) | 0.0192 (16) | −0.0021 (15) |
Geometric parameters (Å, º) top
Co—N4 | 2.128 (3) | N5—H5B | 0.958 |
Co—N1 | 2.137 (3) | N6—C6 | 1.338 (5) |
Co—N2 | 2.155 (3) | N6—H6A | 0.938 |
Co—N3 | 2.188 (3) | N6—H6B | 0.900 |
Co—Cl1 | 2.4994 (11) | N7—C7 | 1.343 (5) |
Co—Cl2 | 2.4998 (11) | N7—H7A | 0.968 |
S1—C2 | 1.724 (4) | N7—H7B | 0.962 |
S1—C1 | 1.733 (4) | N8—C12 | 1.327 (5) |
S2—C5 | 1.719 (4) | N8—H8A | 0.897 |
S2—C6 | 1.743 (4) | N8—H8B | 0.904 |
S3—C8 | 1.714 (5) | C2—C3 | 1.347 (5) |
S3—C7 | 1.739 (4) | C2—H2 | 0.9300 |
S4—C12 | 1.727 (4) | C3—C4 | 1.455 (5) |
S4—C11 | 1.732 (5) | C4—C5 | 1.346 (5) |
N1—C1 | 1.320 (5) | C5—H5 | 0.9300 |
N1—C3 | 1.411 (5) | C8—C9 | 1.340 (5) |
N2—C6 | 1.319 (5) | C8—H8 | 0.9300 |
N2—C4 | 1.382 (5) | C9—C10 | 1.457 (5) |
N3—C7 | 1.323 (5) | C10—C11 | 1.341 (6) |
N3—C9 | 1.404 (5) | C11—H11 | 0.9300 |
N4—C12 | 1.335 (5) | O1—H1A | 0.964 |
N4—C10 | 1.397 (5) | O1—H1B | 0.951 |
N5—C1 | 1.340 (5) | O2—H2A | 0.862 |
N5—H5A | 0.874 | O2—H2B | 0.951 |
| | | |
N4—Co—N1 | 172.64 (12) | C12—N8—H8B | 121.7 |
N4—Co—N2 | 96.38 (12) | H8A—N8—H8B | 123.6 |
N1—Co—N2 | 78.20 (12) | N1—C1—N5 | 124.0 (4) |
N4—Co—N3 | 77.74 (12) | N1—C1—S1 | 114.5 (3) |
N1—Co—N3 | 96.98 (12) | N5—C1—S1 | 121.6 (3) |
N2—Co—N3 | 88.40 (12) | C3—C2—S1 | 110.4 (3) |
N4—Co—Cl1 | 98.03 (9) | C3—C2—H2 | 124.8 |
N1—Co—Cl1 | 87.04 (9) | S1—C2—H2 | 124.8 |
N2—Co—Cl1 | 90.00 (9) | C2—C3—N1 | 115.4 (4) |
N3—Co—Cl1 | 175.27 (9) | C2—C3—C4 | 128.4 (4) |
N4—Co—Cl2 | 86.54 (9) | N1—C3—C4 | 116.1 (3) |
N1—Co—Cl2 | 98.78 (9) | C5—C4—N2 | 115.1 (4) |
N2—Co—Cl2 | 176.86 (9) | C5—C4—C3 | 127.6 (4) |
N3—Co—Cl2 | 91.12 (8) | N2—C4—C3 | 117.2 (3) |
Cl1—Co—Cl2 | 90.72 (4) | C4—C5—S2 | 110.8 (3) |
C2—S1—C1 | 89.7 (2) | C4—C5—H5 | 124.6 |
C5—S2—C6 | 89.43 (19) | S2—C5—H5 | 124.6 |
C8—S3—C7 | 89.1 (2) | N2—C6—N6 | 126.4 (3) |
C12—S4—C11 | 89.6 (2) | N2—C6—S2 | 113.1 (3) |
C1—N1—C3 | 109.8 (3) | N6—C6—S2 | 120.4 (3) |
C1—N1—Co | 135.9 (3) | N3—C7—N7 | 124.9 (4) |
C3—N1—Co | 114.1 (2) | N3—C7—S3 | 114.5 (3) |
C6—N2—C4 | 111.5 (3) | N7—C7—S3 | 120.6 (3) |
C6—N2—Co | 134.5 (3) | C9—C8—S3 | 111.4 (3) |
C4—N2—Co | 113.9 (2) | C9—C8—H8 | 124.3 |
C7—N3—C9 | 109.8 (3) | S3—C8—H8 | 124.3 |
C7—N3—Co | 136.7 (3) | C8—C9—N3 | 115.2 (4) |
C9—N3—Co | 113.5 (2) | C8—C9—C10 | 128.5 (4) |
C12—N4—C10 | 110.3 (3) | N3—C9—C10 | 116.3 (3) |
C12—N4—Co | 133.9 (3) | C11—C10—N4 | 115.5 (4) |
C10—N4—Co | 115.5 (3) | C11—C10—C9 | 127.7 (4) |
C1—N5—H5A | 121.2 | N4—C10—C9 | 116.7 (3) |
C1—N5—H5B | 117.1 | C10—C11—S4 | 110.5 (3) |
H5A—N5—H5B | 121.5 | C10—C11—H11 | 124.7 |
C6—N6—H6A | 119.4 | S4—C11—H11 | 124.7 |
C6—N6—H6B | 109.2 | N8—C12—N4 | 124.1 (4) |
H6A—N6—H6B | 112.8 | N8—C12—S4 | 121.9 (3) |
C7—N7—H7A | 123.6 | N4—C12—S4 | 114.0 (3) |
C7—N7—H7B | 123.2 | H1A—O1—H1B | 101.3 |
H7A—N7—H7B | 113.1 | H2A—O2—H2B | 103.4 |
C12—N8—H8A | 113.5 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···Cl1 | 0.96 | 2.27 | 3.228 (3) | 172 |
O1—H1B···O2i | 0.95 | 1.96 | 2.823 (4) | 150 |
O2—H2A···Cl2 | 0.86 | 2.43 | 3.153 (3) | 142 |
N5—H5A···O1ii | 0.87 | 2.12 | 2.905 (4) | 149 |
N5—H5B···Cl2 | 0.96 | 2.36 | 3.275 (3) | 160 |
N6—H6A···Cl1iii | 0.94 | 2.52 | 3.364 (3) | 150 |
N6—H6A···Cl2iii | 0.94 | 2.78 | 3.419 (3) | 126 |
N6—H6B···N4 | 0.90 | 2.30 | 3.137 (5) | 155 |
N7—H7A···Cl2iv | 0.97 | 2.45 | 3.386 (4) | 164 |
N7—H7B···N1 | 0.96 | 2.41 | 3.217 (5) | 141 |
N8—H8A···O2v | 0.90 | 2.09 | 2.972 (5) | 169 |
N8—H8B···Cl1 | 0.90 | 2.29 | 3.142 (4) | 157 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) x, −y+1/2, z+1/2; (iv) −x+2, y+1/2, −z+1/2; (v) −x+2, y−1/2, −z+1/2. |