The title compound, [CoCl
2(CH
4N
2S)
2].2C
11H
6N
2O, consists of the tetrahedral cobalt(II) complex and free 4,5-diazafluoren-9-one (dafone). Dafone links to the complex through hydrogen bonding between N atoms. The carbonyl bridge in dafone distorts the bipyridine moiety. The longer N
N separations of 3.068 (3) and 3.064 (3) Å in dafone are considered to be the reason for the weaker chelating ability of dafone.
Supporting information
CCDC reference: 189287
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.033
- wR factor = 0.099
- Data-to-parameter ratio = 15.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure
Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985); 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).
Crystal data top
[CoCl2(CH4N2S)2]·2C11H6N2O | Z = 2 |
Mr = 646.45 | F(000) = 658 |
Triclinic, P1 | Dx = 1.532 Mg m−3 |
a = 7.3902 (11) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.9763 (12) Å | Cell parameters from 20 reflections |
c = 15.1615 (18) Å | θ = 4.5–10.2° |
α = 89.111 (10)° | µ = 0.99 mm−1 |
β = 78.107 (11)° | T = 298 K |
γ = 80.045 (10)° | Prism, blue |
V = 1401.0 (3) Å3 | 0.56 × 0.32 × 0.14 mm |
Data collection top
Rigaku AFC-7S diffractometer | Rint = 0.023 |
ω/2θ scans | θmax = 26°, θmin = 2.1° |
Absorption correction: ψ scan (North et. al., 1968) | h = −9→8 |
Tmin = 0.69, Tmax = 0.87 | k = −15→0 |
5748 measured reflections | l = −18→18 |
5495 independent reflections | 3 standard reflections every 100 reflections |
3653 reflections with I > 2σ(I) | intensity decay: 0.2% |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0459P)2 + 0.2616P] where P = (Fo2 + 2Fc2)/3 |
5495 reflections | (Δ/σ)max < 0.001 |
352 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.31 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.2485 (4) | 0.0196 (2) | 0.14120 (18) | 0.0437 (6) | |
C2 | 0.0158 (4) | 0.5134 (2) | 0.15577 (17) | 0.0417 (6) | |
C3 | 0.4956 (4) | −0.3445 (2) | 0.11229 (19) | 0.0539 (7) | |
H9 | 0.5498 | −0.3166 | 0.0584 | 0.065* | |
C4 | 0.5399 (4) | −0.4507 (2) | 0.1223 (2) | 0.0553 (7) | |
H10 | 0.6207 | −0.4922 | 0.0762 | 0.066* | |
C5 | 0.4637 (4) | −0.4953 (2) | 0.20154 (19) | 0.0517 (7) | |
H11 | 0.4912 | −0.5668 | 0.2105 | 0.062* | |
C6 | 0.3453 (4) | −0.4288 (2) | 0.26660 (17) | 0.0419 (6) | |
C7 | 0.2383 (4) | −0.4481 (2) | 0.35809 (19) | 0.0481 (6) | |
C8 | 0.1364 (4) | −0.3430 (2) | 0.39445 (18) | 0.0447 (6) | |
C9 | 0.0212 (4) | −0.3123 (2) | 0.47678 (18) | 0.0520 (7) | |
H12 | −0.0076 | −0.3603 | 0.5214 | 0.062* | |
C10 | −0.0493 (4) | −0.2068 (3) | 0.48963 (19) | 0.0551 (7) | |
H13 | −0.1271 | −0.1819 | 0.5441 | 0.066* | |
C11 | −0.0040 (4) | −0.1382 (2) | 0.42119 (18) | 0.0511 (7) | |
H14 | −0.0561 | −0.0678 | 0.4313 | 0.061* | |
C12 | 0.1774 (3) | −0.2685 (2) | 0.33002 (17) | 0.0395 (6) | |
C13 | 0.3076 (3) | −0.3221 (2) | 0.24984 (17) | 0.0395 (6) | |
C14 | −0.1581 (5) | 0.8859 (3) | 0.1402 (2) | 0.0594 (8) | |
H15 | −0.0740 | 0.8675 | 0.0859 | 0.071* | |
C15 | −0.2405 (5) | 0.9908 (3) | 0.1556 (2) | 0.0672 (9) | |
H16 | −0.2105 | 1.0401 | 0.1123 | 0.081* | |
C16 | −0.3666 (5) | 1.0213 (2) | 0.2351 (2) | 0.0659 (9) | |
H17 | −0.4234 | 1.0908 | 0.2469 | 0.079* | |
C17 | −0.4046 (4) | 0.9445 (2) | 0.2962 (2) | 0.0518 (7) | |
C18 | −0.5294 (4) | 0.9471 (2) | 0.3874 (2) | 0.0571 (8) | |
C19 | −0.4998 (4) | 0.8389 (2) | 0.42034 (19) | 0.0504 (7) | |
C20 | −0.5695 (4) | 0.7954 (3) | 0.5007 (2) | 0.0595 (8) | |
H18 | −0.6522 | 0.8357 | 0.5471 | 0.071* | |
C21 | −0.5115 (4) | 0.6892 (3) | 0.5098 (2) | 0.0609 (8) | |
H19 | −0.5536 | 0.6564 | 0.5632 | 0.073* | |
C22 | −0.3896 (4) | 0.6325 (2) | 0.4381 (2) | 0.0555 (7) | |
H20 | −0.3537 | 0.5611 | 0.4453 | 0.067* | |
C23 | −0.3748 (4) | 0.7754 (2) | 0.35220 (18) | 0.0438 (6) | |
C24 | −0.3149 (4) | 0.8412 (2) | 0.27524 (18) | 0.0454 (6) | |
N1 | 0.3304 (4) | −0.07016 (18) | 0.10086 (17) | 0.0606 (7) | |
H1 | 0.3235 | −0.1276 | 0.1294 | 0.073* | |
H2 | 0.3908 | −0.0715 | 0.0459 | 0.073* | |
N2 | 0.1572 (3) | 0.02008 (18) | 0.22491 (15) | 0.0531 (6) | |
H3 | 0.1514 | −0.0379 | 0.2527 | 0.064* | |
H4 | 0.1029 | 0.0784 | 0.2521 | 0.064* | |
N3 | 0.0156 (3) | 0.60683 (17) | 0.12131 (15) | 0.0525 (6) | |
H5 | −0.0466 | 0.6611 | 0.1524 | 0.063* | |
H6 | 0.0778 | 0.6137 | 0.0676 | 0.063* | |
N4 | −0.0802 (3) | 0.50473 (18) | 0.23800 (15) | 0.0524 (6) | |
H7 | −0.1418 | 0.5597 | 0.2683 | 0.063* | |
H8 | −0.0813 | 0.4440 | 0.2615 | 0.063* | |
N5 | 0.3792 (3) | −0.27765 (17) | 0.17479 (14) | 0.0460 (5) | |
N6 | 0.1108 (3) | −0.16635 (17) | 0.34072 (14) | 0.0453 (5) | |
N7 | −0.1930 (3) | 0.81010 (18) | 0.19917 (15) | 0.0492 (6) | |
N8 | −0.3196 (3) | 0.67337 (17) | 0.35878 (15) | 0.0481 (5) | |
O1 | 0.2361 (3) | −0.53086 (17) | 0.39568 (15) | 0.0713 (6) | |
O2 | −0.6349 (3) | 1.02200 (18) | 0.42620 (17) | 0.0804 (7) | |
S1 | 0.27114 (12) | 0.13338 (6) | 0.08358 (5) | 0.0632 (2) | |
S2 | 0.14841 (11) | 0.40653 (5) | 0.09429 (5) | 0.0558 (2) | |
Cl1 | −0.22205 (12) | 0.26074 (7) | 0.06530 (6) | 0.0666 (2) | |
Cl2 | −0.09294 (13) | 0.25432 (6) | 0.29010 (5) | 0.0705 (2) | |
Co | 0.01017 (5) | 0.26196 (3) | 0.13882 (2) | 0.04409 (12) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0430 (14) | 0.0396 (14) | 0.0460 (15) | −0.0047 (11) | −0.0058 (12) | 0.0039 (11) |
C2 | 0.0431 (14) | 0.0408 (14) | 0.0397 (14) | −0.0066 (11) | −0.0053 (11) | −0.0054 (11) |
C3 | 0.0576 (17) | 0.0513 (17) | 0.0445 (16) | −0.0083 (14) | 0.0073 (13) | 0.0014 (13) |
C4 | 0.0519 (17) | 0.0523 (17) | 0.0523 (17) | −0.0002 (14) | 0.0039 (13) | −0.0089 (13) |
C5 | 0.0550 (17) | 0.0392 (14) | 0.0564 (17) | −0.0020 (13) | −0.0065 (14) | −0.0008 (12) |
C6 | 0.0438 (14) | 0.0398 (14) | 0.0421 (14) | −0.0071 (11) | −0.0090 (11) | 0.0028 (11) |
C7 | 0.0500 (16) | 0.0467 (16) | 0.0471 (16) | −0.0071 (13) | −0.0105 (12) | 0.0062 (12) |
C8 | 0.0419 (14) | 0.0493 (15) | 0.0414 (14) | −0.0060 (12) | −0.0067 (11) | 0.0027 (12) |
C9 | 0.0498 (16) | 0.0647 (19) | 0.0383 (15) | −0.0082 (14) | −0.0040 (12) | 0.0089 (13) |
C10 | 0.0488 (16) | 0.071 (2) | 0.0381 (15) | −0.0011 (15) | 0.0008 (12) | −0.0073 (14) |
C11 | 0.0495 (16) | 0.0514 (17) | 0.0464 (16) | 0.0033 (13) | −0.0055 (13) | −0.0069 (13) |
C12 | 0.0375 (13) | 0.0417 (14) | 0.0394 (14) | −0.0067 (11) | −0.0081 (11) | 0.0000 (11) |
C13 | 0.0386 (13) | 0.0405 (14) | 0.0391 (14) | −0.0073 (11) | −0.0067 (11) | −0.0006 (11) |
C14 | 0.066 (2) | 0.0604 (19) | 0.0535 (18) | −0.0159 (16) | −0.0131 (15) | 0.0023 (15) |
C15 | 0.079 (2) | 0.0531 (19) | 0.076 (2) | −0.0200 (17) | −0.0235 (19) | 0.0095 (16) |
C16 | 0.072 (2) | 0.0438 (17) | 0.087 (3) | −0.0037 (15) | −0.0308 (19) | −0.0067 (16) |
C17 | 0.0529 (17) | 0.0416 (15) | 0.0620 (18) | −0.0001 (13) | −0.0208 (14) | −0.0078 (13) |
C18 | 0.0500 (17) | 0.0536 (18) | 0.0658 (19) | 0.0050 (14) | −0.0174 (14) | −0.0223 (15) |
C19 | 0.0441 (15) | 0.0519 (16) | 0.0528 (17) | 0.0002 (13) | −0.0109 (13) | −0.0160 (13) |
C20 | 0.0464 (16) | 0.075 (2) | 0.0509 (18) | −0.0023 (15) | −0.0018 (13) | −0.0185 (15) |
C21 | 0.0556 (18) | 0.073 (2) | 0.0494 (17) | −0.0085 (16) | −0.0015 (14) | −0.0015 (15) |
C22 | 0.0561 (17) | 0.0532 (17) | 0.0540 (18) | −0.0050 (14) | −0.0075 (14) | −0.0001 (14) |
C23 | 0.0402 (14) | 0.0446 (15) | 0.0461 (15) | −0.0015 (12) | −0.0119 (11) | −0.0114 (12) |
C24 | 0.0450 (15) | 0.0423 (15) | 0.0495 (16) | −0.0041 (12) | −0.0137 (12) | −0.0079 (12) |
N1 | 0.0771 (17) | 0.0380 (13) | 0.0549 (15) | −0.0004 (12) | 0.0055 (13) | 0.0008 (11) |
N2 | 0.0631 (15) | 0.0401 (12) | 0.0489 (14) | −0.0014 (11) | −0.0016 (11) | 0.0062 (10) |
N3 | 0.0658 (15) | 0.0376 (12) | 0.0462 (13) | −0.0034 (11) | 0.0018 (11) | −0.0006 (10) |
N4 | 0.0659 (15) | 0.0383 (12) | 0.0426 (13) | −0.0011 (11) | 0.0068 (11) | −0.0053 (10) |
N5 | 0.0497 (13) | 0.0386 (12) | 0.0437 (12) | −0.0070 (10) | 0.0033 (10) | 0.0005 (9) |
N6 | 0.0475 (13) | 0.0423 (12) | 0.0416 (12) | −0.0017 (10) | −0.0039 (10) | −0.0011 (9) |
N7 | 0.0522 (14) | 0.0465 (13) | 0.0472 (13) | −0.0066 (11) | −0.0075 (11) | −0.0058 (10) |
N8 | 0.0506 (13) | 0.0445 (13) | 0.0457 (13) | −0.0013 (11) | −0.0071 (10) | −0.0081 (10) |
O1 | 0.0924 (17) | 0.0491 (12) | 0.0631 (14) | −0.0054 (12) | −0.0015 (12) | 0.0194 (11) |
O2 | 0.0817 (16) | 0.0611 (14) | 0.0847 (17) | 0.0213 (13) | −0.0118 (13) | −0.0255 (12) |
S1 | 0.0707 (5) | 0.0423 (4) | 0.0567 (5) | 0.0075 (4) | 0.0171 (4) | 0.0115 (3) |
S2 | 0.0659 (5) | 0.0394 (4) | 0.0505 (4) | −0.0105 (3) | 0.0167 (3) | −0.0101 (3) |
Cl1 | 0.0678 (5) | 0.0616 (5) | 0.0731 (5) | −0.0130 (4) | −0.0198 (4) | 0.0060 (4) |
Cl2 | 0.0999 (6) | 0.0578 (5) | 0.0384 (4) | −0.0038 (4) | 0.0125 (4) | 0.0034 (3) |
Co | 0.0555 (2) | 0.03447 (19) | 0.03606 (19) | −0.00296 (16) | 0.00080 (15) | 0.00095 (14) |
Geometric parameters (Å, º) top
C1—N2 | 1.309 (3) | C15—C16 | 1.380 (5) |
C1—N1 | 1.313 (3) | C15—H16 | 0.9300 |
C1—S1 | 1.719 (3) | C16—C17 | 1.376 (4) |
C2—N3 | 1.312 (3) | C16—H17 | 0.9300 |
C2—N4 | 1.315 (3) | C17—C24 | 1.398 (4) |
C2—S2 | 1.717 (3) | C17—C18 | 1.492 (4) |
C3—N5 | 1.350 (3) | C18—O2 | 1.210 (3) |
C3—C4 | 1.373 (4) | C18—C19 | 1.478 (4) |
C3—H9 | 0.9300 | C19—C20 | 1.374 (4) |
C4—C5 | 1.381 (4) | C19—C23 | 1.404 (4) |
C4—H10 | 0.9300 | C20—C21 | 1.384 (4) |
C5—C6 | 1.376 (4) | C20—H18 | 0.9300 |
C5—H11 | 0.9300 | C21—C22 | 1.389 (4) |
C6—C13 | 1.394 (3) | C21—H19 | 0.9300 |
C6—C7 | 1.489 (4) | C22—N8 | 1.346 (4) |
C7—O1 | 1.209 (3) | C22—H20 | 0.9300 |
C7—C8 | 1.492 (4) | C23—N8 | 1.325 (3) |
C8—C9 | 1.379 (4) | C23—C24 | 1.474 (4) |
C8—C12 | 1.390 (4) | C24—N7 | 1.329 (3) |
C9—C10 | 1.379 (4) | N1—H1 | 0.8600 |
C9—H12 | 0.9300 | N1—H2 | 0.8600 |
C10—C11 | 1.383 (4) | N2—H3 | 0.8600 |
C10—H13 | 0.9300 | N2—H4 | 0.8600 |
C11—N6 | 1.350 (3) | N3—H5 | 0.8600 |
C11—H14 | 0.9300 | N3—H6 | 0.8600 |
C12—N6 | 1.332 (3) | N4—H7 | 0.8600 |
C12—C13 | 1.483 (3) | N4—H8 | 0.8600 |
C13—N5 | 1.321 (3) | S1—Co | 2.3387 (9) |
C14—N7 | 1.341 (4) | S2—Co | 2.3147 (8) |
C14—C15 | 1.393 (4) | Cl1—Co | 2.2330 (10) |
C14—H15 | 0.9300 | Cl2—Co | 2.2692 (8) |
| | | |
N2—C1—N1 | 119.1 (2) | C16—C17—C24 | 119.1 (3) |
N2—C1—S1 | 121.9 (2) | C16—C17—C18 | 132.5 (3) |
N1—C1—S1 | 118.9 (2) | C24—C17—C18 | 108.4 (3) |
N3—C2—N4 | 119.0 (2) | O2—C18—C19 | 126.9 (3) |
N3—C2—S2 | 119.3 (2) | O2—C18—C17 | 127.2 (3) |
N4—C2—S2 | 121.7 (2) | C19—C18—C17 | 105.9 (2) |
N5—C3—C4 | 124.9 (3) | C20—C19—C23 | 119.5 (3) |
N5—C3—H9 | 117.6 | C20—C19—C18 | 132.2 (3) |
C4—C3—H9 | 117.6 | C23—C19—C18 | 108.3 (3) |
C3—C4—C5 | 119.5 (3) | C19—C20—C21 | 117.3 (3) |
C3—C4—H10 | 120.3 | C19—C20—H18 | 121.3 |
C5—C4—H10 | 120.3 | C21—C20—H18 | 121.3 |
C6—C5—C4 | 116.8 (3) | C20—C21—C22 | 119.0 (3) |
C6—C5—H11 | 121.6 | C20—C21—H19 | 120.5 |
C4—C5—H11 | 121.6 | C22—C21—H19 | 120.5 |
C5—C6—C13 | 119.5 (2) | N8—C22—C21 | 124.7 (3) |
C5—C6—C7 | 131.9 (2) | N8—C22—H20 | 117.6 |
C13—C6—C7 | 108.7 (2) | C21—C22—H20 | 117.6 |
O1—C7—C6 | 127.5 (3) | N8—C23—C19 | 124.3 (3) |
O1—C7—C8 | 127.1 (3) | N8—C23—C24 | 126.8 (2) |
C6—C7—C8 | 105.3 (2) | C19—C23—C24 | 108.9 (2) |
C9—C8—C12 | 119.7 (3) | N7—C24—C17 | 124.8 (3) |
C9—C8—C7 | 131.4 (3) | N7—C24—C23 | 126.7 (2) |
C12—C8—C7 | 108.9 (2) | C17—C24—C23 | 108.4 (2) |
C10—C9—C8 | 116.7 (3) | C1—N1—H1 | 120.0 |
C10—C9—H12 | 121.6 | C1—N1—H2 | 120.0 |
C8—C9—H12 | 121.6 | H1—N1—H2 | 120.0 |
C9—C10—C11 | 119.8 (3) | C1—N2—H3 | 120.0 |
C9—C10—H13 | 120.1 | C1—N2—H4 | 120.0 |
C11—C10—H13 | 120.1 | H3—N2—H4 | 120.0 |
N6—C11—C10 | 124.5 (3) | C2—N3—H5 | 120.0 |
N6—C11—H14 | 117.8 | C2—N3—H6 | 120.0 |
C10—C11—H14 | 117.8 | H5—N3—H6 | 120.0 |
N6—C12—C8 | 124.7 (2) | C2—N4—H7 | 120.0 |
N6—C12—C13 | 126.8 (2) | C2—N4—H8 | 120.0 |
C8—C12—C13 | 108.5 (2) | H7—N4—H8 | 120.0 |
N5—C13—C6 | 124.8 (2) | C13—N5—C3 | 114.6 (2) |
N5—C13—C12 | 126.6 (2) | C12—N6—C11 | 114.6 (2) |
C6—C13—C12 | 108.7 (2) | C24—N7—C14 | 115.3 (3) |
N7—C14—C15 | 123.8 (3) | C23—N8—C22 | 115.1 (2) |
N7—C14—H15 | 118.1 | C1—S1—Co | 109.43 (9) |
C15—C14—H15 | 118.1 | C2—S2—Co | 108.26 (9) |
C16—C15—C14 | 119.8 (3) | Cl1—Co—Cl2 | 111.42 (4) |
C16—C15—H16 | 120.1 | Cl1—Co—S2 | 108.24 (3) |
C14—C15—H16 | 120.1 | Cl2—Co—S2 | 113.81 (3) |
C17—C16—C15 | 117.1 (3) | Cl1—Co—S1 | 112.26 (4) |
C17—C16—H17 | 121.4 | Cl2—Co—S1 | 112.76 (3) |
C15—C16—H17 | 121.4 | S2—Co—S1 | 97.59 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N5 | 0.86 | 2.06 | 2.894 (3) | 164 |
N1—H2···S1i | 0.86 | 2.84 | 3.606 (3) | 149 |
N2—H3···N6 | 0.86 | 2.14 | 2.993 (3) | 171 |
N2—H4···Cl2 | 0.86 | 2.49 | 3.321 (2) | 163 |
N3—H5···N7 | 0.86 | 2.10 | 2.944 (3) | 167 |
N3—H6···Cl1ii | 0.86 | 2.73 | 3.502 (2) | 150 |
N4—H7···N8 | 0.86 | 2.11 | 2.953 (3) | 169 |
N4—H8···Cl2 | 0.86 | 2.51 | 3.345 (2) | 165 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y+1, −z. |