The molecular structure of the neutral mononuclear title complex, [Mn(NCS)
2(C
12H
8N
4O)
2(H
2O)
2], is centrosymmetric; the Mn
II atom lies on an inversion center and is six-coordinate (MnN
4O
2), with an octahedral geometry comprising two
trans monodentate 2,5-di-3-pyridyl-1,3,4-oxadiazole ligands, two thiocyanate ligands and two bound water molecules. Intermolecular O—H
N hydrogen bonds between these monomeric units result in two-dimensional supramolecular layers with a parallel arrangement, which are stabilized by intralayer aromatic stacking and further extended to a three-dimensional network
via interlayer weak C—H
S interactions.
Supporting information
CCDC reference: 269846
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
Some non-H atoms missing
- R factor = 0.035
- wR factor = 0.099
- Data-to-parameter ratio = 13.0
checkCIF/PLATON results
No syntax errors found
Alert level C
ABSMU01_ALERT_1_C The ratio of given/expected absorption coefficient lies
outside the range 0.99 <> 1.01
Calculated value of mu = 0.657
Value of mu given = 0.648
CHEMW01_ALERT_1_C The ratio of given/expected molecular weight as calculated
from the _chemical_formula_sum lies outside
the range 0.99 <> 1.01
Calculated formula weight = 687.5654
Formula weight given = 655.5800
CHEMW01_ALERT_1_C The difference between the given and expected weight for
compound is greater 1 mass unit. Check that all hydrogen
atoms have been taken into account.
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - C13 .. 5.12 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn1 - N5 .. 6.44 su
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C13
Alert level G
FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C26 H20 Mn1 N10 O6 S2
Atom count from the _atom_site data: C26 H20 Mn1 N10 O4 S2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: Large difference may be due to a
symmetry error - see SYMMG tests
From the CIF: _cell_formula_units_Z 1
From the CIF: _chemical_formula_sum C26 H20 Mn N10 O6 S2
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 26.00 26.00 0.00
H 20.00 20.00 0.00
Mn 1.00 1.00 0.00
N 10.00 10.00 0.00
O 6.00 4.00 2.00
S 2.00 2.00 0.00
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
10 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
4 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
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: Apex II (Bruker, 2003); cell refinement: Apex II; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Diamond (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXTL (Bruker, 2001).
Diaquabis(2,5-di-3-pyridyl-1,3,4-oxadiazole)dithiocyanatomanganese(II)
top
Crystal data top
[Mn(NCS)2(C12H8N4O2)2(H2O)2] | Z = 1 |
Mr = 655.58 | F(000) = 335 |
Triclinic, P1 | Dx = 1.494 Mg m−3 |
a = 8.1951 (19) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.762 (2) Å | Cell parameters from 1513 reflections |
c = 10.619 (3) Å | θ = 2.6–26.7° |
α = 82.472 (3)° | µ = 0.65 mm−1 |
β = 77.181 (3)° | T = 293 K |
γ = 79.873 (3)° | Block, colorless |
V = 728.5 (3) Å3 | 0.40 × 0.24 × 0.11 mm |
Data collection top
Bruker APEX-II CCD area-detector diffractometer | 2540 independent reflections |
Radiation source: fine-focus sealed tube | 2005 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.772, Tmax = 0.931 | k = −10→9 |
4203 measured reflections | l = −10→12 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0576P)2 + 0.1207P] where P = (Fo2 + 2Fc2)/3 |
2540 reflections | (Δ/σ)max < 0.001 |
196 parameters | Δρmax = 0.43 e Å−3 |
3 restraints | Δρmin = −0.36 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 | |
Mn1 | 0.5000 | 0.0000 | 0.5000 | 0.04117 (17) | |
S1 | 0.83885 (8) | 0.33655 (9) | 0.17907 (8) | 0.0771 (3) | |
O1 | 0.42139 (18) | 0.22308 (17) | −0.00282 (13) | 0.0417 (4) | |
O2 | 0.67530 (19) | −0.21189 (18) | 0.43958 (13) | 0.0518 (4) | |
H2A | 0.6905 | −0.2269 | 0.3600 | 0.062* | |
H2B | 0.6658 | −0.2942 | 0.4911 | 0.062* | |
N1 | 0.6863 (3) | 0.5355 (2) | −0.3704 (2) | 0.0612 (6) | |
N2 | 0.3127 (2) | 0.2409 (2) | −0.17602 (16) | 0.0467 (5) | |
N3 | 0.2210 (2) | 0.1467 (2) | −0.07675 (16) | 0.0459 (5) | |
N4 | 0.3229 (2) | −0.0161 (2) | 0.35803 (15) | 0.0408 (4) | |
N5 | 0.6484 (2) | 0.1369 (2) | 0.35059 (18) | 0.0559 (5) | |
C1 | 0.1073 (3) | −0.0160 (3) | 0.1882 (2) | 0.0454 (5) | |
H1 | 0.0353 | −0.0161 | 0.1317 | 0.054* | |
C2 | 0.0761 (3) | −0.0896 (3) | 0.3123 (2) | 0.0482 (6) | |
H2 | −0.0178 | −0.1404 | 0.3412 | 0.058* | |
C3 | 0.1860 (3) | −0.0871 (3) | 0.3930 (2) | 0.0459 (5) | |
H3 | 0.1636 | −0.1375 | 0.4762 | 0.055* | |
C4 | 0.3517 (3) | 0.0557 (2) | 0.23804 (19) | 0.0401 (5) | |
H4 | 0.4457 | 0.1068 | 0.2120 | 0.048* | |
C5 | 0.2485 (2) | 0.0579 (2) | 0.15041 (18) | 0.0370 (5) | |
C6 | 0.2894 (3) | 0.1401 (2) | 0.02165 (19) | 0.0380 (5) | |
C7 | 0.4270 (3) | 0.2823 (2) | −0.12854 (19) | 0.0400 (5) | |
C8 | 0.5603 (3) | 0.3748 (2) | −0.1877 (2) | 0.0440 (5) | |
C9 | 0.6869 (3) | 0.3857 (3) | −0.1240 (2) | 0.0601 (7) | |
H9 | 0.6865 | 0.3363 | −0.0409 | 0.072* | |
C10 | 0.8127 (4) | 0.4698 (3) | −0.1843 (3) | 0.0749 (8) | |
H10 | 0.8999 | 0.4780 | −0.1436 | 0.090* | |
C11 | 0.8071 (4) | 0.5422 (3) | −0.3068 (3) | 0.0712 (8) | |
H11 | 0.8930 | 0.5992 | −0.3475 | 0.085* | |
C12 | 0.5649 (3) | 0.4527 (3) | −0.3110 (2) | 0.0522 (6) | |
H12 | 0.4792 | 0.4465 | −0.3538 | 0.063* | |
C13 | 0.7278 (3) | 0.2203 (3) | 0.2788 (2) | 0.0436 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.0430 (3) | 0.0531 (3) | 0.0307 (3) | −0.0230 (2) | −0.01120 (19) | 0.01186 (19) |
S1 | 0.0502 (4) | 0.0729 (5) | 0.0977 (6) | −0.0277 (4) | −0.0055 (4) | 0.0385 (4) |
O1 | 0.0464 (9) | 0.0486 (9) | 0.0330 (7) | −0.0165 (7) | −0.0122 (6) | 0.0052 (6) |
O2 | 0.0680 (11) | 0.0561 (10) | 0.0333 (8) | −0.0192 (8) | −0.0134 (7) | 0.0070 (7) |
N1 | 0.0692 (14) | 0.0557 (13) | 0.0554 (12) | −0.0234 (11) | −0.0072 (11) | 0.0163 (10) |
N2 | 0.0542 (11) | 0.0539 (12) | 0.0347 (9) | −0.0180 (9) | −0.0132 (8) | 0.0064 (8) |
N3 | 0.0515 (11) | 0.0574 (12) | 0.0324 (9) | −0.0198 (9) | −0.0130 (8) | 0.0066 (8) |
N4 | 0.0400 (10) | 0.0511 (11) | 0.0328 (9) | −0.0159 (8) | −0.0092 (7) | 0.0056 (8) |
N5 | 0.0540 (12) | 0.0681 (14) | 0.0475 (11) | −0.0274 (11) | −0.0135 (10) | 0.0173 (10) |
C1 | 0.0425 (12) | 0.0562 (14) | 0.0406 (12) | −0.0144 (11) | −0.0142 (10) | 0.0032 (10) |
C2 | 0.0390 (12) | 0.0610 (15) | 0.0460 (13) | −0.0216 (11) | −0.0083 (10) | 0.0075 (10) |
C3 | 0.0435 (12) | 0.0572 (14) | 0.0360 (11) | −0.0141 (11) | −0.0074 (10) | 0.0069 (10) |
C4 | 0.0381 (11) | 0.0486 (13) | 0.0352 (11) | −0.0148 (10) | −0.0089 (9) | 0.0041 (9) |
C5 | 0.0374 (11) | 0.0433 (12) | 0.0307 (10) | −0.0084 (9) | −0.0084 (8) | 0.0010 (8) |
C6 | 0.0386 (11) | 0.0420 (12) | 0.0351 (11) | −0.0124 (9) | −0.0086 (9) | 0.0013 (9) |
C7 | 0.0482 (12) | 0.0390 (12) | 0.0310 (11) | −0.0058 (10) | −0.0080 (9) | 0.0027 (9) |
C8 | 0.0494 (13) | 0.0399 (12) | 0.0414 (12) | −0.0119 (10) | −0.0066 (10) | 0.0041 (9) |
C9 | 0.0678 (17) | 0.0614 (16) | 0.0556 (15) | −0.0287 (13) | −0.0178 (13) | 0.0129 (12) |
C10 | 0.0761 (19) | 0.080 (2) | 0.0782 (19) | −0.0417 (16) | −0.0283 (15) | 0.0181 (16) |
C11 | 0.0733 (19) | 0.0624 (18) | 0.0777 (19) | −0.0336 (15) | −0.0089 (15) | 0.0143 (14) |
C12 | 0.0562 (15) | 0.0490 (14) | 0.0496 (13) | −0.0158 (11) | −0.0088 (11) | 0.0084 (11) |
C13 | 0.0376 (11) | 0.0509 (14) | 0.0441 (12) | −0.0148 (11) | −0.0136 (10) | 0.0089 (10) |
Geometric parameters (Å, º) top
Mn1—N5 | 2.1431 (19) | C1—C5 | 1.382 (3) |
Mn1—N5i | 2.1431 (19) | C1—C2 | 1.380 (3) |
Mn1—O2i | 2.2107 (16) | C1—H1 | 0.9300 |
Mn1—O2 | 2.2107 (16) | C2—C3 | 1.378 (3) |
Mn1—N4 | 2.3449 (17) | C2—H2 | 0.9300 |
Mn1—N4i | 2.3449 (17) | C3—H3 | 0.9300 |
S1—C13 | 1.613 (2) | C4—C5 | 1.386 (3) |
O1—C7 | 1.361 (2) | C4—H4 | 0.9300 |
O1—C6 | 1.366 (2) | C5—C6 | 1.458 (3) |
O2—H2A | 0.8501 | C7—C8 | 1.455 (3) |
O2—H2B | 0.8501 | C8—C9 | 1.381 (3) |
N1—C12 | 1.330 (3) | C8—C12 | 1.390 (3) |
N1—C11 | 1.330 (4) | C9—C10 | 1.366 (3) |
N2—C7 | 1.281 (3) | C9—H9 | 0.9300 |
N2—N3 | 1.413 (2) | C10—C11 | 1.377 (4) |
N3—C6 | 1.282 (3) | C10—H10 | 0.9300 |
N4—C3 | 1.335 (3) | C11—H11 | 0.9300 |
N4—C4 | 1.336 (2) | C12—H12 | 0.9300 |
N5—C13 | 1.157 (3) | | |
| | | |
N5—Mn1—N5i | 180.00 (10) | N4—C3—C2 | 123.6 (2) |
N5—Mn1—O2i | 90.61 (7) | N4—C3—H3 | 118.2 |
N5i—Mn1—O2i | 89.39 (7) | C2—C3—H3 | 118.2 |
N5—Mn1—O2 | 89.39 (7) | N4—C4—C5 | 123.27 (19) |
N5i—Mn1—O2 | 90.61 (7) | N4—C4—H4 | 118.4 |
O2i—Mn1—O2 | 180.0 | C5—C4—H4 | 118.4 |
N5—Mn1—N4 | 89.80 (7) | C1—C5—C4 | 119.04 (19) |
N5i—Mn1—N4 | 90.20 (7) | C1—C5—C6 | 121.52 (19) |
O2i—Mn1—N4 | 86.54 (6) | C4—C5—C6 | 119.43 (19) |
O2—Mn1—N4 | 93.46 (6) | N3—C6—O1 | 112.63 (17) |
N5—Mn1—N4i | 90.20 (7) | N3—C6—C5 | 129.9 (2) |
N5i—Mn1—N4i | 89.80 (7) | O1—C6—C5 | 117.49 (17) |
O2i—Mn1—N4i | 93.46 (6) | N2—C7—O1 | 112.03 (18) |
O2—Mn1—N4i | 86.54 (6) | N2—C7—C8 | 130.84 (19) |
N4—Mn1—N4i | 180.0 | O1—C7—C8 | 117.09 (19) |
C7—O1—C6 | 102.77 (15) | C9—C8—C12 | 118.2 (2) |
Mn1—O2—H2A | 115.9 | C9—C8—C7 | 121.0 (2) |
Mn1—O2—H2B | 116.3 | C12—C8—C7 | 120.8 (2) |
H2A—O2—H2B | 113.7 | C10—C9—C8 | 119.3 (2) |
C12—N1—C11 | 117.1 (2) | C10—C9—H9 | 120.4 |
C7—N2—N3 | 106.88 (16) | C8—C9—H9 | 120.4 |
C6—N3—N2 | 105.70 (17) | C9—C10—C11 | 118.3 (3) |
C3—N4—C4 | 116.95 (18) | C9—C10—H10 | 120.9 |
C3—N4—Mn1 | 123.21 (13) | C11—C10—H10 | 120.9 |
C4—N4—Mn1 | 119.73 (13) | N1—C11—C10 | 124.0 (2) |
C13—N5—Mn1 | 173.4 (2) | N1—C11—H11 | 118.0 |
C5—C1—C2 | 117.98 (19) | C10—C11—H11 | 118.0 |
C5—C1—H1 | 121.0 | N1—C12—C8 | 123.1 (2) |
C2—C1—H1 | 121.0 | N1—C12—H12 | 118.5 |
C1—C2—C3 | 119.2 (2) | C8—C12—H12 | 118.5 |
C1—C2—H2 | 120.4 | N5—C13—S1 | 179.8 (2) |
C3—C2—H2 | 120.4 | | |
| | | |
C7—N2—N3—C6 | −0.1 (2) | C7—O1—C6—C5 | 179.30 (18) |
N5—Mn1—N4—C3 | −177.16 (18) | C1—C5—C6—N3 | −7.4 (4) |
N5i—Mn1—N4—C3 | 2.84 (18) | C4—C5—C6—N3 | 173.7 (2) |
O2i—Mn1—N4—C3 | −86.53 (17) | C1—C5—C6—O1 | 173.49 (18) |
O2—Mn1—N4—C3 | 93.47 (17) | C4—C5—C6—O1 | −5.4 (3) |
N5i—Mn1—N4—C4 | 178.83 (16) | N3—N2—C7—O1 | 0.1 (2) |
O2i—Mn1—N4—C4 | 89.46 (16) | N3—N2—C7—C8 | 177.7 (2) |
O2—Mn1—N4—C4 | −90.54 (16) | C6—O1—C7—N2 | −0.1 (2) |
C5—C1—C2—C3 | −0.1 (3) | C6—O1—C7—C8 | −178.06 (17) |
C4—N4—C3—C2 | 0.2 (3) | N2—C7—C8—C9 | −169.9 (2) |
Mn1—N4—C3—C2 | 176.29 (17) | O1—C7—C8—C9 | 7.6 (3) |
C1—C2—C3—N4 | 0.2 (4) | N2—C7—C8—C12 | 9.1 (4) |
C3—N4—C4—C5 | −0.7 (3) | O1—C7—C8—C12 | −173.42 (19) |
Mn1—N4—C4—C5 | −176.90 (15) | C12—C8—C9—C10 | −1.0 (4) |
C2—C1—C5—C4 | −0.3 (3) | C7—C8—C9—C10 | 178.0 (2) |
C2—C1—C5—C6 | −179.2 (2) | C8—C9—C10—C11 | 0.6 (4) |
N4—C4—C5—C1 | 0.7 (3) | C12—N1—C11—C10 | −0.4 (4) |
N4—C4—C5—C6 | 179.64 (19) | C9—C10—C11—N1 | 0.1 (5) |
N2—N3—C6—O1 | 0.0 (2) | C11—N1—C12—C8 | 0.0 (4) |
N2—N3—C6—C5 | −179.1 (2) | C9—C8—C12—N1 | 0.7 (4) |
C7—O1—C6—N3 | 0.0 (2) | C7—C8—C12—N1 | −178.3 (2) |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···N2ii | 0.85 | 1.98 | 2.822 (3) | 170 |
O2—H2B···N1iii | 0.85 | 1.96 | 2.796 (3) | 165 |
C10—H10···S1iv | 0.93 | 2.84 | 3.582 (4) | 138 |
Symmetry codes: (ii) −x+1, −y, −z; (iii) x, y−1, z+1; (iv) −x+2, −y+1, −z. |