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The title compound, [Mn(NCS)
2(C
18H
12N
6)
2(CH
4O)
2], contains a centrosymmetric octahedral Mn
II centre and three pairs of
trans-coordinating ligands. It is the first example of a mononuclear metal complex with the 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) ligand. Intermolecular
-
stacking of the planar tpt ligands, as well as hydrogen bonds between pyridyl N and methanol H atoms, results in the formation of a three-dimensional network.
Supporting information
CCDC reference: 197325
A solution of tpt (quantity?) in dichloromethane (20 ml) was added to a solution
of an excess of potassium thiocyanate in methanol (10 ml). The mixture was
stirred for 10 min and treated with a solution of Mn(ClO4)2·6H2O
(0.1 mmol) in methanol (10 ml). After stirring for 2 h at ambient temperature,
the resulting solution was set aside to crystallize, producing analytically
pure (I). Elemental analysis, found: C 56.1, H 3.4, N 21.9%; CHN requires C
55.9, H 3.75, N 22.8%. A crystal of (I) suitable for single-crystal X-ray
diffraction was selected directly from the analytical sample.
The H atom of the methanol was fixed at the position found from the difference
Fourier map Is this added text OK?, with Uiso(H) = 0.07 Å2. All
other H atoms were introduced at calculated positions as riding atoms, with
C—H distances of 0.93 (CH) and 0.96 Å (CH3), and Uiso(H) =
1.2Ueq(C) for CH and 1.5Ueq(C) for CH3.
Data collection: MACH3 (Enraf-Nonius, 1996); cell refinement: CELDIM (Enraf-Nonius, 1996); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); 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).
trans-Bis(isothiocyanato-
κN)bis(methanol-
κO)bis[2,4,6-tri(4-pyridyl)- 1,3,5-triazine-
κN4]manganese(II)
top
Crystal data top
[Mn(NCS)2(C18H12N6)2(CH4O)2] | Z = 1 |
Mr = 859.86 | F(000) = 443 |
Triclinic, P1 | Dx = 1.406 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.871 (2) Å | Cell parameters from 25 reflections |
b = 8.875 (2) Å | θ = 23–29° |
c = 14.161 (4) Å | µ = 0.48 mm−1 |
α = 106.54 (2)° | T = 293 K |
β = 100.60 (2)° | Needle, yellow |
γ = 100.93 (3)° | 0.32 × 0.17 × 0.15 mm |
V = 1015.3 (4) Å3 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.015 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.4° |
Graphite monochromator | h = −10→10 |
θ/2θ scans | k = −10→10 |
3732 measured reflections | l = 0→16 |
3571 independent reflections | 3 standard reflections every 120 min |
2796 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0374P)2 + 1.8244P] where P = (Fo2 + 2Fc2)/3 |
3571 reflections | (Δ/σ)max = 0.028 |
268 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
Crystal data top
[Mn(NCS)2(C18H12N6)2(CH4O)2] | γ = 100.93 (3)° |
Mr = 859.86 | V = 1015.3 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.871 (2) Å | Mo Kα radiation |
b = 8.875 (2) Å | µ = 0.48 mm−1 |
c = 14.161 (4) Å | T = 293 K |
α = 106.54 (2)° | 0.32 × 0.17 × 0.15 mm |
β = 100.60 (2)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.015 |
3732 measured reflections | 3 standard reflections every 120 min |
3571 independent reflections | intensity decay: none |
2796 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.33 e Å−3 |
3571 reflections | Δρmin = −0.40 e Å−3 |
268 parameters | |
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 | |
Mn | 0.0000 | 0.5000 | 0.5000 | 0.0432 (2) | |
S1 | 0.47224 (15) | 0.94996 (17) | 0.64967 (12) | 0.1000 (5) | |
O1 | 0.1548 (3) | 0.3334 (3) | 0.50854 (18) | 0.0533 (6) | |
N1 | 0.0756 (3) | 0.5107 (3) | 0.3506 (2) | 0.0449 (7) | |
N2 | −0.0462 (4) | −0.0343 (4) | −0.3631 (2) | 0.0521 (8) | |
N3 | 0.7438 (4) | 0.9846 (4) | −0.0133 (3) | 0.0675 (10) | |
N4 | 0.1260 (3) | 0.3744 (3) | −0.00988 (19) | 0.0387 (6) | |
N5 | 0.2930 (3) | 0.4871 (3) | −0.0984 (2) | 0.0394 (6) | |
N6 | 0.3276 (3) | 0.6188 (3) | 0.0776 (2) | 0.0393 (6) | |
N7 | 0.1939 (4) | 0.7064 (4) | 0.5872 (2) | 0.0578 (9) | |
C1 | 0.2076 (4) | 0.4987 (4) | 0.0733 (2) | 0.0363 (7) | |
C2 | 0.1639 (4) | 0.5025 (4) | 0.1700 (2) | 0.0370 (7) | |
C3 | 0.2435 (4) | 0.6251 (4) | 0.2606 (2) | 0.0469 (9) | |
H3 | 0.3276 | 0.7073 | 0.2624 | 0.056* | |
C4 | 0.1969 (4) | 0.6243 (4) | 0.3480 (3) | 0.0502 (9) | |
H4 | 0.2526 | 0.7069 | 0.4085 | 0.060* | |
C5 | 0.0011 (4) | 0.3934 (4) | 0.2626 (3) | 0.0478 (9) | |
H5 | −0.0825 | 0.3125 | 0.2628 | 0.057* | |
C6 | 0.0389 (4) | 0.3835 (4) | 0.1717 (2) | 0.0447 (8) | |
H6 | −0.0180 | 0.2987 | 0.1125 | 0.054* | |
C7 | 0.1752 (4) | 0.3728 (4) | −0.0934 (2) | 0.0367 (7) | |
C8 | 0.0955 (4) | 0.2325 (4) | −0.1874 (2) | 0.0372 (7) | |
C9 | −0.0346 (4) | 0.1154 (4) | −0.1909 (3) | 0.0475 (9) | |
H9 | −0.0767 | 0.1241 | −0.1347 | 0.057* | |
C10 | −0.1004 (5) | −0.0139 (5) | −0.2793 (3) | 0.0555 (10) | |
H10 | −0.1879 | −0.0922 | −0.2811 | 0.067* | |
C11 | 0.0791 (5) | 0.0787 (4) | −0.3582 (3) | 0.0535 (10) | |
H11 | 0.1203 | 0.0662 | −0.4149 | 0.064* | |
C12 | 0.1514 (4) | 0.2139 (4) | −0.2733 (3) | 0.0497 (9) | |
H12 | 0.2371 | 0.2919 | −0.2741 | 0.060* | |
C13 | 0.3636 (4) | 0.6082 (4) | −0.0108 (2) | 0.0360 (7) | |
C14 | 0.4958 (4) | 0.7385 (4) | −0.0122 (3) | 0.0406 (8) | |
C15 | 0.5396 (5) | 0.7360 (5) | −0.1013 (3) | 0.0547 (10) | |
H15 | 0.4874 | 0.6531 | −0.1623 | 0.066* | |
C16 | 0.6650 (5) | 0.8621 (6) | −0.0966 (4) | 0.0684 (12) | |
H16 | 0.6950 | 0.8596 | −0.1565 | 0.082* | |
C17 | 0.6980 (5) | 0.9843 (5) | 0.0704 (4) | 0.0600 (11) | |
H17 | 0.7511 | 1.0698 | 0.1300 | 0.072* | |
C18 | 0.5770 (4) | 0.8658 (4) | 0.0755 (3) | 0.0465 (8) | |
H18 | 0.5508 | 0.8718 | 0.1369 | 0.056* | |
C19 | 0.3104 (4) | 0.8081 (4) | 0.6145 (3) | 0.0489 (9) | |
C20 | 0.3237 (5) | 0.3697 (6) | 0.5338 (4) | 0.0860 (15) | |
H20A | 0.3565 | 0.2719 | 0.5312 | 0.129* | |
H20B | 0.3655 | 0.4472 | 0.6012 | 0.129* | |
H20C | 0.3627 | 0.4144 | 0.4861 | 0.129* | |
HO1 | 0.1106 | 0.2263 | 0.4600 | 0.070* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn | 0.0467 (4) | 0.0380 (4) | 0.0323 (4) | −0.0092 (3) | 0.0170 (3) | 0.0012 (3) |
S1 | 0.0584 (7) | 0.0829 (9) | 0.1141 (11) | −0.0299 (7) | 0.0238 (7) | −0.0047 (8) |
O1 | 0.0539 (15) | 0.0430 (14) | 0.0493 (14) | −0.0024 (11) | 0.0150 (12) | 0.0031 (11) |
N1 | 0.0499 (17) | 0.0417 (15) | 0.0356 (15) | −0.0031 (13) | 0.0169 (13) | 0.0070 (12) |
N2 | 0.062 (2) | 0.0448 (17) | 0.0392 (16) | 0.0033 (15) | 0.0156 (14) | 0.0031 (13) |
N3 | 0.056 (2) | 0.056 (2) | 0.100 (3) | 0.0045 (17) | 0.031 (2) | 0.038 (2) |
N4 | 0.0396 (15) | 0.0407 (15) | 0.0323 (14) | 0.0026 (12) | 0.0143 (12) | 0.0086 (12) |
N5 | 0.0392 (15) | 0.0401 (15) | 0.0392 (15) | 0.0049 (12) | 0.0163 (12) | 0.0132 (12) |
N6 | 0.0403 (15) | 0.0364 (14) | 0.0381 (15) | 0.0009 (12) | 0.0159 (12) | 0.0100 (12) |
N7 | 0.061 (2) | 0.0466 (18) | 0.0457 (18) | −0.0127 (16) | 0.0201 (15) | −0.0017 (14) |
C1 | 0.0357 (17) | 0.0384 (17) | 0.0350 (17) | 0.0079 (14) | 0.0130 (13) | 0.0109 (14) |
C2 | 0.0389 (17) | 0.0358 (17) | 0.0355 (17) | 0.0048 (14) | 0.0166 (14) | 0.0092 (13) |
C3 | 0.047 (2) | 0.0432 (19) | 0.0399 (19) | −0.0082 (15) | 0.0160 (15) | 0.0076 (15) |
C4 | 0.056 (2) | 0.047 (2) | 0.0348 (18) | −0.0079 (17) | 0.0161 (16) | 0.0051 (15) |
C5 | 0.050 (2) | 0.0443 (19) | 0.0388 (18) | −0.0087 (16) | 0.0218 (16) | 0.0056 (15) |
C6 | 0.049 (2) | 0.0403 (18) | 0.0334 (17) | −0.0049 (15) | 0.0136 (15) | 0.0040 (14) |
C7 | 0.0347 (16) | 0.0369 (17) | 0.0377 (17) | 0.0066 (13) | 0.0140 (14) | 0.0096 (14) |
C8 | 0.0407 (18) | 0.0374 (17) | 0.0310 (16) | 0.0057 (14) | 0.0094 (14) | 0.0099 (13) |
C9 | 0.047 (2) | 0.048 (2) | 0.0419 (19) | 0.0020 (16) | 0.0203 (16) | 0.0064 (16) |
C10 | 0.050 (2) | 0.051 (2) | 0.051 (2) | −0.0069 (17) | 0.0184 (17) | 0.0037 (17) |
C11 | 0.065 (2) | 0.054 (2) | 0.0323 (18) | −0.0005 (19) | 0.0197 (17) | 0.0068 (16) |
C12 | 0.055 (2) | 0.047 (2) | 0.0406 (19) | −0.0025 (17) | 0.0181 (16) | 0.0112 (16) |
C13 | 0.0351 (16) | 0.0377 (17) | 0.0367 (17) | 0.0070 (13) | 0.0134 (13) | 0.0136 (14) |
C14 | 0.0388 (18) | 0.0378 (17) | 0.051 (2) | 0.0079 (14) | 0.0188 (15) | 0.0195 (15) |
C15 | 0.060 (2) | 0.050 (2) | 0.059 (2) | 0.0075 (18) | 0.0312 (19) | 0.0209 (18) |
C16 | 0.074 (3) | 0.069 (3) | 0.084 (3) | 0.016 (2) | 0.049 (3) | 0.041 (3) |
C17 | 0.048 (2) | 0.043 (2) | 0.081 (3) | −0.0017 (17) | 0.009 (2) | 0.023 (2) |
C18 | 0.0418 (19) | 0.0435 (19) | 0.053 (2) | 0.0026 (15) | 0.0125 (16) | 0.0187 (16) |
C19 | 0.051 (2) | 0.048 (2) | 0.0358 (18) | −0.0002 (18) | 0.0157 (16) | 0.0008 (15) |
C20 | 0.057 (3) | 0.072 (3) | 0.109 (4) | −0.002 (2) | 0.018 (3) | 0.013 (3) |
Geometric parameters (Å, º) top
Mn—N7 | 2.139 (3) | C3—H3 | 0.9300 |
Mn—N7i | 2.139 (3) | C4—H4 | 0.9300 |
Mn—O1i | 2.213 (3) | C5—C6 | 1.372 (4) |
Mn—O1 | 2.213 (3) | C5—H5 | 0.9300 |
Mn—N1i | 2.355 (3) | C6—H6 | 0.9300 |
Mn—N1 | 2.355 (3) | C7—C8 | 1.482 (4) |
S1—C19 | 1.609 (4) | C8—C12 | 1.375 (5) |
O1—C20 | 1.425 (5) | C8—C9 | 1.382 (4) |
O1—HO1 | 0.9578 | C9—C10 | 1.373 (5) |
N1—C5 | 1.331 (4) | C9—H9 | 0.9300 |
N1—C4 | 1.342 (4) | C10—H10 | 0.9300 |
N2—C11 | 1.325 (5) | C11—C12 | 1.378 (5) |
N2—C10 | 1.338 (5) | C11—H11 | 0.9300 |
N3—C16 | 1.320 (6) | C12—H12 | 0.9300 |
N3—C17 | 1.321 (5) | C13—C14 | 1.490 (4) |
N4—C1 | 1.331 (4) | C14—C18 | 1.379 (5) |
N4—C7 | 1.332 (4) | C14—C15 | 1.383 (5) |
N5—C13 | 1.337 (4) | C15—C16 | 1.398 (5) |
N5—C7 | 1.339 (4) | C15—H15 | 0.9300 |
N6—C13 | 1.330 (4) | C16—H16 | 0.9300 |
N6—C1 | 1.335 (4) | C17—C18 | 1.381 (5) |
N7—C19 | 1.155 (4) | C17—H17 | 0.9300 |
C1—C2 | 1.484 (4) | C18—H18 | 0.9300 |
C2—C3 | 1.381 (4) | C20—H20A | 0.9600 |
C2—C6 | 1.388 (4) | C20—H20B | 0.9600 |
C3—C4 | 1.377 (5) | C20—H20C | 0.9600 |
| | | |
N7—Mn—N7i | 180.0 | C2—C6—H6 | 120.7 |
N7—Mn—O1i | 88.97 (12) | N4—C7—N5 | 124.9 (3) |
N7i—Mn—O1i | 91.03 (12) | N4—C7—C8 | 117.5 (3) |
N7—Mn—O1 | 91.03 (12) | N5—C7—C8 | 117.6 (3) |
N7i—Mn—O1 | 88.97 (12) | C12—C8—C9 | 118.1 (3) |
O1i—Mn—O1 | 180.000 (1) | C12—C8—C7 | 120.6 (3) |
N7—Mn—N1i | 90.43 (11) | C9—C8—C7 | 121.3 (3) |
N7i—Mn—N1i | 89.57 (11) | C10—C9—C8 | 118.5 (3) |
O1i—Mn—N1i | 86.55 (10) | C10—C9—H9 | 120.8 |
O1—Mn—N1i | 93.45 (10) | C8—C9—H9 | 120.8 |
N7—Mn—N1 | 89.57 (11) | N2—C10—C9 | 124.0 (3) |
N7i—Mn—N1 | 90.43 (11) | N2—C10—H10 | 118.0 |
O1i—Mn—N1 | 93.45 (10) | C9—C10—H10 | 118.0 |
O1—Mn—N1 | 86.55 (10) | N2—C11—C12 | 123.4 (3) |
N1i—Mn—N1 | 180.000 (1) | N2—C11—H11 | 118.3 |
C20—O1—Mn | 128.8 (3) | C12—C11—H11 | 118.3 |
C20—O1—HO1 | 110.2 | C11—C12—C8 | 119.3 (3) |
Mn—O1—HO1 | 113.6 | C11—C12—H12 | 120.3 |
C5—N1—C4 | 116.1 (3) | C8—C12—H12 | 120.3 |
C5—N1—Mn | 119.5 (2) | N6—C13—N5 | 125.1 (3) |
C4—N1—Mn | 124.3 (2) | N6—C13—C14 | 117.8 (3) |
C11—N2—C10 | 116.6 (3) | N5—C13—C14 | 117.1 (3) |
C16—N3—C17 | 116.0 (3) | C18—C14—C15 | 118.2 (3) |
C1—N4—C7 | 114.8 (3) | C18—C14—C13 | 120.7 (3) |
C13—N5—C7 | 115.0 (3) | C15—C14—C13 | 121.1 (3) |
C13—N6—C1 | 114.6 (3) | C14—C15—C16 | 117.9 (4) |
C19—N7—Mn | 164.5 (3) | C14—C15—H15 | 121.1 |
N4—C1—N6 | 125.6 (3) | C16—C15—H15 | 121.1 |
N4—C1—C2 | 117.3 (3) | N3—C16—C15 | 124.6 (4) |
N6—C1—C2 | 117.0 (3) | N3—C16—H16 | 117.7 |
C3—C2—C6 | 117.8 (3) | C15—C16—H16 | 117.7 |
C3—C2—C1 | 121.6 (3) | N3—C17—C18 | 124.7 (4) |
C6—C2—C1 | 120.6 (3) | N3—C17—H17 | 117.7 |
C2—C3—C4 | 119.3 (3) | C18—C17—H17 | 117.7 |
C2—C3—H3 | 120.3 | C14—C18—C17 | 118.6 (4) |
C4—C3—H3 | 120.3 | C14—C18—H18 | 120.7 |
N1—C4—C3 | 123.5 (3) | C17—C18—H18 | 120.7 |
N1—C4—H4 | 118.2 | N7—C19—S1 | 178.5 (3) |
C3—C4—H4 | 118.3 | O1—C20—H20A | 109.5 |
N1—C5—C6 | 124.6 (3) | O1—C20—H20B | 109.5 |
N1—C5—H5 | 117.7 | H20A—C20—H20B | 109.5 |
C6—C5—H5 | 117.7 | O1—C20—H20C | 109.5 |
C5—C6—C2 | 118.6 (3) | H20A—C20—H20C | 109.5 |
C5—C6—H6 | 120.7 | H20B—C20—H20C | 109.5 |
Symmetry code: (i) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—HO1···N2ii | 0.96 | 1.77 | 2.721 (4) | 173 |
Symmetry code: (ii) −x, −y, −z. |
Experimental details
Crystal data |
Chemical formula | [Mn(NCS)2(C18H12N6)2(CH4O)2] |
Mr | 859.86 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.871 (2), 8.875 (2), 14.161 (4) |
α, β, γ (°) | 106.54 (2), 100.60 (2), 100.93 (3) |
V (Å3) | 1015.3 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.32 × 0.17 × 0.15 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3732, 3571, 2796 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.132, 1.01 |
No. of reflections | 3571 |
No. of parameters | 268 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.40 |
Selected geometric parameters (Å, º) topMn—N7 | 2.139 (3) | S1—C19 | 1.609 (4) |
Mn—O1 | 2.213 (3) | O1—C20 | 1.425 (5) |
Mn—N1 | 2.355 (3) | N7—C19 | 1.155 (4) |
| | | |
N7—Mn—O1 | 91.03 (12) | C20—O1—Mn | 128.8 (3) |
N7—Mn—N1 | 89.57 (11) | C19—N7—Mn | 164.5 (3) |
O1—Mn—N1 | 86.55 (10) | N7—C19—S1 | 178.5 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—HO1···N2i | 0.96 | 1.77 | 2.721 (4) | 173 |
Symmetry code: (i) −x, −y, −z. |
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The simple trigonal building block 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) has been utilized as a bridging unit for coordination polymers with diverse structures (Batten et al., 1995a,b; Abrahams, Batten, Hamit et al., 1996; Abrahams, Batten, Grannas et al., 1996; Abrahams et al., 1999), and as a template in the synthesis of porphyrin (Anderson et al., 1995) or phthalocyanine (Hanak et al., 1999) oligomers. In the course of our efforts to explore new supramolecular architectures using tpt and NCS- ligands, the title compound, (I), was unexpectedly isolated and it has been characterized by single-crystal X-ray analysis. To our knowlege, it is the first example of a mononuclear tpt metal complex. \sch
The molecular unit of (I) comprises two tpt ligands, two NCS- anions and two methanol ligands. As shown in Fig. 1, the molecule possesses crystallographic inversion symmetry on the metal ion, and thus each ligand pair is coordinated with trans geometry, resulting in a distorted octahedral environment around MnII.
It should be noted that tpt uses only one of three N atoms in coordinating to the metal ion. The Mn—Ntpt bond distances are longer than the Mn—O and Mn—NNCS distances. The Mn—Ntpt bond distance is 2.355 (3) Å, which is consistent with the value of 2.360 (4) Å found in [MnL2(H2O)2(SCN)2] [L is 2,5-bis(4-pyridyl)-1,3,4-oxadiazole; Fang et al., 2002], but somewhat longer than the value of 2.31 (1) Å in the linear polymeric complex [Mn(bpe)(NCS)2(CH3OH)2] [bpe is trans-1,2-bis(4-pyridyl)ethene; De Munno et al., 1999].
The Mn—NNCS bond distance is 2.139 (3) Å, in good agreement with the sum of the Shannon (1976) ionic radii (2.13 Å) and the MnII—NNCS distance of 2.141 (7) Å observed in [Mn(tbr)3(NCS)(H2O)]n (tbr is 4,4'-bis-1,2,4-triazole; Zilverentant et al., 1998). However, this Mn—NNCS distance is slightly shorter than that found in [Mn(µ-4,4'-bipyridine)(4,4'-bipyridine)(NCS)2(H2O)2]n [2.188 (8) Å; Li et al., 1995] and considrably shorter than that found in [Mn(bpe)(NCS)2(CH3OH)2]n [2.24 (2) Å; De Munno et al., 1999]. As an explanation of such bond lengthening in this last complex, it was suggested that the thiocyanate groups are involved in hydrogen-bond formation. The Mn—O1 distance in (I) [2.213 (3) Å] is in an usual range. The thiocyanate ligand has the expected linear geometry, with an N—C—S angle of 178.5 (3)°.
The mean atomic displacement from the least-squares plane of the tpt ligand is 0.079 Å. However, the value for the ring Plane? excluding the N2-pyridyl ring is only 0.018 Å. The N2-pyridyl ring forms a dihedral angle of 7.8 (2)° with the central C3N3 ring, while the corresponding values for the N1- and N3-pyridyl rings are 1.9 (2) and 0.9 (2)°, respectively. The distortion of the N2-pyridyl ring is caused by the hydrogen bond between N2 and the methanol H atom (Table 2), and this hydrogen bond forms a one-dimensional linear chain structure along the [011] direction, as shown in Fig. 2.
The shortest intrachain separation of Mn atoms is 14.413 (4) Å. In addition, the molecules are stacked with the closest approach between the aromatic rings being ca 3.29 Å, leading to formation of a two-dimensional structure, as depicted in Fig. 3. These two-dimensional layers are stacked further by π–π interactions to form a three-dimensional network.