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The title compound, [Mn(NCS)2(C18H12N6)2(CH4O)2], con­tains a centrosymmetric octahedral MnII 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 [pi]-[pi] 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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102016475/ob1080sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102016475/ob1080Isup2.hkl
Contains datablock I

CCDC reference: 197325

Comment top

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 ππ interactions to form a three-dimensional network.

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The one-dimensional linear chain structure of (I) formed by hydrogen bonding.
[Figure 3] Fig. 3. A two-dimensional molecular packing diagram for (I).
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 = 859.86F(000) = 443
Triclinic, P1Dx = 1.406 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.871 (2) ÅCell parameters from 25 reflections
b = 8.875 (2) Åθ = 23–29°
c = 14.161 (4) ŵ = 0.48 mm1
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 tubeθmax = 25.0°, θmin = 2.4°
Graphite monochromatorh = 1010
θ/2θ scansk = 1010
3732 measured reflectionsl = 016
3571 independent reflections3 standard reflections every 120 min
2796 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-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 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
[Mn(NCS)2(C18H12N6)2(CH4O)2]γ = 100.93 (3)°
Mr = 859.86V = 1015.3 (4) Å3
Triclinic, P1Z = 1
a = 8.871 (2) ÅMo Kα radiation
b = 8.875 (2) ŵ = 0.48 mm1
c = 14.161 (4) ÅT = 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 reflections3 standard reflections every 120 min
3571 independent reflections intensity decay: none
2796 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.132H-atom parameters constrained
S = 1.01Δρmax = 0.33 e Å3
3571 reflectionsΔρmin = 0.40 e Å3
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
xyzUiso*/Ueq
Mn0.00000.50000.50000.0432 (2)
S10.47224 (15)0.94996 (17)0.64967 (12)0.1000 (5)
O10.1548 (3)0.3334 (3)0.50854 (18)0.0533 (6)
N10.0756 (3)0.5107 (3)0.3506 (2)0.0449 (7)
N20.0462 (4)0.0343 (4)0.3631 (2)0.0521 (8)
N30.7438 (4)0.9846 (4)0.0133 (3)0.0675 (10)
N40.1260 (3)0.3744 (3)0.00988 (19)0.0387 (6)
N50.2930 (3)0.4871 (3)0.0984 (2)0.0394 (6)
N60.3276 (3)0.6188 (3)0.0776 (2)0.0393 (6)
N70.1939 (4)0.7064 (4)0.5872 (2)0.0578 (9)
C10.2076 (4)0.4987 (4)0.0733 (2)0.0363 (7)
C20.1639 (4)0.5025 (4)0.1700 (2)0.0370 (7)
C30.2435 (4)0.6251 (4)0.2606 (2)0.0469 (9)
H30.32760.70730.26240.056*
C40.1969 (4)0.6243 (4)0.3480 (3)0.0502 (9)
H40.25260.70690.40850.060*
C50.0011 (4)0.3934 (4)0.2626 (3)0.0478 (9)
H50.08250.31250.26280.057*
C60.0389 (4)0.3835 (4)0.1717 (2)0.0447 (8)
H60.01800.29870.11250.054*
C70.1752 (4)0.3728 (4)0.0934 (2)0.0367 (7)
C80.0955 (4)0.2325 (4)0.1874 (2)0.0372 (7)
C90.0346 (4)0.1154 (4)0.1909 (3)0.0475 (9)
H90.07670.12410.13470.057*
C100.1004 (5)0.0139 (5)0.2793 (3)0.0555 (10)
H100.18790.09220.28110.067*
C110.0791 (5)0.0787 (4)0.3582 (3)0.0535 (10)
H110.12030.06620.41490.064*
C120.1514 (4)0.2139 (4)0.2733 (3)0.0497 (9)
H120.23710.29190.27410.060*
C130.3636 (4)0.6082 (4)0.0108 (2)0.0360 (7)
C140.4958 (4)0.7385 (4)0.0122 (3)0.0406 (8)
C150.5396 (5)0.7360 (5)0.1013 (3)0.0547 (10)
H150.48740.65310.16230.066*
C160.6650 (5)0.8621 (6)0.0966 (4)0.0684 (12)
H160.69500.85960.15650.082*
C170.6980 (5)0.9843 (5)0.0704 (4)0.0600 (11)
H170.75111.06980.13000.072*
C180.5770 (4)0.8658 (4)0.0755 (3)0.0465 (8)
H180.55080.87180.13690.056*
C190.3104 (4)0.8081 (4)0.6145 (3)0.0489 (9)
C200.3237 (5)0.3697 (6)0.5338 (4)0.0860 (15)
H20A0.35650.27190.53120.129*
H20B0.36550.44720.60120.129*
H20C0.36270.41440.48610.129*
HO10.11060.22630.46000.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.0467 (4)0.0380 (4)0.0323 (4)0.0092 (3)0.0170 (3)0.0012 (3)
S10.0584 (7)0.0829 (9)0.1141 (11)0.0299 (7)0.0238 (7)0.0047 (8)
O10.0539 (15)0.0430 (14)0.0493 (14)0.0024 (11)0.0150 (12)0.0031 (11)
N10.0499 (17)0.0417 (15)0.0356 (15)0.0031 (13)0.0169 (13)0.0070 (12)
N20.062 (2)0.0448 (17)0.0392 (16)0.0033 (15)0.0156 (14)0.0031 (13)
N30.056 (2)0.056 (2)0.100 (3)0.0045 (17)0.031 (2)0.038 (2)
N40.0396 (15)0.0407 (15)0.0323 (14)0.0026 (12)0.0143 (12)0.0086 (12)
N50.0392 (15)0.0401 (15)0.0392 (15)0.0049 (12)0.0163 (12)0.0132 (12)
N60.0403 (15)0.0364 (14)0.0381 (15)0.0009 (12)0.0159 (12)0.0100 (12)
N70.061 (2)0.0466 (18)0.0457 (18)0.0127 (16)0.0201 (15)0.0017 (14)
C10.0357 (17)0.0384 (17)0.0350 (17)0.0079 (14)0.0130 (13)0.0109 (14)
C20.0389 (17)0.0358 (17)0.0355 (17)0.0048 (14)0.0166 (14)0.0092 (13)
C30.047 (2)0.0432 (19)0.0399 (19)0.0082 (15)0.0160 (15)0.0076 (15)
C40.056 (2)0.047 (2)0.0348 (18)0.0079 (17)0.0161 (16)0.0051 (15)
C50.050 (2)0.0443 (19)0.0388 (18)0.0087 (16)0.0218 (16)0.0056 (15)
C60.049 (2)0.0403 (18)0.0334 (17)0.0049 (15)0.0136 (15)0.0040 (14)
C70.0347 (16)0.0369 (17)0.0377 (17)0.0066 (13)0.0140 (14)0.0096 (14)
C80.0407 (18)0.0374 (17)0.0310 (16)0.0057 (14)0.0094 (14)0.0099 (13)
C90.047 (2)0.048 (2)0.0419 (19)0.0020 (16)0.0203 (16)0.0064 (16)
C100.050 (2)0.051 (2)0.051 (2)0.0069 (17)0.0184 (17)0.0037 (17)
C110.065 (2)0.054 (2)0.0323 (18)0.0005 (19)0.0197 (17)0.0068 (16)
C120.055 (2)0.047 (2)0.0406 (19)0.0025 (17)0.0181 (16)0.0112 (16)
C130.0351 (16)0.0377 (17)0.0367 (17)0.0070 (13)0.0134 (13)0.0136 (14)
C140.0388 (18)0.0378 (17)0.051 (2)0.0079 (14)0.0188 (15)0.0195 (15)
C150.060 (2)0.050 (2)0.059 (2)0.0075 (18)0.0312 (19)0.0209 (18)
C160.074 (3)0.069 (3)0.084 (3)0.016 (2)0.049 (3)0.041 (3)
C170.048 (2)0.043 (2)0.081 (3)0.0017 (17)0.009 (2)0.023 (2)
C180.0418 (19)0.0435 (19)0.053 (2)0.0026 (15)0.0125 (16)0.0187 (16)
C190.051 (2)0.048 (2)0.0358 (18)0.0002 (18)0.0157 (16)0.0008 (15)
C200.057 (3)0.072 (3)0.109 (4)0.002 (2)0.018 (3)0.013 (3)
Geometric parameters (Å, º) top
Mn—N72.139 (3)C3—H30.9300
Mn—N7i2.139 (3)C4—H40.9300
Mn—O1i2.213 (3)C5—C61.372 (4)
Mn—O12.213 (3)C5—H50.9300
Mn—N1i2.355 (3)C6—H60.9300
Mn—N12.355 (3)C7—C81.482 (4)
S1—C191.609 (4)C8—C121.375 (5)
O1—C201.425 (5)C8—C91.382 (4)
O1—HO10.9578C9—C101.373 (5)
N1—C51.331 (4)C9—H90.9300
N1—C41.342 (4)C10—H100.9300
N2—C111.325 (5)C11—C121.378 (5)
N2—C101.338 (5)C11—H110.9300
N3—C161.320 (6)C12—H120.9300
N3—C171.321 (5)C13—C141.490 (4)
N4—C11.331 (4)C14—C181.379 (5)
N4—C71.332 (4)C14—C151.383 (5)
N5—C131.337 (4)C15—C161.398 (5)
N5—C71.339 (4)C15—H150.9300
N6—C131.330 (4)C16—H160.9300
N6—C11.335 (4)C17—C181.381 (5)
N7—C191.155 (4)C17—H170.9300
C1—C21.484 (4)C18—H180.9300
C2—C31.381 (4)C20—H20A0.9600
C2—C61.388 (4)C20—H20B0.9600
C3—C41.377 (5)C20—H20C0.9600
N7—Mn—N7i180.0C2—C6—H6120.7
N7—Mn—O1i88.97 (12)N4—C7—N5124.9 (3)
N7i—Mn—O1i91.03 (12)N4—C7—C8117.5 (3)
N7—Mn—O191.03 (12)N5—C7—C8117.6 (3)
N7i—Mn—O188.97 (12)C12—C8—C9118.1 (3)
O1i—Mn—O1180.000 (1)C12—C8—C7120.6 (3)
N7—Mn—N1i90.43 (11)C9—C8—C7121.3 (3)
N7i—Mn—N1i89.57 (11)C10—C9—C8118.5 (3)
O1i—Mn—N1i86.55 (10)C10—C9—H9120.8
O1—Mn—N1i93.45 (10)C8—C9—H9120.8
N7—Mn—N189.57 (11)N2—C10—C9124.0 (3)
N7i—Mn—N190.43 (11)N2—C10—H10118.0
O1i—Mn—N193.45 (10)C9—C10—H10118.0
O1—Mn—N186.55 (10)N2—C11—C12123.4 (3)
N1i—Mn—N1180.000 (1)N2—C11—H11118.3
C20—O1—Mn128.8 (3)C12—C11—H11118.3
C20—O1—HO1110.2C11—C12—C8119.3 (3)
Mn—O1—HO1113.6C11—C12—H12120.3
C5—N1—C4116.1 (3)C8—C12—H12120.3
C5—N1—Mn119.5 (2)N6—C13—N5125.1 (3)
C4—N1—Mn124.3 (2)N6—C13—C14117.8 (3)
C11—N2—C10116.6 (3)N5—C13—C14117.1 (3)
C16—N3—C17116.0 (3)C18—C14—C15118.2 (3)
C1—N4—C7114.8 (3)C18—C14—C13120.7 (3)
C13—N5—C7115.0 (3)C15—C14—C13121.1 (3)
C13—N6—C1114.6 (3)C14—C15—C16117.9 (4)
C19—N7—Mn164.5 (3)C14—C15—H15121.1
N4—C1—N6125.6 (3)C16—C15—H15121.1
N4—C1—C2117.3 (3)N3—C16—C15124.6 (4)
N6—C1—C2117.0 (3)N3—C16—H16117.7
C3—C2—C6117.8 (3)C15—C16—H16117.7
C3—C2—C1121.6 (3)N3—C17—C18124.7 (4)
C6—C2—C1120.6 (3)N3—C17—H17117.7
C2—C3—C4119.3 (3)C18—C17—H17117.7
C2—C3—H3120.3C14—C18—C17118.6 (4)
C4—C3—H3120.3C14—C18—H18120.7
N1—C4—C3123.5 (3)C17—C18—H18120.7
N1—C4—H4118.2N7—C19—S1178.5 (3)
C3—C4—H4118.3O1—C20—H20A109.5
N1—C5—C6124.6 (3)O1—C20—H20B109.5
N1—C5—H5117.7H20A—C20—H20B109.5
C6—C5—H5117.7O1—C20—H20C109.5
C5—C6—C2118.6 (3)H20A—C20—H20C109.5
C5—C6—H6120.7H20B—C20—H20C109.5
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—HO1···N2ii0.961.772.721 (4)173
Symmetry code: (ii) x, y, z.

Experimental details

Crystal data
Chemical formula[Mn(NCS)2(C18H12N6)2(CH4O)2]
Mr859.86
Crystal system, space groupTriclinic, 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)
V3)1015.3 (4)
Z1
Radiation typeMo Kα
µ (mm1)0.48
Crystal size (mm)0.32 × 0.17 × 0.15
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3732, 3571, 2796
Rint0.015
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.132, 1.01
No. of reflections3571
No. of parameters268
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.40

Computer programs: MACH3 (Enraf-Nonius, 1996), CELDIM (Enraf-Nonius, 1996), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Mn—N72.139 (3)S1—C191.609 (4)
Mn—O12.213 (3)O1—C201.425 (5)
Mn—N12.355 (3)N7—C191.155 (4)
N7—Mn—O191.03 (12)C20—O1—Mn128.8 (3)
N7—Mn—N189.57 (11)C19—N7—Mn164.5 (3)
O1—Mn—N186.55 (10)N7—C19—S1178.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—HO1···N2i0.961.772.721 (4)173
Symmetry code: (i) x, y, z.
 

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