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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): m932.
Published online 2010 July 14. doi:  10.1107/S1600536810026322
PMCID: PMC3007432

Poly[bis­[μ-1,4-bis­(1,2,4-triazol-1-ylmeth­yl)benzene-κ2 N 4:N 4′]dichloridomanganese(II)]

Abstract

The MnII atom in the title coordination polymer, [MnCl2(C12H12N6)2]n, lies on a center of inversion in a six-coordinate octa­hedral environment comprising four N-atom donors from four N-heterocyclic ligands and two chloride atoms. Bridging by the ligands results in a layer structure of a 14.79 (5) × 14.79 (5) Å (4,4) rhombic net topology, with the MnII atoms all lying on a plane. The parallel layers stack in an ABCABC… manner through inter­layer C—H(...)N and C—H(...)Cl hydrogen bonds.

Related literature

For the preparation of highly stable, infinite metal–ligand frameworks by hydro­thermal methods, see: Chui et al. (1999 [triangle]); Gerrard & Wood (2000 [triangle]); Gutschke et al. (1996 [triangle]). For a three-dimensional self-catenating network involving the 1,4-bis­(triazol-1-ylmeth­yl)benzene ligand (L) which contains two different types of layers, see: Li et al. (2005 [triangle]). For a manganese inorganic–organic hybrid compound cont­ain­ing the flexible L ligand, [Mn2(H2O)4(L)3][SiMo12O40]·4H2O, see: Dong & Xu (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m932-scheme1.jpg

Experimental

Crystal data

  • [MnCl2(C12H12N6)2]
  • M r = 606.39
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m932-efi4.jpg
  • a = 7.5863 (16) Å
  • b = 21.925 (5) Å
  • c = 8.8442 (18) Å
  • β = 108.775 (4)°
  • V = 1392.8 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.70 mm−1
  • T = 294 K
  • 0.20 × 0.14 × 0.08 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.645, T max = 1.000
  • 7263 measured reflections
  • 2587 independent reflections
  • 1660 reflections with I > 2σ(I)
  • R int = 0.050

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.090
  • S = 1.00
  • 2587 reflections
  • 178 parameters
  • H-atom parameters constrained
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]) and DIAMOND (Brandenburg & Berndt, 2005 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810026322/ng2796sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026322/ng2796Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This present work was supported financially by Tianjin Educational Committee (20090504).

supplementary crystallographic information

Comment

The design and synthesis of highly-dimensional metal-organic framework (MOF) structures is becoming an increasing popular field of research in view of the formation of fascinating structures and their potentially useful ion-exchange, adsorption, catalytic, fluorescence, and magnetic properties. Triazole-containing ligands, such as 1,4-bis(triazol-1-ylmethyl)benzene, 1,2-bis(1,2,4-triazole-1-yl)ethane, 1,2-bis(1,2,4-triazole-1-yl)hexane and related species, represent another class of N-donor organic linkers for constructing coordination polymers, and these ligands have been proved to be able to produce architectures different from those obtained from pyridyl-based ligands.With two methylene sp3-carbon atoms, the ligand 1,4-bis(triazol-1-ylmethyl)benzene L is highly flexible and can assume variable trans and gauche conformations. It can generate unusual 2-D polyrotaxane networks, 3-D entangled networks and 3-D self-catenating network containing two different types of layers (Li et al., 2005). However, to date, only one manganese hybrid compound [Mn2(H2O)4(L)3][SiMo12O40].4H2O with the flexible L ligands has been reported in the present of molybdate recently (Dong et al., 2009).

Several synthetic methods can be used to obtain new polymeric complexes. In the previous literatures the hydrothermal method has been a promising technique in preparing highly stable, infinite metal–ligand frameworks (Gutschke et al., 1996; Chui et al., 1999; Gerrard et al., 2000). Taking the advantage of bridging ability of L in the chemical design of metal-organic molecular assemblies, under hydrothermal condition, we synthesized a novel 2-D (4,4) square grid layer manganese(II) coordination polymer, poly-[[bis[µ2-1,4-bis(triazol-1-ylmethyl)benzene-bis(chloride)manganese(II)].

Selected bond distances and bond angles are listed in Table 1. Fig. 1 shows the coordination environment of the metal ions in 1. The asymmetric unit of (I) contains one MnII cation, four-half of L ligands and two chloride atoms. The Mn(II) ion, which resides at an inversion center, is octahedrally coordinated by two pairs of equivalent imine nitrogen atoms from L ligands in the equatorial plane (N1, N6i, N6ii, N1iii) and two equivalent terminal chloride ions occupying the axial positions (Cl1 and Cl1iii). Two triazole rings of the ligand rotate along the C—C single bond axis with the dihedral of 52.1°. The benzene groups have different twists relative to their adjacent triazole ring with the dihedral of 70.2° and 71.0°, respectively. The cis N–Mn–N bond angles range from 87.4 (8)° to 92.5 (2)°, and the axial Mn–Cl(chloride) distances (2.5666 (5) Å) are much longer than the equatorial Mn–N(imine) distances (2.251 (3) and 2.268 (3) Å), indicative of the distorted octahedral environment with a slight axial elongated. Each Mn(II) ion is linked by four equivalent L ligands in the trans- conformation to its four neighboring Mn(II) ions, thus affording 2-D (4,4) grid layers parallel to the crystallographic ab plane (Fig. 2). All the Mn(II) ions in each layer are strictly coplanar.

The grid motif has the dimensions of 14.79 (5) Å × 14.79 (5) Å (metal- to-metal distances), and the Mn···Mn···Mn corner angles (84.3 (7)° and 95.6 (3)°) within the motif are close to 90°, suggesting a rhombic geometry. The grid layers are closely stacked in an offset way (Fig. 3), with the cavity of each layer being occupied by the groups from the two neighboring layers, which are generated from the original one by unit translations along the a direction. Due to the interdigitation between neighboring layers. The nearest interlayer Mn···Mn distances are 7.568 (2) and 8.844 (2)Å between the neighboring layers [Mn1···Mn1(x + 1, y, z)] and between the next-nearest neighboring layers [Mn1···Mn1(x, y, z - 1)], respectively, both being much shorter than the intralayer one. Further inspection into the structure revealed that there exist interlayer weak C–H···N and C–H···Cl hydrogen bonds. The uncoordinated L nitrogen atoms and chloride ions of one layer, forms the hydrogen bonds with a triazole C–H groups from different L ligands of the neighboring layer: C(9)–H(9)···N(5) (1 + x,1/2 - y,1/2 + z) and C(11)–H(11)···Cl(1) (x,1/2 - y,1/2 + z). The C—H···N and C—H···Cl distances and the correpsonding angle are, respectively, 3.523 (4) Å and 168.0 (8)° for the former, and 3.635 (2) Å and 154.8 (5)° for the latter. The result also reveals that there is still great potential in the construction of those novel coordination polymers with highly flexible bis-triazole ligands.

Experimental

A mixture of MnCl2.6H2O (0.2 mmol, 46.6 mg), L (0.4 mmol, 96.8 mg) and H2O (18.0 ml) in the molar radio of 1: 2:5000 was sealed in a 25 ml stainless steel reactor with Teflon liner and directly heated to 453 K ke pt at 453 K for 72 h, and then slowly cooled to 303 K at a rate for 4 K/h. Colorless block crystals of the title complex were collected by filtration and washed with ethanol (2 × 5 ml). Yield: 35%.

Refinement

The H atoms of the aromatic rings were placed at calculated positions, with C—H = 0.93 Å. All H atoms were assigned fixed isotropic displacement parameters, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).

Figures

Fig. 1.
A view of the local coordination of the MnII cations in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) 1 + x,-1/2 - y,-1/2 + z; (ii) -x,1/2 + y, 1/2 - z; (iii) 1 - x, 1 - y, ...
Fig. 2.
Schematic representation of the (4,4) network topology of (I) viewed down the c axis.
Fig. 3.
Top (a) and side (b) views showing the packing of the grid layers in (I).

Crystal data

[MnCl2(C12H12N6)2]F(000) = 622
Mr = 606.39Dx = 1.446 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1682 reflections
a = 7.5863 (16) Åθ = 2.8–23.5°
b = 21.925 (5) ŵ = 0.70 mm1
c = 8.8442 (18) ÅT = 294 K
β = 108.775 (4)°Block, colorless
V = 1392.8 (5) Å30.20 × 0.14 × 0.08 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer2587 independent reflections
Radiation source: fine-focus sealed tube1660 reflections with I > 2σ(I)
graphiteRint = 0.050
phi and ω scansθmax = 25.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.645, Tmax = 1.000k = −19→26
7263 measured reflectionsl = −7→10

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0412P)2] where P = (Fo2 + 2Fc2)/3
2587 reflections(Δ/σ)max < 0.001
178 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = −0.27 e Å3

Special details

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)

xyzUiso*/Ueq
Mn10.50000.50000.00000.03010 (18)
Cl10.15989 (9)0.47621 (4)−0.16003 (8)0.0404 (2)
N10.4590 (3)0.45414 (11)0.2160 (3)0.0350 (6)
N20.5081 (3)0.42190 (13)0.4681 (3)0.0549 (8)
N30.3232 (3)0.42456 (11)0.3864 (3)0.0339 (6)
N4−0.2711 (3)0.14940 (11)0.2963 (3)0.0357 (6)
N5−0.4262 (3)0.17945 (12)0.2994 (3)0.0462 (7)
N6−0.4061 (3)0.08737 (11)0.4162 (3)0.0345 (6)
C10.5808 (4)0.44071 (16)0.3598 (4)0.0528 (9)
H10.70870.44450.38150.063*
C20.2973 (4)0.44391 (13)0.2394 (3)0.0372 (7)
H20.18140.44960.16260.045*
C30.1824 (4)0.40794 (15)0.4602 (3)0.0451 (8)
H3A0.08680.43910.43660.054*
H3B0.24010.40610.57520.054*
C40.0941 (4)0.34717 (14)0.4007 (3)0.0343 (7)
C5−0.0630 (4)0.34410 (15)0.2691 (4)0.0493 (8)
H5−0.11700.37990.21910.059*
C6−0.1420 (4)0.28890 (16)0.2101 (4)0.0528 (9)
H6−0.24860.28800.12100.063*
C7−0.0655 (4)0.23505 (14)0.2810 (4)0.0379 (7)
C80.0892 (4)0.23780 (15)0.4153 (4)0.0462 (8)
H80.14050.20200.46750.055*
C90.1687 (4)0.29315 (15)0.4731 (4)0.0450 (8)
H90.27470.29410.56270.054*
C10−0.1494 (4)0.17476 (15)0.2130 (4)0.0494 (9)
H10A−0.22050.18010.10100.059*
H10B−0.05010.14600.21950.059*
C11−0.2619 (4)0.09541 (14)0.3656 (3)0.0363 (7)
H11−0.16710.06710.37710.044*
C12−0.5005 (4)0.13984 (15)0.3729 (3)0.0420 (8)
H12−0.61110.14760.39350.050*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mn10.0284 (3)0.0335 (4)0.0321 (3)0.0000 (3)0.0150 (3)0.0012 (3)
Cl10.0284 (4)0.0517 (5)0.0421 (4)−0.0048 (3)0.0130 (3)−0.0030 (4)
N10.0309 (13)0.0435 (17)0.0337 (14)−0.0009 (11)0.0147 (11)0.0074 (11)
N20.0436 (17)0.072 (2)0.0460 (17)−0.0027 (14)0.0098 (14)0.0184 (14)
N30.0342 (14)0.0362 (16)0.0342 (14)−0.0088 (11)0.0150 (12)0.0015 (11)
N40.0338 (14)0.0381 (17)0.0365 (14)−0.0072 (12)0.0131 (11)−0.0015 (11)
N50.0372 (15)0.0432 (19)0.0556 (17)0.0008 (13)0.0112 (13)0.0039 (13)
N60.0284 (13)0.0368 (17)0.0402 (14)−0.0008 (11)0.0139 (11)0.0026 (11)
C10.0334 (18)0.074 (3)0.053 (2)0.0024 (17)0.0168 (17)0.0196 (18)
C20.0343 (17)0.045 (2)0.0317 (17)−0.0052 (14)0.0096 (13)0.0052 (14)
C30.053 (2)0.050 (2)0.0429 (18)−0.0138 (16)0.0298 (16)−0.0023 (15)
C40.0370 (17)0.041 (2)0.0308 (17)−0.0088 (14)0.0194 (14)0.0019 (13)
C50.056 (2)0.040 (2)0.046 (2)−0.0011 (17)0.0080 (17)0.0124 (15)
C60.052 (2)0.055 (3)0.039 (2)−0.0102 (18)−0.0037 (16)0.0065 (16)
C70.0440 (19)0.035 (2)0.0407 (18)−0.0093 (15)0.0226 (15)−0.0005 (14)
C80.0414 (19)0.038 (2)0.055 (2)0.0044 (16)0.0105 (17)0.0117 (16)
C90.0341 (18)0.047 (2)0.048 (2)−0.0074 (16)0.0036 (15)0.0023 (16)
C100.061 (2)0.050 (2)0.047 (2)−0.0185 (17)0.0307 (17)−0.0056 (16)
C110.0314 (16)0.038 (2)0.0403 (17)0.0006 (14)0.0122 (14)0.0005 (14)
C120.0276 (16)0.042 (2)0.058 (2)−0.0003 (15)0.0167 (15)−0.0029 (16)

Geometric parameters (Å, °)

Mn1—N6i2.251 (2)C2—H20.9300
Mn1—N6ii2.251 (2)C3—C41.508 (4)
Mn1—N1iii2.267 (2)C3—H3A0.9700
Mn1—N12.267 (2)C3—H3B0.9700
Mn1—Cl1iii2.5655 (8)C4—C51.373 (4)
Mn1—Cl12.5655 (8)C4—C91.378 (4)
N1—C21.327 (3)C5—C61.377 (4)
N1—C11.342 (3)C5—H50.9300
N2—C11.316 (3)C6—C71.375 (4)
N2—N31.357 (3)C6—H60.9300
N3—C21.321 (3)C7—C81.376 (4)
N3—C31.466 (3)C7—C101.506 (4)
N4—C111.325 (3)C8—C91.378 (4)
N4—N51.356 (3)C8—H80.9300
N4—C101.464 (3)C9—H90.9300
N5—C121.315 (4)C10—H10A0.9700
N6—C111.320 (3)C10—H10B0.9700
N6—C121.344 (4)C11—H110.9300
N6—Mn1iv2.251 (2)C12—H120.9300
C1—H10.9300
N6i—Mn1—N6ii180.0N3—C3—H3A109.3
N6i—Mn1—N1iii92.51 (8)C4—C3—H3A109.3
N6ii—Mn1—N1iii87.49 (8)N3—C3—H3B109.3
N6i—Mn1—N187.49 (8)C4—C3—H3B109.3
N6ii—Mn1—N192.51 (8)H3A—C3—H3B107.9
N1iii—Mn1—N1180.00 (12)C5—C4—C9117.8 (3)
N6i—Mn1—Cl1iii90.81 (6)C5—C4—C3120.4 (3)
N6ii—Mn1—Cl1iii89.19 (6)C9—C4—C3121.8 (3)
N1iii—Mn1—Cl1iii89.34 (6)C4—C5—C6121.2 (3)
N1—Mn1—Cl1iii90.66 (6)C4—C5—H5119.4
N6i—Mn1—Cl189.19 (6)C6—C5—H5119.4
N6ii—Mn1—Cl190.81 (6)C7—C6—C5120.9 (3)
N1iii—Mn1—Cl190.66 (6)C7—C6—H6119.6
N1—Mn1—Cl189.34 (6)C5—C6—H6119.6
Cl1iii—Mn1—Cl1180.0C6—C7—C8118.3 (3)
C2—N1—C1101.8 (2)C6—C7—C10120.6 (3)
C2—N1—Mn1126.18 (18)C8—C7—C10121.1 (3)
C1—N1—Mn1131.04 (18)C7—C8—C9120.6 (3)
C1—N2—N3101.7 (2)C7—C8—H8119.7
C2—N3—N2109.8 (2)C9—C8—H8119.7
C2—N3—C3128.3 (2)C8—C9—C4121.3 (3)
N2—N3—C3121.9 (2)C8—C9—H9119.4
C11—N4—N5110.0 (2)C4—C9—H9119.4
C11—N4—C10128.7 (2)N4—C10—C7112.7 (2)
N5—N4—C10121.2 (2)N4—C10—H10A109.0
C12—N5—N4101.6 (2)C7—C10—H10A109.0
C11—N6—C12102.3 (2)N4—C10—H10B109.0
C11—N6—Mn1iv127.6 (2)C7—C10—H10B109.0
C12—N6—Mn1iv128.76 (18)H10A—C10—H10B107.8
N2—C1—N1115.9 (3)N6—C11—N4110.5 (3)
N2—C1—H1122.1N6—C11—H11124.8
N1—C1—H1122.1N4—C11—H11124.8
N3—C2—N1110.8 (2)N5—C12—N6115.6 (2)
N3—C2—H2124.6N5—C12—H12122.2
N1—C2—H2124.6N6—C12—H12122.2
N3—C3—C4111.7 (2)
N6i—Mn1—N1—C269.1 (2)N3—C3—C4—C5−90.4 (3)
N6ii—Mn1—N1—C2−110.9 (2)N3—C3—C4—C988.3 (3)
N1iii—Mn1—N1—C2−133 (100)C9—C4—C5—C6−0.9 (4)
Cl1iii—Mn1—N1—C2159.9 (2)C3—C4—C5—C6177.9 (3)
Cl1—Mn1—N1—C2−20.1 (2)C4—C5—C6—C7−0.2 (5)
N6i—Mn1—N1—C1−97.5 (3)C5—C6—C7—C81.8 (5)
N6ii—Mn1—N1—C182.5 (3)C5—C6—C7—C10−178.3 (3)
N1iii—Mn1—N1—C160 (100)C6—C7—C8—C9−2.4 (4)
Cl1iii—Mn1—N1—C1−6.7 (3)C10—C7—C8—C9177.7 (3)
Cl1—Mn1—N1—C1173.3 (3)C7—C8—C9—C41.3 (5)
C1—N2—N3—C20.2 (3)C5—C4—C9—C80.3 (4)
C1—N2—N3—C3−179.4 (3)C3—C4—C9—C8−178.5 (2)
C11—N4—N5—C120.0 (3)C11—N4—C10—C7−124.3 (3)
C10—N4—N5—C12175.2 (2)N5—N4—C10—C761.5 (4)
N3—N2—C1—N1−1.0 (4)C6—C7—C10—N4−98.4 (3)
C2—N1—C1—N21.4 (4)C8—C7—C10—N481.5 (4)
Mn1—N1—C1—N2170.3 (2)C12—N6—C11—N4−0.1 (3)
N2—N3—C2—N10.7 (3)Mn1iv—N6—C11—N4167.33 (17)
C3—N3—C2—N1−179.7 (3)N5—N4—C11—N60.1 (3)
C1—N1—C2—N3−1.2 (3)C10—N4—C11—N6−174.7 (2)
Mn1—N1—C2—N3−170.87 (18)N4—N5—C12—N6−0.1 (3)
C2—N3—C3—C474.3 (4)C11—N6—C12—N50.1 (3)
N2—N3—C3—C4−106.2 (3)Mn1iv—N6—C12—N5−167.11 (19)

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x+1, −y+1/2, z−1/2; (iii) −x+1, −y+1, −z; (iv) −x, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9···N5v0.932.613.523 (4)168
C11—H11···Cl1vi0.932.773.635 (3)155

Symmetry codes: (v) x+1, −y+1/2, z+1/2; (vi) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2796).

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