supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

cs2107 scheme

Acta Cryst. (2009). E65, m249    [ doi:10.1107/S1600536809003663 ]

[[mu]-N,N,N',N'-Tetrakis(2-pyridylmethyl)hexane-1,6-diamine]bis[dichloridomanganese(II)]

I.-C. Hwang, N.-H. Kim and K. Ha

Abstract top

The asymmetric unit of the title compound, [Mn2Cl4(C30H36N6)], contains one-half of the formula unit; a centre of inversion is located at the mid-point of the molecule. The two Mn2+ ions are bridged by the dual tridentate N,N,N',N'-tetrakis(2-pyridylmethyl)hexane-1,6-diamine ligand to form a dinuclear complex. Each Mn atom is five-coordinated in an approximately square-pyramidal geometry by three N atoms from the ligand and two Cl atoms. Intermolecular [pi]-[pi] interactions between adjacent pyridine rings with a centroid-centroid distance of 3.576 (2) Å are reported.

Comment top

The asymmetric unit of the title compound, [Mn2Cl4(C30H36N6)], contains one half of the formula unit; a centre of inversion is located in the midpoint of the compound (Figs. 1 and 2). In the complex, the two Mn2+ ions are bridged by the hexadentate ligand N,N,N',N'-tetrakis(2-pyridylmethyl)hexane-1,6-diamine (tphn) to form a centrosymmetric dinuclear complex. Mn atoms are five-coordinated in an approximately square pyramidal geometry by three N atoms from the tphn ligand and two Cl atoms. The Mn—N(amine) bond length (2.339 (2) Å) is slightly longer than the Mn—N(pyridyl) bond lengths (2.246 (3) and 2.232 (2) Å). The complex displays intermolecular π-π interactions between adjacent pyridine rings. The shortest distance between Cg1 (the centroid of six-membered ring N1—C5) and Cg1i (symmetry code i: 2 - x, 1 - y, 1 - z) is 3.576 (2) Å.

Related literature top

For structural details of some related complexes, see: Hwang & Ha (2007); Song et al., 2008).

Experimental top

To a solution of N,N,N',N'-tetrakis(2-pyridylmethyl)hexane-1,6-diamine (0.50 g, 1.04 mmol) in EtOH (15 ml) was added MnCl2.4H2O (0.21 g, 1.06 mmol) and stirred for 1 h at room temparature. The volume of the solvent was reduced to 3 ml and ether (20 ml) was added. The so formed precipitate was separated by filtration and washed with EtOH/ether and dried under vacuum, to give a pale yellow powder (0.36 g). Crystals suitable for X-ray analysis were obtained from the slow evaporation of a MeOH solution. MS (FAB): m/z 570, 572 (Mn(tphn)Cl+).

Refinement top

H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.93 Å (aromatic) or 0.97 Å (CH2) and Uiso(H) = 1.2Ueq(C)].

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound, with displacement ellipsoids drawn at the 50% probability level for non-H atoms [Symmetry code: (a) 1 - x, 1 - y, -z]. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. View of a packing detail of the title compound.
[µ-N,N,N',N'-Tetrakis(2-pyridylmethyl)hexane-1,6- diamine]bis[dichloridomanganese(II)] top
Crystal data top
[Mn2Cl4(C30H36N6)]Z = 1
Mr = 732.33F(000) = 376
Triclinic, P1Dx = 1.432 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.7149 (13) ÅCell parameters from 886 reflections
b = 8.4660 (14) Åθ = 2.6–26.3°
c = 14.263 (2) ŵ = 1.09 mm−1
α = 83.309 (3)°T = 293 K
β = 88.329 (3)°Plate, colourless
γ = 66.666 (3)°0.35 × 0.18 × 0.06 mm
V = 849.4 (2) Å3
Data collection top
Bruker SMART 1000 CCD
diffractometer		3368 independent reflections
Radiation source: fine-focus sealed tube2705 reflections with I > 2σ(I)
graphiteRint = 0.013
φ and ω scansθmax = 26.4°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −8→9
Tmin = 0.707, Tmax = 0.937k = −10→10
4845 measured reflectionsl = −17→15
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0564P)2 + 0.3638P]
where P = (Fo2 + 2Fc2)/3
3368 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 0.42 e Å−3
0 restraintsΔρmin = −0.29 e Å−3
Crystal data top
[Mn2Cl4(C30H36N6)]γ = 66.666 (3)°
Mr = 732.33V = 849.4 (2) Å3
Triclinic, P1Z = 1
a = 7.7149 (13) ÅMo Kα radiation
b = 8.4660 (14) ŵ = 1.09 mm−1
c = 14.263 (2) ÅT = 293 K
α = 83.309 (3)°0.35 × 0.18 × 0.06 mm
β = 88.329 (3)°
Data collection top
Bruker SMART 1000 CCD
diffractometer		3368 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2705 reflections with I > 2σ(I)
Tmin = 0.707, Tmax = 0.937Rint = 0.013
4845 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.118Δρmax = 0.42 e Å−3
S = 1.07Δρmin = −0.29 e Å−3
3368 reflectionsAbsolute structure: ?
190 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn11.04002 (6)0.18359 (5)0.26548 (3)0.04078 (16)
Cl11.23775 (14)−0.01680 (11)0.38692 (7)0.0661 (3)
Cl21.19512 (14)0.26409 (14)0.13691 (7)0.0677 (3)
N10.9580 (4)0.4267 (3)0.33551 (19)0.0477 (6)
N20.9371 (3)0.0059 (3)0.20318 (19)0.0456 (6)
N30.7153 (3)0.2854 (3)0.29208 (17)0.0410 (6)
C11.0607 (6)0.5221 (5)0.3353 (3)0.0633 (10)
H11.17110.49090.30080.076*
C21.0105 (8)0.6646 (5)0.3840 (3)0.0790 (14)
H21.08680.72640.38390.095*
C30.8461 (8)0.7127 (5)0.4324 (3)0.0820 (15)
H30.81010.80690.46700.098*
C40.7338 (7)0.6216 (5)0.4298 (2)0.0715 (12)
H40.61780.65710.45950.086*
C50.7963 (5)0.4759 (4)0.3822 (2)0.0504 (8)
C60.6920 (5)0.3593 (4)0.3819 (2)0.0532 (8)
H6A0.73930.26650.43320.064*
H6B0.55890.42470.39190.064*
C71.0319 (5)−0.0980 (5)0.1386 (3)0.0601 (9)
H71.1506−0.10240.12100.072*
C80.9591 (6)−0.1979 (5)0.0977 (3)0.0752 (11)
H81.0272−0.26830.05270.090*
C90.7868 (6)−0.1926 (5)0.1237 (3)0.0767 (12)
H90.7360−0.26010.09670.092*
C100.6872 (5)−0.0877 (5)0.1898 (3)0.0634 (10)
H100.5691−0.08340.20860.076*
C110.7668 (4)0.0118 (4)0.2281 (2)0.0464 (7)
C120.6656 (5)0.1324 (4)0.2993 (2)0.0527 (8)
H12A0.53050.17080.28960.063*
H12B0.69770.07080.36220.063*
C130.5988 (4)0.4236 (4)0.2181 (2)0.0469 (7)
H13A0.62650.52510.22090.056*
H13B0.46670.45510.23320.056*
C140.6265 (4)0.3777 (4)0.1184 (2)0.0465 (7)
H14A0.60500.27310.11510.056*
H14B0.75570.35470.10050.056*
C150.4928 (5)0.5226 (4)0.0496 (2)0.0497 (8)
H15A0.36420.55080.07050.060*
H15B0.52000.62490.05050.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0360 (3)0.0418 (3)0.0450 (3)−0.01554 (19)−0.00546 (18)−0.00439 (19)
Cl10.0736 (6)0.0526 (5)0.0663 (6)−0.0198 (4)−0.0295 (5)0.0050 (4)
Cl20.0703 (6)0.0923 (7)0.0568 (6)−0.0500 (5)0.0078 (4)−0.0076 (5)
N10.0516 (15)0.0433 (14)0.0476 (15)−0.0178 (12)−0.0088 (12)−0.0046 (12)
N20.0448 (14)0.0425 (14)0.0498 (15)−0.0177 (11)−0.0097 (11)−0.0021 (12)
N30.0406 (13)0.0416 (13)0.0382 (14)−0.0157 (11)−0.0018 (10)0.0035 (10)
C10.070 (2)0.055 (2)0.070 (2)−0.0309 (18)−0.0226 (19)0.0017 (18)
C20.126 (4)0.050 (2)0.068 (3)−0.043 (2)−0.047 (3)0.012 (2)
C30.151 (5)0.0364 (18)0.046 (2)−0.024 (2)−0.030 (3)0.0022 (16)
C40.106 (3)0.0458 (19)0.0382 (19)−0.005 (2)−0.0046 (19)−0.0018 (15)
C50.068 (2)0.0416 (16)0.0297 (16)−0.0101 (15)−0.0117 (14)0.0024 (13)
C60.0564 (19)0.0550 (19)0.0384 (18)−0.0143 (16)0.0050 (14)0.0037 (14)
C70.055 (2)0.059 (2)0.067 (2)−0.0202 (17)−0.0004 (17)−0.0171 (18)
C80.084 (3)0.068 (2)0.080 (3)−0.032 (2)−0.005 (2)−0.027 (2)
C90.091 (3)0.068 (2)0.085 (3)−0.044 (2)−0.022 (2)−0.013 (2)
C100.061 (2)0.059 (2)0.079 (3)−0.0354 (18)−0.0168 (19)0.0048 (19)
C110.0487 (17)0.0397 (15)0.0500 (18)−0.0200 (14)−0.0132 (14)0.0106 (14)
C120.0511 (18)0.0532 (18)0.056 (2)−0.0268 (15)−0.0002 (15)0.0078 (16)
C130.0403 (16)0.0483 (17)0.0444 (18)−0.0124 (14)−0.0087 (13)0.0080 (14)
C140.0429 (16)0.0492 (17)0.0429 (17)−0.0159 (14)−0.0110 (13)0.0070 (14)
C150.0505 (18)0.0470 (17)0.0500 (18)−0.0200 (14)−0.0175 (14)0.0072 (14)
Geometric parameters (Å, °) top
Mn1—N22.232 (2)C6—H6B0.9700
Mn1—N12.246 (3)C7—C81.372 (5)
Mn1—N32.339 (2)C7—H70.9300
Mn1—Cl22.3422 (10)C8—C91.355 (6)
Mn1—Cl12.3716 (9)C8—H80.9300
N1—C51.334 (4)C9—C101.372 (6)
N1—C11.337 (4)C9—H90.9300
N2—C111.334 (4)C10—C111.386 (5)
N2—C71.340 (4)C10—H100.9300
N3—C61.465 (4)C11—C121.499 (5)
N3—C121.482 (4)C12—H12A0.9700
N3—C131.492 (4)C12—H12B0.9700
C1—C21.377 (6)C13—C141.504 (4)
C1—H10.9300C13—H13A0.9700
C2—C31.362 (7)C13—H13B0.9700
C2—H20.9300C14—C151.519 (4)
C3—C41.372 (6)C14—H14A0.9700
C3—H30.9300C14—H14B0.9700
C4—C51.386 (5)C15—C15i1.499 (6)
C4—H40.9300C15—H15A0.9700
C5—C61.501 (5)C15—H15B0.9700
C6—H6A0.9700
N2—Mn1—N1145.81 (10)C5—C6—H6B109.4
N2—Mn1—N373.58 (9)H6A—C6—H6B108.0
N1—Mn1—N372.37 (9)N2—C7—C8122.0 (4)
N2—Mn1—Cl2101.15 (8)N2—C7—H7119.0
N1—Mn1—Cl297.35 (8)C8—C7—H7119.0
N3—Mn1—Cl2128.09 (6)C9—C8—C7119.1 (4)
N2—Mn1—Cl198.49 (7)C9—C8—H8120.4
N1—Mn1—Cl198.94 (7)C7—C8—H8120.4
N3—Mn1—Cl1116.01 (7)C8—C9—C10120.0 (4)
Cl2—Mn1—Cl1115.84 (4)C8—C9—H9120.0
C5—N1—C1118.3 (3)C10—C9—H9120.0
C5—N1—Mn1116.8 (2)C9—C10—C11118.4 (4)
C1—N1—Mn1124.9 (3)C9—C10—H10120.8
C11—N2—C7118.7 (3)C11—C10—H10120.8
C11—N2—Mn1117.6 (2)N2—C11—C10121.8 (3)
C7—N2—Mn1123.6 (2)N2—C11—C12116.5 (3)
C6—N3—C12112.0 (2)C10—C11—C12121.7 (3)
C6—N3—C13108.5 (2)N3—C12—C11111.9 (3)
C12—N3—C13111.5 (2)N3—C12—H12A109.2
C6—N3—Mn1104.43 (18)C11—C12—H12A109.2
C12—N3—Mn1106.39 (18)N3—C12—H12B109.2
C13—N3—Mn1113.75 (18)C11—C12—H12B109.2
N1—C1—C2122.9 (4)H12A—C12—H12B107.9
N1—C1—H1118.5N3—C13—C14115.8 (3)
C2—C1—H1118.5N3—C13—H13A108.3
C3—C2—C1118.3 (4)C14—C13—H13A108.3
C3—C2—H2120.8N3—C13—H13B108.3
C1—C2—H2120.8C14—C13—H13B108.3
C2—C3—C4119.8 (4)H13A—C13—H13B107.4
C2—C3—H3120.1C13—C14—C15111.5 (3)
C4—C3—H3120.1C13—C14—H14A109.3
C3—C4—C5118.8 (4)C15—C14—H14A109.3
C3—C4—H4120.6C13—C14—H14B109.3
C5—C4—H4120.6C15—C14—H14B109.3
N1—C5—C4121.8 (4)H14A—C14—H14B108.0
N1—C5—C6115.2 (3)C15i—C15—C14113.2 (3)
C4—C5—C6123.0 (4)C15i—C15—H15A108.9
N3—C6—C5111.0 (3)C14—C15—H15A108.9
N3—C6—H6A109.4C15i—C15—H15B108.9
C5—C6—H6A109.4C14—C15—H15B108.9
N3—C6—H6B109.4H15A—C15—H15B107.8
N2—Mn1—N1—C525.2 (3)C1—N1—C5—C40.0 (4)
N3—Mn1—N1—C519.9 (2)Mn1—N1—C5—C4178.6 (2)
Cl2—Mn1—N1—C5147.7 (2)C1—N1—C5—C6−178.1 (3)
Cl1—Mn1—N1—C5−94.6 (2)Mn1—N1—C5—C60.5 (3)
N2—Mn1—N1—C1−156.3 (2)C3—C4—C5—N1−3.1 (5)
N3—Mn1—N1—C1−161.6 (3)C3—C4—C5—C6174.9 (3)
Cl2—Mn1—N1—C1−33.9 (3)C12—N3—C6—C5162.7 (3)
Cl1—Mn1—N1—C183.9 (3)C13—N3—C6—C5−73.7 (3)
N1—Mn1—N2—C11−20.5 (3)Mn1—N3—C6—C547.9 (3)
N3—Mn1—N2—C11−15.3 (2)N1—C5—C6—N3−34.7 (4)
Cl2—Mn1—N2—C11−142.0 (2)C4—C5—C6—N3147.2 (3)
Cl1—Mn1—N2—C1199.5 (2)C11—N2—C7—C8−0.1 (5)
N1—Mn1—N2—C7155.5 (2)Mn1—N2—C7—C8−176.0 (3)
N3—Mn1—N2—C7160.7 (3)N2—C7—C8—C9−0.5 (6)
Cl2—Mn1—N2—C734.0 (3)C7—C8—C9—C100.3 (7)
Cl1—Mn1—N2—C7−84.5 (3)C8—C9—C10—C110.4 (6)
N2—Mn1—N3—C6147.77 (19)C7—N2—C11—C100.8 (5)
N1—Mn1—N3—C6−35.30 (18)Mn1—N2—C11—C10177.0 (2)
Cl2—Mn1—N3—C6−120.79 (17)C7—N2—C11—C12−178.9 (3)
Cl1—Mn1—N3—C656.21 (19)Mn1—N2—C11—C12−2.7 (3)
N2—Mn1—N3—C1229.15 (19)C9—C10—C11—N2−0.9 (5)
N1—Mn1—N3—C12−153.9 (2)C9—C10—C11—C12178.8 (3)
Cl2—Mn1—N3—C12120.59 (18)C6—N3—C12—C11−154.0 (3)
Cl1—Mn1—N3—C12−62.4 (2)C13—N3—C12—C1184.1 (3)
N2—Mn1—N3—C13−94.1 (2)Mn1—N3—C12—C11−40.4 (3)
N1—Mn1—N3—C1382.9 (2)N2—C11—C12—N330.8 (4)
Cl2—Mn1—N3—C13−2.6 (2)C10—C11—C12—N3−148.9 (3)
Cl1—Mn1—N3—C13174.37 (18)C6—N3—C13—C14171.8 (3)
C5—N1—C1—C22.5 (5)C12—N3—C13—C14−64.3 (3)
Mn1—N1—C1—C2−176.0 (3)Mn1—N3—C13—C1456.0 (3)
N1—C1—C2—C3−1.8 (5)N3—C13—C14—C15176.4 (2)
C1—C2—C3—C4−1.4 (6)C13—C14—C15—C15i−176.3 (3)
C2—C3—C4—C53.7 (5)
Symmetry codes: (i) −x+1, −y+1, −z.
Acknowledgements top

This work was supported by the Korea Research Foundation (grant No. 2006-353-C00028).

references
References top

Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Hwang, I.-C. & Ha, K. (2007). Acta Cryst. E63, m2302.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Song, A.-R., Hwang, I.-C. & Ha, K. (2008). Acta Cryst. E64, m44. Please check; originally author Song was missing from original reference

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.