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Acta Cryst. (2007). E63, m2337    [ doi:10.1107/S1600536807039475 ]

Diaqua[N,N'-bis(salicylidene)propanediamine(2-)]manganese(III) chloride

I.-C. Hwang and K. Ha

Abstract top

The title compound (systematic name: diaqua{2,2'-[propane-1,3-diylbis(nitrilomethylidyne)]diphenolato}manganese(III) chloride), [Mn(C17H16N2O2)(H2O)2]Cl, consists of an MnIII cation complex and a counter-anion. In the complex, the Mn3+ ion is six-coordinated by the dianion of the tetradentate ligand N,N'-bis(salicylidene)-1,3-diaminopropane and two water molecules in a distorted octahedral geometry. The molecules are assembled through intermolecular O-H...Cl and O-H...O hydrogen bonds and [pi]-[pi] interactions [the centroid-centroid distance is 3.865 Å and the dihedral angle between the ring planes is 12.9°] along the a axis.

Comment top

The crystal structure of the title compound consists of cation complex [Mn(salpn)(H2O)2]+ (salpn = N,N'-bis(salicylidene)-1,3-diiminopropane dianion) and a chloride counter anion. MnIII ion is six-coordinated by two N and two O atoms from the tetradentate ligand (salpn) occupying the four equatorial positions and two O atoms of water molecules in the axial positions (Fig.1). The coordination environment around the Mn centre is distorted octahedral. Within the equatorial plane, the chelating angles lie in the range of 90.39 (7)°–94.19 (8)° and the O1—Mn—O2 bond angle is 84.41 (6)°. The apical O3w—Mn—O4w bond angle is 173.95 (8)° (Table 1). The Mn—N bond lengths [2.0190 (18) and 2.0369 (18) Å] are longer than the Mn—O bond [1.8843 (14) and 1.8861 (15) Å] but the bond distances between the Mn atom and the O atoms of the water ligands are considerably longer [2.195 (2) and 2.240 (2) Å]. The compound displays the intermolecular hydrogen bonds between the O atoms of the water molecules and the O atoms of the chelate ligand, and water molecules and Cl anions (Table 2, Fig. 2). Moreover, there are intermolecular π-π interactions between the adjacent benzene rings. For Cg1 (the centroid of six-membered ring C1–C6) and Cg2i (ring C12–C17; symmetry code i: −x, 1 − y, −z), the centroid-centroid distance is 3.865 Å and the dihedral angle between the ring planes is 12.9°. The compounds are assembled through these hydrogen-bonding and π-π interactions along the a axis (Fig. 2).

Related literature top

For related literature, see: Gohdes & Armstrong (1992); Huang et al. (2002).

Experimental top

Mn(CH3COO)3·2H2O (1.00 g, 3.73 mmol), NaCl (0.22 g, 3.76 mmol) and N,N'-bis(salicylidene)-1,3-diiminopropane (H2salpn; 1.06 g, 3.75 mmol) in EtOH (70 ml) and H2O (10 ml) were stirred for 3 h at room temparature and then filtered. The solvent was reduced to 2 ml, the residue washed with acetone and dried under vacuum, to give a dark green powder (0.79 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a MeOH solution. MS (FAB): m/z 335 (Mn(salpn)+); IR (KBr): 3446 cm−1 (broad).

Refinement top

H atoms were positioned geometrically and allowed to ride on their respective carrier atoms [C—H = 0.93 (sp2) or 0.97 Å (sp3) and Uiso(H) = 1.2Ueq(C)]. The H atoms of the water ligands were localized from Fourier difference maps and refined with isotropic thermal parameters.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms at C atoms have been omitted for clarity.
[Figure 2] Fig. 2. View of the crystal packing of (I). Hydrogen-bond interactions are drawn with dashed lines.
diaqua{2,2'-[propane-1,3-diylbis(nitrilomethylidyne)]diphenolato}manganese(III) chloride top
Crystal data top
[Mn(C17H16N2O2)(H2O)2]ClZ = 2
Mr = 406.74F000 = 420
Triclinic, P1Dx = 1.536 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.6540 (8) ÅCell parameters from 3154 reflections
b = 10.2633 (10) Åθ = 2.4–23.6º
c = 11.5050 (12) ŵ = 0.93 mm−1
α = 102.622 (2)ºT = 293 (2) K
β = 92.777 (2)ºPlate, green
γ = 92.852 (2)º0.30 × 0.15 × 0.03 mm
V = 879.21 (16) Å3
Data collection top
Bruker SMART 1000 CCD
diffractometer		3030 independent reflections
Radiation source: fine-focus sealed tube2333 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
T = 293(2) Kθmax = 25.1º
φ and ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −9→8
Tmin = 0.857, Tmax = 0.973k = −12→10
12748 measured reflectionsl = −13→13
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.069  w = 1/[σ2(Fo2) + (0.0313P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.95(Δ/σ)max < 0.001
3030 reflectionsΔρmax = 0.32 e Å−3
242 parametersΔρmin = −0.20 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mn(C17H16N2O2)(H2O)2]Clγ = 92.852 (2)º
Mr = 406.74V = 879.21 (16) Å3
Triclinic, P1Z = 2
a = 7.6540 (8) ÅMo Kα
b = 10.2633 (10) ŵ = 0.93 mm−1
c = 11.5050 (12) ÅT = 293 (2) K
α = 102.622 (2)º0.30 × 0.15 × 0.03 mm
β = 92.777 (2)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		3030 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2333 reflections with I > 2σ(I)
Tmin = 0.857, Tmax = 0.973Rint = 0.033
12748 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.032242 parameters
wR(F2) = 0.069H atoms treated by a mixture of
independent and constrained refinement
S = 0.95Δρmax = 0.32 e Å−3
3030 reflectionsΔρmin = −0.20 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 > 2sigma(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
Mn0.24240 (5)0.35744 (3)0.06024 (3)0.03003 (12)
O10.2431 (2)0.39908 (14)−0.09134 (13)0.0359 (4)
O20.2259 (2)0.54309 (14)0.11629 (13)0.0369 (4)
O3W0.5292 (3)0.3795 (2)0.0863 (2)0.0482 (5)
H3A0.572 (4)0.349 (3)0.137 (2)0.062 (11)*
H3B0.586 (4)0.444 (3)0.084 (2)0.064 (11)*
O4W−0.0482 (3)0.3126 (2)0.03569 (19)0.0421 (5)
H4A−0.106 (4)0.300 (3)0.093 (2)0.065 (10)*
H4B−0.087 (3)0.357 (3)0.003 (2)0.040 (10)*
N10.2679 (2)0.16265 (17)−0.01432 (17)0.0326 (5)
N20.2398 (3)0.32827 (19)0.22969 (16)0.0337 (5)
C10.1984 (3)0.3203 (2)−0.1983 (2)0.0322 (6)
C20.1508 (3)0.3789 (3)−0.2925 (2)0.0419 (7)
H20.15050.4715−0.28040.050*
C30.1044 (4)0.2999 (3)−0.4032 (2)0.0527 (8)
H30.06910.3398−0.46500.063*
C40.1090 (4)0.1626 (3)−0.4248 (2)0.0601 (9)
H40.07980.1107−0.50090.072*
C50.1565 (4)0.1040 (3)−0.3341 (2)0.0519 (8)
H50.16070.0114−0.34870.062*
C60.1995 (3)0.1809 (2)−0.2188 (2)0.0357 (6)
C70.2451 (3)0.1126 (2)−0.1270 (2)0.0377 (6)
H70.25990.0215−0.15150.045*
C80.3028 (3)0.0704 (2)0.0646 (2)0.0430 (7)
H8A0.41880.09210.10410.052*
H8B0.2992−0.02070.01780.052*
C90.1670 (3)0.0818 (2)0.1566 (2)0.0449 (7)
H9A0.05390.09190.11890.054*
H9B0.1589−0.00060.18480.054*
C100.2061 (4)0.1967 (2)0.2614 (2)0.0495 (7)
H10A0.10790.20270.31220.059*
H10B0.30790.17830.30730.059*
C110.2778 (3)0.4259 (3)0.3199 (2)0.0413 (6)
H110.28450.40300.39380.050*
C120.3113 (3)0.5647 (2)0.3226 (2)0.0392 (6)
C130.3625 (4)0.6512 (3)0.4327 (2)0.0556 (8)
H130.37530.61660.50070.067*
C140.3938 (4)0.7852 (3)0.4417 (3)0.0665 (9)
H140.42760.84160.51500.080*
C150.3746 (4)0.8359 (3)0.3408 (3)0.0618 (9)
H150.39810.92690.34630.074*
C160.3215 (4)0.7547 (2)0.2322 (2)0.0494 (7)
H160.30900.79120.16530.059*
C170.2863 (3)0.6180 (2)0.2213 (2)0.0350 (6)
Cl0.74037 (10)0.24095 (6)0.24821 (6)0.0510 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.0350 (2)0.0248 (2)0.0309 (2)−0.00026 (16)0.00138 (15)0.00799 (15)
O10.0526 (12)0.0253 (9)0.0292 (9)−0.0035 (8)−0.0001 (8)0.0063 (7)
O20.0535 (12)0.0242 (9)0.0313 (9)0.0030 (8)−0.0043 (8)0.0039 (7)
O3W0.0357 (13)0.0492 (13)0.0670 (14)−0.0081 (10)−0.0038 (10)0.0330 (11)
O4W0.0391 (13)0.0447 (12)0.0472 (12)0.0052 (9)0.0019 (10)0.0201 (10)
N10.0321 (13)0.0261 (11)0.0404 (12)0.0009 (9)0.0018 (9)0.0094 (9)
N20.0358 (13)0.0331 (12)0.0351 (11)0.0005 (9)0.0007 (9)0.0144 (10)
C10.0319 (15)0.0328 (14)0.0300 (13)−0.0027 (11)0.0046 (11)0.0033 (11)
C20.0523 (19)0.0384 (15)0.0349 (14)−0.0030 (13)0.0023 (12)0.0094 (12)
C30.062 (2)0.060 (2)0.0358 (15)−0.0107 (16)−0.0035 (13)0.0154 (14)
C40.083 (2)0.0532 (19)0.0348 (16)−0.0251 (17)−0.0012 (15)−0.0026 (14)
C50.067 (2)0.0385 (16)0.0438 (17)−0.0130 (14)0.0032 (14)−0.0004 (13)
C60.0381 (17)0.0315 (14)0.0349 (14)−0.0050 (12)0.0033 (11)0.0034 (11)
C70.0369 (17)0.0241 (13)0.0498 (17)−0.0014 (11)0.0071 (12)0.0034 (12)
C80.0489 (19)0.0294 (14)0.0543 (17)0.0075 (12)0.0014 (13)0.0164 (12)
C90.0469 (19)0.0348 (15)0.0596 (18)−0.0001 (13)0.0035 (14)0.0254 (14)
C100.064 (2)0.0445 (16)0.0465 (16)−0.0010 (14)0.0029 (14)0.0264 (14)
C110.0411 (17)0.0531 (17)0.0323 (14)0.0011 (13)−0.0003 (12)0.0157 (13)
C120.0420 (18)0.0407 (16)0.0323 (14)0.0012 (13)−0.0024 (12)0.0036 (12)
C130.064 (2)0.059 (2)0.0394 (16)0.0050 (16)−0.0098 (14)0.0044 (14)
C140.080 (3)0.056 (2)0.0490 (19)0.0029 (18)−0.0205 (17)−0.0141 (16)
C150.075 (2)0.0373 (17)0.064 (2)−0.0030 (15)−0.0143 (17)−0.0030 (15)
C160.066 (2)0.0327 (15)0.0455 (16)0.0004 (14)−0.0073 (14)0.0037 (13)
C170.0353 (16)0.0304 (14)0.0370 (14)0.0043 (11)0.0007 (11)0.0021 (11)
Cl0.0629 (5)0.0414 (4)0.0525 (4)0.0080 (3)0.0046 (3)0.0176 (3)
Geometric parameters (Å, °) top
Mn—O11.8843 (14)C5—C61.403 (3)
Mn—O21.8861 (15)C5—H50.9300
Mn—N12.0191 (18)C6—C71.429 (3)
Mn—N22.0369 (18)C7—H70.9300
Mn—O3W2.195 (2)C8—C91.510 (3)
Mn—O4W2.240 (2)C8—H8A0.9700
O1—C11.335 (2)C8—H8B0.9700
O2—C171.330 (3)C9—C101.498 (3)
O3W—H3A0.78 (3)C9—H9A0.9700
O3W—H3B0.79 (3)C9—H9B0.9700
O4W—H4A0.84 (3)C10—H10A0.9700
O4W—H4B0.72 (2)C10—H10B0.9700
N1—C71.285 (3)C11—C121.428 (3)
N1—C81.473 (3)C11—H110.9300
N2—C111.286 (3)C12—C171.400 (3)
N2—C101.488 (3)C12—C131.404 (3)
C1—C21.392 (3)C13—C141.365 (4)
C1—C61.399 (3)C13—H130.9300
C2—C31.372 (3)C14—C151.376 (4)
C2—H20.9300C14—H140.9300
C3—C41.379 (4)C15—C161.372 (3)
C3—H30.9300C15—H150.9300
C4—C51.358 (3)C16—C171.392 (3)
C4—H40.9300C16—H160.9300
O1—Mn—O284.41 (6)C1—C6—C7122.7 (2)
O1—Mn—N190.39 (7)C5—C6—C7118.0 (2)
O2—Mn—N1174.54 (7)N1—C7—C6127.4 (2)
O1—Mn—N2175.42 (7)N1—C7—H7116.3
O2—Mn—N291.01 (7)C6—C7—H7116.3
N1—Mn—N294.19 (8)N1—C8—C9109.7 (2)
O1—Mn—O3W93.00 (8)N1—C8—H8A109.7
O2—Mn—O3W91.15 (8)C9—C8—H8A109.7
N1—Mn—O3W87.45 (8)N1—C8—H8B109.7
N2—Mn—O3W87.16 (8)C9—C8—H8B109.7
O1—Mn—O4W90.08 (8)H8A—C8—H8B108.2
O2—Mn—O4W94.33 (7)C10—C9—C8113.6 (2)
N1—Mn—O4W87.33 (7)C10—C9—H9A108.8
N2—Mn—O4W90.18 (8)C8—C9—H9A108.8
O3W—Mn—O4W173.95 (8)C10—C9—H9B108.8
C1—O1—Mn129.05 (14)C8—C9—H9B108.8
C17—O2—Mn127.51 (14)H9A—C9—H9B107.7
Mn—O3W—H3A117 (2)N2—C10—C9114.5 (2)
Mn—O3W—H3B125 (2)N2—C10—H10A108.6
H3A—O3W—H3B108 (3)C9—C10—H10A108.6
Mn—O4W—H4A120.5 (19)N2—C10—H10B108.6
Mn—O4W—H4B110 (2)C9—C10—H10B108.6
H4A—O4W—H4B114 (3)H10A—C10—H10B107.6
C7—N1—C8117.68 (19)N2—C11—C12129.1 (2)
C7—N1—Mn123.57 (16)N2—C11—H11115.5
C8—N1—Mn118.61 (15)C12—C11—H11115.5
C11—N2—C10114.2 (2)C17—C12—C13119.2 (2)
C11—N2—Mn120.71 (16)C17—C12—C11122.5 (2)
C10—N2—Mn125.04 (16)C13—C12—C11118.2 (2)
O1—C1—C2118.9 (2)C14—C13—C12121.1 (3)
O1—C1—C6122.0 (2)C14—C13—H13119.4
C2—C1—C6119.1 (2)C12—C13—H13119.4
C3—C2—C1119.9 (2)C13—C14—C15119.2 (3)
C3—C2—H2120.0C13—C14—H14120.4
C1—C2—H2120.0C15—C14—H14120.4
C2—C3—C4121.4 (3)C16—C15—C14121.2 (3)
C2—C3—H3119.3C16—C15—H15119.4
C4—C3—H3119.3C14—C15—H15119.4
C5—C4—C3119.4 (2)C15—C16—C17120.6 (3)
C5—C4—H4120.3C15—C16—H16119.7
C3—C4—H4120.3C17—C16—H16119.7
C4—C5—C6120.9 (3)O2—C17—C16119.2 (2)
C4—C5—H5119.5O2—C17—C12122.2 (2)
C6—C5—H5119.5C16—C17—C12118.6 (2)
C1—C6—C5119.2 (2)
O2—Mn—O1—C1−156.77 (19)C2—C1—C6—C51.4 (4)
N1—Mn—O1—C124.90 (19)O1—C1—C6—C71.2 (4)
O3W—Mn—O1—C1112.37 (19)C2—C1—C6—C7−179.4 (2)
O4W—Mn—O1—C1−62.42 (19)C4—C5—C6—C1−2.0 (4)
O1—Mn—O2—C17−150.14 (19)C4—C5—C6—C7178.8 (3)
N2—Mn—O2—C1729.9 (2)C8—N1—C7—C6175.9 (2)
O3W—Mn—O2—C17−57.24 (19)Mn—N1—C7—C60.2 (3)
O4W—Mn—O2—C17120.20 (19)C1—C6—C7—N19.7 (4)
O1—Mn—N1—C7−13.38 (19)C5—C6—C7—N1−171.1 (2)
N2—Mn—N1—C7166.67 (18)C7—N1—C8—C9−122.8 (2)
O3W—Mn—N1—C7−106.37 (19)Mn—N1—C8—C953.1 (2)
O4W—Mn—N1—C776.68 (19)N1—C8—C9—C10−82.3 (3)
O1—Mn—N1—C8170.94 (17)C11—N2—C10—C9−178.2 (2)
N2—Mn—N1—C8−9.02 (17)Mn—N2—C10—C9−1.8 (3)
O3W—Mn—N1—C877.95 (17)C8—C9—C10—N252.7 (3)
O4W—Mn—N1—C8−99.00 (17)C10—N2—C11—C12−177.6 (3)
O2—Mn—N2—C11−19.4 (2)Mn—N2—C11—C125.8 (4)
N1—Mn—N2—C11158.91 (19)N2—C11—C12—C177.8 (4)
O3W—Mn—N2—C1171.67 (19)N2—C11—C12—C13−175.6 (3)
O4W—Mn—N2—C11−113.76 (19)C17—C12—C13—C14−2.2 (4)
O2—Mn—N2—C10164.4 (2)C11—C12—C13—C14−178.9 (3)
N1—Mn—N2—C10−17.3 (2)C12—C13—C14—C150.0 (5)
O3W—Mn—N2—C10−104.5 (2)C13—C14—C15—C161.3 (5)
O4W—Mn—N2—C1070.0 (2)C14—C15—C16—C17−0.3 (5)
Mn—O1—C1—C2158.04 (17)Mn—O2—C17—C16156.36 (19)
Mn—O1—C1—C6−22.6 (3)Mn—O2—C17—C12−25.4 (3)
O1—C1—C2—C3180.0 (2)C15—C16—C17—O2176.3 (2)
C6—C1—C2—C30.6 (4)C15—C16—C17—C12−1.9 (4)
C1—C2—C3—C4−2.1 (4)C13—C12—C17—O2−175.1 (2)
C2—C3—C4—C51.5 (4)C11—C12—C17—O21.5 (4)
C3—C4—C5—C60.5 (4)C13—C12—C17—C163.1 (4)
O1—C1—C6—C5−178.0 (2)C11—C12—C17—C16179.7 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H3A···Cl0.78 (3)2.27 (3)3.033 (2)166 (3)
O3W—H3B···O1i0.79 (3)2.00 (3)2.782 (3)172 (3)
O4W—H4A···Clii0.84 (3)2.36 (3)3.192 (2)173 (3)
O4W—H4B···O2iii0.72 (2)2.15 (2)2.864 (3)169 (3)
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y, z; (iii) −x, −y+1, −z.
Selected geometric parameters (Å, °) top
Mn—O11.8843 (14)Mn—N22.0369 (18)
Mn—O21.8861 (15)Mn—O3W2.195 (2)
Mn—N12.0191 (18)Mn—O4W2.240 (2)
O1—Mn—O284.41 (6)N1—Mn—N294.19 (8)
O1—Mn—N190.39 (7)O3W—Mn—O4W173.95 (8)
O2—Mn—N291.01 (7)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H3A···Cl0.78 (3)2.27 (3)3.033 (2)166 (3)
O3W—H3B···O1i0.79 (3)2.00 (3)2.782 (3)172 (3)
O4W—H4A···Clii0.84 (3)2.36 (3)3.192 (2)173 (3)
O4W—H4B···O2iii0.72 (2)2.15 (2)2.864 (3)169 (3)
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y, z; (iii) −x, −y+1, −z.
Acknowledgements top

This research was supported in part by the BK21 program from the Ministry of Education and Human Resources Development, Republic of Korea.

references
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