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Acta Cryst. (2007). E63, m3096    [ doi:10.1107/S1600536807059090 ]

[mu]-Fumarato-[kappa]4O,O';O'',O'''-bis[aqua(2,9-dimethyl-1,10-phenanthroline-[kappa]2N,N)(nitrato-[kappa]2O,O')manganese(II)]

L. Li, H. Zhang, M.-L. Zhang and S. Bi

Abstract top

In the centrosymmetric title compound, [Mn2(C4H2O4)(NO3)2(C14H12N2)2(H2O)2], each Mn atom is six-coordinate in a distorted octahedral geometry. Molecules form stacks by [pi]-[pi] interactions (centroid-centroid distances of 3.826, 3.708 and 3.719 Å). The water molecules act as donors to form O-H...O hydrogen bonds. Moreover, the molecules are linked into chains along the a axis by C-H...O intermolecular hydrogen bonds.

Comment top

Metal-phenanthroline complexes are good indicators for hydridization detection in DNA electrochemical biosensors (Wang et al., 1996). In our search for new indicators, the title complex was synthesized and its structure is presented here.

The binuclear manganese complex in (I) possesses a crystallographically imposed centre of symmetry (Fig. 1). Each MnII atom is six-coordinated by two N atoms from one 9,10-dimethyl-phennathroline ligand, one O atoms from water, one O atom from fumaric acid, and two O atom from nitrate anion in a distorted octahedral environment. The axial position is occupied by water molecule O atom and one N atom from 9,10-dimethyl-phennathroline ligand, with an O1W—Mn1—N1 bond angle of 167.68 (1)°.

In the crystal structure, the short interplanar distances between the phenanthroline moieties suggest strong π···π interactions. The distances between benzene rings are Cg1···Cg2iii = 3.826, Cg1···Cg3iii = 3.708 and Cg3···Cg3iii = 3.719 Å, where Cg1, Cg2 and Cg3 denote the centroids of N1/C2—C5/C13, N2/C8—C12 and C5—C8/C12/C13 rings, respectively, which contribure to the crystal packing [symmetry code: (i) −x + 1, −y, −z + 1]. The water molecules act as donors to form O—H···O hydrogen bonds (Table 2). Moreover, the molecules are linked into chains along the a axis by C6—H6A···O4 and C9—H9A···O1 intermolecular hydrogen bonds.

Related literature top

For details of the DNA electrochemical biosensors of metal–phenanthroline complexes, see: Wang et al. (1996). For bond-length data, see: Allen et al. (1987).

Experimental top

To a solution of 2,9-dimethyl-1,10-phenanthroline (0.21 g, 1 mmol) and fumaric acid (0.058 g, 0.5 mmol) in ethanol (10 ml) was added a solution of Mn(Ac)2 (0.11 g, 1 mmol) in distilled water (10 ml). The mixture was stirred and then refluxed for 2 h. The hot solution was then filtered into another flask containing ethanol-water. Brown crystals appeared over a period of one week by slow evaporation at room temperature.

Refinement top

All H atoms were located in difference Fourier map. Water H atoms were refined with O1W—H1W1 and O1W—H2W1 distance restrains of 0.82 Å [1.5 Ueq(O)]. The remaining H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.96 Å, and with Uiso(H) = 1.2 Ueq(C) and 1.5 Ueq(methyl C) H atoms.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The structure of the compound (I) showing 50% probability displacement ellipsoids and the atom numbering scheme. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. A packing diagram of (I), viewed down the b axis. Hydrogen bonds are indicated by dashed lines.
µ-Fumarato-κ4O,O';O'',O'''-bis[aqua(2,9- dimethyl-1,10-phenanthroline-κ2N,N)(nitrato- κ2O,O')manganese(II)] top
Crystal data top
[Mn2(C4H2O4)(NO3)2(C14H12N2)2(H2O)2]F000 = 820
Mr = 800.50Dx = 1.587 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5923 reflections
a = 12.034 (2) Åθ = 2.2–26.0º
b = 9.1824 (16) ŵ = 0.83 mm−1
c = 16.416 (2) ÅT = 293 (2) K
β = 113.532 (10)ºBlock, colourless
V = 1663.1 (4) Å30.42 × 0.33 × 0.20 mm
Z = 2
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer		3266 independent reflections
Radiation source: fine-focus sealed tube2951 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.013
Detector resolution: 8.33 pixels mm-1θmax = 26.1º
T = 293(2) Kθmin = 1.9º
ω scansh = −14→13
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −10→11
Tmin = 0.723, Tmax = 0.852l = −20→18
8963 measured reflections
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)] = 0.043H-atom parameters constrained
wR(F2) = 0.134  w = 1/[σ2(Fo2) + (0.0858P)2 + 1.1575P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
3266 reflectionsΔρmax = 0.77 e Å−3
230 parametersΔρmin = −0.86 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mn2(C4H2O4)(NO3)2(C14H12N2)2(H2O)2]V = 1663.1 (4) Å3
Mr = 800.50Z = 2
Monoclinic, P21/cMo Kα
a = 12.034 (2) ŵ = 0.83 mm−1
b = 9.1824 (16) ÅT = 293 (2) K
c = 16.416 (2) Å0.42 × 0.33 × 0.20 mm
β = 113.532 (10)º
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer		3266 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2951 reflections with I > 2σ(I)
Tmin = 0.723, Tmax = 0.852Rint = 0.013
8963 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043230 parameters
wR(F2) = 0.134H-atom parameters constrained
S = 1.06Δρmax = 0.77 e Å−3
3266 reflectionsΔρmin = −0.86 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 > 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
Mn10.17583 (3)0.18538 (4)0.32962 (2)0.03045 (16)
O20.1578 (2)0.4355 (3)0.31837 (15)0.0611 (6)
C130.4425 (3)0.1767 (3)0.43220 (19)0.0417 (6)
C170.0603 (2)0.0233 (3)0.40796 (17)0.0428 (6)
N10.3457 (2)0.2379 (3)0.44183 (15)0.0428 (5)
O10.2395 (2)0.3349 (2)0.2384 (2)0.0683 (7)
O30.0941 (2)0.1538 (2)0.41663 (15)0.0567 (5)
N20.3019 (2)0.0450 (2)0.30670 (14)0.0397 (5)
N30.2067 (2)0.4487 (2)0.26373 (17)0.0484 (6)
O40.07726 (19)−0.0591 (2)0.35325 (14)0.0544 (5)
C120.4195 (2)0.0740 (3)0.36088 (18)0.0414 (6)
C180.0025 (2)−0.0354 (3)0.46628 (18)0.0441 (6)
H18A−0.0319−0.12780.45390.066*
C20.3652 (3)0.3286 (3)0.5095 (2)0.0511 (7)
C80.5185 (3)0.0068 (3)0.3506 (2)0.0504 (7)
C70.6398 (3)0.0422 (4)0.4098 (3)0.0644 (9)
H7A0.7047−0.00160.40230.077*
C90.4917 (3)−0.0945 (4)0.2813 (2)0.0600 (8)
H9A0.5539−0.14060.27130.072*
C50.5638 (3)0.2069 (3)0.4898 (2)0.0528 (7)
C100.3740 (3)−0.1249 (3)0.2288 (2)0.0565 (8)
H10A0.3560−0.19410.18390.068*
C30.4854 (3)0.3626 (4)0.5702 (2)0.0635 (9)
H3A0.49760.42560.61740.076*
C140.1502 (3)−0.0849 (4)0.1806 (2)0.0568 (7)
H14A0.0965−0.02750.19790.085*
H14B0.1336−0.18640.18430.085*
H14C0.1380−0.06130.12070.085*
C40.5817 (3)0.3042 (4)0.5597 (2)0.0633 (9)
H4A0.65990.32840.59890.076*
C110.2793 (3)−0.0527 (3)0.24174 (18)0.0442 (6)
C10.2607 (4)0.3946 (4)0.5233 (2)0.0686 (9)
H1A0.18620.36160.47760.103*
H1B0.26520.49880.52100.103*
H1C0.26340.36570.58030.103*
C60.6609 (3)0.1381 (4)0.4763 (2)0.0626 (9)
H6A0.74040.15970.51400.075*
O1W0.0156 (2)0.1824 (2)0.21622 (17)0.0578 (6)
H1W1−0.03270.12650.22370.069*
H2W1−0.00540.26610.19990.087*
O50.2199 (2)0.5687 (3)0.23736 (19)0.0756 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0309 (2)0.0322 (2)0.0326 (2)−0.00011 (12)0.01727 (17)0.00015 (13)
O20.0537 (12)0.0752 (16)0.0575 (13)−0.0015 (11)0.0255 (10)0.0064 (11)
C130.0423 (14)0.0407 (14)0.0415 (14)−0.0010 (10)0.0162 (11)0.0109 (10)
C170.0358 (12)0.0532 (15)0.0381 (13)−0.0041 (11)0.0136 (10)0.0003 (11)
N10.0481 (12)0.0426 (12)0.0398 (11)−0.0047 (10)0.0198 (9)0.0004 (9)
O10.0637 (15)0.0486 (13)0.102 (2)0.0047 (10)0.0423 (14)−0.0012 (12)
O30.0667 (14)0.0573 (12)0.0567 (12)−0.0170 (10)0.0358 (11)−0.0034 (10)
N20.0453 (12)0.0376 (11)0.0415 (11)−0.0011 (9)0.0228 (9)0.0032 (9)
N30.0459 (12)0.0379 (12)0.0585 (14)−0.0027 (9)0.0178 (11)0.0094 (10)
O40.0573 (12)0.0651 (13)0.0474 (11)0.0009 (10)0.0278 (9)−0.0037 (10)
C120.0426 (13)0.0400 (13)0.0451 (13)0.0035 (10)0.0213 (11)0.0132 (11)
C180.0422 (13)0.0474 (15)0.0442 (13)−0.0074 (11)0.0189 (11)−0.0016 (11)
C20.0658 (19)0.0458 (16)0.0423 (15)−0.0082 (13)0.0223 (14)−0.0016 (11)
C80.0516 (15)0.0492 (15)0.0602 (17)0.0110 (12)0.0327 (14)0.0188 (13)
C70.0453 (16)0.074 (2)0.078 (2)0.0169 (15)0.0287 (15)0.0304 (19)
C90.068 (2)0.0586 (18)0.070 (2)0.0212 (15)0.0448 (17)0.0157 (16)
C50.0458 (15)0.0536 (17)0.0506 (16)−0.0047 (13)0.0104 (13)0.0191 (13)
C100.080 (2)0.0460 (16)0.0567 (17)0.0093 (15)0.0415 (17)0.0026 (14)
C30.079 (2)0.0575 (18)0.0435 (16)−0.0178 (17)0.0134 (15)−0.0053 (14)
C140.0668 (19)0.0561 (17)0.0536 (17)−0.0095 (15)0.0304 (15)−0.0129 (14)
C40.0570 (19)0.064 (2)0.0495 (18)−0.0160 (15)0.0014 (15)0.0098 (14)
C110.0577 (16)0.0393 (13)0.0441 (14)−0.0016 (12)0.0293 (12)0.0020 (11)
C10.084 (2)0.070 (2)0.063 (2)−0.0124 (18)0.0406 (19)−0.0252 (17)
C60.0400 (15)0.071 (2)0.068 (2)0.0019 (15)0.0119 (14)0.0243 (18)
O1W0.0517 (12)0.0504 (13)0.0666 (14)−0.0075 (9)0.0186 (11)0.0087 (9)
Geometric parameters (Å, °) top
Mn1—O32.053 (2)C8—C91.404 (5)
Mn1—O1W2.078 (2)C8—C71.430 (5)
Mn1—N22.136 (2)C7—C61.345 (6)
Mn1—N12.191 (2)C7—H7A0.9300
Mn1—O22.307 (3)C9—C101.361 (5)
Mn1—O12.372 (3)C9—H9A0.9300
O2—N31.260 (3)C5—C41.401 (5)
C13—N11.358 (4)C5—C61.422 (5)
C13—C51.415 (4)C10—C111.406 (4)
C13—C121.441 (4)C10—H10A0.9300
C17—O31.255 (4)C3—C41.349 (6)
C17—O41.251 (3)C3—H3A0.9300
C17—C181.491 (4)C14—C111.505 (4)
N1—C21.333 (4)C14—H14A0.9600
O1—N31.246 (3)C14—H14B0.9600
N2—C111.336 (4)C14—H14C0.9600
N2—C121.364 (3)C4—H4A0.9300
N3—O51.217 (4)C1—H1A0.9600
C12—C81.411 (4)C1—H1B0.9600
C18—C18i1.306 (5)C1—H1C0.9600
C18—H18A0.9300C6—H6A0.9300
C2—C31.425 (5)O1W—H1W10.8200
C2—C11.493 (5)O1W—H2W10.8199
O3—Mn1—O1W95.18 (10)C9—C8—C12117.1 (3)
O3—Mn1—N2127.51 (9)C9—C8—C7122.9 (3)
O1W—Mn1—N2107.74 (9)C12—C8—C7120.0 (3)
O3—Mn1—N189.52 (9)C6—C7—C8120.8 (3)
O1W—Mn1—N1167.68 (8)C6—C7—H7A119.6
N2—Mn1—N177.92 (9)C8—C7—H7A119.6
O3—Mn1—O298.08 (8)C10—C9—C8119.6 (3)
O1W—Mn1—O285.28 (8)C10—C9—H9A120.2
N2—Mn1—O2129.58 (8)C8—C9—H9A120.2
N1—Mn1—O282.78 (9)C13—C5—C4116.9 (3)
O3—Mn1—O1152.37 (9)C13—C5—C6120.1 (3)
O1W—Mn1—O181.98 (9)C4—C5—C6123.0 (3)
N2—Mn1—O178.87 (8)C9—C10—C11120.6 (3)
N1—Mn1—O188.57 (9)C9—C10—H10A119.7
O2—Mn1—O154.35 (8)C11—C10—H10A119.7
N3—O2—Mn195.62 (18)C4—C3—C2120.5 (3)
N1—C13—C5123.0 (3)C4—C3—H3A119.8
N1—C13—C12118.1 (2)C2—C3—H3A119.8
C5—C13—C12118.9 (3)C11—C14—H14A109.5
O3—C17—O4121.4 (3)C11—C14—H14B109.5
O3—C17—C18119.0 (3)H14A—C14—H14B109.5
O4—C17—C18119.6 (3)C11—C14—H14C109.5
C13—N1—C2118.8 (3)H14A—C14—H14C109.5
C13—N1—Mn1111.50 (18)H14B—C14—H14C109.5
C2—N1—Mn1129.3 (2)C3—C4—C5119.9 (3)
N3—O1—Mn192.88 (18)C3—C4—H4A120.0
C17—O3—Mn1106.22 (18)C5—C4—H4A120.0
C11—N2—C12118.6 (2)N2—C11—C10121.2 (3)
C11—N2—Mn1127.84 (19)N2—C11—C14119.4 (2)
C12—N2—Mn1113.10 (17)C10—C11—C14119.4 (3)
O5—N3—O1122.5 (3)C2—C1—H1A109.5
O5—N3—O2120.3 (3)C2—C1—H1B109.5
O1—N3—O2117.1 (2)H1A—C1—H1B109.5
N2—C12—C13118.0 (2)C2—C1—H1C109.5
N2—C12—C8122.9 (3)H1A—C1—H1C109.5
C13—C12—C8119.1 (3)H1B—C1—H1C109.5
C18i—C18—C17123.8 (3)C7—C6—C5121.1 (3)
C18i—C18—H18A118.1C7—C6—H6A119.4
C17—C18—H18A118.1C5—C6—H6A119.4
N1—C2—C3120.8 (3)Mn1—O1W—H1W1109.5
N1—C2—C1120.1 (3)Mn1—O1W—H2W1109.6
C3—C2—C1119.1 (3)H1W1—O1W—H2W1119.4
O3—Mn1—O2—N3−178.89 (17)Mn1—O2—N3—O5−179.0 (2)
O1W—Mn1—O2—N3−84.32 (17)Mn1—O2—N3—O11.4 (3)
N2—Mn1—O2—N324.9 (2)C11—N2—C12—C13−178.3 (2)
N1—Mn1—O2—N392.62 (17)Mn1—N2—C12—C138.5 (3)
O1—Mn1—O2—N3−0.82 (16)C11—N2—C12—C80.9 (4)
C5—C13—N1—C2−1.4 (4)Mn1—N2—C12—C8−172.3 (2)
C12—C13—N1—C2177.4 (2)N1—C13—C12—N20.4 (3)
C5—C13—N1—Mn1172.5 (2)C5—C13—C12—N2179.2 (2)
C12—C13—N1—Mn1−8.8 (3)N1—C13—C12—C8−178.8 (2)
O3—Mn1—N1—C13138.51 (18)C5—C13—C12—C80.0 (4)
O1W—Mn1—N1—C13−108.9 (4)O3—C17—C18—C18i−8.6 (5)
N2—Mn1—N1—C139.86 (17)O4—C17—C18—C18i169.5 (4)
O2—Mn1—N1—C13−123.29 (18)C13—N1—C2—C30.9 (4)
O1—Mn1—N1—C13−69.06 (18)Mn1—N1—C2—C3−171.7 (2)
O3—Mn1—N1—C2−48.5 (2)C13—N1—C2—C1−178.3 (3)
O1W—Mn1—N1—C264.2 (5)Mn1—N1—C2—C19.1 (4)
N2—Mn1—N1—C2−177.1 (3)N2—C12—C8—C9−0.4 (4)
O2—Mn1—N1—C249.7 (2)C13—C12—C8—C9178.8 (2)
O1—Mn1—N1—C2104.0 (2)N2—C12—C8—C7−180.0 (2)
O3—Mn1—O1—N34.9 (3)C13—C12—C8—C7−0.8 (4)
O1W—Mn1—O1—N390.76 (19)C9—C8—C7—C6−178.8 (3)
N2—Mn1—O1—N3−159.3 (2)C12—C8—C7—C60.7 (5)
N1—Mn1—O1—N3−81.31 (19)C12—C8—C9—C10−0.9 (4)
O2—Mn1—O1—N30.82 (16)C7—C8—C9—C10178.6 (3)
O4—C17—O3—Mn1−1.0 (3)N1—C13—C5—C40.5 (4)
C18—C17—O3—Mn1176.98 (19)C12—C13—C5—C4−178.2 (2)
O1W—Mn1—O3—C1772.8 (2)N1—C13—C5—C6179.6 (3)
N2—Mn1—O3—C17−44.2 (2)C12—C13—C5—C60.8 (4)
N1—Mn1—O3—C17−118.6 (2)C8—C9—C10—C111.8 (5)
O2—Mn1—O3—C17158.80 (19)N1—C2—C3—C40.5 (5)
O1—Mn1—O3—C17155.4 (2)C1—C2—C3—C4179.7 (3)
O3—Mn1—N2—C1197.9 (2)C2—C3—C4—C5−1.3 (5)
O1W—Mn1—N2—C11−13.5 (2)C13—C5—C4—C30.8 (5)
N1—Mn1—N2—C11177.8 (2)C6—C5—C4—C3−178.2 (3)
O2—Mn1—N2—C11−112.3 (2)C12—N2—C11—C100.0 (4)
O1—Mn1—N2—C11−91.3 (2)Mn1—N2—C11—C10172.1 (2)
O3—Mn1—N2—C12−89.66 (18)C12—N2—C11—C14−179.3 (2)
O1W—Mn1—N2—C12158.93 (16)Mn1—N2—C11—C14−7.2 (4)
N1—Mn1—N2—C12−9.73 (16)C9—C10—C11—N2−1.4 (4)
O2—Mn1—N2—C1260.2 (2)C9—C10—C11—C14177.9 (3)
O1—Mn1—N2—C1281.19 (17)C8—C7—C6—C50.1 (5)
Mn1—O1—N3—O5179.0 (3)C13—C5—C6—C7−0.9 (5)
Mn1—O1—N3—O2−1.4 (3)C4—C5—C6—C7178.1 (3)
Symmetry codes: (i) −x, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2ii0.822.232.978 (4)151
O1W—H2W1···O4iii0.821.872.677 (3)170
C6—H6A···O4iv0.932.573.353 (4)142
C9—H9A···O1v0.932.563.439 (5)157
Symmetry codes: (ii) −x, y−1/2, −z+1/2; (iii) −x, y+1/2, −z+1/2; (iv) −x+1, −y, −z+1; (v) −x+1, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2i0.822.232.978 (4)151
O1W—H2W1···O4ii0.821.872.677 (3)170
C6—H6A···O4iii0.932.573.353 (4)142
C9—H9A···O1iv0.932.563.439 (5)157
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, −y, −z+1; (iv) −x+1, y−1/2, −z+1/2.
Acknowledgements top

This project was supported by the Natural Science Foundation of Shandong Province (grant Nos. Z2006B01 and Y2006B07).

references
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