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Acta Cryst. (2007). E63, m1472    [ doi:10.1107/S1600536807019332 ]

Bis([mu]2-dihydrogen phosphato-[kappa]2O:O')([mu]2-hydrogen phosphato-[kappa]2O:O')bis[(1,10-phenanthroline-[kappa]2N,N')manganese(II)]

H.-X. Liu, X. Jiang and Y. Liang

Abstract top

In the title manganese phosphate, [Mn2(C12H8N2)2(H1.5PO4)2(H2PO4)], a crystallographic twofold rotation axis passes through the bridging H atom and the P atom carrying two OH groups. The structure consists of distorted trigonal-bipyramidal MnO3N2 and tetrahedral PO4 units linked through their vertices, giving rise to a discrete dinuclear molecular structure. The crystal structure is stabilized by intermolecular hydrogen bonds and strong [pi]-[pi] stacking interactions (the distance between adjacent phenanthroline rings is 3.24 Å).

Comment top

The molecular structure of the title compound, (I), which is isostructural with the previously reported zinc analogue (Ganesan et al., 2003) is illustrated in Fig 1. It consists of distorted trigonal-bipyramidal MnO3N2 and tetrahedral PO4 units. The Mn(II) cation is five coordinated by three oxygen and two nitrogen atoms, with Mn–O distances in of 2.039 (2)—2.088 (1) Å and Mn–N distances in the range 2.250 (2)–2.281 (2) Å. While all the O atoms bonded to Mn are connected to P atoms, only two oxygen atoms attached to P atoms are engaged in P–O–Mn bonds and the other two are terminal ones. The P–O distances range from 1.500 (1)–1.572 (1) Å and O–P–O bond angles fall in the range of 104.71 (8)–116.5 (1)°. It is noteworthy that the hydrogen atom attached to the O(4) atom is shared by two symmetry related H1.5P(1)O4 groups. Such O–H–O linkages have been found in zinc carbonate (Zheng et al., 1995) and also described in zinc phosphate (Lin et al., 2003) and gallophosphate (Chen et al., 2000).

The zero-dimensional molecular manganese phosphate is stably stacked into three-dimensional supramolecular arrays via strong H-bonding and π–π stacking interactions. The extensive multi-point hydrogen bonds involving the phosphate groups, forming a sheet-like structure parallel to the bc plane. Neighboring phen ligands from two adjacent layers exhibit a parallel stacking mode and are separated by 3.24 Å indicating significant attractive intermolecular aromatic interaction (Fig. 2).

Related literature top

The title complex is isostructural with the previously reported zinc analogue (Ganesan et al., 2003;Lin et al., 2003).

For related literature, see: Chen et al. (2000); Zheng & Adam (1995).

Experimental top

Compound (I) was prepared hydrothermally from a mixture of MnCO3 (0.2294 g), H3PO4 (0.4 ml 85wt%), H3BO3 (0.7287 g), phen (0.3980 g) and H2O(18 ml) in the molar ratio of 1:3:6:1:500, which was stirred for 30 min and heated at 443 K for 5 days in a Teflon-lined stainless steel autoclave (27 ml) under autogenous pressure. After cooling to room temperature, orange block-shaped crystals of (I) were obtained and washed with distilled water and dried in air. The product cannot be obtained without H3BO3 in the reaction system, although H3BO3 is absent in it.

Refinement top

All H atoms bound to C were generated geometrically and refined as riding, with C–H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atom attached to O4 was located from the difference Fourier map and refined with Uiso(H) = 1.5Ueq(O). All other hydrogen atoms attached to O were located from the difference Fourier map and refined freely.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson,1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The complex molecule [(C12H8N2Mn)2(H1.5PO4)2(H2PO4)] with displacement ellipsoids drawn at the 45% probability level.
[Figure 2] Fig. 2. View of the π–π stacking interactions between neighboring chains.
Bis(µ2-dihydrogen phosphato-κ2O:O')(µ2-hydrogen phosphate-κ2O:O')bis[(1,10-phenanthroline-κ2N,N')manganese(II)] top
Crystal data top
[Mn2(C12H8N2)2(H1.5PO4)2(H2PO4)]F(000) = 3072
Mr = 760.24Dx = 1.903 Mg m−3
Orthorhombic, Fdd2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F2-2dCell parameters from 12033 reflections
a = 40.837 (8) Åθ = 3.0–27.5°
b = 7.457 (2) ŵ = 1.21 mm−1
c = 17.424 (4) ÅT = 298 K
V = 5306 (2) Å3Block, orange
Z = 80.24 × 0.21 × 0.20 mm
Data collection top
Rigaku R AXIS RAPID IP
diffractometer		2965 independent reflections
Radiation source: fine-focus sealed tube2889 reflections with I > 2σ(I)
graphiteRint = 0.021
ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −52→52
Tmin = 0.781, Tmax = 0.785k = −8→9
11691 measured reflectionsl = −22→22
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)] = 0.021H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.050 w = 1/[σ2(Fo2) + (0.0237P)2 + 5.2948P]
where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max = 0.002
2965 reflectionsΔρmax = 0.34 e Å−3
212 parametersΔρmin = −0.32 e Å−3
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.001 (11)
Crystal data top
[Mn2(C12H8N2)2(H1.5PO4)2(H2PO4)]V = 5306 (2) Å3
Mr = 760.24Z = 8
Orthorhombic, Fdd2Mo Kα radiation
a = 40.837 (8) ŵ = 1.21 mm−1
b = 7.457 (2) ÅT = 298 K
c = 17.424 (4) Å0.24 × 0.21 × 0.20 mm
Data collection top
Rigaku R AXIS RAPID IP
diffractometer		2965 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2889 reflections with I > 2σ(I)
Tmin = 0.781, Tmax = 0.785Rint = 0.021
11691 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.021H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.050Δρmax = 0.34 e Å−3
S = 1.15Δρmin = −0.32 e Å−3
2965 reflectionsAbsolute structure: Flack (1983)
212 parametersFlack parameter: −0.001 (11)
1 restraint
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
Mn10.044642 (7)0.13553 (4)0.281370 (17)0.00725 (7)
N10.09857 (4)0.0839 (2)0.26712 (9)0.0089 (3)
N20.07098 (4)0.3889 (2)0.32082 (10)0.0098 (3)
C10.05716 (5)0.5367 (3)0.34805 (12)0.0118 (4)
H3A0.03440.54420.34820.014*
C20.07522 (5)0.6825 (3)0.37674 (12)0.0128 (4)
H5A0.06460.78320.39600.015*
C30.10869 (5)0.6737 (3)0.37589 (12)0.0111 (4)
H9A0.12100.76880.39470.013*
C40.12447 (5)0.5194 (2)0.34630 (12)0.0091 (4)
C50.15935 (5)0.5011 (3)0.34250 (12)0.0119 (4)
H2A0.17260.59520.35860.014*
C60.17320 (5)0.3490 (3)0.31582 (12)0.0114 (4)
H10A0.19590.33930.31420.014*
C70.15337 (5)0.2018 (2)0.28990 (12)0.0097 (4)
C80.16672 (5)0.0404 (3)0.25998 (12)0.0123 (4)
H8A0.18930.02340.25840.015*
C90.14595 (5)−0.0896 (3)0.23344 (13)0.0128 (4)
H11A0.1543−0.19490.21260.015*
C100.11195 (5)−0.0634 (3)0.23779 (11)0.0100 (4)
H7A0.0982−0.15290.21940.012*
C110.11897 (4)0.2161 (2)0.29182 (11)0.0089 (4)
C120.10420 (5)0.3798 (3)0.32039 (11)0.0087 (4)
O1−0.03585 (3)0.10010 (17)0.22335 (9)0.0121 (3)
O20.01414 (3)0.29950 (17)0.21556 (8)0.0109 (3)
O3−0.03932 (3)0.40311 (19)0.16080 (9)0.0115 (3)
H3−0.0326 (7)0.495 (4)0.1817 (19)0.039 (9)*
O4−0.00937 (3)0.15818 (18)0.09524 (8)0.0100 (3)
H10.00000.00000.09590.015*
P1−0.017240 (11)0.23433 (6)0.17636 (3)0.00712 (10)
O50.02678 (3)0.08838 (19)0.38875 (9)0.0141 (3)
O60.01809 (4)−0.1380 (2)0.48733 (9)0.0156 (3)
H20.0070 (8)−0.188 (4)0.5200 (18)0.035 (9)*
P20.00000.00000.43408 (4)0.00887 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.00656 (12)0.00744 (12)0.00776 (14)−0.00075 (10)−0.00106 (11)0.00038 (10)
N10.0104 (7)0.0097 (7)0.0067 (9)0.0004 (6)−0.0003 (6)0.0022 (6)
N20.0103 (8)0.0101 (8)0.0089 (9)0.0003 (6)−0.0010 (6)0.0014 (6)
C10.0107 (9)0.0132 (9)0.0114 (10)0.0015 (7)0.0000 (7)0.0010 (8)
C20.0172 (10)0.0107 (9)0.0104 (10)0.0023 (7)−0.0002 (8)−0.0001 (7)
C30.0149 (9)0.0093 (9)0.0090 (10)−0.0021 (7)−0.0009 (8)0.0003 (7)
C40.0115 (9)0.0111 (9)0.0048 (9)−0.0022 (7)−0.0017 (7)0.0027 (7)
C50.0097 (9)0.0136 (10)0.0125 (10)−0.0044 (7)−0.0022 (7)0.0021 (8)
C60.0070 (8)0.0174 (9)0.0100 (10)−0.0011 (7)−0.0002 (7)0.0031 (8)
C70.0105 (8)0.0126 (9)0.0061 (9)0.0000 (7)0.0001 (7)0.0032 (7)
C80.0089 (9)0.0173 (10)0.0108 (10)0.0029 (7)0.0017 (7)0.0035 (8)
C90.0168 (10)0.0099 (10)0.0118 (10)0.0040 (7)0.0023 (8)0.0016 (8)
C100.0132 (9)0.0102 (9)0.0066 (10)−0.0026 (7)−0.0006 (8)0.0020 (7)
C110.0103 (9)0.0099 (8)0.0065 (9)−0.0001 (6)−0.0010 (7)0.0021 (7)
C120.0090 (8)0.0109 (9)0.0062 (9)−0.0011 (7)−0.0002 (7)0.0021 (7)
O10.0140 (7)0.0090 (6)0.0134 (8)−0.0016 (5)0.0023 (6)0.0016 (6)
O20.0113 (7)0.0082 (6)0.0132 (7)−0.0007 (5)−0.0041 (5)0.0020 (5)
O30.0106 (6)0.0069 (6)0.0169 (8)0.0012 (5)−0.0048 (5)−0.0015 (5)
O40.0119 (7)0.0100 (6)0.0082 (7)−0.0001 (5)0.0009 (5)0.0008 (5)
P10.0068 (2)0.0062 (2)0.0084 (2)−0.00046 (16)−0.00107 (17)0.00098 (18)
O50.0138 (7)0.0174 (7)0.0111 (7)−0.0058 (5)0.0005 (6)0.0019 (6)
O60.0122 (7)0.0199 (8)0.0147 (9)0.0044 (5)0.0032 (6)0.0077 (6)
P20.0089 (3)0.0111 (3)0.0066 (3)−0.0004 (2)0.0000.000
Geometric parameters (Å, °) top
Mn1—O52.0386 (16)C7—C111.409 (3)
Mn1—O1i2.0587 (14)C7—C81.420 (3)
Mn1—O22.0884 (14)C8—C91.369 (3)
Mn1—N12.2495 (17)C8—H8A0.9300
Mn1—N22.2805 (16)C9—C101.404 (3)
N1—C101.329 (2)C9—H11A0.9300
N1—C111.360 (2)C10—H7A0.9300
N2—C11.326 (2)C11—C121.450 (3)
N2—C121.358 (2)O1—P11.4998 (14)
C1—C21.406 (3)O1—Mn1i2.0587 (14)
C1—H3A0.9300O2—P11.5313 (13)
C2—C31.369 (3)O3—P11.5718 (14)
C2—H5A0.9300O3—H30.82 (3)
C3—C41.416 (3)O4—P11.5568 (15)
C3—H9A0.9300O4—H11.2402
C4—C121.404 (3)O5—P21.5015 (14)
C4—C51.433 (3)O6—P21.5704 (15)
C5—C61.350 (3)O6—H20.82 (3)
C5—H2A0.9300P2—O5i1.5015 (14)
C6—C71.437 (3)P2—O6i1.5704 (15)
C6—H10A0.9300
O5—Mn1—O1i103.95 (6)C11—C7—C6119.76 (17)
O5—Mn1—O2113.05 (6)C8—C7—C6123.10 (17)
O1i—Mn1—O297.24 (6)C9—C8—C7119.11 (18)
O5—Mn1—N1114.96 (6)C9—C8—H8A120.4
O1i—Mn1—N188.32 (6)C7—C8—H8A120.4
O2—Mn1—N1128.57 (6)C8—C9—C10119.70 (18)
O5—Mn1—N292.01 (6)C8—C9—H11A120.1
O1i—Mn1—N2159.64 (6)C10—C9—H11A120.1
O2—Mn1—N287.80 (6)N1—C10—C9122.85 (18)
N1—Mn1—N273.33 (6)N1—C10—H7A118.6
C10—N1—C11117.97 (16)C9—C10—H7A118.6
C10—N1—Mn1125.88 (13)N1—C11—C7123.22 (17)
C11—N1—Mn1116.15 (12)N1—C11—C12117.64 (16)
C1—N2—C12117.95 (17)C7—C11—C12119.14 (17)
C1—N2—Mn1126.56 (13)N2—C12—C4123.35 (18)
C12—N2—Mn1115.34 (13)N2—C12—C11117.36 (17)
N2—C1—C2123.14 (18)C4—C12—C11119.29 (17)
N2—C1—H3A118.4P1—O1—Mn1i157.83 (9)
C2—C1—H3A118.4P1—O2—Mn1123.93 (8)
C3—C2—C1118.89 (18)P1—O3—H3113 (2)
C3—C2—H5A120.6P1—O4—H1113.7
C1—C2—H5A120.6O1—P1—O2113.10 (8)
C2—C3—C4119.83 (18)O1—P1—O4110.90 (8)
C2—C3—H9A120.1O2—P1—O4110.36 (8)
C4—C3—H9A120.1O1—P1—O3109.76 (8)
C12—C4—C3116.82 (17)O2—P1—O3107.63 (8)
C12—C4—C5120.03 (17)O4—P1—O3104.71 (8)
C3—C4—C5123.15 (18)P2—O5—Mn1144.99 (10)
C6—C5—C4120.84 (18)P2—O6—H2117 (2)
C6—C5—H2A119.6O5i—P2—O5116.52 (13)
C4—C5—H2A119.6O5i—P2—O6111.46 (8)
C5—C6—C7120.93 (17)O5—P2—O6104.82 (8)
C5—C6—H10A119.5O5i—P2—O6i104.82 (8)
C7—C6—H10A119.5O5—P2—O6i111.46 (8)
C11—C7—C8117.12 (17)O6—P2—O6i107.57 (12)
Symmetry codes: (i) −x, −y, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2ii0.82 (3)1.81 (3)2.624 (2)172 (3)
O4—H1···O4iii1.241.242.480 (2)179
O6—H2···O4iv0.82 (3)1.87 (3)2.665 (2)166 (3)
Symmetry codes: (ii) −x, −y+1, z; (iii) −x, −y, z; (iv) x, y−1/2, z+1/2.
references
References top

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