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Acta Cryst. (2008). E64, m547    [ doi:10.1107/S1600536808006533 ]

Poly[[bis[[mu]2-8-ethyl-5-oxo-2-(piperazin-1-yl)-5,8-dihydropyrido[2,3-d]pyrimidine-6-carboxylato]manganese(II)] dihydrate]

J. Huang, W.-P. Hu and Z. An

Abstract top

In the title compound, {[Mn(C14H16N5O3)2]·2H2O}n, the MnII atom (site symmetry \overline{1}) exhibits a distorted trans-MnN2O4 octahedral geometry defined by two monodentate N-bonded and two bidentate O,O'-bonded 8-ethyl-5-oxo-2-(piperazin-1-yl)-5,8-dihydropyrido[2,3-d]pyrimidine-6-carboxylate anions. An N-H...O hydrogen bond is present in the crystal structure. The extended two-dimensional structure is a square grid and the disordered uncoordinated water molecules occupy cavities within the grid.

Comment top

Pipemidic acid (Hppa, C14H17N5O3, 8-Ethyl-5,8-dihydro-5-oxo-2- (1-piperazinyl)-pyrido(2,3 - d)-pyrimidine-6-carboxylic acid) is member of a class of quinolones used to treat infections (Mizuki et al., 1996). The metal complexes of the ppa anion have not been reported; the title manganese(II) complex, (I), is reported here (Fig. 1).

The MnII atom in (I) with site symmetry 1 is coordinated by four oxygen atoms and two N atoms from four ppa ligands (two monodentate-N and two O,O-bidentate) (Table 1) to form a square grid propagating in (Fig. 2). An N—H···O hydrogen bond (Table 2) helps to stabilize this arrangement.

The disordered, uncoordinated, water molecules occupy cavities within the grid. In the present study, their attached H atoms could not be located.

Related literature top

For background, see: Mizuki et al. (1996).

Experimental top

A mixture of Mn(CH3COO)2.4H2O (0.061 g, 0.25 mmol), Hppa (0.15 g, 0.5 mmol), sodium hydroxide (0.04 g, 1 mmol) and water (12 ml) was stirred for 30 min in air. The mixture was then transferred to a 23 ml Teflon-lined hydrothermal bomb. The bomb was kept at 433 K for 72 h under autogenous pressure. Upon cooling, colourless prisms of (I) were obtained from the reaction mixture.

Refinement top

The carbon-bound H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The N-bound H atom was located in a difference map and its position was freely refined with Uiso(H) = 1.2Ueq(N).

The water H atoms could not be placed due to disorder.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I) showing the showing 50% displacement ellipsoids (water molecule O atoms have been omitted for clarity).
[Figure 2] Fig. 2. A view of part of a two-dimensional polymeric sheet in (I) showing the square-grid connectivity (H atoms and water molecule O atoms omitted for clarity).
Poly[[bis[µ2-8-ethyl-5-oxo-2-(piperazin-1-yl)-5,8- dihydropyrido[2,3-d]pyrimidine-6-carboxylato]manganese(II)] dihydrate] top
Crystal data top
[Mn(C14H16N5O3)2]·2H2OF000 = 718.0
Mr = 695.58Dx = 1.399 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4747 reflections
a = 6.0422 (2) Åθ = 2.5–28.3º
b = 21.5673 (8) ŵ = 0.47 mm−1
c = 12.7395 (5) ÅT = 295 (2) K
β = 99.617 (1)ºPrism, colorless
V = 1636.8 (1) Å30.34 × 0.26 × 0.18 mm
Z = 2
Data collection top
Bruker SMART CCD
diffractometer		3938 independent reflections
Radiation source: fine-focus sealed tube3465 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
T = 295(2) Kθmax = 28.3º
ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −6→8
Tmin = 0.861, Tmax = 0.910k = −27→28
10030 measured reflectionsl = −15→16
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)] = 0.061H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.191  w = 1/[σ2(Fo2) + (0.1066P)2 + 1.0983P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
3938 reflectionsΔρmax = 0.98 e Å−3
227 parametersΔρmin = −0.48 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Mn(C14H16N5O3)2]·2H2OV = 1636.8 (1) Å3
Mr = 695.58Z = 2
Monoclinic, P21/cMo Kα
a = 6.0422 (2) ŵ = 0.47 mm−1
b = 21.5673 (8) ÅT = 295 (2) K
c = 12.7395 (5) Å0.34 × 0.26 × 0.18 mm
β = 99.617 (1)º
Data collection top
Bruker SMART CCD
diffractometer		3938 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3465 reflections with I > 2σ(I)
Tmin = 0.861, Tmax = 0.910Rint = 0.019
10030 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0611 restraint
wR(F2) = 0.191H atoms treated by a mixture of
independent and constrained refinement
S = 1.11Δρmax = 0.98 e Å−3
3938 reflectionsΔρmin = −0.48 e Å−3
227 parameters
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*/UeqOcc. (<1)
Mn10.50000.50000.50000.02831 (19)
O1W0.388 (4)0.5235 (7)0.9613 (10)0.244 (9)0.50
O10.7068 (3)0.49893 (7)0.38228 (16)0.0341 (4)
O2W−0.081 (2)0.4426 (8)0.9246 (7)0.194 (6)0.50
O20.8721 (5)0.51863 (13)0.2451 (2)0.0717 (8)
O30.3574 (3)0.58106 (8)0.41354 (14)0.0378 (4)
N10.5078 (5)0.67158 (12)0.1504 (2)0.0533 (7)
N2−0.0007 (4)0.73723 (11)0.2985 (2)0.0464 (6)
N30.2395 (4)0.74681 (10)0.16596 (18)0.0432 (5)
N4−0.0102 (4)0.82368 (10)0.19027 (19)0.0384 (5)
N5−0.2339 (3)0.93726 (9)0.11005 (17)0.0322 (4)
H5N−0.140 (4)0.9649 (12)0.146 (2)0.048*
C10.7282 (4)0.52991 (11)0.3018 (2)0.0358 (5)
C20.5782 (4)0.58537 (11)0.2731 (2)0.0354 (5)
C30.4044 (4)0.60559 (10)0.33118 (19)0.0313 (5)
C40.2852 (4)0.66087 (11)0.28824 (19)0.0336 (5)
C50.1042 (5)0.68542 (12)0.3304 (2)0.0425 (6)
H5A0.05460.66350.38480.051*
C60.0805 (4)0.76813 (12)0.2189 (2)0.0360 (5)
C70.3383 (5)0.69362 (12)0.2010 (2)0.0395 (6)
C80.6170 (5)0.61896 (14)0.1875 (2)0.0496 (7)
H8A0.72820.60460.15120.059*
C90.5717 (8)0.7043 (2)0.0566 (3)0.0725 (12)
H9A0.55310.74860.06450.087*
H9B0.72850.69630.05370.087*
C100.4373 (10)0.6840 (4)−0.0400 (5)0.116 (2)
H10A0.45830.6403−0.04880.174*
H10B0.48110.7059−0.09890.174*
H10C0.28220.6923−0.03750.174*
C11−0.1446 (6)0.85820 (14)0.2560 (2)0.0499 (7)
H11A−0.04770.88520.30450.060*
H11B−0.21700.82950.29800.060*
C12−0.3226 (5)0.89702 (13)0.1855 (2)0.0433 (6)
H12A−0.43260.86930.14600.052*
H12B−0.39960.92250.23080.052*
C13−0.1018 (4)0.89946 (12)0.0466 (2)0.0372 (5)
H13A−0.03470.9264−0.00030.045*
H13B−0.20150.87100.00250.045*
C140.0812 (4)0.86281 (12)0.1146 (2)0.0382 (6)
H14A0.15730.83710.06930.046*
H14B0.19060.89110.15300.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0350 (3)0.0187 (3)0.0304 (3)−0.00041 (16)0.0030 (2)0.00255 (16)
O1W0.47 (3)0.155 (12)0.111 (9)0.000 (15)0.058 (14)−0.057 (9)
O10.0407 (10)0.0237 (9)0.0383 (10)0.0041 (6)0.0073 (8)0.0040 (6)
O2W0.203 (11)0.307 (17)0.088 (6)−0.110 (12)0.076 (7)−0.028 (8)
O20.0854 (18)0.0730 (16)0.0674 (16)0.0491 (15)0.0441 (14)0.0338 (13)
O30.0448 (10)0.0297 (9)0.0403 (9)0.0085 (7)0.0110 (7)0.0122 (7)
N10.0730 (17)0.0433 (13)0.0500 (14)0.0245 (12)0.0294 (12)0.0196 (11)
N20.0498 (13)0.0386 (12)0.0550 (14)0.0152 (10)0.0211 (11)0.0213 (11)
N30.0549 (13)0.0339 (11)0.0434 (12)0.0165 (10)0.0157 (10)0.0150 (9)
N40.0418 (11)0.0301 (10)0.0458 (12)0.0107 (9)0.0146 (9)0.0133 (9)
N50.0344 (10)0.0231 (9)0.0382 (10)0.0029 (7)0.0034 (8)0.0012 (8)
C10.0410 (13)0.0311 (12)0.0355 (12)0.0080 (10)0.0071 (10)0.0029 (9)
C20.0429 (13)0.0281 (11)0.0360 (12)0.0084 (9)0.0092 (10)0.0040 (9)
C30.0367 (11)0.0227 (10)0.0337 (11)0.0032 (9)0.0033 (9)0.0042 (8)
C40.0396 (12)0.0265 (11)0.0352 (12)0.0060 (9)0.0073 (9)0.0067 (9)
C50.0491 (15)0.0339 (13)0.0475 (15)0.0103 (11)0.0167 (12)0.0168 (11)
C60.0377 (12)0.0307 (12)0.0398 (13)0.0066 (9)0.0066 (10)0.0090 (10)
C70.0506 (14)0.0313 (12)0.0386 (13)0.0109 (11)0.0132 (11)0.0082 (10)
C80.0609 (17)0.0438 (15)0.0485 (16)0.0220 (13)0.0219 (13)0.0120 (12)
C90.091 (3)0.071 (2)0.065 (2)0.035 (2)0.041 (2)0.0293 (19)
C100.111 (4)0.154 (6)0.085 (4)0.032 (4)0.022 (3)0.021 (4)
C110.0604 (17)0.0465 (15)0.0478 (15)0.0251 (14)0.0234 (13)0.0176 (13)
C120.0427 (13)0.0368 (13)0.0535 (16)0.0129 (11)0.0169 (12)0.0133 (12)
C130.0394 (13)0.0308 (12)0.0414 (13)0.0087 (10)0.0071 (10)0.0078 (10)
C140.0365 (12)0.0304 (12)0.0497 (14)0.0075 (9)0.0128 (11)0.0136 (10)
Geometric parameters (Å, °) top
Mn1—O12.106 (2)C2—C81.361 (4)
Mn1—O1i2.106 (2)C2—C31.450 (3)
Mn1—O32.1667 (16)C3—C41.452 (3)
Mn1—O3i2.1667 (16)C4—C71.399 (3)
Mn1—N5ii2.372 (2)C4—C51.400 (4)
Mn1—N5iii2.3723 (19)C5—H5A0.9300
O1—C11.248 (3)C8—H8A0.9300
O2—C11.244 (3)C9—C101.425 (8)
O3—C31.249 (3)C9—H9A0.9700
N1—C81.357 (3)C9—H9B0.9700
N1—C71.382 (4)C10—H10A0.9600
N1—C91.493 (4)C10—H10B0.9600
N2—C51.315 (3)C10—H10C0.9600
N2—C61.371 (4)C11—C121.531 (4)
N3—C71.335 (3)C11—H11A0.9700
N3—C61.344 (3)C11—H11B0.9700
N4—C61.343 (3)C12—H12A0.9700
N4—C141.457 (3)C12—H12B0.9700
N4—C111.463 (3)C13—C141.510 (3)
N5—C121.461 (3)C13—H13A0.9700
N5—C131.474 (3)C13—H13B0.9700
N5—Mn1iv2.3723 (19)C14—H14A0.9700
N5—H5N0.90 (3)C14—H14B0.9700
C1—C21.508 (3)
O1—Mn1—O1i180.0N4—C6—N3117.5 (2)
O1—Mn1—O383.09 (6)N4—C6—N2117.0 (2)
O1i—Mn1—O396.91 (6)N3—C6—N2125.4 (2)
O1—Mn1—O3i96.91 (6)N3—C7—N1117.7 (2)
O1i—Mn1—O3i83.09 (6)N3—C7—C4123.4 (2)
O3—Mn1—O3i180.0N1—C7—C4118.9 (2)
O1—Mn1—N5ii90.17 (7)N1—C8—C2125.8 (3)
O1i—Mn1—N5ii89.83 (7)N1—C8—H8A117.1
O3—Mn1—N5ii90.74 (7)C2—C8—H8A117.1
O3i—Mn1—N5ii89.26 (7)C10—C9—N1111.2 (5)
O1—Mn1—N5iii89.83 (7)C10—C9—H9A109.4
O1i—Mn1—N5iii90.17 (7)N1—C9—H9A109.4
O3—Mn1—N5iii89.26 (7)C10—C9—H9B109.4
O3i—Mn1—N5iii90.73 (7)N1—C9—H9B109.4
N5ii—Mn1—N5iii180.0H9A—C9—H9B108.0
C1—O1—Mn1137.22 (16)C9—C10—H10A109.5
C3—O3—Mn1129.93 (16)C9—C10—H10B109.5
C8—N1—C7118.7 (2)H10A—C10—H10B109.5
C8—N1—C9119.8 (3)C9—C10—H10C109.5
C7—N1—C9121.4 (2)H10A—C10—H10C109.5
C5—N2—C6115.3 (2)H10B—C10—H10C109.5
C7—N3—C6116.3 (2)N4—C11—C12110.2 (2)
C6—N4—C14120.9 (2)N4—C11—H11A109.6
C6—N4—C11122.6 (2)C12—C11—H11A109.6
C14—N4—C11113.1 (2)N4—C11—H11B109.6
C12—N5—C13108.90 (19)C12—C11—H11B109.6
C12—N5—Mn1iv116.15 (15)H11A—C11—H11B108.1
C13—N5—Mn1iv111.54 (14)N5—C12—C11114.3 (2)
C12—N5—H5N110 (2)N5—C12—H12A108.7
C13—N5—H5N107 (2)C11—C12—H12A108.7
Mn1iv—N5—H5N103 (2)N5—C12—H12B108.7
O2—C1—O1123.4 (2)C11—C12—H12B108.7
O2—C1—C2117.6 (2)H12A—C12—H12B107.6
O1—C1—C2118.9 (2)N5—C13—C14112.8 (2)
C8—C2—C3119.0 (2)N5—C13—H13A109.0
C8—C2—C1116.1 (2)C14—C13—H13A109.0
C3—C2—C1124.9 (2)N5—C13—H13B109.0
O3—C3—C2126.0 (2)C14—C13—H13B109.0
O3—C3—C4119.8 (2)H13A—C13—H13B107.8
C2—C3—C4114.3 (2)N4—C14—C13111.1 (2)
C7—C4—C5114.3 (2)N4—C14—H14A109.4
C7—C4—C3123.3 (2)C13—C14—H14A109.4
C5—C4—C3122.4 (2)N4—C14—H14B109.4
N2—C5—C4124.8 (2)C13—C14—H14B109.4
N2—C5—H5A117.6H14A—C14—H14B108.0
C4—C5—H5A117.6
O3—Mn1—O1—C1−1.4 (3)C7—N3—C6—N4175.3 (3)
O3i—Mn1—O1—C1178.6 (3)C7—N3—C6—N2−6.2 (4)
N5ii—Mn1—O1—C1−92.1 (3)C5—N2—C6—N4−174.7 (3)
N5iii—Mn1—O1—C187.9 (3)C5—N2—C6—N36.8 (4)
O1—Mn1—O3—C31.4 (2)C6—N3—C7—N1−177.9 (3)
O1i—Mn1—O3—C3−178.6 (2)C6—N3—C7—C4−0.5 (4)
N5ii—Mn1—O3—C391.5 (2)C8—N1—C7—N3177.3 (3)
N5iii—Mn1—O3—C3−88.5 (2)C9—N1—C7—N3−2.9 (5)
Mn1—O1—C1—O2179.3 (2)C8—N1—C7—C4−0.1 (5)
Mn1—O1—C1—C21.5 (4)C9—N1—C7—C4179.7 (3)
O2—C1—C2—C8−1.0 (4)C5—C4—C7—N35.6 (4)
O1—C1—C2—C8177.0 (3)C3—C4—C7—N3−175.2 (3)
O2—C1—C2—C3−179.1 (3)C5—C4—C7—N1−177.1 (3)
O1—C1—C2—C3−1.2 (4)C3—C4—C7—N12.1 (4)
Mn1—O3—C3—C2−1.8 (4)C7—N1—C8—C2−1.3 (5)
Mn1—O3—C3—C4−179.39 (16)C9—N1—C8—C2178.8 (4)
C8—C2—C3—O3−176.6 (3)C3—C2—C8—N10.8 (5)
C1—C2—C3—O31.5 (4)C1—C2—C8—N1−177.5 (3)
C8—C2—C3—C41.1 (4)C8—N1—C9—C1092.7 (5)
C1—C2—C3—C4179.2 (2)C7—N1—C9—C10−87.1 (5)
O3—C3—C4—C7175.3 (2)C6—N4—C11—C12−148.9 (3)
C2—C3—C4—C7−2.5 (4)C14—N4—C11—C1251.9 (3)
O3—C3—C4—C5−5.6 (4)C13—N5—C12—C1154.0 (3)
C2—C3—C4—C5176.6 (3)Mn1iv—N5—C12—C11−179.1 (2)
C6—N2—C5—C4−0.7 (5)N4—C11—C12—N5−52.9 (4)
C7—C4—C5—N2−5.0 (4)C12—N5—C13—C14−55.0 (3)
C3—C4—C5—N2175.8 (3)Mn1iv—N5—C13—C14175.47 (16)
C14—N4—C6—N3−8.0 (4)C6—N4—C14—C13146.2 (3)
C11—N4—C6—N3−165.6 (3)C11—N4—C14—C13−54.2 (3)
C14—N4—C6—N2173.4 (3)N5—C13—C14—N455.9 (3)
C11—N4—C6—N215.8 (4)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, −y+3/2, z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N5—H5N···O2v0.893 (10)2.268 (12)3.149 (3)169 (3)
Symmetry codes: (v) −x+1, y+1/2, −z+1/2.
Table 1
Selected geometric parameters (Å) top
Mn1—O12.106 (2)Mn1—N5i2.372 (2)
Mn1—O32.1667 (16)
Symmetry codes: (i) x+1, −y+3/2, z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N5—H5N···O2ii0.893 (10)2.268 (12)3.149 (3)169 (3)
Symmetry codes: (ii) −x+1, y+1/2, −z+1/2.
Acknowledgements top

The authors thank the Innovation Science Foundation of Harbin Medical University for financial support (grant No. 060041).

references
References top

Bruker (1998). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Mizuki, Y., Fujiwara, I. & Yamaguchi, T. (1996). J. Antimicrob. Chemother. 37 Suppl. A, 41–45.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

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