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Acta Crystallogr Sect E Struct Rep Online. 2008 April 1; 64(Pt 4): m547.
Published online 2008 March 14. doi:  10.1107/S1600536808006533
PMCID: PMC2961022

Poly[[bis­[μ2-8-ethyl-5-oxo-2-(piperazin-1-yl)-5,8-dihydro­pyrido[2,3-d]pyrimidine-6-carboxyl­ato]manganese(II)] dihydrate]

Abstract

In the title compound, {[Mn(C14H16N5O3)2]·2H2O}n, the MnII atom (site symmetry An external file that holds a picture, illustration, etc.
Object name is e-64-0m547-efi1.jpg) 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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-0m547-scheme1.jpg

Experimental

Crystal data

  • [Mn(C14H16N5O3)2]·2H2O
  • M r = 695.58
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m547-efi2.jpg
  • a = 6.0422 (2) Å
  • b = 21.5673 (8) Å
  • c = 12.7395 (5) Å
  • β = 99.617 (1)°
  • V = 1636.8 (1) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.47 mm−1
  • T = 295 (2) K
  • 0.34 × 0.26 × 0.18 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1998 [triangle]) T min = 0.861, T max = 0.910
  • 10030 measured reflections
  • 3938 independent reflections
  • 3465 reflections with I > 2σ(I)
  • R int = 0.019

Refinement

  • R[F 2 > 2σ(F 2)] = 0.060
  • wR(F 2) = 0.191
  • S = 1.10
  • 3938 reflections
  • 227 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.97 e Å−3
  • Δρmin = −0.48 e Å−3

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

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808006533/hb2703sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006533/hb2703Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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

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.

Figures

Fig. 1.
The asymmetric unit of (I) showing the showing 50% displacement ellipsoids (water molecule O atoms have been omitted for clarity).
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).

Crystal data

[Mn(C14H16N5O3)2]·2H2OF000 = 718.0
Mr = 695.58Dx = 1.399 Mg m3
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 mm1
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

Bruker SMART CCD diffractometer3938 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

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 Å3
227 parametersΔρmin = −0.48 e Å3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2703).

References

  • Bruker (1998). SMART, SAINT-Plus and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Mizuki, Y., Fujiwara, I. & Yamaguchi, T. (1996). J. Antimicrob. Chemother. Suppl. A, 37, 41–45. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography