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Acta Cryst. (2009). E65, m1334    [ doi:10.1107/S1600536809040185 ]

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

X. Qi, M. Shao and C.-X. Li

Abstract top

The title compound, {[Co(C14H16N5O3)2]·2H2O}n or [Co(ppa)2]·2H2O}n, where ppa denotes the 8-ethyl-5-oxo-2-(piperazin-1-yl)-5,8-dihydropyrido[2,3-d]pyrimidine-6-carboxylate anion, was synthesized under hydrothermal conditions. The CoII atom (site symmetry \overline{1}) exhibits a distorted trans-CoN2O4 octahedral geometry defined by two monodentate N-bonded and two bidentate O,O'-bonded ppa anions. The extended two-dimensional structure is a square grid, which is consolidated by N-H...O hydrogen bonds. The disordered uncoordinated water molecules occupy cavities within the grid.

Comment top

Pipemidic acid (Hppa, C14H16N5O3, 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 manganese and cobalt complexes of the ppa anion have been reported (Huang et al., 2008; Xu et al. 2009). The title cobalt(II) complex is reported here(Fig. 1).

The cobalt(II) atom is coordinated by four oxygen atoms and two N atoms from four ppa ligands (two monodentate-N and two O,O-bidentate) to form a square grid propagating in (Fig. 2). The disordered, uncoordinated, water molecules occupy the cavities.

Related literature top

For the manganese and zinc complexe of the ppa anion, see: Huang et al. (2008); Xu et al. (2009). For background to the medicinal uses of pipemidic acid, see: Mizuki et al. (1996).

Experimental top

A mixture of Co(CH3COO)2.4H2O (0.25 mmol), Hppa (0.5 mmol), sodium hydroxide (1 mmol) and water (12 ml) was stirred for 40 min in air. The mixture was then transferred to a 23 ml Teflon-lined hydrothermal bomb. The bomb was kept at 433 K for 96 h under autogenous pressure. Upon cooling, pink 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 were included in the refinement in the riding model approximation, with U(H) = 1.2Ueq(C). The H on Nitrogen atoms were located in a difference Fourier map, and were refined with a distance restraint of N—H = 0.86 (1) /%A and with Uiso(H) = 1.2Ueq(N).

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

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (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) expanded to show the metal coordination and polymeric connectivity 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]cobalt(II)] dihydrate] top
Crystal data top
[Co(C14H16N5O3)2]·2H2OF(000) = 722
Mr = 699.58Dx = 1.433 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4362 reflections
a = 6.1093 (3) Åθ = 2.5–28.2°
b = 21.3690 (11) ŵ = 0.60 mm−1
c = 12.5944 (6) ÅT = 295 K
β = 101.254 (1)°Prism, pink
V = 1612.58 (14) Å30.32 × 0.26 × 0.18 mm
Z = 2
Data collection top
Bruker SMART CCD
diffractometer		3894 independent reflections
Radiation source: fine-focus sealed tube3327 reflections with I > 2σ(I)
graphiteRint = 0.029
ω scansθmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→6
Tmin = 0.832, Tmax = 0.900k = −27→28
9807 measured reflectionsl = −15→15
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.181H atoms treated by a mixture of independent and constrained refinement
S = 1.12 w = 1/[σ2(Fo2) + (0.0899P)2 + 1.3252P]
where P = (Fo2 + 2Fc2)/3
3894 reflections(Δ/σ)max = 0.003
227 parametersΔρmax = 0.77 e Å−3
1 restraintΔρmin = −0.46 e Å−3
Crystal data top
[Co(C14H16N5O3)2]·2H2OV = 1612.58 (14) Å3
Mr = 699.58Z = 2
Monoclinic, P21/cMo Kα radiation
a = 6.1093 (3) ŵ = 0.60 mm−1
b = 21.3690 (11) ÅT = 295 K
c = 12.5944 (6) Å0.32 × 0.26 × 0.18 mm
β = 101.254 (1)°
Data collection top
Bruker SMART CCD
diffractometer		3894 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3327 reflections with I > 2σ(I)
Tmin = 0.832, Tmax = 0.900Rint = 0.029
9807 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.060H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.181Δρmax = 0.77 e Å−3
S = 1.12Δρmin = −0.46 e Å−3
3894 reflectionsAbsolute structure: ?
227 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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)
O1W0.669 (4)0.5177 (8)0.5335 (9)0.255 (11)0.50
O2W−0.024 (4)0.5581 (10)0.4291 (11)0.254 (10)0.50
Co10.50000.50000.00000.02469 (18)
O10.6496 (3)0.57810 (9)0.08289 (16)0.0324 (4)
O20.1437 (5)0.51651 (14)0.2499 (2)0.0626 (8)
N10.5101 (5)0.67072 (13)0.3478 (2)0.0487 (7)
N20.7758 (5)0.74617 (12)0.3332 (2)0.0390 (6)
N31.0138 (5)0.73519 (13)0.2023 (2)0.0437 (7)
N41.0250 (4)0.82327 (11)0.3106 (2)0.0362 (6)
C10.2840 (5)0.52788 (13)0.1939 (2)0.0328 (6)
C20.4347 (5)0.58348 (13)0.2241 (2)0.0330 (6)
C30.6059 (4)0.60347 (12)0.1662 (2)0.0275 (5)
C40.7269 (5)0.65898 (13)0.2104 (2)0.0318 (6)
C50.9081 (5)0.68298 (14)0.1695 (3)0.0398 (7)
H50.95660.66030.11550.048*
C60.9339 (5)0.76685 (13)0.2815 (2)0.0334 (6)
C70.6763 (5)0.69244 (13)0.2976 (3)0.0364 (6)
C80.3996 (6)0.61779 (15)0.3104 (3)0.0452 (8)
H80.29050.60360.34670.054*
C90.4470 (8)0.7043 (2)0.4423 (4)0.0646 (12)
H9A0.46930.74890.43510.078*
H9B0.29020.69720.44250.078*
C100.5781 (12)0.6828 (4)0.5417 (5)0.118 (2)
H10A0.54740.63930.55130.177*
H10B0.54170.70650.60060.177*
H10C0.73350.68800.54010.177*
C111.1614 (6)0.85706 (17)0.2461 (3)0.0478 (8)
H11A1.06670.88390.19430.057*
H11B1.23450.82740.20620.057*
C121.3372 (5)0.89675 (15)0.3196 (3)0.0400 (7)
H12A1.44480.86900.36300.048*
H12B1.41620.92160.27470.048*
C131.1106 (5)0.90153 (13)0.4537 (2)0.0330 (6)
H13A1.04240.92930.49890.040*
H13B1.20780.87310.50110.040*
C140.9295 (5)0.86418 (14)0.3823 (3)0.0353 (6)
H14A0.85050.83920.42700.042*
H14B0.82330.89250.33950.042*
N51.2458 (4)0.93890 (10)0.39246 (19)0.0286 (5)
O30.3027 (3)0.49641 (8)0.11147 (17)0.0295 (4)
H5N1.155 (5)0.9660 (14)0.350 (2)0.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1W0.52 (4)0.180 (13)0.073 (8)−0.084 (17)0.063 (13)0.045 (8)
O2W0.35 (2)0.33 (2)0.122 (10)−0.09 (2)0.147 (13)−0.030 (13)
Co10.0276 (3)0.0158 (3)0.0304 (3)−0.00028 (17)0.0050 (2)−0.00242 (17)
O10.0350 (10)0.0243 (9)0.0395 (11)−0.0065 (8)0.0113 (8)−0.0089 (8)
O20.0732 (18)0.0635 (16)0.0631 (17)−0.0401 (15)0.0429 (15)−0.0297 (14)
N10.0630 (18)0.0404 (15)0.0494 (16)−0.0222 (14)0.0271 (14)−0.0189 (12)
N20.0494 (15)0.0296 (12)0.0413 (14)−0.0138 (11)0.0167 (11)−0.0129 (10)
N30.0454 (15)0.0348 (14)0.0556 (16)−0.0152 (12)0.0221 (13)−0.0200 (12)
N40.0390 (13)0.0268 (12)0.0462 (14)−0.0093 (10)0.0169 (11)−0.0132 (10)
C10.0354 (14)0.0250 (13)0.0379 (15)−0.0061 (11)0.0068 (12)−0.0030 (11)
C20.0409 (15)0.0244 (13)0.0343 (14)−0.0074 (11)0.0091 (12)−0.0035 (10)
C30.0309 (13)0.0192 (12)0.0314 (13)−0.0023 (10)0.0034 (10)−0.0024 (10)
C40.0354 (14)0.0241 (12)0.0365 (14)−0.0064 (11)0.0082 (11)−0.0064 (11)
C50.0434 (16)0.0300 (14)0.0498 (18)−0.0102 (12)0.0186 (14)−0.0180 (13)
C60.0338 (14)0.0248 (13)0.0427 (16)−0.0058 (11)0.0097 (12)−0.0087 (11)
C70.0449 (16)0.0269 (13)0.0397 (15)−0.0099 (12)0.0139 (13)−0.0087 (11)
C80.057 (2)0.0352 (16)0.0486 (18)−0.0198 (15)0.0238 (16)−0.0107 (14)
C90.080 (3)0.058 (2)0.065 (3)−0.030 (2)0.035 (2)−0.025 (2)
C100.121 (5)0.155 (7)0.082 (4)−0.025 (5)0.028 (4)−0.020 (4)
C110.055 (2)0.0429 (18)0.0501 (19)−0.0253 (15)0.0221 (16)−0.0187 (15)
C120.0370 (15)0.0326 (15)0.0537 (18)−0.0113 (12)0.0167 (13)−0.0110 (13)
C130.0334 (14)0.0266 (13)0.0402 (15)−0.0067 (11)0.0104 (12)−0.0072 (11)
C140.0290 (13)0.0276 (13)0.0507 (17)−0.0062 (11)0.0114 (12)−0.0119 (12)
N50.0283 (11)0.0208 (10)0.0362 (12)−0.0017 (8)0.0053 (9)−0.0010 (9)
O30.0337 (10)0.0199 (9)0.0353 (11)−0.0035 (7)0.0072 (8)−0.0029 (7)
Geometric parameters (Å, °) top
Co1—O3i2.022 (2)C4—C51.405 (4)
Co1—O32.022 (2)C5—H50.9300
Co1—O1i2.0829 (18)C8—H80.9300
Co1—O12.0829 (18)C9—C101.425 (9)
Co1—N5ii2.265 (2)C9—H9A0.9700
Co1—N5iii2.265 (2)C9—H9B0.9700
O1—C31.255 (3)C10—H10A0.9600
O2—C11.235 (4)C10—H10B0.9600
N1—C81.354 (4)C10—H10C0.9600
N1—C71.376 (4)C11—C121.530 (4)
N1—C91.503 (5)C11—H11A0.9700
N2—C71.335 (4)C11—H11B0.9700
N2—C61.341 (4)C12—N51.471 (4)
N3—C51.315 (4)C12—H12A0.9700
N3—C61.371 (4)C12—H12B0.9700
N4—C61.348 (3)C13—N51.471 (3)
N4—C141.459 (3)C13—C141.510 (4)
N4—C111.462 (4)C13—H13A0.9700
C1—O31.261 (3)C13—H13B0.9700
C1—C21.506 (4)C14—H14A0.9700
C2—C81.362 (4)C14—H14B0.9700
C2—C31.451 (4)N5—Co1iv2.265 (2)
C3—C41.450 (4)N5—H5N0.900 (10)
C4—C71.396 (4)
O3i—Co1—O3180.0N1—C8—H8117.2
O3i—Co1—O1i86.86 (7)C2—C8—H8117.2
O3—Co1—O1i93.14 (7)C10—C9—N1110.8 (5)
O3i—Co1—O193.14 (7)C10—C9—H9A109.5
O3—Co1—O186.86 (7)N1—C9—H9A109.5
O1i—Co1—O1180.0C10—C9—H9B109.5
O3i—Co1—N5ii90.28 (8)N1—C9—H9B109.5
O3—Co1—N5ii89.72 (8)H9A—C9—H9B108.1
O1i—Co1—N5ii91.18 (8)C9—C10—H10A109.5
O1—Co1—N5ii88.82 (8)C9—C10—H10B109.5
O3i—Co1—N5iii89.72 (8)H10A—C10—H10B109.5
O3—Co1—N5iii90.28 (8)C9—C10—H10C109.5
O1i—Co1—N5iii88.82 (8)H10A—C10—H10C109.5
O1—Co1—N5iii91.18 (8)H10B—C10—H10C109.5
N5ii—Co1—N5iii180.0N4—C11—C12110.3 (3)
C3—O1—Co1128.37 (17)N4—C11—H11A109.6
C8—N1—C7119.0 (3)C12—C11—H11A109.6
C8—N1—C9119.1 (3)N4—C11—H11B109.6
C7—N1—C9121.9 (3)C12—C11—H11B109.6
C7—N2—C6116.4 (2)H11A—C11—H11B108.1
C5—N3—C6115.1 (3)N5—C12—C11114.2 (3)
C6—N4—C14120.7 (2)N5—C12—H12A108.7
C6—N4—C11122.7 (2)C11—C12—H12A108.7
C14—N4—C11112.8 (2)N5—C12—H12B108.7
O2—C1—O3123.3 (3)C11—C12—H12B108.7
O2—C1—C2118.0 (3)H12A—C12—H12B107.6
O3—C1—C2118.6 (2)N5—C13—C14113.3 (2)
C8—C2—C3118.9 (3)N5—C13—H13A108.9
C8—C2—C1116.3 (3)C14—C13—H13A108.9
C3—C2—C1124.8 (2)N5—C13—H13B108.9
O1—C3—C4119.9 (2)C14—C13—H13B108.9
O1—C3—C2125.8 (2)H13A—C13—H13B107.7
C4—C3—C2114.3 (2)N4—C14—C13110.5 (2)
C7—C4—C5114.4 (2)N4—C14—H14A109.5
C7—C4—C3123.1 (3)C13—C14—H14A109.5
C5—C4—C3122.5 (3)N4—C14—H14B109.5
N3—C5—C4124.7 (3)C13—C14—H14B109.5
N3—C5—H5117.7H14A—C14—H14B108.1
C4—C5—H5117.7C13—N5—C12108.4 (2)
N2—C6—N4117.5 (2)C13—N5—Co1iv112.89 (17)
N2—C6—N3125.7 (3)C12—N5—Co1iv115.23 (17)
N4—C6—N3116.9 (3)C13—N5—H5N108 (2)
N2—C7—N1117.7 (3)C12—N5—H5N107 (2)
N2—C7—C4123.3 (3)Co1iv—N5—H5N105 (2)
N1—C7—C4119.0 (3)C1—O3—Co1135.54 (18)
N1—C8—C2125.6 (3)
O3i—Co1—O1—C3−179.8 (2)C8—N1—C7—N2177.2 (3)
O3—Co1—O1—C30.2 (2)C9—N1—C7—N2−2.4 (5)
N5ii—Co1—O1—C3−89.6 (2)C8—N1—C7—C4−0.5 (5)
N5iii—Co1—O1—C390.4 (2)C9—N1—C7—C4179.9 (4)
O2—C1—C2—C8−1.4 (5)C5—C4—C7—N26.3 (5)
O3—C1—C2—C8176.6 (3)C3—C4—C7—N2−174.7 (3)
O2—C1—C2—C3−179.3 (3)C5—C4—C7—N1−176.2 (3)
O3—C1—C2—C3−1.3 (4)C3—C4—C7—N12.8 (5)
Co1—O1—C3—C4−178.49 (19)C7—N1—C8—C2−1.4 (6)
Co1—O1—C3—C2−0.6 (4)C9—N1—C8—C2178.2 (4)
C8—C2—C3—O1−176.7 (3)C3—C2—C8—N10.9 (6)
C1—C2—C3—O11.2 (5)C1—C2—C8—N1−177.2 (3)
C8—C2—C3—C41.3 (4)C8—N1—C9—C1091.4 (5)
C1—C2—C3—C4179.2 (3)C7—N1—C9—C10−89.0 (5)
O1—C3—C4—C7175.0 (3)C6—N4—C11—C12−149.0 (3)
C2—C3—C4—C7−3.1 (4)C14—N4—C11—C1252.8 (4)
O1—C3—C4—C5−6.0 (4)N4—C11—C12—N5−53.2 (4)
C2—C3—C4—C5175.8 (3)C6—N4—C14—C13146.4 (3)
C6—N3—C5—C4−0.5 (5)C11—N4—C14—C13−54.9 (4)
C7—C4—C5—N3−5.4 (5)N5—C13—C14—N456.7 (3)
C3—C4—C5—N3175.5 (3)C14—C13—N5—C12−55.3 (3)
C7—N2—C6—N4175.2 (3)C14—C13—N5—Co1iv175.84 (18)
C7—N2—C6—N3−5.8 (5)C11—C12—N5—C1353.7 (4)
C14—N4—C6—N2−9.8 (4)C11—C12—N5—Co1iv−178.7 (2)
C11—N4—C6—N2−166.4 (3)O2—C1—O3—Co1178.9 (3)
C14—N4—C6—N3171.1 (3)C2—C1—O3—Co11.0 (4)
C11—N4—C6—N314.5 (5)O1i—Co1—O3—C1179.6 (3)
C5—N3—C6—N26.6 (5)O1—Co1—O3—C1−0.4 (3)
C5—N3—C6—N4−174.4 (3)N5ii—Co1—O3—C188.4 (3)
C6—N2—C7—N1−178.7 (3)N5iii—Co1—O3—C1−91.6 (3)
C6—N2—C7—C4−1.1 (5)
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, y−1/2, −z+1/2; (iii) x−1, −y+3/2, z−1/2; (iv) −x+2, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N5—H5N···O2v0.90 (1)2.28 (1)3.156 (4)165 (3)
Symmetry codes: (v) −x+1, y+1/2, −z+1/2.
Table 1
Selected geometric parameters (Å) top
Co1—O32.022 (2)Co1—N5i2.265 (2)
Co1—O12.0829 (18)
Symmetry codes: (i) −x+2, y−1/2, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N5—H5N···O2ii0.90 (1)2.28 (1)3.156 (4)165 (3)
Symmetry codes: (ii) −x+1, y+1/2, −z+1/2.
Acknowledgements top

The authors acknowledge financial support from the Foundation for Youth of Heilongjiang Province (grant No. QC07C97).

references
References top

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

Huang, J., Hu, W.-P. & An, Z. (2008). Acta Cryst. E64, m547.

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.

Xu, W., Zhu, D.-S., Song, X.-D. & An, Z. (2009). Acta Cryst. E65, m1223.