PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): m123.
Published online 2010 January 9. doi:  10.1107/S1600536809055408
PMCID: PMC2979888

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

Abstract

The title compound, [Ni(C14H16N5O3)2]n or [Ni(ppa)2]n, where ppa is 8-ethyl-5-oxo-2-(piperazin-1-yl)-5,8-dihydro­pyrido[2,3-d]pyrimidine-6-carboxyl­ate, was synthesized under hydro­thermal conditions. The NiII atom (site symmetry An external file that holds a picture, illustration, etc.
Object name is e-66-0m123-efi1.jpg) exhibits a distorted trans-NiN2O4 octa­hedral geometry defined by two monodentate N-bonded and two bidentate O,O′-bonded ppa monoanions. The extended two-dimensional structure is a square grid. An inter­molecular N—H(...)O hydrogen bond occurs.

Related literature

For manganese, cobalt and zinc complexes of the ppa anion, see: Huang et al. (2008 [triangle]); Xu et al. (2009 [triangle]); Qi et al. (2009 [triangle]), respectively. For background to the medicinal uses of pipemidic acid, see: Mizuki et al. (1996 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m123-scheme1.jpg

Experimental

Crystal data

  • [Ni(C14H16N5O3)2]
  • M r = 663.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m123-efi2.jpg
  • a = 6.1249 (6) Å
  • b = 21.250 (2) Å
  • c = 12.5511 (12) Å
  • β = 101.846 (2)°
  • V = 1598.8 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.66 mm−1
  • T = 296 K
  • 0.43 × 0.28 × 0.22 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2004 [triangle]) T min = 0.764, T max = 0.868
  • 7593 measured reflections
  • 2762 independent reflections
  • 2389 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.066
  • wR(F 2) = 0.199
  • S = 1.00
  • 2762 reflections
  • 209 parameters
  • 1 restraint
  • H-atom parameters not refined
  • Δρmax = 0.89 e Å−3
  • Δρmin = −0.39 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT-Plus (Bruker, 2004 [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/S1600536809055408/hb5292sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809055408/hb5292Isup2.hkl

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

Acknowledgments

The authors acknowledge financial support from the program for talent introduction in Guangdong Higher Education Institutions (grant No. 201191) and the scientific research start-up funds for talent introduction in Maoming University (grant No. 208058).

supplementary crystallographic information

Comment

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, cobalt and zinc complexes of the ppa anion have been reported (Huang et al., 2008; Xu et al. 2009; Qi Xu et al.2009). The title nickel(II) complex, (I), is reported here (Fig. 1).

The nickel(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).

Experimental

A mixture of Ni(CH3COO)2.4H2O (0.063 g, 0.25 mmol), Hppa (0.15 g, 0.5 mmol), sodium hydroxide (0.04 g, 1 mmol) and water (15 ml) was stirred for 30 min in air. The mixture was then transferred to a 25 ml Teflon-lined hydrothermal bomb. The bomb was kept at 443 K for 72 h under autogenous pressure. Upon cooling, green 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 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).

Figures

Fig. 1.
The asymmetric unit of (I), expanded to show the metal atom coordination showing 50% displacement ellipsoids.
Fig. 2.
A view of part of a two-dimensional polymeric sheet in (I) showing the square-grid connectivity.

Crystal data

[Ni(C14H16N5O3)2]F(000) = 692
Mr = 663.35Dx = 1.378 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3258 reflections
a = 6.1249 (6) Åθ = 2.5–28.3°
b = 21.250 (2) ŵ = 0.66 mm1
c = 12.5511 (12) ÅT = 296 K
β = 101.846 (2)°Prism, green
V = 1598.8 (3) Å30.43 × 0.28 × 0.22 mm
Z = 2

Data collection

Bruker APEXII CCD diffractometer2762 independent reflections
Radiation source: fine-focus sealed tube2389 reflections with I > 2σ(I)
graphiteRint = 0.034
[var phi] and ω scansθmax = 25.1°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)h = −7→7
Tmin = 0.764, Tmax = 0.868k = −25→23
7593 measured reflectionsl = −14→9

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.199H-atom parameters not refined
S = 1.00w = 1/[σ2(Fo2) + (0.122P)2 + 2.8827P] where P = (Fo2 + 2Fc2)/3
2762 reflections(Δ/σ)max = 0.007
209 parametersΔρmax = 0.89 e Å3
1 restraintΔρmin = −0.39 e Å3

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*/Ueq
Ni10.50000.50000.50000.0219 (3)
C10.7141 (7)0.47283 (19)0.3080 (4)0.0293 (9)
C20.5607 (7)0.41749 (19)0.2771 (3)0.0310 (9)
C30.3908 (6)0.39745 (18)0.3348 (3)0.0250 (8)
C40.2685 (7)0.34232 (19)0.2900 (3)0.0287 (9)
C50.0880 (8)0.3175 (2)0.3310 (4)0.0380 (11)
H50.04160.33970.38630.046*
C60.0596 (7)0.2340 (2)0.2186 (4)0.0310 (9)
C70.3168 (7)0.3083 (2)0.2024 (4)0.0333 (10)
C80.5934 (9)0.3829 (2)0.1908 (4)0.0448 (12)
H80.70170.39720.15440.054*
C90.5451 (11)0.2956 (3)0.0587 (6)0.0655 (18)
H9A0.70270.30140.05990.079*
H9B0.51790.25100.06520.079*
C100.4140 (17)0.3190 (6)−0.0446 (8)0.0426 (8)
H10A0.26010.3080−0.05010.168*
H10B0.46810.3005−0.10390.168*
H10C0.42780.3640−0.04730.168*
C11−0.1716 (9)0.1431 (2)0.2519 (4)0.0462 (13)
H11A−0.24570.17310.29080.055*
H11B−0.07780.11640.30510.055*
C12−0.3438 (8)0.1034 (2)0.1784 (4)0.0375 (10)
H12A−0.42240.07850.22330.045*
H12B−0.45170.13110.13430.045*
C130.0646 (7)0.1360 (2)0.1181 (4)0.0330 (10)
H13A0.17110.10800.16220.040*
H13B0.14350.16110.07350.040*
C14−0.1164 (7)0.0976 (2)0.0452 (4)0.0297 (9)
H14A−0.21290.1259−0.00390.036*
H14B−0.04690.06940.00130.036*
H5N−0.163 (7)0.035 (2)0.152 (3)0.044*
N10.4839 (7)0.3299 (2)0.1527 (3)0.0454 (11)
N20.2161 (6)0.25401 (17)0.1666 (3)0.0354 (9)
N3−0.0183 (7)0.26577 (19)0.2969 (4)0.0427 (10)
N4−0.0326 (6)0.17705 (17)0.1881 (3)0.0327 (8)
N5−0.2530 (5)0.06053 (15)0.1053 (3)0.0262 (7)
O10.3477 (5)0.42282 (13)0.4188 (2)0.0288 (7)
O20.6982 (5)0.50474 (11)0.3906 (2)0.0270 (7)
O30.8546 (7)0.4840 (2)0.2525 (3)0.0579 (11)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ni10.0256 (4)0.0139 (4)0.0257 (4)−0.0008 (2)0.0040 (3)−0.0028 (3)
C10.032 (2)0.022 (2)0.034 (2)−0.0029 (17)0.0055 (18)−0.0007 (17)
C20.041 (2)0.022 (2)0.031 (2)−0.0069 (17)0.0088 (18)−0.0052 (17)
C30.0291 (19)0.0178 (18)0.026 (2)−0.0008 (15)0.0020 (16)−0.0002 (16)
C40.034 (2)0.023 (2)0.030 (2)−0.0027 (17)0.0072 (17)−0.0047 (17)
C50.040 (2)0.032 (2)0.046 (3)−0.0112 (19)0.019 (2)−0.019 (2)
C60.032 (2)0.024 (2)0.038 (2)−0.0061 (17)0.0082 (18)−0.0090 (18)
C70.041 (2)0.028 (2)0.034 (2)−0.0039 (18)0.0117 (19)−0.0074 (18)
C80.059 (3)0.037 (3)0.043 (3)−0.017 (2)0.022 (2)−0.012 (2)
C90.077 (4)0.060 (4)0.068 (4)−0.025 (3)0.034 (3)−0.018 (3)
C100.0396 (18)0.047 (2)0.0409 (17)0.0122 (15)0.0083 (14)0.0059 (15)
C110.052 (3)0.041 (3)0.053 (3)−0.025 (2)0.028 (2)−0.021 (2)
C120.039 (2)0.031 (2)0.045 (3)−0.0097 (19)0.015 (2)−0.011 (2)
C130.029 (2)0.029 (2)0.045 (2)−0.0055 (17)0.0152 (19)−0.0153 (19)
C140.032 (2)0.0219 (19)0.037 (2)−0.0034 (16)0.0120 (18)−0.0042 (17)
N10.061 (3)0.040 (2)0.042 (2)−0.025 (2)0.026 (2)−0.0145 (18)
N20.047 (2)0.0271 (18)0.035 (2)−0.0156 (16)0.0169 (17)−0.0112 (16)
N30.044 (2)0.030 (2)0.057 (3)−0.0140 (17)0.0198 (19)−0.0192 (19)
N40.0348 (18)0.0239 (18)0.042 (2)−0.0081 (15)0.0143 (16)−0.0121 (16)
N50.0275 (17)0.0193 (16)0.0303 (18)−0.0026 (13)0.0020 (14)−0.0004 (14)
O10.0317 (15)0.0215 (14)0.0351 (16)−0.0043 (11)0.0111 (12)−0.0069 (12)
O20.0329 (16)0.0184 (14)0.0298 (16)0.0003 (11)0.0066 (12)−0.0026 (11)
O30.069 (3)0.061 (2)0.055 (2)−0.037 (2)0.040 (2)−0.026 (2)

Geometric parameters (Å, °)

Ni1—O2i2.013 (3)C9—C101.464 (12)
Ni1—O22.013 (3)C9—N11.498 (7)
Ni1—O1i2.051 (3)C9—H9A0.9700
Ni1—O12.051 (3)C9—H9B0.9700
Ni1—N5ii2.207 (3)C10—H10A0.9600
Ni1—N5iii2.207 (3)C10—H10B0.9600
C1—O31.236 (6)C10—H10C0.9600
C1—O21.260 (5)C11—N41.472 (6)
C1—C21.505 (6)C11—C121.509 (6)
C2—C81.358 (6)C11—H11A0.9700
C2—C31.448 (6)C11—H11B0.9700
C3—O11.260 (5)C12—N51.480 (6)
C3—C41.441 (6)C12—H12A0.9700
C4—C71.398 (6)C12—H12B0.9700
C4—C51.413 (6)C13—N41.450 (5)
C5—N31.305 (6)C13—C141.522 (6)
C5—H50.9300C13—H13A0.9700
C6—N21.334 (6)C13—H13B0.9700
C6—N41.357 (5)C14—N51.467 (5)
C6—N31.357 (6)C14—H14A0.9700
C7—N21.341 (6)C14—H14B0.9700
C7—N11.382 (6)N5—Ni1iv2.207 (3)
C8—N11.348 (6)N5—H5N0.90 (4)
C8—H80.9300
O2i—Ni1—O2180.0C9—C10—H10B109.5
O2i—Ni1—O1i88.73 (11)H10A—C10—H10B109.5
O2—Ni1—O1i91.27 (11)C9—C10—H10C109.5
O2i—Ni1—O191.27 (11)H10A—C10—H10C109.5
O2—Ni1—O188.73 (11)H10B—C10—H10C109.5
O1i—Ni1—O1180.0N4—C11—C12110.6 (4)
O2i—Ni1—N5ii90.14 (12)N4—C11—H11A109.5
O2—Ni1—N5ii89.86 (12)C12—C11—H11A109.5
O1i—Ni1—N5ii91.00 (11)N4—C11—H11B109.5
O1—Ni1—N5ii89.00 (11)C12—C11—H11B109.5
O2i—Ni1—N5iii89.86 (12)H11A—C11—H11B108.1
O2—Ni1—N5iii90.14 (12)N5—C12—C11114.8 (4)
O1i—Ni1—N5iii89.00 (11)N5—C12—H12A108.6
O1—Ni1—N5iii91.00 (11)C11—C12—H12A108.6
N5ii—Ni1—N5iii180.0N5—C12—H12B108.6
O3—C1—O2122.8 (4)C11—C12—H12B108.6
O3—C1—C2118.4 (4)H12A—C12—H12B107.6
O2—C1—C2118.9 (4)N4—C13—C14110.4 (3)
C8—C2—C3118.6 (4)N4—C13—H13A109.6
C8—C2—C1116.2 (4)C14—C13—H13A109.6
C3—C2—C1125.1 (4)N4—C13—H13B109.6
O1—C3—C4119.5 (4)C14—C13—H13B109.6
O1—C3—C2126.1 (4)H13A—C13—H13B108.1
C4—C3—C2114.4 (4)N5—C14—C13113.6 (4)
C7—C4—C5113.6 (4)N5—C14—H14A108.8
C7—C4—C3123.4 (4)C13—C14—H14A108.8
C5—C4—C3122.9 (4)N5—C14—H14B108.8
N3—C5—C4124.7 (4)C13—C14—H14B108.8
N3—C5—H5117.6H14A—C14—H14B107.7
C4—C5—H5117.6C8—N1—C7118.6 (4)
N2—C6—N4116.5 (4)C8—N1—C9119.9 (4)
N2—C6—N3126.2 (4)C7—N1—C9121.5 (4)
N4—C6—N3117.4 (4)C6—N2—C7115.9 (4)
N2—C7—N1117.8 (4)C5—N3—C6115.5 (4)
N2—C7—C4123.5 (4)C6—N4—C13120.5 (4)
N1—C7—C4118.6 (4)C6—N4—C11122.5 (4)
N1—C8—C2126.3 (5)C13—N4—C11113.0 (3)
N1—C8—H8116.9C14—N5—C12108.4 (3)
C2—C8—H8116.9C14—N5—Ni1iv113.5 (2)
C10—C9—N1110.6 (7)C12—N5—Ni1iv115.6 (2)
C10—C9—H9A109.5C14—N5—H5N109 (3)
N1—C9—H9A109.5C12—N5—H5N103 (4)
C10—C9—H9B109.5Ni1iv—N5—H5N107 (3)
N1—C9—H9B109.5C3—O1—Ni1127.3 (3)
H9A—C9—H9B108.1C1—O2—Ni1134.0 (3)
C9—C10—H10A109.5
O3—C1—C2—C81.5 (7)N3—C6—N2—C75.9 (7)
O2—C1—C2—C8−176.7 (4)N1—C7—N2—C6178.4 (4)
O3—C1—C2—C3178.7 (4)C4—C7—N2—C61.4 (7)
O2—C1—C2—C30.6 (6)C4—C5—N3—C62.0 (8)
C8—C2—C3—O1176.7 (4)N2—C6—N3—C5−7.5 (8)
C1—C2—C3—O1−0.5 (7)N4—C6—N3—C5174.0 (4)
C8—C2—C3—C4−1.8 (6)N2—C6—N4—C1311.1 (6)
C1—C2—C3—C4−178.9 (4)N3—C6—N4—C13−170.2 (4)
O1—C3—C4—C7−174.8 (4)N2—C6—N4—C11167.2 (4)
C2—C3—C4—C73.8 (6)N3—C6—N4—C11−14.2 (7)
O1—C3—C4—C55.1 (6)C14—C13—N4—C6−147.5 (4)
C2—C3—C4—C5−176.4 (4)C14—C13—N4—C1154.4 (5)
C7—C4—C5—N34.1 (7)C12—C11—N4—C6149.6 (4)
C3—C4—C5—N3−175.8 (5)C12—C11—N4—C13−52.7 (6)
C5—C4—C7—N2−5.8 (7)C13—C14—N5—C1254.2 (5)
C3—C4—C7—N2174.0 (4)C13—C14—N5—Ni1iv−176.1 (3)
C5—C4—C7—N1177.2 (4)C11—C12—N5—C14−53.0 (5)
C3—C4—C7—N1−2.9 (7)C11—C12—N5—Ni1iv178.4 (3)
C3—C2—C8—N1−1.0 (8)C4—C3—O1—Ni1178.8 (3)
C1—C2—C8—N1176.4 (5)C2—C3—O1—Ni10.4 (6)
N4—C11—C12—N552.7 (6)O2i—Ni1—O1—C3179.7 (3)
N4—C13—C14—N5−56.3 (5)O2—Ni1—O1—C3−0.3 (3)
C2—C8—N1—C72.0 (8)N5ii—Ni1—O1—C389.6 (3)
C2—C8—N1—C9−177.7 (6)N5iii—Ni1—O1—C3−90.4 (3)
N2—C7—N1—C8−177.2 (5)O3—C1—O2—Ni1−178.7 (4)
C4—C7—N1—C80.0 (7)C2—C1—O2—Ni1−0.7 (6)
N2—C7—N1—C92.6 (8)O1i—Ni1—O2—C1−179.5 (4)
C4—C7—N1—C9179.8 (5)O1—Ni1—O2—C10.5 (4)
C10—C9—N1—C8−89.8 (8)N5ii—Ni1—O2—C1−88.5 (4)
C10—C9—N1—C790.4 (7)N5iii—Ni1—O2—C191.5 (4)
N4—C6—N2—C7−175.6 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y+1/2, −z+1/2; (iii) x+1, −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···O3v0.90 (4)2.29 (4)3.161 (5)163 (5)

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: HB5292).

References

  • Bruker (2004). APEX2, SAINT-Plus and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Huang, J., Hu, W.-P. & An, Z. (2008). Acta Cryst. E64, m547. [PMC free article] [PubMed]
  • Mizuki, Y., Fujiwara, I. & Yamaguchi, T. (1996). J. Antimicrob. Chemother.37 (Suppl. A), 41–45. [PubMed]
  • Qi, X., Shao, M. & Li, C.-X. (2009). Acta Cryst. E65, m1334. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Xu, W., Zhu, D.-S., Song, X.-D. & An, Z. (2009). Acta Cryst. E65, m1223. [PMC free article] [PubMed]

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