Poly[bis-[μ(2)-8-ethyl-5-oxo-2-(piperazin-1-yl)-5,8-dihydro-pyrido[2,3-d]pyrimidine-6-carboxyl-ato]nickel(II)].

The title compound, [Ni(C(14)H(16)N(5)O(3))(2)](n) or [Ni(ppa)(2)](n), where ppa is 8-ethyl-5-oxo-2-(piperazin-1-yl)-5,8-dihydro-pyrido[2,3-d]pyrimidine-6-carboxyl-ate, was synthesized under hydro-thermal conditions. The Ni(II) atom (site symmetry ) exhibits a distorted trans-NiN(2)O(4) octa-hedral 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 inter-molecular N-H⋯O hydrogen bond occurs.

Related literature

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

Experimental

Crystal data

[Ni(C14H16N5O3)2]

M = 663.35

Monoclinic,

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 ▶) 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 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; 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.

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

[Ni(C14H16N5O3)2]	F(000) = 692
Mr = 663.35	Dx = 1.378 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3258 reflections
a = 6.1249 (6) Å	θ = 2.5–28.3°
b = 21.250 (2) Å	µ = 0.66 mm−1
c = 12.5511 (12) Å	T = 296 K
β = 101.846 (2)°	Prism, green
V = 1598.8 (3) Å3	0.43 × 0.28 × 0.22 mm
Z = 2

Bruker APEXII CCD diffractometer	2762 independent reflections
Radiation source: fine-focus sealed tube	2389 reflections with I > 2σ(I)
graphite	Rint = 0.034
φ and ω scans	θmax = 25.1°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −7→7
Tmin = 0.764, Tmax = 0.868	k = −25→23
7593 measured reflections	l = −14→9

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

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.

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.5000	0.0219 (3)
C1	0.7141 (7)	0.47283 (19)	0.3080 (4)	0.0293 (9)
C2	0.5607 (7)	0.41749 (19)	0.2771 (3)	0.0310 (9)
C3	0.3908 (6)	0.39745 (18)	0.3348 (3)	0.0250 (8)
C4	0.2685 (7)	0.34232 (19)	0.2900 (3)	0.0287 (9)
C5	0.0880 (8)	0.3175 (2)	0.3310 (4)	0.0380 (11)
H5	0.0416	0.3397	0.3863	0.046*
C6	0.0596 (7)	0.2340 (2)	0.2186 (4)	0.0310 (9)
C7	0.3168 (7)	0.3083 (2)	0.2024 (4)	0.0333 (10)
C8	0.5934 (9)	0.3829 (2)	0.1908 (4)	0.0448 (12)
H8	0.7017	0.3972	0.1544	0.054*
C9	0.5451 (11)	0.2956 (3)	0.0587 (6)	0.0655 (18)
H9A	0.7027	0.3014	0.0599	0.079*
H9B	0.5179	0.2510	0.0652	0.079*
C10	0.4140 (17)	0.3190 (6)	−0.0446 (8)	0.0426 (8)
H10A	0.2601	0.3080	−0.0501	0.168*
H10B	0.4681	0.3005	−0.1039	0.168*
H10C	0.4278	0.3640	−0.0473	0.168*
C11	−0.1716 (9)	0.1431 (2)	0.2519 (4)	0.0462 (13)
H11A	−0.2457	0.1731	0.2908	0.055*
H11B	−0.0778	0.1164	0.3051	0.055*
C12	−0.3438 (8)	0.1034 (2)	0.1784 (4)	0.0375 (10)
H12A	−0.4224	0.0785	0.2233	0.045*
H12B	−0.4517	0.1311	0.1343	0.045*
C13	0.0646 (7)	0.1360 (2)	0.1181 (4)	0.0330 (10)
H13A	0.1711	0.1080	0.1622	0.040*
H13B	0.1435	0.1611	0.0735	0.040*
C14	−0.1164 (7)	0.0976 (2)	0.0452 (4)	0.0297 (9)
H14A	−0.2129	0.1259	−0.0039	0.036*
H14B	−0.0469	0.0694	0.0013	0.036*
H5N	−0.163 (7)	0.035 (2)	0.152 (3)	0.044*
N1	0.4839 (7)	0.3299 (2)	0.1527 (3)	0.0454 (11)
N2	0.2161 (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)
O1	0.3477 (5)	0.42282 (13)	0.4188 (2)	0.0288 (7)
O2	0.6982 (5)	0.50474 (11)	0.3906 (2)	0.0270 (7)
O3	0.8546 (7)	0.4840 (2)	0.2525 (3)	0.0579 (11)

	U11	U22	U33	U12	U13	U23
Ni1	0.0256 (4)	0.0139 (4)	0.0257 (4)	−0.0008 (2)	0.0040 (3)	−0.0028 (3)
C1	0.032 (2)	0.022 (2)	0.034 (2)	−0.0029 (17)	0.0055 (18)	−0.0007 (17)
C2	0.041 (2)	0.022 (2)	0.031 (2)	−0.0069 (17)	0.0088 (18)	−0.0052 (17)
C3	0.0291 (19)	0.0178 (18)	0.026 (2)	−0.0008 (15)	0.0020 (16)	−0.0002 (16)
C4	0.034 (2)	0.023 (2)	0.030 (2)	−0.0027 (17)	0.0072 (17)	−0.0047 (17)
C5	0.040 (2)	0.032 (2)	0.046 (3)	−0.0112 (19)	0.019 (2)	−0.019 (2)
C6	0.032 (2)	0.024 (2)	0.038 (2)	−0.0061 (17)	0.0082 (18)	−0.0090 (18)
C7	0.041 (2)	0.028 (2)	0.034 (2)	−0.0039 (18)	0.0117 (19)	−0.0074 (18)
C8	0.059 (3)	0.037 (3)	0.043 (3)	−0.017 (2)	0.022 (2)	−0.012 (2)
C9	0.077 (4)	0.060 (4)	0.068 (4)	−0.025 (3)	0.034 (3)	−0.018 (3)
C10	0.0396 (18)	0.047 (2)	0.0409 (17)	0.0122 (15)	0.0083 (14)	0.0059 (15)
C11	0.052 (3)	0.041 (3)	0.053 (3)	−0.025 (2)	0.028 (2)	−0.021 (2)
C12	0.039 (2)	0.031 (2)	0.045 (3)	−0.0097 (19)	0.015 (2)	−0.011 (2)
C13	0.029 (2)	0.029 (2)	0.045 (2)	−0.0055 (17)	0.0152 (19)	−0.0153 (19)
C14	0.032 (2)	0.0219 (19)	0.037 (2)	−0.0034 (16)	0.0120 (18)	−0.0042 (17)
N1	0.061 (3)	0.040 (2)	0.042 (2)	−0.025 (2)	0.026 (2)	−0.0145 (18)
N2	0.047 (2)	0.0271 (18)	0.035 (2)	−0.0156 (16)	0.0169 (17)	−0.0112 (16)
N3	0.044 (2)	0.030 (2)	0.057 (3)	−0.0140 (17)	0.0198 (19)	−0.0192 (19)
N4	0.0348 (18)	0.0239 (18)	0.042 (2)	−0.0081 (15)	0.0143 (16)	−0.0121 (16)
N5	0.0275 (17)	0.0193 (16)	0.0303 (18)	−0.0026 (13)	0.0020 (14)	−0.0004 (14)
O1	0.0317 (15)	0.0215 (14)	0.0351 (16)	−0.0043 (11)	0.0111 (12)	−0.0069 (12)
O2	0.0329 (16)	0.0184 (14)	0.0298 (16)	0.0003 (11)	0.0066 (12)	−0.0026 (11)
O3	0.069 (3)	0.061 (2)	0.055 (2)	−0.037 (2)	0.040 (2)	−0.026 (2)

Ni1—O2i	2.013 (3)	C9—C10	1.464 (12)
Ni1—O2	2.013 (3)	C9—N1	1.498 (7)
Ni1—O1i	2.051 (3)	C9—H9A	0.9700
Ni1—O1	2.051 (3)	C9—H9B	0.9700
Ni1—N5ii	2.207 (3)	C10—H10A	0.9600
Ni1—N5iii	2.207 (3)	C10—H10B	0.9600
C1—O3	1.236 (6)	C10—H10C	0.9600
C1—O2	1.260 (5)	C11—N4	1.472 (6)
C1—C2	1.505 (6)	C11—C12	1.509 (6)
C2—C8	1.358 (6)	C11—H11A	0.9700
C2—C3	1.448 (6)	C11—H11B	0.9700
C3—O1	1.260 (5)	C12—N5	1.480 (6)
C3—C4	1.441 (6)	C12—H12A	0.9700
C4—C7	1.398 (6)	C12—H12B	0.9700
C4—C5	1.413 (6)	C13—N4	1.450 (5)
C5—N3	1.305 (6)	C13—C14	1.522 (6)
C5—H5	0.9300	C13—H13A	0.9700
C6—N2	1.334 (6)	C13—H13B	0.9700
C6—N4	1.357 (5)	C14—N5	1.467 (5)
C6—N3	1.357 (6)	C14—H14A	0.9700
C7—N2	1.341 (6)	C14—H14B	0.9700
C7—N1	1.382 (6)	N5—Ni1iv	2.207 (3)
C8—N1	1.348 (6)	N5—H5N	0.90 (4)
C8—H8	0.9300
O2i—Ni1—O2	180.0	C9—C10—H10B	109.5
O2i—Ni1—O1i	88.73 (11)	H10A—C10—H10B	109.5
O2—Ni1—O1i	91.27 (11)	C9—C10—H10C	109.5
O2i—Ni1—O1	91.27 (11)	H10A—C10—H10C	109.5
O2—Ni1—O1	88.73 (11)	H10B—C10—H10C	109.5
O1i—Ni1—O1	180.0	N4—C11—C12	110.6 (4)
O2i—Ni1—N5ii	90.14 (12)	N4—C11—H11A	109.5
O2—Ni1—N5ii	89.86 (12)	C12—C11—H11A	109.5
O1i—Ni1—N5ii	91.00 (11)	N4—C11—H11B	109.5
O1—Ni1—N5ii	89.00 (11)	C12—C11—H11B	109.5
O2i—Ni1—N5iii	89.86 (12)	H11A—C11—H11B	108.1
O2—Ni1—N5iii	90.14 (12)	N5—C12—C11	114.8 (4)
O1i—Ni1—N5iii	89.00 (11)	N5—C12—H12A	108.6
O1—Ni1—N5iii	91.00 (11)	C11—C12—H12A	108.6
N5ii—Ni1—N5iii	180.0	N5—C12—H12B	108.6
O3—C1—O2	122.8 (4)	C11—C12—H12B	108.6
O3—C1—C2	118.4 (4)	H12A—C12—H12B	107.6
O2—C1—C2	118.9 (4)	N4—C13—C14	110.4 (3)
C8—C2—C3	118.6 (4)	N4—C13—H13A	109.6
C8—C2—C1	116.2 (4)	C14—C13—H13A	109.6
C3—C2—C1	125.1 (4)	N4—C13—H13B	109.6
O1—C3—C4	119.5 (4)	C14—C13—H13B	109.6
O1—C3—C2	126.1 (4)	H13A—C13—H13B	108.1
C4—C3—C2	114.4 (4)	N5—C14—C13	113.6 (4)
C7—C4—C5	113.6 (4)	N5—C14—H14A	108.8
C7—C4—C3	123.4 (4)	C13—C14—H14A	108.8
C5—C4—C3	122.9 (4)	N5—C14—H14B	108.8
N3—C5—C4	124.7 (4)	C13—C14—H14B	108.8
N3—C5—H5	117.6	H14A—C14—H14B	107.7
C4—C5—H5	117.6	C8—N1—C7	118.6 (4)
N2—C6—N4	116.5 (4)	C8—N1—C9	119.9 (4)
N2—C6—N3	126.2 (4)	C7—N1—C9	121.5 (4)
N4—C6—N3	117.4 (4)	C6—N2—C7	115.9 (4)
N2—C7—N1	117.8 (4)	C5—N3—C6	115.5 (4)
N2—C7—C4	123.5 (4)	C6—N4—C13	120.5 (4)
N1—C7—C4	118.6 (4)	C6—N4—C11	122.5 (4)
N1—C8—C2	126.3 (5)	C13—N4—C11	113.0 (3)
N1—C8—H8	116.9	C14—N5—C12	108.4 (3)
C2—C8—H8	116.9	C14—N5—Ni1iv	113.5 (2)
C10—C9—N1	110.6 (7)	C12—N5—Ni1iv	115.6 (2)
C10—C9—H9A	109.5	C14—N5—H5N	109 (3)
N1—C9—H9A	109.5	C12—N5—H5N	103 (4)
C10—C9—H9B	109.5	Ni1iv—N5—H5N	107 (3)
N1—C9—H9B	109.5	C3—O1—Ni1	127.3 (3)
H9A—C9—H9B	108.1	C1—O2—Ni1	134.0 (3)
C9—C10—H10A	109.5
O3—C1—C2—C8	1.5 (7)	N3—C6—N2—C7	5.9 (7)
O2—C1—C2—C8	−176.7 (4)	N1—C7—N2—C6	178.4 (4)
O3—C1—C2—C3	178.7 (4)	C4—C7—N2—C6	1.4 (7)
O2—C1—C2—C3	0.6 (6)	C4—C5—N3—C6	2.0 (8)
C8—C2—C3—O1	176.7 (4)	N2—C6—N3—C5	−7.5 (8)
C1—C2—C3—O1	−0.5 (7)	N4—C6—N3—C5	174.0 (4)
C8—C2—C3—C4	−1.8 (6)	N2—C6—N4—C13	11.1 (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—C11	167.2 (4)
C2—C3—C4—C7	3.8 (6)	N3—C6—N4—C11	−14.2 (7)
O1—C3—C4—C5	5.1 (6)	C14—C13—N4—C6	−147.5 (4)
C2—C3—C4—C5	−176.4 (4)	C14—C13—N4—C11	54.4 (5)
C7—C4—C5—N3	4.1 (7)	C12—C11—N4—C6	149.6 (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—C12	54.2 (5)
C3—C4—C7—N2	174.0 (4)	C13—C14—N5—Ni1iv	−176.1 (3)
C5—C4—C7—N1	177.2 (4)	C11—C12—N5—C14	−53.0 (5)
C3—C4—C7—N1	−2.9 (7)	C11—C12—N5—Ni1iv	178.4 (3)
C3—C2—C8—N1	−1.0 (8)	C4—C3—O1—Ni1	178.8 (3)
C1—C2—C8—N1	176.4 (5)	C2—C3—O1—Ni1	0.4 (6)
N4—C11—C12—N5	52.7 (6)	O2i—Ni1—O1—C3	179.7 (3)
N4—C13—C14—N5	−56.3 (5)	O2—Ni1—O1—C3	−0.3 (3)
C2—C8—N1—C7	2.0 (8)	N5ii—Ni1—O1—C3	89.6 (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—C8	0.0 (7)	C2—C1—O2—Ni1	−0.7 (6)
N2—C7—N1—C9	2.6 (8)	O1i—Ni1—O2—C1	−179.5 (4)
C4—C7—N1—C9	179.8 (5)	O1—Ni1—O2—C1	0.5 (4)
C10—C9—N1—C8	−89.8 (8)	N5ii—Ni1—O2—C1	−88.5 (4)
C10—C9—N1—C7	90.4 (7)	N5iii—Ni1—O2—C1	91.5 (4)
N4—C6—N2—C7	−175.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···O3v	0.90 (4)	2.29 (4)	3.161 (5)	163 (5)

Table 1

Selected bond lengths (Å)

Ni1—O2	2.013 (3)
Ni1—O1	2.051 (3)
Ni1—N5i	2.207 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5N⋯O3ii	0.90 (4)	2.29 (4)	3.161 (5)	163 (5)

Symmetry code: (ii) .