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

The title compound, {[Co(C(14)H(16)N(5)O(3))(2)]·2H(2)O}(n) or [Co(ppa)(2)]·2H(2)O}(n), where ppa denotes the 8-ethyl-5-oxo-2-(piperazin-1-yl)-5,8-dihydro-pyrido[2,3-d]pyrimidine-6-carb-ox-yl-ate anion, was synthesized under hydro-thermal conditions. The Co(II) atom (site symmetry ) exhibits a distorted trans-CoN(2)O(4) octa-hedral 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 mol-ecules occupy cavities within the grid.

Related literature

For the manganese and zinc complexes 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

Crystal data

[Co(C14H16N5O3)2]·2H2O

M = 699.58

Monoclinic,

a = 6.1093 (3) Å

b = 21.3690 (11) Å

c = 12.5944 (6) Å

β = 101.254 (1)°

V = 1612.58 (14) Å3

Z = 2

Mo Kα radiation

μ = 0.60 mm−1

T = 295 K

0.32 × 0.26 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.832, T max = 0.900

9807 measured reflections

3894 independent reflections

3327 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.181

S = 1.12

3894 reflections

227 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.77 e Å−3

Δρmin = −0.46 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; 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/S1600536809040185/hb5124sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040185/hb5124Isup2.hkl

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

[Co(C14H16N5O3)2]·2H2O	F(000) = 722
Mr = 699.58	Dx = 1.433 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4362 reflections
a = 6.1093 (3) Å	θ = 2.5–28.2°
b = 21.3690 (11) Å	µ = 0.60 mm−1
c = 12.5944 (6) Å	T = 295 K
β = 101.254 (1)°	Prism, pink
V = 1612.58 (14) Å3	0.32 × 0.26 × 0.18 mm
Z = 2

Bruker SMART CCD diffractometer	3894 independent reflections
Radiation source: fine-focus sealed tube	3327 reflections with I > 2σ(I)
graphite	Rint = 0.029
ω scans	θmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→6
Tmin = 0.832, Tmax = 0.900	k = −27→28
9807 measured reflections	l = −15→15

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.181	H 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 parameters	Δρmax = 0.77 e Å−3
1 restraint	Δρmin = −0.46 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	Occ. (<1)
O1W	0.669 (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
Co1	0.5000	0.5000	0.0000	0.02469 (18)
O1	0.6496 (3)	0.57810 (9)	0.08289 (16)	0.0324 (4)
O2	0.1437 (5)	0.51651 (14)	0.2499 (2)	0.0626 (8)
N1	0.5101 (5)	0.67072 (13)	0.3478 (2)	0.0487 (7)
N2	0.7758 (5)	0.74617 (12)	0.3332 (2)	0.0390 (6)
N3	1.0138 (5)	0.73519 (13)	0.2023 (2)	0.0437 (7)
N4	1.0250 (4)	0.82327 (11)	0.3106 (2)	0.0362 (6)
C1	0.2840 (5)	0.52788 (13)	0.1939 (2)	0.0328 (6)
C2	0.4347 (5)	0.58348 (13)	0.2241 (2)	0.0330 (6)
C3	0.6059 (4)	0.60347 (12)	0.1662 (2)	0.0275 (5)
C4	0.7269 (5)	0.65898 (13)	0.2104 (2)	0.0318 (6)
C5	0.9081 (5)	0.68298 (14)	0.1695 (3)	0.0398 (7)
H5	0.9566	0.6603	0.1155	0.048*
C6	0.9339 (5)	0.76685 (13)	0.2815 (2)	0.0334 (6)
C7	0.6763 (5)	0.69244 (13)	0.2976 (3)	0.0364 (6)
C8	0.3996 (6)	0.61779 (15)	0.3104 (3)	0.0452 (8)
H8	0.2905	0.6036	0.3467	0.054*
C9	0.4470 (8)	0.7043 (2)	0.4423 (4)	0.0646 (12)
H9A	0.4693	0.7489	0.4351	0.078*
H9B	0.2902	0.6972	0.4425	0.078*
C10	0.5781 (12)	0.6828 (4)	0.5417 (5)	0.118 (2)
H10A	0.5474	0.6393	0.5513	0.177*
H10B	0.5417	0.7065	0.6006	0.177*
H10C	0.7335	0.6880	0.5401	0.177*
C11	1.1614 (6)	0.85706 (17)	0.2461 (3)	0.0478 (8)
H11A	1.0667	0.8839	0.1943	0.057*
H11B	1.2345	0.8274	0.2062	0.057*
C12	1.3372 (5)	0.89675 (15)	0.3196 (3)	0.0400 (7)
H12A	1.4448	0.8690	0.3630	0.048*
H12B	1.4162	0.9216	0.2747	0.048*
C13	1.1106 (5)	0.90153 (13)	0.4537 (2)	0.0330 (6)
H13A	1.0424	0.9293	0.4989	0.040*
H13B	1.2078	0.8731	0.5011	0.040*
C14	0.9295 (5)	0.86418 (14)	0.3823 (3)	0.0353 (6)
H14A	0.8505	0.8392	0.4270	0.042*
H14B	0.8233	0.8925	0.3395	0.042*
N5	1.2458 (4)	0.93890 (10)	0.39246 (19)	0.0286 (5)
O3	0.3027 (3)	0.49641 (8)	0.11147 (17)	0.0295 (4)
H5N	1.155 (5)	0.9660 (14)	0.350 (2)	0.044*

	U11	U22	U33	U12	U13	U23
O1W	0.52 (4)	0.180 (13)	0.073 (8)	−0.084 (17)	0.063 (13)	0.045 (8)
O2W	0.35 (2)	0.33 (2)	0.122 (10)	−0.09 (2)	0.147 (13)	−0.030 (13)
Co1	0.0276 (3)	0.0158 (3)	0.0304 (3)	−0.00028 (17)	0.0050 (2)	−0.00242 (17)
O1	0.0350 (10)	0.0243 (9)	0.0395 (11)	−0.0065 (8)	0.0113 (8)	−0.0089 (8)
O2	0.0732 (18)	0.0635 (16)	0.0631 (17)	−0.0401 (15)	0.0429 (15)	−0.0297 (14)
N1	0.0630 (18)	0.0404 (15)	0.0494 (16)	−0.0222 (14)	0.0271 (14)	−0.0189 (12)
N2	0.0494 (15)	0.0296 (12)	0.0413 (14)	−0.0138 (11)	0.0167 (11)	−0.0129 (10)
N3	0.0454 (15)	0.0348 (14)	0.0556 (16)	−0.0152 (12)	0.0221 (13)	−0.0200 (12)
N4	0.0390 (13)	0.0268 (12)	0.0462 (14)	−0.0093 (10)	0.0169 (11)	−0.0132 (10)
C1	0.0354 (14)	0.0250 (13)	0.0379 (15)	−0.0061 (11)	0.0068 (12)	−0.0030 (11)
C2	0.0409 (15)	0.0244 (13)	0.0343 (14)	−0.0074 (11)	0.0091 (12)	−0.0035 (10)
C3	0.0309 (13)	0.0192 (12)	0.0314 (13)	−0.0023 (10)	0.0034 (10)	−0.0024 (10)
C4	0.0354 (14)	0.0241 (12)	0.0365 (14)	−0.0064 (11)	0.0082 (11)	−0.0064 (11)
C5	0.0434 (16)	0.0300 (14)	0.0498 (18)	−0.0102 (12)	0.0186 (14)	−0.0180 (13)
C6	0.0338 (14)	0.0248 (13)	0.0427 (16)	−0.0058 (11)	0.0097 (12)	−0.0087 (11)
C7	0.0449 (16)	0.0269 (13)	0.0397 (15)	−0.0099 (12)	0.0139 (13)	−0.0087 (11)
C8	0.057 (2)	0.0352 (16)	0.0486 (18)	−0.0198 (15)	0.0238 (16)	−0.0107 (14)
C9	0.080 (3)	0.058 (2)	0.065 (3)	−0.030 (2)	0.035 (2)	−0.025 (2)
C10	0.121 (5)	0.155 (7)	0.082 (4)	−0.025 (5)	0.028 (4)	−0.020 (4)
C11	0.055 (2)	0.0429 (18)	0.0501 (19)	−0.0253 (15)	0.0221 (16)	−0.0187 (15)
C12	0.0370 (15)	0.0326 (15)	0.0537 (18)	−0.0113 (12)	0.0167 (13)	−0.0110 (13)
C13	0.0334 (14)	0.0266 (13)	0.0402 (15)	−0.0067 (11)	0.0104 (12)	−0.0072 (11)
C14	0.0290 (13)	0.0276 (13)	0.0507 (17)	−0.0062 (11)	0.0114 (12)	−0.0119 (12)
N5	0.0283 (11)	0.0208 (10)	0.0362 (12)	−0.0017 (8)	0.0053 (9)	−0.0010 (9)
O3	0.0337 (10)	0.0199 (9)	0.0353 (11)	−0.0035 (7)	0.0072 (8)	−0.0029 (7)

Co1—O3i	2.022 (2)	C4—C5	1.405 (4)
Co1—O3	2.022 (2)	C5—H5	0.9300
Co1—O1i	2.0829 (18)	C8—H8	0.9300
Co1—O1	2.0829 (18)	C9—C10	1.425 (9)
Co1—N5ii	2.265 (2)	C9—H9A	0.9700
Co1—N5iii	2.265 (2)	C9—H9B	0.9700
O1—C3	1.255 (3)	C10—H10A	0.9600
O2—C1	1.235 (4)	C10—H10B	0.9600
N1—C8	1.354 (4)	C10—H10C	0.9600
N1—C7	1.376 (4)	C11—C12	1.530 (4)
N1—C9	1.503 (5)	C11—H11A	0.9700
N2—C7	1.335 (4)	C11—H11B	0.9700
N2—C6	1.341 (4)	C12—N5	1.471 (4)
N3—C5	1.315 (4)	C12—H12A	0.9700
N3—C6	1.371 (4)	C12—H12B	0.9700
N4—C6	1.348 (3)	C13—N5	1.471 (3)
N4—C14	1.459 (3)	C13—C14	1.510 (4)
N4—C11	1.462 (4)	C13—H13A	0.9700
C1—O3	1.261 (3)	C13—H13B	0.9700
C1—C2	1.506 (4)	C14—H14A	0.9700
C2—C8	1.362 (4)	C14—H14B	0.9700
C2—C3	1.451 (4)	N5—Co1iv	2.265 (2)
C3—C4	1.450 (4)	N5—H5N	0.900 (10)
C4—C7	1.396 (4)
O3i—Co1—O3	180.0	N1—C8—H8	117.2
O3i—Co1—O1i	86.86 (7)	C2—C8—H8	117.2
O3—Co1—O1i	93.14 (7)	C10—C9—N1	110.8 (5)
O3i—Co1—O1	93.14 (7)	C10—C9—H9A	109.5
O3—Co1—O1	86.86 (7)	N1—C9—H9A	109.5
O1i—Co1—O1	180.0	C10—C9—H9B	109.5
O3i—Co1—N5ii	90.28 (8)	N1—C9—H9B	109.5
O3—Co1—N5ii	89.72 (8)	H9A—C9—H9B	108.1
O1i—Co1—N5ii	91.18 (8)	C9—C10—H10A	109.5
O1—Co1—N5ii	88.82 (8)	C9—C10—H10B	109.5
O3i—Co1—N5iii	89.72 (8)	H10A—C10—H10B	109.5
O3—Co1—N5iii	90.28 (8)	C9—C10—H10C	109.5
O1i—Co1—N5iii	88.82 (8)	H10A—C10—H10C	109.5
O1—Co1—N5iii	91.18 (8)	H10B—C10—H10C	109.5
N5ii—Co1—N5iii	180.0	N4—C11—C12	110.3 (3)
C3—O1—Co1	128.37 (17)	N4—C11—H11A	109.6
C8—N1—C7	119.0 (3)	C12—C11—H11A	109.6
C8—N1—C9	119.1 (3)	N4—C11—H11B	109.6
C7—N1—C9	121.9 (3)	C12—C11—H11B	109.6
C7—N2—C6	116.4 (2)	H11A—C11—H11B	108.1
C5—N3—C6	115.1 (3)	N5—C12—C11	114.2 (3)
C6—N4—C14	120.7 (2)	N5—C12—H12A	108.7
C6—N4—C11	122.7 (2)	C11—C12—H12A	108.7
C14—N4—C11	112.8 (2)	N5—C12—H12B	108.7
O2—C1—O3	123.3 (3)	C11—C12—H12B	108.7
O2—C1—C2	118.0 (3)	H12A—C12—H12B	107.6
O3—C1—C2	118.6 (2)	N5—C13—C14	113.3 (2)
C8—C2—C3	118.9 (3)	N5—C13—H13A	108.9
C8—C2—C1	116.3 (3)	C14—C13—H13A	108.9
C3—C2—C1	124.8 (2)	N5—C13—H13B	108.9
O1—C3—C4	119.9 (2)	C14—C13—H13B	108.9
O1—C3—C2	125.8 (2)	H13A—C13—H13B	107.7
C4—C3—C2	114.3 (2)	N4—C14—C13	110.5 (2)
C7—C4—C5	114.4 (2)	N4—C14—H14A	109.5
C7—C4—C3	123.1 (3)	C13—C14—H14A	109.5
C5—C4—C3	122.5 (3)	N4—C14—H14B	109.5
N3—C5—C4	124.7 (3)	C13—C14—H14B	109.5
N3—C5—H5	117.7	H14A—C14—H14B	108.1
C4—C5—H5	117.7	C13—N5—C12	108.4 (2)
N2—C6—N4	117.5 (2)	C13—N5—Co1iv	112.89 (17)
N2—C6—N3	125.7 (3)	C12—N5—Co1iv	115.23 (17)
N4—C6—N3	116.9 (3)	C13—N5—H5N	108 (2)
N2—C7—N1	117.7 (3)	C12—N5—H5N	107 (2)
N2—C7—C4	123.3 (3)	Co1iv—N5—H5N	105 (2)
N1—C7—C4	119.0 (3)	C1—O3—Co1	135.54 (18)
N1—C8—C2	125.6 (3)
O3i—Co1—O1—C3	−179.8 (2)	C8—N1—C7—N2	177.2 (3)
O3—Co1—O1—C3	0.2 (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—C3	90.4 (2)	C9—N1—C7—C4	179.9 (4)
O2—C1—C2—C8	−1.4 (5)	C5—C4—C7—N2	6.3 (5)
O3—C1—C2—C8	176.6 (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—N1	2.8 (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—C2	178.2 (4)
C8—C2—C3—O1	−176.7 (3)	C3—C2—C8—N1	0.9 (6)
C1—C2—C3—O1	1.2 (5)	C1—C2—C8—N1	−177.2 (3)
C8—C2—C3—C4	1.3 (4)	C8—N1—C9—C10	91.4 (5)
C1—C2—C3—C4	179.2 (3)	C7—N1—C9—C10	−89.0 (5)
O1—C3—C4—C7	175.0 (3)	C6—N4—C11—C12	−149.0 (3)
C2—C3—C4—C7	−3.1 (4)	C14—N4—C11—C12	52.8 (4)
O1—C3—C4—C5	−6.0 (4)	N4—C11—C12—N5	−53.2 (4)
C2—C3—C4—C5	175.8 (3)	C6—N4—C14—C13	146.4 (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—N4	56.7 (3)
C3—C4—C5—N3	175.5 (3)	C14—C13—N5—C12	−55.3 (3)
C7—N2—C6—N4	175.2 (3)	C14—C13—N5—Co1iv	175.84 (18)
C7—N2—C6—N3	−5.8 (5)	C11—C12—N5—C13	53.7 (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—Co1	178.9 (3)
C14—N4—C6—N3	171.1 (3)	C2—C1—O3—Co1	1.0 (4)
C11—N4—C6—N3	14.5 (5)	O1i—Co1—O3—C1	179.6 (3)
C5—N3—C6—N2	6.6 (5)	O1—Co1—O3—C1	−0.4 (3)
C5—N3—C6—N4	−174.4 (3)	N5ii—Co1—O3—C1	88.4 (3)
C6—N2—C7—N1	−178.7 (3)	N5iii—Co1—O3—C1	−91.6 (3)
C6—N2—C7—C4	−1.1 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···O2v	0.90 (1)	2.28 (1)	3.156 (4)	165 (3)

Table 1

Selected bond lengths (Å)

Co1—O3	2.022 (2)
Co1—O1	2.0829 (18)
Co1—N5i	2.265 (2)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5N⋯O2ii	0.900 (10)	2.278 (14)	3.156 (4)	165 (3)

Symmetry code: (ii) .