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

The title compound, {[Zn(C(14)H(16)N(5)O(3))(2)]·2H(2)O}(n) or [Zn(ppa)(2)]·2H(2)O}(n), where ppa = 8-ethyl-5,8-dihydro-5-oxo-2-(1-piperazin-yl)-pyrido(2,3-d)-pyrimidine-6-carboxyl-ate, was synthesized under hydro-thermal conditions. The Zn(II) atom (site symmetry ) exhibits a distorted trans-ZnN(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 arising from this connectivity is a square grid and the disordered uncoordinated water mol-ecules occupy cavities within the grid. An N-H⋯O hydrogen bond occurs.

Related literature

For manganese complexes of the ppa anion, see: Huang et al. (2008 ▶). For background to the medicinal uses of pipemidic acid, see: Mizuki et al. (1996 ▶).

Experimental

Crystal data

[Zn(C14H16N5O3)2]·2H2O

M = 704.05

Monoclinic,

a = 6.1146 (12) Å

b = 21.424 (4) Å

c = 12.577 (3) Å

β = 101.10 (3)°

V = 1616.9 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.82 mm−1

T = 295 K

0.36 × 0.28 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (CrystalStructure; Rigaku/MSC, 2002 ▶) T min = 0.756, T max = 0.866

15697 measured reflections

3684 independent reflections

2570 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.210

S = 1.06

3684 reflections

228 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.83 e Å−3

Δρmin = −0.83 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809036939/hb5062sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036939/hb5062Isup2.hkl

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

[Zn(C14H16N5O3)2]·2H2O	Z = 2
Mr = 704.05	F(000) = 728
Monoclinic, P21/c	Dx = 1.442 Mg m−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 6.1146 (12) Å	µ = 0.82 mm−1
b = 21.424 (4) Å	T = 295 K
c = 12.577 (3) Å	Prism, colorless
β = 101.10 (3)°	0.36 × 0.28 × 0.18 mm
V = 1616.9 (6) Å3

Rigaku R-AXIS RAPID diffractometer	3684 independent reflections
Radiation source: fine-focus sealed tube	2570 reflections with I > 2σ(I)
graphite	Rint = 0.045
Detector resolution: 10.000 pixels mm-1	θmax = 27.5°, θmin = 3.3°
ω scans	h = −7→7
Absorption correction: multi-scan (CrystalStructure; Rigaku/MSC, 2002)	k = −27→25
Tmin = 0.756, Tmax = 0.866	l = −16→16
15697 measured reflections

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.210	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.1254P)2 + 1.7801P] where P = (Fo2 + 2Fc2)/3
3684 reflections	(Δ/σ)max < 0.001
228 parameters	Δρmax = 0.83 e Å−3
1 restraint	Δρmin = −0.83 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	−0.045 (3)	−0.0632 (10)	−0.0746 (11)	0.187 (8)	0.50
O2W	0.340 (5)	0.0205 (10)	−0.0364 (12)	0.251 (14)	0.50
Zn1	0.5000	0.0000	0.5000	0.0265 (2)
O1	0.6981 (4)	−0.00325 (10)	0.3877 (2)	0.0271 (6)
O2	0.8573 (7)	0.01818 (18)	0.2500 (3)	0.0616 (11)
O3	0.3495 (5)	0.07935 (11)	0.4179 (2)	0.0317 (6)
N1	0.4916 (7)	0.17173 (17)	0.1532 (3)	0.0481 (10)
N2	0.2252 (6)	0.24690 (15)	0.1677 (3)	0.0386 (8)
N3	−0.0127 (6)	0.23572 (16)	0.2988 (3)	0.0436 (9)
N4	−0.0227 (6)	0.32384 (15)	0.1907 (3)	0.0349 (8)
N5	−0.2450 (5)	0.43908 (14)	0.1084 (2)	0.0273 (7)
H5N	−0.154 (8)	0.466 (2)	0.152 (4)	0.065 (16)*
C1	0.7147 (7)	0.02891 (17)	0.3064 (3)	0.0316 (8)
C2	0.5658 (7)	0.08450 (17)	0.2772 (3)	0.0317 (8)
C3	0.3947 (6)	0.10453 (16)	0.3346 (3)	0.0271 (7)
C4	0.2744 (7)	0.15974 (16)	0.2910 (3)	0.0303 (8)
C5	0.0937 (8)	0.18359 (19)	0.3318 (3)	0.0398 (10)
H5	0.0454	0.1610	0.3861	0.048*
C6	0.0671 (7)	0.26762 (18)	0.2197 (3)	0.0327 (8)
C7	0.3246 (7)	0.19340 (18)	0.2034 (3)	0.0360 (9)
C8	0.6010 (8)	0.1189 (2)	0.1902 (4)	0.0457 (11)
H8	0.7096	0.1047	0.1535	0.055*
C9	0.5540 (11)	0.2051 (3)	0.0585 (5)	0.0665 (16)
H9B	0.5306	0.2496	0.0653	0.080*
H9A	0.7107	0.1983	0.0582	0.080*
C10	0.4247 (16)	0.1834 (5)	−0.0401 (7)	0.116 (3)
H10C	0.4566	0.1401	−0.0496	0.174*
H10B	0.4605	0.2071	−0.0993	0.174*
H10A	0.2693	0.1883	−0.0385	0.174*
C11	−0.1608 (8)	0.3572 (2)	0.2553 (4)	0.0475 (11)
H11B	−0.0673	0.3839	0.3077	0.057*
H11A	−0.2346	0.3275	0.2947	0.057*
C12	−0.3356 (7)	0.3970 (2)	0.1813 (4)	0.0398 (10)
H12B	−0.4429	0.3694	0.1379	0.048*
H12A	−0.4150	0.4218	0.2262	0.048*
C13	−0.1090 (6)	0.40176 (17)	0.0469 (3)	0.0317 (8)
H13A	−0.0405	0.4295	0.0018	0.038*
H13B	−0.2057	0.3734	−0.0006	0.038*
C14	0.0708 (7)	0.36460 (18)	0.1185 (4)	0.0369 (9)
H14B	0.1500	0.3397	0.0737	0.044*
H14A	0.1768	0.3929	0.1610	0.044*

	U11	U22	U33	U12	U13	U23
O1W	0.209 (18)	0.28 (2)	0.094 (9)	−0.004 (16)	0.091 (11)	0.013 (12)
O2W	0.47 (4)	0.202 (17)	0.077 (9)	0.11 (2)	0.049 (16)	−0.057 (12)
Zn1	0.0317 (4)	0.0194 (3)	0.0294 (3)	0.0006 (2)	0.0079 (2)	0.0028 (2)
O1	0.0276 (13)	0.0218 (12)	0.0333 (14)	0.0019 (9)	0.0089 (10)	0.0029 (10)
O2	0.073 (3)	0.062 (2)	0.060 (2)	0.040 (2)	0.0387 (19)	0.0275 (18)
O3	0.0378 (15)	0.0223 (12)	0.0368 (14)	0.0092 (10)	0.0116 (11)	0.0121 (11)
N1	0.065 (3)	0.0398 (19)	0.046 (2)	0.0223 (18)	0.0265 (19)	0.0195 (17)
N2	0.051 (2)	0.0282 (16)	0.0400 (18)	0.0135 (15)	0.0160 (16)	0.0124 (14)
N3	0.044 (2)	0.0361 (18)	0.055 (2)	0.0166 (16)	0.0219 (17)	0.0231 (17)
N4	0.0390 (19)	0.0283 (16)	0.0415 (18)	0.0096 (14)	0.0177 (15)	0.0119 (14)
N5	0.0265 (16)	0.0219 (14)	0.0324 (15)	0.0064 (12)	0.0028 (12)	0.0034 (13)
C1	0.037 (2)	0.0274 (18)	0.0316 (18)	0.0046 (15)	0.0112 (16)	−0.0002 (16)
C2	0.038 (2)	0.0238 (17)	0.0354 (19)	0.0070 (15)	0.0110 (16)	0.0035 (15)
C3	0.0283 (18)	0.0219 (16)	0.0302 (17)	0.0007 (13)	0.0032 (14)	0.0013 (14)
C4	0.036 (2)	0.0242 (17)	0.0318 (18)	0.0021 (15)	0.0087 (15)	0.0055 (15)
C5	0.048 (3)	0.033 (2)	0.043 (2)	0.0088 (18)	0.0188 (19)	0.0174 (18)
C6	0.033 (2)	0.0273 (18)	0.0380 (19)	0.0046 (15)	0.0078 (16)	0.0077 (16)
C7	0.044 (2)	0.0323 (19)	0.0347 (19)	0.0092 (17)	0.0137 (17)	0.0067 (17)
C8	0.060 (3)	0.037 (2)	0.046 (2)	0.018 (2)	0.026 (2)	0.0107 (19)
C9	0.083 (4)	0.063 (3)	0.062 (3)	0.030 (3)	0.038 (3)	0.024 (3)
C10	0.117 (7)	0.144 (9)	0.090 (5)	0.031 (6)	0.028 (5)	0.024 (6)
C11	0.055 (3)	0.045 (2)	0.047 (2)	0.025 (2)	0.021 (2)	0.020 (2)
C12	0.040 (2)	0.036 (2)	0.047 (2)	0.0157 (17)	0.0179 (18)	0.0161 (19)
C13	0.035 (2)	0.0247 (17)	0.0366 (19)	0.0101 (15)	0.0094 (16)	0.0081 (15)
C14	0.033 (2)	0.0293 (18)	0.051 (2)	0.0043 (16)	0.0147 (17)	0.0119 (18)

Zn1—O1	2.031 (3)	C2—C8	1.370 (6)
Zn1—O1i	2.031 (3)	C2—C3	1.446 (5)
Zn1—O3i	2.107 (2)	C3—C4	1.444 (5)
Zn1—O3	2.107 (2)	C4—C7	1.399 (5)
Zn1—N5ii	2.275 (3)	C4—C5	1.401 (6)
Zn1—N5iii	2.275 (3)	C5—H5	0.9300
O1—C1	1.253 (5)	C8—H8	0.9300
O2—C1	1.247 (5)	C9—C10	1.415 (11)
O3—C3	1.256 (4)	C9—H9B	0.9700
N1—C8	1.351 (5)	C9—H9A	0.9700
N1—C7	1.381 (5)	C10—H10C	0.9600
N1—C9	1.500 (6)	C10—H10B	0.9600
N2—C7	1.334 (5)	C10—H10A	0.9600
N2—C6	1.343 (5)	C11—C12	1.534 (5)
N3—C5	1.319 (5)	C11—H11B	0.9700
N3—C6	1.373 (5)	C11—H11A	0.9700
N4—C6	1.345 (5)	C12—H12B	0.9700
N4—C14	1.454 (5)	C12—H12A	0.9700
N4—C11	1.466 (5)	C13—C14	1.508 (5)
N5—C12	1.468 (5)	C13—H13A	0.9700
N5—C13	1.475 (5)	C13—H13B	0.9700
N5—Zn1iv	2.275 (3)	C14—H14B	0.9700
N5—H5N	0.900 (10)	C14—H14A	0.9700
C1—C2	1.501 (5)
O1—Zn1—O1i	180.0	N2—C6—N4	117.3 (3)
O1—Zn1—O3i	92.90 (10)	N2—C6—N3	125.3 (4)
O1i—Zn1—O3i	87.10 (10)	N4—C6—N3	117.3 (4)
O1—Zn1—O3	87.10 (10)	N2—C7—N1	117.6 (3)
O1i—Zn1—O3	92.90 (10)	N2—C7—C4	123.6 (4)
O3i—Zn1—O3	180.0	N1—C7—C4	118.7 (3)
O1—Zn1—N5ii	89.74 (11)	N1—C8—C2	125.6 (4)
O1i—Zn1—N5ii	90.26 (11)	N1—C8—H8	117.2
O3i—Zn1—N5ii	90.86 (11)	C2—C8—H8	117.2
O3—Zn1—N5ii	89.14 (11)	C10—C9—N1	110.8 (7)
O1—Zn1—N5iii	90.26 (11)	C10—C9—H9B	109.5
O1i—Zn1—N5iii	89.74 (11)	N1—C9—H9B	109.5
O3i—Zn1—N5iii	89.14 (11)	C10—C9—H9A	109.5
O3—Zn1—N5iii	90.86 (11)	N1—C9—H9A	109.5
N5ii—Zn1—N5iii	180.0	H9B—C9—H9A	108.1
C1—O1—Zn1	134.5 (2)	C9—C10—H10C	109.5
C3—O3—Zn1	127.6 (2)	C9—C10—H10B	109.5
C8—N1—C7	119.0 (3)	H10C—C10—H10B	109.5
C8—N1—C9	119.2 (4)	C9—C10—H10A	109.5
C7—N1—C9	121.8 (4)	H10C—C10—H10A	109.5
C7—N2—C6	116.3 (3)	H10B—C10—H10A	109.5
C5—N3—C6	115.3 (4)	N4—C11—C12	110.0 (3)
C6—N4—C14	121.2 (3)	N4—C11—H11B	109.7
C6—N4—C11	122.4 (3)	C12—C11—H11B	109.7
C14—N4—C11	113.0 (3)	N4—C11—H11A	109.7
C12—N5—C13	108.3 (3)	C12—C11—H11A	109.7
C12—N5—Zn1iv	115.4 (2)	H11B—C11—H11A	108.2
C13—N5—Zn1iv	112.8 (2)	N5—C12—C11	114.7 (3)
C12—N5—H5N	106 (4)	N5—C12—H12B	108.6
C13—N5—H5N	108 (4)	C11—C12—H12B	108.6
Zn1iv—N5—H5N	106 (4)	N5—C12—H12A	108.6
O2—C1—O1	122.6 (4)	C11—C12—H12A	108.6
O2—C1—C2	117.7 (3)	H12B—C12—H12A	107.6
O1—C1—C2	119.7 (3)	N5—C13—C14	113.1 (3)
C8—C2—C3	118.6 (3)	N5—C13—H13A	109.0
C8—C2—C1	116.2 (3)	C14—C13—H13A	109.0
C3—C2—C1	125.2 (3)	N5—C13—H13B	109.0
O3—C3—C4	119.4 (3)	C14—C13—H13B	109.0
O3—C3—C2	125.8 (3)	H13A—C13—H13B	107.8
C4—C3—C2	114.7 (3)	N4—C14—C13	111.2 (3)
C7—C4—C5	114.1 (3)	N4—C14—H14B	109.4
C7—C4—C3	123.2 (4)	C13—C14—H14B	109.4
C5—C4—C3	122.6 (3)	N4—C14—H14A	109.4
N3—C5—C4	124.7 (4)	C13—C14—H14A	109.4
N3—C5—H5	117.6	H14B—C14—H14A	108.0
C4—C5—H5	117.6
O1i—Zn1—O1—C1	−50 (2)	C11—N4—C6—N2	−167.0 (4)
O3i—Zn1—O1—C1	179.5 (4)	C14—N4—C6—N3	171.7 (4)
O3—Zn1—O1—C1	−0.5 (4)	C11—N4—C6—N3	14.0 (6)
N5ii—Zn1—O1—C1	88.7 (4)	C5—N3—C6—N2	7.0 (7)
N5iii—Zn1—O1—C1	−91.3 (4)	C5—N3—C6—N4	−174.0 (4)
O1—Zn1—O3—C3	0.4 (3)	C6—N2—C7—N1	−178.5 (4)
O1i—Zn1—O3—C3	−179.6 (3)	C6—N2—C7—C4	−1.0 (6)
O3i—Zn1—O3—C3	65 (100)	C8—N1—C7—N2	177.5 (4)
N5ii—Zn1—O3—C3	−89.4 (3)	C9—N1—C7—N2	−2.7 (7)
N5iii—Zn1—O3—C3	90.6 (3)	C8—N1—C7—C4	−0.1 (7)
Zn1—O1—C1—O2	178.2 (3)	C9—N1—C7—C4	179.7 (5)
Zn1—O1—C1—C2	1.0 (6)	C5—C4—C7—N2	6.2 (6)
O2—C1—C2—C8	−0.1 (6)	C3—C4—C7—N2	−174.9 (4)
O1—C1—C2—C8	177.1 (4)	C5—C4—C7—N1	−176.3 (4)
O2—C1—C2—C3	−178.8 (4)	C3—C4—C7—N1	2.5 (6)
O1—C1—C2—C3	−1.6 (6)	C7—N1—C8—C2	−1.9 (8)
Zn1—O3—C3—C4	−179.0 (2)	C9—N1—C8—C2	178.3 (5)
Zn1—O3—C3—C2	−1.1 (5)	C3—C2—C8—N1	1.4 (7)
C8—C2—C3—O3	−177.0 (4)	C1—C2—C8—N1	−177.4 (4)
C1—C2—C3—O3	1.7 (6)	C8—N1—C9—C10	90.7 (7)
C8—C2—C3—C4	1.0 (6)	C7—N1—C9—C10	−89.1 (7)
C1—C2—C3—C4	179.7 (4)	C6—N4—C11—C12	−148.9 (4)
O3—C3—C4—C7	175.2 (4)	C14—N4—C11—C12	51.8 (5)
C2—C3—C4—C7	−2.9 (6)	C13—N5—C12—C11	53.7 (5)
O3—C3—C4—C5	−6.0 (6)	Zn1iv—N5—C12—C11	−178.8 (3)
C2—C3—C4—C5	175.9 (4)	N4—C11—C12—N5	−52.7 (5)
C6—N3—C5—C4	−0.8 (7)	C12—N5—C13—C14	−55.0 (4)
C7—C4—C5—N3	−5.2 (7)	Zn1iv—N5—C13—C14	176.0 (2)
C3—C4—C5—N3	175.9 (4)	C6—N4—C14—C13	145.9 (4)
C7—N2—C6—N4	174.8 (4)	C11—N4—C14—C13	−54.5 (5)
C7—N2—C6—N3	−6.2 (7)	N5—C13—C14—N4	56.5 (5)
C14—N4—C6—N2	−9.3 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···O2v	0.91 (5)	2.28 (5)	3.168 (5)	166 (4)

Table 1

Selected bond lengths (Å)

Zn1—O1	2.031 (3)
Zn1—O3	2.107 (2)
Zn1—N5i	2.275 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5N⋯O2ii	0.91 (5)	2.28 (5)	3.168 (5)	166 (4)

Symmetry code: (ii) .