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

In the title compound, {[Mn(C(14)H(16)N(5)O(3))(2)]·2H(2)O}(n), the Mn(II) atom (site symmetry ) exhibits a distorted trans-MnN(2)O(4) octa-hedral geometry defined by two monodentate N-bonded and two bidentate O,O'-bonded 8-ethyl-5-oxo-2-(piperazin-1-yl)-5,8-dihydro-pyrido[2,3-d]pyrimidine-6-carboxyl-ate anions. An N-H⋯O hydrogen bond is present in the crystal structure. The extended two-dimensional structure is a square grid and the disordered uncoordinated water mol-ecules occupy cavities within the grid.

Related literature

For background, see: Mizuki et al. (1996 ▶).

Experimental

Crystal data

[Mn(C14H16N5O3)2]·2H2O

M = 695.58

Monoclinic,

a = 6.0422 (2) Å

b = 21.5673 (8) Å

c = 12.7395 (5) Å

β = 99.617 (1)°

V = 1636.8 (1) Å3

Z = 2

Mo Kα radiation

μ = 0.47 mm−1

T = 295 (2) K

0.34 × 0.26 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.861, T max = 0.910

10030 measured reflections

3938 independent reflections

3465 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.191

S = 1.10

3938 reflections

227 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.97 e Å−3

Δρmin = −0.48 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); 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/S1600536808006533/hb2703sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006533/hb2703Isup2.hkl

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

[Mn(C14H16N5O3)2]·2H2O	F000 = 718.0
Mr = 695.58	Dx = 1.399 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4747 reflections
a = 6.0422 (2) Å	θ = 2.5–28.3º
b = 21.5673 (8) Å	µ = 0.47 mm−1
c = 12.7395 (5) Å	T = 295 (2) K
β = 99.617 (1)º	Prism, colorless
V = 1636.8 (1) Å3	0.34 × 0.26 × 0.18 mm
Z = 2

Bruker SMART CCD diffractometer	3938 independent reflections
Radiation source: fine-focus sealed tube	3465 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.019
T = 295(2) K	θmax = 28.3º
ω scans	θmin = 2.5º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −6→8
Tmin = 0.861, Tmax = 0.910	k = −27→28
10030 measured reflections	l = −15→16

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.191	w = 1/[σ2(Fo2) + (0.1066P)2 + 1.0983P] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max < 0.001
3938 reflections	Δρmax = 0.98 e Å−3
227 parameters	Δρmin = −0.48 e Å−3
1 restraint	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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)
Mn1	0.5000	0.5000	0.5000	0.02831 (19)
O1W	0.388 (4)	0.5235 (7)	0.9613 (10)	0.244 (9)	0.50
O1	0.7068 (3)	0.49893 (7)	0.38228 (16)	0.0341 (4)
O2W	−0.081 (2)	0.4426 (8)	0.9246 (7)	0.194 (6)	0.50
O2	0.8721 (5)	0.51863 (13)	0.2451 (2)	0.0717 (8)
O3	0.3574 (3)	0.58106 (8)	0.41354 (14)	0.0378 (4)
N1	0.5078 (5)	0.67158 (12)	0.1504 (2)	0.0533 (7)
N2	−0.0007 (4)	0.73723 (11)	0.2985 (2)	0.0464 (6)
N3	0.2395 (4)	0.74681 (10)	0.16596 (18)	0.0432 (5)
N4	−0.0102 (4)	0.82368 (10)	0.19027 (19)	0.0384 (5)
N5	−0.2339 (3)	0.93726 (9)	0.11005 (17)	0.0322 (4)
H5N	−0.140 (4)	0.9649 (12)	0.146 (2)	0.048*
C1	0.7282 (4)	0.52991 (11)	0.3018 (2)	0.0358 (5)
C2	0.5782 (4)	0.58537 (11)	0.2731 (2)	0.0354 (5)
C3	0.4044 (4)	0.60559 (10)	0.33118 (19)	0.0313 (5)
C4	0.2852 (4)	0.66087 (11)	0.28824 (19)	0.0336 (5)
C5	0.1042 (5)	0.68542 (12)	0.3304 (2)	0.0425 (6)
H5A	0.0546	0.6635	0.3848	0.051*
C6	0.0805 (4)	0.76813 (12)	0.2189 (2)	0.0360 (5)
C7	0.3383 (5)	0.69362 (12)	0.2010 (2)	0.0395 (6)
C8	0.6170 (5)	0.61896 (14)	0.1875 (2)	0.0496 (7)
H8A	0.7282	0.6046	0.1512	0.059*
C9	0.5717 (8)	0.7043 (2)	0.0566 (3)	0.0725 (12)
H9A	0.5531	0.7486	0.0645	0.087*
H9B	0.7285	0.6963	0.0537	0.087*
C10	0.4373 (10)	0.6840 (4)	−0.0400 (5)	0.116 (2)
H10A	0.4583	0.6403	−0.0488	0.174*
H10B	0.4811	0.7059	−0.0989	0.174*
H10C	0.2822	0.6923	−0.0375	0.174*
C11	−0.1446 (6)	0.85820 (14)	0.2560 (2)	0.0499 (7)
H11A	−0.0477	0.8852	0.3045	0.060*
H11B	−0.2170	0.8295	0.2980	0.060*
C12	−0.3226 (5)	0.89702 (13)	0.1855 (2)	0.0433 (6)
H12A	−0.4326	0.8693	0.1460	0.052*
H12B	−0.3996	0.9225	0.2308	0.052*
C13	−0.1018 (4)	0.89946 (12)	0.0466 (2)	0.0372 (5)
H13A	−0.0347	0.9264	−0.0003	0.045*
H13B	−0.2015	0.8710	0.0025	0.045*
C14	0.0812 (4)	0.86281 (12)	0.1146 (2)	0.0382 (6)
H14A	0.1573	0.8371	0.0693	0.046*
H14B	0.1906	0.8911	0.1530	0.046*

	U11	U22	U33	U12	U13	U23
Mn1	0.0350 (3)	0.0187 (3)	0.0304 (3)	−0.00041 (16)	0.0030 (2)	0.00255 (16)
O1W	0.47 (3)	0.155 (12)	0.111 (9)	0.000 (15)	0.058 (14)	−0.057 (9)
O1	0.0407 (10)	0.0237 (9)	0.0383 (10)	0.0041 (6)	0.0073 (8)	0.0040 (6)
O2W	0.203 (11)	0.307 (17)	0.088 (6)	−0.110 (12)	0.076 (7)	−0.028 (8)
O2	0.0854 (18)	0.0730 (16)	0.0674 (16)	0.0491 (15)	0.0441 (14)	0.0338 (13)
O3	0.0448 (10)	0.0297 (9)	0.0403 (9)	0.0085 (7)	0.0110 (7)	0.0122 (7)
N1	0.0730 (17)	0.0433 (13)	0.0500 (14)	0.0245 (12)	0.0294 (12)	0.0196 (11)
N2	0.0498 (13)	0.0386 (12)	0.0550 (14)	0.0152 (10)	0.0211 (11)	0.0213 (11)
N3	0.0549 (13)	0.0339 (11)	0.0434 (12)	0.0165 (10)	0.0157 (10)	0.0150 (9)
N4	0.0418 (11)	0.0301 (10)	0.0458 (12)	0.0107 (9)	0.0146 (9)	0.0133 (9)
N5	0.0344 (10)	0.0231 (9)	0.0382 (10)	0.0029 (7)	0.0034 (8)	0.0012 (8)
C1	0.0410 (13)	0.0311 (12)	0.0355 (12)	0.0080 (10)	0.0071 (10)	0.0029 (9)
C2	0.0429 (13)	0.0281 (11)	0.0360 (12)	0.0084 (9)	0.0092 (10)	0.0040 (9)
C3	0.0367 (11)	0.0227 (10)	0.0337 (11)	0.0032 (9)	0.0033 (9)	0.0042 (8)
C4	0.0396 (12)	0.0265 (11)	0.0352 (12)	0.0060 (9)	0.0073 (9)	0.0067 (9)
C5	0.0491 (15)	0.0339 (13)	0.0475 (15)	0.0103 (11)	0.0167 (12)	0.0168 (11)
C6	0.0377 (12)	0.0307 (12)	0.0398 (13)	0.0066 (9)	0.0066 (10)	0.0090 (10)
C7	0.0506 (14)	0.0313 (12)	0.0386 (13)	0.0109 (11)	0.0132 (11)	0.0082 (10)
C8	0.0609 (17)	0.0438 (15)	0.0485 (16)	0.0220 (13)	0.0219 (13)	0.0120 (12)
C9	0.091 (3)	0.071 (2)	0.065 (2)	0.035 (2)	0.041 (2)	0.0293 (19)
C10	0.111 (4)	0.154 (6)	0.085 (4)	0.032 (4)	0.022 (3)	0.021 (4)
C11	0.0604 (17)	0.0465 (15)	0.0478 (15)	0.0251 (14)	0.0234 (13)	0.0176 (13)
C12	0.0427 (13)	0.0368 (13)	0.0535 (16)	0.0129 (11)	0.0169 (12)	0.0133 (12)
C13	0.0394 (13)	0.0308 (12)	0.0414 (13)	0.0087 (10)	0.0071 (10)	0.0078 (10)
C14	0.0365 (12)	0.0304 (12)	0.0497 (14)	0.0075 (9)	0.0128 (11)	0.0136 (10)

Mn1—O1	2.106 (2)	C2—C8	1.361 (4)
Mn1—O1i	2.106 (2)	C2—C3	1.450 (3)
Mn1—O3	2.1667 (16)	C3—C4	1.452 (3)
Mn1—O3i	2.1667 (16)	C4—C7	1.399 (3)
Mn1—N5ii	2.372 (2)	C4—C5	1.400 (4)
Mn1—N5iii	2.3723 (19)	C5—H5A	0.9300
O1—C1	1.248 (3)	C8—H8A	0.9300
O2—C1	1.244 (3)	C9—C10	1.425 (8)
O3—C3	1.249 (3)	C9—H9A	0.9700
N1—C8	1.357 (3)	C9—H9B	0.9700
N1—C7	1.382 (4)	C10—H10A	0.9600
N1—C9	1.493 (4)	C10—H10B	0.9600
N2—C5	1.315 (3)	C10—H10C	0.9600
N2—C6	1.371 (4)	C11—C12	1.531 (4)
N3—C7	1.335 (3)	C11—H11A	0.9700
N3—C6	1.344 (3)	C11—H11B	0.9700
N4—C6	1.343 (3)	C12—H12A	0.9700
N4—C14	1.457 (3)	C12—H12B	0.9700
N4—C11	1.463 (3)	C13—C14	1.510 (3)
N5—C12	1.461 (3)	C13—H13A	0.9700
N5—C13	1.474 (3)	C13—H13B	0.9700
N5—Mn1iv	2.3723 (19)	C14—H14A	0.9700
N5—H5N	0.90 (3)	C14—H14B	0.9700
C1—C2	1.508 (3)
O1—Mn1—O1i	180.0	N4—C6—N3	117.5 (2)
O1—Mn1—O3	83.09 (6)	N4—C6—N2	117.0 (2)
O1i—Mn1—O3	96.91 (6)	N3—C6—N2	125.4 (2)
O1—Mn1—O3i	96.91 (6)	N3—C7—N1	117.7 (2)
O1i—Mn1—O3i	83.09 (6)	N3—C7—C4	123.4 (2)
O3—Mn1—O3i	180.0	N1—C7—C4	118.9 (2)
O1—Mn1—N5ii	90.17 (7)	N1—C8—C2	125.8 (3)
O1i—Mn1—N5ii	89.83 (7)	N1—C8—H8A	117.1
O3—Mn1—N5ii	90.74 (7)	C2—C8—H8A	117.1
O3i—Mn1—N5ii	89.26 (7)	C10—C9—N1	111.2 (5)
O1—Mn1—N5iii	89.83 (7)	C10—C9—H9A	109.4
O1i—Mn1—N5iii	90.17 (7)	N1—C9—H9A	109.4
O3—Mn1—N5iii	89.26 (7)	C10—C9—H9B	109.4
O3i—Mn1—N5iii	90.73 (7)	N1—C9—H9B	109.4
N5ii—Mn1—N5iii	180.0	H9A—C9—H9B	108.0
C1—O1—Mn1	137.22 (16)	C9—C10—H10A	109.5
C3—O3—Mn1	129.93 (16)	C9—C10—H10B	109.5
C8—N1—C7	118.7 (2)	H10A—C10—H10B	109.5
C8—N1—C9	119.8 (3)	C9—C10—H10C	109.5
C7—N1—C9	121.4 (2)	H10A—C10—H10C	109.5
C5—N2—C6	115.3 (2)	H10B—C10—H10C	109.5
C7—N3—C6	116.3 (2)	N4—C11—C12	110.2 (2)
C6—N4—C14	120.9 (2)	N4—C11—H11A	109.6
C6—N4—C11	122.6 (2)	C12—C11—H11A	109.6
C14—N4—C11	113.1 (2)	N4—C11—H11B	109.6
C12—N5—C13	108.90 (19)	C12—C11—H11B	109.6
C12—N5—Mn1iv	116.15 (15)	H11A—C11—H11B	108.1
C13—N5—Mn1iv	111.54 (14)	N5—C12—C11	114.3 (2)
C12—N5—H5N	110 (2)	N5—C12—H12A	108.7
C13—N5—H5N	107 (2)	C11—C12—H12A	108.7
Mn1iv—N5—H5N	103 (2)	N5—C12—H12B	108.7
O2—C1—O1	123.4 (2)	C11—C12—H12B	108.7
O2—C1—C2	117.6 (2)	H12A—C12—H12B	107.6
O1—C1—C2	118.9 (2)	N5—C13—C14	112.8 (2)
C8—C2—C3	119.0 (2)	N5—C13—H13A	109.0
C8—C2—C1	116.1 (2)	C14—C13—H13A	109.0
C3—C2—C1	124.9 (2)	N5—C13—H13B	109.0
O3—C3—C2	126.0 (2)	C14—C13—H13B	109.0
O3—C3—C4	119.8 (2)	H13A—C13—H13B	107.8
C2—C3—C4	114.3 (2)	N4—C14—C13	111.1 (2)
C7—C4—C5	114.3 (2)	N4—C14—H14A	109.4
C7—C4—C3	123.3 (2)	C13—C14—H14A	109.4
C5—C4—C3	122.4 (2)	N4—C14—H14B	109.4
N2—C5—C4	124.8 (2)	C13—C14—H14B	109.4
N2—C5—H5A	117.6	H14A—C14—H14B	108.0
C4—C5—H5A	117.6
O3—Mn1—O1—C1	−1.4 (3)	C7—N3—C6—N4	175.3 (3)
O3i—Mn1—O1—C1	178.6 (3)	C7—N3—C6—N2	−6.2 (4)
N5ii—Mn1—O1—C1	−92.1 (3)	C5—N2—C6—N4	−174.7 (3)
N5iii—Mn1—O1—C1	87.9 (3)	C5—N2—C6—N3	6.8 (4)
O1—Mn1—O3—C3	1.4 (2)	C6—N3—C7—N1	−177.9 (3)
O1i—Mn1—O3—C3	−178.6 (2)	C6—N3—C7—C4	−0.5 (4)
N5ii—Mn1—O3—C3	91.5 (2)	C8—N1—C7—N3	177.3 (3)
N5iii—Mn1—O3—C3	−88.5 (2)	C9—N1—C7—N3	−2.9 (5)
Mn1—O1—C1—O2	179.3 (2)	C8—N1—C7—C4	−0.1 (5)
Mn1—O1—C1—C2	1.5 (4)	C9—N1—C7—C4	179.7 (3)
O2—C1—C2—C8	−1.0 (4)	C5—C4—C7—N3	5.6 (4)
O1—C1—C2—C8	177.0 (3)	C3—C4—C7—N3	−175.2 (3)
O2—C1—C2—C3	−179.1 (3)	C5—C4—C7—N1	−177.1 (3)
O1—C1—C2—C3	−1.2 (4)	C3—C4—C7—N1	2.1 (4)
Mn1—O3—C3—C2	−1.8 (4)	C7—N1—C8—C2	−1.3 (5)
Mn1—O3—C3—C4	−179.39 (16)	C9—N1—C8—C2	178.8 (4)
C8—C2—C3—O3	−176.6 (3)	C3—C2—C8—N1	0.8 (5)
C1—C2—C3—O3	1.5 (4)	C1—C2—C8—N1	−177.5 (3)
C8—C2—C3—C4	1.1 (4)	C8—N1—C9—C10	92.7 (5)
C1—C2—C3—C4	179.2 (2)	C7—N1—C9—C10	−87.1 (5)
O3—C3—C4—C7	175.3 (2)	C6—N4—C11—C12	−148.9 (3)
C2—C3—C4—C7	−2.5 (4)	C14—N4—C11—C12	51.9 (3)
O3—C3—C4—C5	−5.6 (4)	C13—N5—C12—C11	54.0 (3)
C2—C3—C4—C5	176.6 (3)	Mn1iv—N5—C12—C11	−179.1 (2)
C6—N2—C5—C4	−0.7 (5)	N4—C11—C12—N5	−52.9 (4)
C7—C4—C5—N2	−5.0 (4)	C12—N5—C13—C14	−55.0 (3)
C3—C4—C5—N2	175.8 (3)	Mn1iv—N5—C13—C14	175.47 (16)
C14—N4—C6—N3	−8.0 (4)	C6—N4—C14—C13	146.2 (3)
C11—N4—C6—N3	−165.6 (3)	C11—N4—C14—C13	−54.2 (3)
C14—N4—C6—N2	173.4 (3)	N5—C13—C14—N4	55.9 (3)
C11—N4—C6—N2	15.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···O2v	0.893 (10)	2.268 (12)	3.149 (3)	169 (3)

Table 1

Selected bond lengths (Å)

Mn1—O1	2.106 (2)
Mn1—O3	2.1667 (16)
Mn1—N5i	2.372 (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	0.893 (10)	2.268 (12)	3.149 (3)	169 (3)

Symmetry code: (ii) .