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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 5| May 2005| Pages m224-m227
doi:10.1107/S0108270105008474

catena-Poly[[[N-(4-amino-1,6-di­hydro-1-meth­yl-5-nitroso-6-oxopyrimidin-2-yl)-(S)-glutamato]hexa­aqua­barium]-μ-N-(4-amino-1,6-di­hydro-1-meth­yl-5-nitroso-6-oxopyrimidin-2-yl)-(S)-glutamato]: coordination polymer chains linked into a three-dimensional framework by N—H⋯O and O—H⋯O hydrogen bonds

CROSSMARK_Color_square_no_text.svg
Rafael López Garzón,a M. Dolores López León,a John N. Lowb and Christopher Glidewellc*

aDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 11 March 2005; accepted 16 March 2005; online 23 April 2005)

In the title complex, [Ba(C10H12N5O6)2(H2O)6]n, the Ba atom is nine-coordinated by six water ligands and three carboxyl­ate O atoms. The Ba2+ cations and the anionic glutamate ligands form coordination polymer chains, and these chains are linked by pairs of N—H⋯O hydrogen bonds and pairs of O—H⋯O hydrogen bonds to form a continuous three-dimensional framework of cations and anions, which is reinforced by hydrogen bonds involving the water mol­ecules.

Comment

In view of the contrast between the structural motifs found in a range of N-(6-amino-3,4-dihydro-3-meth­yl-5-nitroso-4-oxopyrimidin-2-yl derivatives of simple amino acids on the one

[Scheme 1]
hand (Low et al., 2000[Low, J. N., López, M. D., Arranz Mascarós, P., Cobo Domingo, J., Godino, M. L., López Garzón, R., Gutiérrez, M. D., Melguizo, M., Ferguson, G. & Glidewell, C. (2000). Acta Cryst. B56, 882-892.]), and their hydrated metal(II) salts on the other (Godino Salido et al., 2004[Godino Salido, M. L., Arranz Mascarós, P., López Garzón, R., Gutiérrez Valero, M. D., Low, J. N., Gallagher, J. F. & Glidewell, C. (2004). Acta Cryst. B60, 46-64.]), we have now investigated the title barium complex, (I)[link], derived from N-(6-amino-3,4-dihydro-3-meth­yl-5-nitroso-4-oxopyrimidin-2-yl)-(S)-glutamic acid, (II) [(S)-glutamic acid is (S)-(+)-2-amino­penta­ne-1,5-dioic acid]. We have recently reported the mol­ecular and supramolecular structure of (II) (Arranz Mascarós et al., 2003[Arranz Mascarós, P., Gutiérrez Valero, M. D., Low, J. N. & Glidewell, C. (2003). Acta Cryst. C59, o210-o212.]), where the mol­ecules are linked into a three-dimensional framework by a combination of three hydrogen bonds, one each of the O—H⋯O, O—H⋯N and N—H⋯O types. A feature of inter­est here is that a rather short and nearly symmetrical O—H⋯O hydrogen bond, augmented by a rather weaker N—H⋯O hydrogen bond, links the mol­ecules into double helices, which are themselves linked by the O—H⋯N hydrogen bond to form the framework.

In compound (I)[link] (Fig. 1[link]), the Ba atom is nine-coordinate. The ligating atoms are all oxygen, namely three carboxyl O atoms from three different glutamate ligands together with the O atoms from six water mol­ecules (Table 1[link]). The anion containing atom O221 (Fig. 1[link]) bridges pairs of Ba centres, while the anion containing atom O121 is bonded to only one Ba atom. The irregular coordination (Fig. 2[link]) is probably best described as a distorted monocapped square antiprism, in which atom O121 is the capping atom.

It is of inter­est to note the subtle effect upon the metal coordination of the amino acid component of the anionic ligand. In the barium complex derived from the glycine analogue of (II), the metal is eight-coordinate, while in the complexes formed by the serine and methio­nine analogues, the Ba atom is ten-coordinate (Godino Salido et al., 2004[Godino Salido, M. L., Arranz Mascarós, P., López Garzón, R., Gutiérrez Valero, M. D., Low, J. N., Gallagher, J. F. & Glidewell, C. (2004). Acta Cryst. B60, 46-64.]). Moreover, the mean Ba—O distances in these complexes for eight-, nine- and ten-coordination are 2.777, 2.836 and 2.881 Å, respectively. The trend in these values closely follows the increase with coordination number in the radius of Ba2+, viz. 1.42, 1.47 and 1.52 Å for eight-, nine- and ten-coordination, respectively (Shannon & Prewitt, 1969[Shannon, R. D. & Prewitt, C. T. (1969). Acta Cryst. B25, 925-946.]). A further difference arises within the composition of the metal coordination sphere. Nitroso O atoms are coordinated to the Ba centres in the complexes of the glycine- and methio­nine-based ligands, but not in those of the serine- and glutamic acid-based ligands.

Both of the organic ligands in (I)[link] show the pattern of bond distances (Table 1[link]) which is characteristic of amino–nitroso–pyrimidines. Thus, the bonds Nn1—Cn2 (n = 1 or 2), which are formally double bonds, are longer than the bonds Cn2—Nn2, Cn6—Nn6 and Cn6—Nn1, all of which are formally single bonds, while the bonds Cn2—Nn3 and Nn3—Cn4 are longer than all of the other C—N bonds in the system. In addition, the bonds Cn4—Cn5 and Cn5—Cn6, which are formally single and double bonds, respectively, are very similar in length. Finally, the bonds Cn5—Nn5 and Nn5—On5, which again are formally single and double bonds, respectively, differ in length by less than 0.06 Å. These observations, taken together, indicate that the polarized form (A)[link] (see scheme[link]) is an important contributor to the overall mol­ecular electronic structure, alongside the classically localized form (B)[link]. The C—O distances at C125 and C225 are fully consistent with the locations of the carbox­yl H atoms as deduced from difference maps. The C—O distances at C122 and C222 are fully consistent with their carboxyl­ate formulations.

Within each of the organic ligands, there are two intra­molecular hydrogen bonds, both of the N—H⋯O type (Table 2[link]). Amino atoms N16 and N26 act as hydrogen-bond donors via atoms H16B and H26B, respectively, to nitroso atoms O15 and O25, so forming an S(6) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) motif in each ligand. Each ligand adopts a synclinal conformation about the Cn21—Cn23 and Cn23—Cn24 bonds, possibly associated with the coordination and hydrogen-bonding behaviour of these ligands. The overall conformation of the two ligands is very close to twofold rotational symmetry, deviating significantly only around the bonds Cn21—Cn22, where the Nn2—Cn21 and Cn22—On21 bonds are antiperiplanar when n = 1 and synperiplanar when n = 2 (Table 1[link] and Fig. 1[link]).

The metal ions and the organic ligands together form a three-dimensional structure, the formation of which is readily analysed in terms of three rather simple one-dimensional sub-structures. The Ba atom at (x, y, z) is coordinated by the carboxyl­ate atoms O121 and O221 in the organic ligands at (x, y, z) and also by the carbox­yl atom O223 in the type 2 ligand at (x, 1 + y, z). In this manner, a one-dimensional coordination polymer in the form of a C(8) chain (Starbuck et al., 1999[Starbuck, J., Norman, N. C. & Orpen, A. G. (1999). New J. Chem. 23, 969-972.]) running parallel to the [010] direction is generated by translation (Fig. 3[link]).

The cations and anions of (I)[link] are linked into a three-dimensional framework by means of paired N—H⋯O and paired O—H⋯O hydrogen bonds. Amino atoms N16 and N26 in the glutamate ligands at (x, y, z) acts as donors, via atoms H16A and H26A, respectively, to carbon­yl atoms O14 at (x − 1, y, z) and O24 at (1 + x, y, z), so generating by translation a mol­ecular ladder running parallel to the [100] direction. Within this ladder, a pair of antiparallel C(6) chains (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) acts as the uprights, while the Ba2+ cations lie at the centres of the rungs (Fig. 4[link]). This motif can be alternatively described as a chain of edge-fused R22(36) rings. In the second motif involving the anions, carbox­yl atoms O124 and O224 at (x, y, z) act as donors to, respectively, amidic atoms O14 at (2 − x, y − [{1\over 2}], −z) and O24 at (1 − x, y − [{1\over 2}], 1 − z), and the combination of these two hydrogen bonds generates a C22(34) chain running parallel to the [10[\overline{1}]] direction (Fig. 5[link]). The combination of [100], [010] and [10[\overline{1}]] chains is sufficient to generate a three-dimensional framework built solely from cations and anions.

It is striking that, despite the occurrence in (I)[link] of both un-ionized carbox­yl groups and polarized nitros­yl groups, there are no short O—H⋯O hydrogen bonds with a carbox­yl donor and a nitros­yl acceptor. Such hydrogen bonds are found not only in the corresponding acid, (II) (Arranz Mascarós et al., 2003[Arranz Mascarós, P., Gutiérrez Valero, M. D., Low, J. N. & Glidewell, C. (2003). Acta Cryst. C59, o210-o212.]), but also in the analogous acids derived from glycine, methio­nine, serine, threonine and valine (Low et al., 2000[Low, J. N., López, M. D., Arranz Mascarós, P., Cobo Domingo, J., Godino, M. L., López Garzón, R., Gutiérrez, M. D., Melguizo, M., Ferguson, G. & Glidewell, C. (2000). Acta Cryst. B56, 882-892.]), in all of which such O—H⋯O hydrogen bonds have an O⋯O distance of around 2.50 Å. Instead, the un-ionized carbox­yl group in (I)[link] acts as hydrogen-bond donor towards the amidic O atom, while the nitros­yl O atom does not accept any inter­molecular hydrogen bonds. In the metal(II) complexes formed by similar ligands based on monocarboxylic amino acids, and therefore lacking free un-ionized carbox­yl groups, the only inter­molecular hydrogen-bond donors to nitros­yl O atoms are water mol­ecules (Godino Salido et al., 2004[Godino Salido, M. L., Arranz Mascarós, P., López Garzón, R., Gutiérrez Valero, M. D., Low, J. N., Gallagher, J. F. & Glidewell, C. (2004). Acta Cryst. B60, 46-64.]).

It may be noted, therefore, that the cations and anions in (I)[link] can generate the framework without any contribution from the hydrogen bonds formed by the water mol­ecules. Those involving atoms O1 and O6 undoubtedly reinforce the framework, but we were unable to locate with any confidence the H atoms bonded to water atoms O2, O3 and O4, although each of these atoms is within hydrogen-bonding distance of at least two other O atoms.

[Figure 1]
Figure 1
The independent components of compound (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and, for the sake of clarity, H atoms have been omitted.
[Figure 2]
Figure 2
The coordination of the Ba atom in (I)[link]. The atom marked with an asterisk (*) is at the symmetry position (x, 1 + y, z).
[Figure 3]
Figure 3
Part of the crystal structure of (I)[link], showing the formation of a coordination polymer chain along [010]. For the sake of clarity, the water mol­ecules and the H atoms have been omitted, as has the unit-cell outline. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, 1 + y, z) and (x, y − 1, z), respectively.
[Figure 4]
Figure 4
Part of the crystal structure of (I)[link], showing the formation of a mol­ecular ladder along [100]. For the sake of clarity, the water mol­ecules and the H atoms bonded to C and O atoms have been omitted, as has the unit-cell outline. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x − 1, y, z) and (1 + x, y, z), respectively.
[Figure 5]
Figure 5
A stereoview of part of the crystal structure of (I)[link], showing the formation of a C22(34) chain along [10[\overline{1}]]. For the sake of clarity, the water mol­ecules and the H atoms bonded to C and N atoms have been omitted.

Experimental

Barium chloride dihydrate (0.33 mmol) was added to a solution of N-(6-amino-3,4-dihydro-3-meth­yl-5-nitroso-4-oxopyridin-2-yl)glutamic acid (0.33 mmol) in water (40 ml). Slow evaporation of the resulting solution yielded pink crystals of the title complex, which were collected by filtration and washed with ethanol. Analysis found: C 28.7, H 4.6, N 16.5%; C20H36BaN10O18 requires: C 28.5, H 4.3, N 16.6%.

Crystal data

  • [Ba(C10H12N5O6)2(H2O)6]

  • Mr = 841.92

  • Monoclinic, P 21

  • a = 7.5404 (2) Å

  • b = 6.5754 (2) Å

  • c = 31.4285 (10) Å

  • β = 94.6675 (15)°

  • V = 1553.09 (8) Å3

  • Z = 2

  • Dx = 1.805 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 6791 reflections

  • θ = 3.1–27.5°

  • μ = 1.38 mm−1

  • T = 120 (2) K

  • Block, colourless

  • 0.30 × 0.20 × 0.20 mm
Data collection

  • Nonius KappaCCD area-detector diffractometer

  • φ scans, and ω scans with κ offsets

  • Absorption correction: multi-scan(DENZO-SMN; Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.])Tmin = 0.676, Tmax = 0.763

  • 15 610 measured reflections

  • 6791 independent reflections

  • 5620 reflections with I > 2σ(I)

  • Rint = 0.063

  • θmax = 27.5°

  • h = −9 → 9

  • k = −8 → 8

  • l = −39 → 40
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.083

  • S = 1.00

  • 6791 reflections

  • 445 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0321P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 1.49 e Å−3

  • Δρmin = −0.96 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), with 2923 Friedel pairs

  • Flack parameter: −0.034 (14)

Table 1
Selected geometric parameters (Å, °)[link]

N11—C12 1.333 (6)
C12—N13 1.380 (6)
N13—C14 1.398 (6)
C14—C15 1.461 (7)
C15—C16 1.453 (7)
C16—N11 1.338 (6)
C12—N12 1.316 (6)
C14—O14 1.223 (6)
C15—N15 1.335 (6)
N15—O15 1.279 (5)
C16—N16 1.312 (6)
C122—O121 1.255 (7)
C122—O122 1.262 (7)
C125—O123 1.213 (6)
C125—O124 1.334 (6)
Ba1—O1 2.715 (3)
Ba1—O2 2.777 (4)
Ba1—O3 2.796 (4)
Ba1—O4 2.806 (4)
Ba1—O5 2.887 (3)
N21—C22 1.326 (6)
C22—N23 1.387 (6)
N23—C24 1.388 (6)
C24—C25 1.465 (6)
C25—C26 1.440 (7)
C26—N21 1.340 (6)
C22—N22 1.329 (6)
C24—O24 1.225 (6)
C25—N25 1.328 (6)
N25—O25 1.291 (5)
C26—N26 1.317 (6)
C222—O221 1.256 (6)
C222—O222 1.255 (7)
C225—O223 1.212 (6)
C225—O224 1.320 (6)
Ba1—O6 2.910 (4)
Ba1—O121 2.788 (4)
Ba1—O221 2.881 (3)
Ba1—O223i 2.939 (4)
N13—C12—N12—C121 −176.7 (4)
C12—N12—C121—C122 −162.3 (5)
N12—C121—C122—O121 −174.2 (5)
C121—C122—O121—Ba1 −141.9 (4)
C12—N12—C121—C123 74.2 (6)
N12—C121—C123—C124 61.8 (6)
C121—C123—C124—C125 −61.2 (7)
C123—C124—C125—O123 111.2 (6)
C14—C15—N15—O15 176.9 (4)
N23—C22—N22—C221 −179.6 (4)
C22—N22—C221—C222 −162.3 (4)
N22—C221—C222—O221 −10.6 (7)
C221—C222—O221—Ba1 143.9 (4)
C22—N22—C221—C223 75.4 (6)
N22—C221—C223—C224 61.6 (6)
C221—C223—C224—C225 −63.7 (6)
C223—C224—C225—O223 126.0 (6)
C24—C25—N25—O25 179.2 (4)
Symmetry code: (i) x, y+1, z.

Table 2
Hydrogen-bond geometry (Å, °)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N16—H16A⋯O14ii 0.88 2.04 2.888 (5) 161
N16—H16B⋯O15 0.88 1.98 2.625 (5) 129
N26—H26A⋯O24iii 0.88 2.06 2.892 (5) 159
N26—H26B⋯O25 0.88 1.98 2.629 (5) 129
O124—H124⋯N15iv 0.84 2.10 2.936 (5) 174
O224—H224⋯N25v 0.84 2.05 2.886 (5) 174
O1—H1A⋯O15vi 0.90 1.95 2.853 (5) 175
O1—H1B⋯O123vii 0.83 1.92 2.743 (6) 169
O5—H5A⋯O122 0.93 1.86 2.709 (5) 151
O5—H5B⋯O222 0.94 1.94 2.746 (5) 142
O6—H6A⋯O122ii 0.81 2.33 2.987 (5) 139
O6—H6B⋯O222ii 1.04 1.94 2.794 (5) 137
Symmetry codes: (ii) x-1, y, z; (iii) x+1, y, z; (iv) [-x+2, y-{\script{1\over 2}}, -z]; (v) -x+1, [y-{\script{1\over 2}}, -z+1]; (vi) [-x+1, y+{\script{1\over 2}}, -z]; (vii) x-1, y+1, z.

The systematic absences permitted P21 and P21/m as possible space groups. In view of the enantiopure nature of the starting (S)-glutamic acid, space group P21 was selected and subsequently confirmed by the analysis. It was consistently found that free refinement caused the Ba atom to edge steadily along the y-axis direction. Accordingly, the y coordinate was fixed at 0.75. The H atoms in the organic ligands were all located from difference maps and then treated as riding atoms with C—H distances of 0.98 (CH3), 0.99 (CH2) or 1.00 Å (CH), N—H distances of 0.88 Å and O—H distances of 0.84 Å, and with Uiso(H) = 1.2Ueq(C,N), or 1.5Ueq(C) for the meth­yl groups, and 1.5Ueq(O). The H atoms bonded to water atoms O1, O5 and O6 were located from difference maps and then allowed to ride at the O—H distances (0.81–1.04 Å) located from the difference maps, with Uiso(H) = 1.2Ueq(O). No clear indications could be found for the positions of the H atoms bonded to O2, O3 and O4. The absolute configuration was established by means of the Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) parameter and confirmed the expected S configuration of the glu­tamic acid fragments.

Data collection: KappaCCD Server Software (Nonius, 1997[Nonius (1997). KappaCCD Server Software. Windows 3.11 Version. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO-SMN; program(s) used to solve structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270105008474/sk1826sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105008474/sk1826Isup2.hkl


Comment top

In view of the contrast between the structural motifs found in a range of N-(6-amino-3,4-dihydro-3-methyl-5-nitroso-4-oxopyrimidin-2-yl derivatives of simple amino acids on the one hand (Low et al., 2000), and their hydrated metal(II) salts on the other (Godino Salido et al., 2004), we have now investigated the title barium complex, (I), derived from N-(6-amino-3,4-dihydro-3-methyl-5-nitroso-4-oxopyrimidin-2-yl)-(S)-glutamic acid, C10H13N5O6, (II) [(S)-glutamic acid is (S)-(+)-2-aminopentane-1,5-dioic acid]. We have recently reported the molecular and supramolecular structure of (II) (Arranz Mascarós et al., 2003), where the molecules are linked into a three-dimensional framework by a combination of three hydrogen bonds, one each of O—H···O, O—H···N and N—H···O types. A feature of interest here is that a rather short and nearly symmetrical O—H···O hydrogen bond, augmented by a rather weaker N—H···O hydrogen bond, links the molecules into double helices, which are themselves linked by the O—H···N hydrogen bond to form the framework.

In compound (I) (Fig. 1), the Ba is nine-coordinate. The ligating atoms are all O, namely three carboxylic O atoms from three different glutamate ligands together with the O atoms from six water molecules (Table 1). The anion containing atom O221 (Fig. 1) bridges pairs of Ba centres, while the anion containing atom O121 is bonded to only one Ba atom. The irregular coordination (Fig. 2) is probably best described as a distorted mono-capped square antiprism, in which O121 is the capping atom.

It is of interest to note the subtle effect upon the metal coordination of the amino acid component of the anionic ligand. In the barium complex derived from the glycine analogue of (II), the metal is eight-coordinate, while in the complexes formed by the serine and methionine analogues, the Ba is ten-coordinate (Godino Salido et al., 2004). Moreover, the mean Ba—O distances in these complexes for eight-, nine- and ten-coordination are 2.777, 2.836 and 2.881 Å, respectively. The trend in these values closely follows the increase with coordination number in the radius of Ba2+, 1.42, 1.47 and 1.52 Å for eight-, nine- and ten-coordination, respectively (Shannon & Prewitt, 1969). A further difference arises within the composition of the metal coordination sphere. Nitroso O atoms are coordinated to the Ba centres in the complexes of the glycine- and methionine-based ligands, but not in those of the serine- and glutamic acid-based ligands.

Both of the organic ligands in (I) show the pattern of bond distances (Table 1) which is characteristic of amino-nitrosopyrimidines. Thus, the bonds Nn1—Cn2 (n = 1 or 2), which are formally double bonds, are longer than the bonds Cn2—Nn2, Cn6—Nn6 and Cn6—Nn1, all of which are formally single bonds, while the bonds Cn2—Nn3 and Nn3—Cn4 are longer than all of the other C—N bonds in the system. In addition, the bonds Cn4—Cn5 and Cn5—Cn6, which are formally single and double bonds, respectively, are very similar in length. Finally, the bonds Cn5—Nn5 and Nn5—On5, which again are formally single and double bonds, respectively, differ in length by less than 0.06 Å. These observations, taken together, indicate that the polarized form (A) is an important contributor to the overall molecular electronic structure, alongside the classically localized form (B). The C—O distances at C125 and C225 are fully consistent with the locations of the carboxyl H atoms as deduced from difference maps. The C—O distances at C122 and C222 are fully consistent with their carboxylate formulations.

Within each of the organic ligands, there are two intramolecular hydrogen bonds, both of N—H···O type (Table 2). Amino atoms N16 and N26 act as hydrogen-bond donors via atoms H16B and H26B, respectively, to nitroso atoms O15 and O25, so forming an S(6) (Bernstein et al., 1995) motif in each ligand. Each ligand adopts a synclinal conformation about the Cn21—Cn23 and Cn23—Cn24 bonds, possibly associated with the coordination and hydrogen-bonding behaviour of these ligands. The overall conformation of the two ligands is very close to twofold rotational symmetry, deviating significantly only around the bonds Cn21—Cn22, where the Nn2—Cn21 and Cn22—On21 bonds are antiperiplanar when n = 1 and synperiplanar when n = 2 (Table 1, Fig. 1).

The metal ions and the organic ligands together form a three-dimensional structure, the formation of which is readily analysed in terms of three rather simple one-dimensional sub-structures. The Ba atom at (x, y, z) is coordinated by the carboxylate atoms O121 and O221 in the organic ligands at (x, y, z) and also by the carboxyl atom O223 in the type 2 ligand at (x, 1 + y, z). In this manner, a one-dimensional coordination polymer in the form of a C(8) chain (Starbuck et al., 1999) running parallel to the [010] direction is generated by translation (Fig. 3).

The cations and anions of (I) are linked into a three-dimensional framework by means of paired N—H···O and paired O—H···O hydrogen bonds. The amino atoms N16 and N26 in the glutamate ligands at (x, y, z) acts as donors, via atoms H16A and H26A, respectively, to carbonyl O atoms O14 at (x − 1, y, z) and O24 at (1 + x, y, z), so generating by translation a molecular ladder running parallel to the [100] direction. Within this ladder, a pair of antiparallel C(6) chains (Bernstein et al., 1995) acts as the uprights, while the Ba cations lie at the centres of the rungs (Fig. 4). This motif can be alternatively described as a chain of edge-fused R22(36) rings. In the second motif involving the anions, the carboxyl atoms O124 and O224 at (x, y, z) act as donors to, respectively, the amidic O atoms O14 at (2 − x, y − 1/2, −z) and O24 at (1 − x, y − 1/2, 1 − z), and the combination of these two hydrogen bonds generates a C22(34) chain running parallel to the [101] direction (Fig. 5). The combination of [100], [010] and [101] chains is sufficient to generate a three-dimensional framework built solely from cations and anions.

It is striking that, despite the occurrence in (I) of both un-ionized carboxyl groups and polarized nitrosyl groups, there are no short O—H···O hydrogen bonds with a carboxyl donor and a nitrosyl acceptor. Such hydrogen bonds are found not only in the corresponding acid, (II) (Arranz Mascarós et al., 2003), but also in the analogous acids derived from glycine, methionine, serine, threonine and valine (Low et al., 2000), in all of which such O—H···O hydrogen bonds have an O···O distance of around 2.50 Å. Instead, the un-ionized carboxyl group in (I) acts as hydrogen-bond donor towards the amidic O atom, while the nitrosyl O atom does not accept any intermolecular hydrogen bonds. In the metal(II) complexes formed by similar ligands based on monocarboxylic amino acids, and therefore lacking free un-ionized carboxyl groups, the only intermolecular hydrogen-bond donors to nitrosyl O atoms are water molecules (Godino Salido et al., 2004).

It may be noted, therefore, that the cations and anions in (I) can generate the framework without any contribution from the hydrogen bonds formed by the water molecules. Those involving atoms O1 and O6 undoubtedly reinforce the framework, but we were unable to locate with any confidence the H atoms bonded to water atoms O2, O3 and O4, although each of these atoms is within hydrogen-bonding distance of at least two other O atoms.

Experimental top

Barium chloride dihydrate (0.33 mmol) was added to a solution of N-(6-amino-3,4-dihydro-3-methyl-5-nitroso-4-oxopyridin-2-yl) glutamic acid (0.33 mmol) in water (40 ml). Slow evaporation of the resulting solution yielded pink crystals of the title complex, which were collected by filtration and washed with ethanol. Analysis found: C 28.7, H 4.6, N 16.5%; C20H36BaN10O18 requires: C 28.5, H 4.3, N 16.6%.

Refinement top

The systematic absences permitted P21 and P21/m as possible space groups. In view of the enantiopure nature of the starting (S)-glutamic acid, the space group P21 was selected and subsequently confirmed by the analysis. It was consistently found that free refinement caused the Ba to edge steadily along the y-axis direction. Accordingly, the y coordinate was fixed at 0.7500. The H atoms in the organic ligands were all located from difference maps, and then treated as riding atoms with C—H distances of 0.98 (CH3), 0.99 (CH2) or 1.00 Å (CH), N—H distances of 0.88 Å and O—H distances of 0.84 Å, and with Uiso(H) = 1.2Ueq(C,N), or 1.5Ueq(C) for the methyl groups, and 1.5Ueq(O). The H atoms bonded to water atoms O1, O5 and O6 were located from difference maps, and then allowed to ride at the O—H distances (0.81–1.04 Å) located from the difference maps, with Uiso(H) = 1.2Ueq(O). No clear indications could be found for the positions of the H atoms bonded to O2, O3 and O4. The absolute configuration was established by means of the Flack parameter (Flack, 1983), and confirmed the expected (S) configuration of the glutamic acid fragments.

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The independent components of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and, for the sake of clarity, the H atoms have been omitted.
[Figure 2] Fig. 2. The coordination of Ba in (I). The atom marked with an asterisk (*) is at the symmetry position (x, 1 + y, z).
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the formation of a coordination polymer chain along [010]. For the sake of clarity, the water molecules and the H atoms have been omitted, as has the unit-cell outline. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, 1 + y, z) and (x, y − 1, z), respectively.
[Figure 4] Fig. 4. Part of the crystal structure of (I), showing the formation of a molecular ladder along [100]. For the sake of clarity, the water molecules and the H atoms bonded to C and O atoms have been omitted, as has the unit-cell outline. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 + x, y, z) and (x − 1, y, z), respectively.
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of (I), showing the formation of a C22(34) chain along [101]. For the sake of clarity, the water molecules and the H atoms bonded to C and N atoms have been omitted.
catena-Poly[[[N-(4-amino-1,6-dihydro-1-methyl-5-nitroso-6-oxopyrimidin- 2-yl)-(S)-glutamato]hexaaquabarium]-µ-N-(4-amino-1,6-dihydro-1-methyl-5- nitroso-6-oxopyrimidin-2-yl)-(S)-glutamato] top
Crystal data top
[Ba(C10H12N5O6)2(H2O)6]F(000) = 852
Mr = 841.92Dx = 1.805 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 6791 reflections
a = 7.5404 (2) Åθ = 3.1–27.5°
b = 6.5754 (2) ŵ = 1.38 mm−1
c = 31.4285 (10) ÅT = 120 K
β = 94.6675 (15)°Block, colourless
V = 1553.09 (8) Å30.30 × 0.20 × 0.20 mm
Z = 2
Data collection top
Nonius KappaCCD area-detector
diffractometer		6791 independent reflections
Radiation source: rotating anode5620 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.063
ϕ scans, and ω scans with κ offsetsθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)		h = −9→9
Tmin = 0.676, Tmax = 0.763k = −8→8
15610 measured reflectionsl = −39→40
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.083 w = 1/[σ2(Fo2) + (0.0321P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
6791 reflectionsΔρmax = 1.49 e Å−3
445 parametersΔρmin = −0.96 e Å−3
0 restraintsAbsolute structure: Flack (1983), with 2923 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: −0.034 (14)
Crystal data top
[Ba(C10H12N5O6)2(H2O)6]V = 1553.09 (8) Å3
Mr = 841.92Z = 2
Monoclinic, P21Mo Kα radiation
a = 7.5404 (2) ŵ = 1.38 mm−1
b = 6.5754 (2) ÅT = 120 K
c = 31.4285 (10) Å0.30 × 0.20 × 0.20 mm
β = 94.6675 (15)°
Data collection top
Nonius KappaCCD area-detector
diffractometer		6791 independent reflections
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)		5620 reflections with I > 2σ(I)
Tmin = 0.676, Tmax = 0.763Rint = 0.063
15610 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.083Δρmax = 1.49 e Å−3
S = 1.00Δρmin = −0.96 e Å−3
6791 reflectionsAbsolute structure: Flack (1983), with 2923 Friedel pairs
445 parametersAbsolute structure parameter: −0.034 (14)
0 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba10.42870 (3)0.75000.259573 (8)0.01281 (8)
N110.6469 (5)0.3762 (6)0.03952 (13)0.0111 (9)
C120.7995 (7)0.3837 (8)0.06411 (16)0.0138 (11)
N120.7924 (5)0.4017 (6)0.10565 (13)0.0125 (9)
C1210.6285 (7)0.4081 (8)0.12773 (17)0.0132 (11)
C1220.6754 (8)0.4963 (8)0.17247 (19)0.0137 (13)
O1210.5535 (5)0.4971 (5)0.19734 (11)0.0190 (9)
O1220.8302 (5)0.5662 (6)0.18066 (11)0.0191 (9)
C1230.5417 (6)0.1990 (7)0.12951 (16)0.0156 (14)
C1240.6574 (8)0.0373 (9)0.1542 (2)0.0164 (14)
C1250.8285 (7)−0.0051 (8)0.13563 (17)0.0141 (12)
O1230.9736 (5)0.0404 (6)0.15246 (12)0.0215 (9)
O1240.8071 (4)−0.0969 (6)0.09769 (11)0.0185 (8)
N130.9662 (5)0.3698 (6)0.04923 (13)0.0131 (9)
C131.1262 (6)0.3587 (8)0.07945 (16)0.0164 (12)
C140.9863 (6)0.3595 (8)0.00545 (16)0.0136 (11)
O141.1346 (4)0.3516 (6)−0.00758 (11)0.0217 (9)
C150.8216 (6)0.3534 (8)−0.02243 (16)0.0131 (11)
N150.8447 (5)0.3433 (6)−0.06404 (13)0.0151 (10)
O150.7065 (4)0.3282 (5)−0.09029 (11)0.0180 (9)
C160.6539 (6)0.3589 (7)−0.00274 (15)0.0117 (11)
N160.5029 (5)0.3522 (6)−0.02657 (13)0.0157 (10)
N210.8272 (5)0.3454 (6)0.45924 (13)0.0121 (9)
C220.6748 (6)0.3454 (8)0.43501 (16)0.0130 (11)
N220.6805 (5)0.3627 (6)0.39302 (12)0.0100 (9)
C2210.8457 (7)0.3837 (8)0.37248 (16)0.0138 (11)
C2220.8001 (7)0.4661 (8)0.32733 (18)0.0124 (12)
O2210.6392 (4)0.4714 (6)0.31339 (11)0.0167 (8)
O2220.9293 (4)0.5242 (5)0.30766 (11)0.0174 (8)
C2230.9491 (7)0.1847 (7)0.37068 (16)0.0139 (12)
C2240.8502 (7)0.0139 (9)0.34511 (18)0.0151 (13)
C2250.6833 (7)−0.0585 (8)0.36301 (16)0.0141 (11)
O2230.5397 (5)−0.0657 (6)0.34270 (11)0.0200 (9)
O2240.7097 (4)−0.1180 (6)0.40314 (11)0.0172 (8)
N230.5077 (5)0.3251 (6)0.44995 (12)0.0105 (9)
C230.3484 (6)0.3093 (8)0.41990 (15)0.0142 (13)
C240.4879 (6)0.3172 (7)0.49344 (16)0.0126 (12)
O240.3396 (4)0.3061 (5)0.50658 (10)0.0180 (10)
C250.6536 (6)0.3207 (7)0.52122 (15)0.0125 (11)
N250.6290 (5)0.3150 (6)0.56257 (13)0.0135 (10)
O250.7677 (4)0.3151 (5)0.58952 (11)0.0167 (9)
C260.8193 (6)0.3309 (7)0.50156 (15)0.0114 (11)
N260.9711 (5)0.3288 (6)0.52549 (13)0.0155 (10)
O10.2684 (5)0.8184 (6)0.18036 (11)0.0352 (13)
O20.2720 (5)0.6223 (6)0.33193 (12)0.0221 (9)
O30.1355 (5)1.0094 (6)0.26124 (14)0.0253 (11)
O40.5008 (5)1.1670 (5)0.25299 (12)0.0225 (9)
O50.8020 (4)0.8102 (5)0.24924 (10)0.0147 (9)
O60.1437 (5)0.4575 (7)0.24056 (12)0.0206 (10)
H120.89410.41050.12140.015*
H1210.54290.50240.11180.016*
H12A0.51280.15020.10000.019*
H12B0.42840.21300.14310.019*
H12C0.68300.08380.18400.020*
H12D0.5888−0.09080.15490.020*
H1240.9058−0.10520.08720.028*
H13A1.13370.48120.09730.025*
H13B1.23240.34910.06350.025*
H13C1.11890.23850.09760.025*
H16A0.40140.3590−0.01470.019*
H16B0.50300.3409−0.05450.019*
H220.57950.36140.37690.012*
H2210.92260.48550.38880.017*
H22A0.97890.13620.40020.017*
H22B1.06240.21210.35790.017*
H22C0.81990.06270.31560.018*
H22D0.9319−0.10320.34350.018*
H2240.6115−0.14670.41250.021*
H23A0.24360.28720.43580.021*
H23B0.36200.19470.40050.021*
H23C0.33360.43540.40340.021*
H26A1.07240.33670.51350.019*
H26B0.97110.31940.55340.019*
H1A0.28190.81650.15210.042*
H1B0.18030.89260.17520.042*
H5A0.84860.74970.22570.018*
H5B0.87910.76200.27190.018*
H6A0.08130.43470.21890.025*
H6B0.03940.53130.25390.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.01080 (12)0.01423 (14)0.01330 (13)0.0001 (2)0.00039 (9)0.0006 (2)
N110.009 (2)0.011 (2)0.012 (2)−0.0003 (17)−0.0034 (17)0.0014 (18)
C120.019 (3)0.011 (3)0.012 (3)0.000 (2)0.002 (2)0.004 (2)
N120.011 (2)0.015 (2)0.012 (2)0.0029 (18)−0.0005 (17)0.000 (2)
C1210.011 (3)0.018 (3)0.010 (3)0.002 (2)0.000 (2)−0.003 (2)
C1220.015 (3)0.007 (3)0.020 (3)0.002 (2)0.004 (3)0.004 (3)
O1210.020 (2)0.019 (2)0.019 (2)−0.0009 (16)0.0055 (16)−0.0044 (17)
O1220.019 (2)0.024 (2)0.014 (2)−0.0028 (17)−0.0011 (16)−0.0050 (17)
C1230.010 (2)0.022 (4)0.014 (3)−0.001 (2)0.0010 (19)0.001 (2)
C1240.019 (3)0.015 (3)0.016 (4)0.001 (2)0.004 (3)0.002 (3)
C1250.018 (3)0.010 (3)0.014 (3)0.001 (2)0.003 (2)0.002 (2)
O1230.015 (2)0.025 (2)0.024 (2)0.0025 (17)−0.0023 (16)0.0015 (18)
O1240.0128 (18)0.024 (2)0.019 (2)0.0015 (17)0.0032 (15)−0.0012 (18)
N130.008 (2)0.015 (2)0.016 (2)−0.0011 (18)0.0010 (17)0.0002 (19)
C130.016 (3)0.020 (3)0.013 (3)−0.003 (2)−0.004 (2)0.002 (2)
C140.013 (3)0.010 (3)0.018 (3)−0.002 (2)0.003 (2)−0.003 (2)
O140.0130 (19)0.035 (2)0.018 (2)−0.0019 (17)0.0066 (16)−0.0020 (17)
C150.014 (3)0.009 (3)0.016 (3)0.001 (2)0.002 (2)0.005 (2)
N150.018 (2)0.012 (2)0.015 (2)0.0016 (18)−0.0009 (19)0.0023 (18)
O150.0154 (18)0.023 (2)0.0144 (19)0.0024 (15)−0.0034 (15)−0.0007 (15)
C160.014 (3)0.008 (3)0.013 (3)0.002 (2)−0.002 (2)0.004 (2)
N160.011 (2)0.021 (2)0.015 (2)0.0019 (19)0.0005 (18)0.0035 (19)
N210.012 (2)0.013 (2)0.011 (2)−0.0018 (17)−0.0001 (17)0.0028 (18)
C220.014 (3)0.012 (3)0.013 (3)0.000 (2)0.000 (2)0.000 (2)
N220.008 (2)0.012 (2)0.010 (2)−0.0019 (17)−0.0015 (17)−0.0002 (18)
C2210.012 (3)0.016 (3)0.013 (3)−0.003 (2)0.001 (2)0.000 (2)
C2220.017 (3)0.003 (3)0.016 (3)−0.002 (2)0.001 (2)−0.002 (2)
O2210.0150 (19)0.020 (2)0.015 (2)0.0010 (16)−0.0001 (15)0.0026 (16)
O2220.0124 (18)0.025 (2)0.016 (2)−0.0018 (16)0.0040 (15)0.0026 (17)
C2230.011 (2)0.017 (3)0.014 (3)0.000 (2)−0.001 (2)0.004 (2)
C2240.019 (3)0.015 (3)0.012 (3)0.001 (2)0.000 (2)0.006 (3)
C2250.018 (3)0.008 (3)0.016 (3)0.001 (2)−0.001 (2)−0.004 (2)
O2230.0143 (19)0.025 (2)0.020 (2)−0.0058 (16)−0.0049 (16)−0.0022 (18)
O2240.0131 (18)0.023 (2)0.016 (2)−0.0053 (16)0.0019 (15)0.0037 (17)
N230.0078 (19)0.011 (2)0.013 (2)0.0012 (15)0.0027 (16)−0.0037 (16)
C230.008 (2)0.021 (4)0.013 (3)−0.0026 (19)−0.0051 (19)0.002 (2)
C240.012 (2)0.011 (3)0.014 (3)−0.0021 (18)−0.002 (2)−0.003 (2)
O240.0116 (16)0.028 (3)0.0152 (18)−0.0004 (14)0.0061 (14)−0.0003 (15)
C250.014 (2)0.012 (3)0.011 (3)0.0012 (19)−0.001 (2)−0.003 (2)
N250.013 (2)0.011 (3)0.016 (2)−0.0013 (16)0.0001 (17)−0.0006 (17)
O250.0115 (17)0.021 (2)0.0168 (19)−0.0001 (14)−0.0037 (14)−0.0003 (15)
C260.011 (2)0.010 (2)0.014 (3)−0.0013 (19)0.002 (2)0.001 (2)
N260.011 (2)0.025 (3)0.012 (2)0.0008 (17)0.0025 (17)−0.0021 (18)
O10.027 (2)0.064 (4)0.0145 (19)0.022 (2)−0.0002 (16)0.0064 (19)
O20.020 (2)0.026 (2)0.021 (2)−0.0056 (17)0.0046 (16)0.0000 (18)
O30.017 (2)0.019 (2)0.039 (3)0.0003 (17)0.000 (2)0.002 (2)
O40.0187 (19)0.020 (2)0.029 (2)−0.0028 (15)0.0035 (17)−0.0008 (17)
O50.0138 (16)0.019 (2)0.0112 (17)0.0008 (14)−0.0016 (13)−0.0032 (14)
O60.016 (2)0.024 (2)0.021 (2)0.0017 (17)−0.0030 (18)−0.005 (2)
Geometric parameters (Å, º) top
N11—C121.333 (6)C24—C251.465 (6)
C12—N131.380 (6)C25—C261.440 (7)
N13—C141.398 (6)C26—N211.340 (6)
C14—C151.461 (7)C22—N221.329 (6)
C15—C161.453 (7)C24—O241.225 (6)
C16—N111.338 (6)C25—N251.328 (6)
C12—N121.316 (6)N25—O251.291 (5)
C14—O141.223 (6)C26—N261.317 (6)
C15—N151.335 (6)C222—O2211.256 (6)
N15—O151.279 (5)C222—O2221.255 (7)
C16—N161.312 (6)C225—O2231.212 (6)
C122—O1211.255 (7)C225—O2241.320 (6)
C122—O1221.262 (7)N22—C2211.456 (6)
C125—O1231.213 (6)N22—H220.88
C125—O1241.334 (6)C221—C2231.527 (7)
N12—C1211.466 (6)C221—C2221.532 (7)
N12—H120.88C221—H2211.00
C121—C1231.526 (7)C223—C2241.538 (7)
C121—C1221.536 (7)C223—H22A0.99
C121—H1211.00C223—H22B0.99
C123—C1241.544 (7)C224—C2251.498 (7)
C123—H12A0.99C224—H22C0.99
C123—H12B0.99C224—H22D0.99
C124—C1251.485 (7)O224—H2240.84
C124—H12C0.99N23—C231.470 (5)
C124—H12D0.99C23—H23A0.98
O124—H1240.84C23—H23B0.98
N13—C131.475 (6)C23—H23C0.98
C13—H13A0.98N26—H26A0.88
C13—H13B0.98N26—H26B0.88
C13—H13C0.98O1—H1A0.9024
N16—H16A0.88O1—H1B0.83
N16—H16B0.88O5—H5A0.93
Ba1—O12.715 (3)O5—H5B0.94
Ba1—O22.777 (4)O6—H6A0.81
Ba1—O32.796 (4)O6—H6B1.04
Ba1—O42.806 (4)Ba1—O62.910 (4)
Ba1—O52.887 (3)Ba1—O1212.788 (4)
N21—C221.326 (6)Ba1—O2212.881 (3)
C22—N231.387 (6)Ba1—O223i2.939 (4)
N23—C241.388 (6)
O1—Ba1—O2127.85 (11)O14—C14—N13120.4 (4)
O1—Ba1—O12166.81 (11)O14—C14—C15123.6 (5)
O2—Ba1—O121125.77 (11)N13—C14—C15115.9 (4)
O1—Ba1—O367.81 (12)N15—C15—C16127.3 (4)
O2—Ba1—O377.24 (12)N15—C15—C14114.6 (4)
O121—Ba1—O3133.58 (12)C16—C15—C14118.1 (4)
O1—Ba1—O481.08 (12)O15—N15—C15118.1 (4)
O2—Ba1—O4116.98 (11)N16—C16—N11117.9 (5)
O121—Ba1—O4116.90 (11)N16—C16—C15120.1 (4)
O3—Ba1—O464.13 (11)N11—C16—C15122.0 (4)
O1—Ba1—O221145.76 (11)C16—N16—H16A120.0
O2—Ba1—O22165.02 (10)C16—N16—H16B120.0
O121—Ba1—O22180.30 (10)H16A—N16—H16B120.0
O3—Ba1—O221140.85 (12)C22—N21—C26117.6 (4)
O4—Ba1—O221124.32 (10)N21—C22—N22118.3 (5)
O1—Ba1—O5103.87 (10)N21—C22—N23125.1 (5)
O2—Ba1—O5128.13 (10)N22—C22—N23116.6 (4)
O121—Ba1—O567.37 (9)C22—N22—C221123.1 (4)
O3—Ba1—O5134.27 (10)C22—N22—H22118.4
O4—Ba1—O570.19 (10)C221—N22—H22118.4
O221—Ba1—O569.98 (9)N22—C221—C223113.1 (4)
O1—Ba1—O669.82 (12)N22—C221—C222108.0 (4)
O2—Ba1—O667.17 (11)C223—C221—C222110.2 (4)
O121—Ba1—O675.37 (11)N22—C221—H221108.5
O3—Ba1—O680.52 (10)C223—C221—H221108.5
O4—Ba1—O6140.82 (11)C222—C221—H221108.5
O221—Ba1—O693.59 (11)O222—C222—O221125.9 (5)
O5—Ba1—O6141.09 (10)O222—C222—C221116.0 (5)
O1—Ba1—O223i145.09 (12)O221—C222—C221118.1 (5)
O2—Ba1—O223i60.40 (11)C222—O221—Ba1133.8 (3)
O121—Ba1—O223i141.38 (10)C221—C223—C224114.7 (4)
O3—Ba1—O223i84.28 (12)C221—C223—H22A108.6
O4—Ba1—O223i67.66 (11)C224—C223—H22A108.6
O221—Ba1—O223i68.70 (10)C221—C223—H22B108.6
O5—Ba1—O223i80.42 (9)C224—C223—H22B108.6
O6—Ba1—O223i127.39 (11)H22A—C223—H22B107.6
C12—N11—C16118.5 (4)C225—C224—C223115.0 (5)
N12—C12—N11118.4 (5)C225—C224—H22C108.5
N12—C12—N13117.0 (4)C223—C224—H22C108.5
N11—C12—N13124.6 (5)C225—C224—H22D108.5
C12—N12—C121125.1 (4)C223—C224—H22D108.5
C12—N12—H12117.4H22C—C224—H22D107.5
C121—N12—H12117.4O223—C225—O224123.4 (5)
N12—C121—C123111.9 (4)O223—C225—C224123.8 (5)
N12—C121—C122107.7 (4)O224—C225—C224112.8 (4)
C123—C121—C122112.0 (5)C225—O223—Ba1ii131.4 (3)
N12—C121—H121108.4C225—O224—H224109.5
C123—C121—H121108.4C22—N23—C24120.7 (4)
C122—C121—H121108.4C22—N23—C23120.4 (4)
O121—C122—O122125.7 (5)C24—N23—C23118.8 (4)
O121—C122—C121116.5 (5)N23—C23—H23A109.5
O122—C122—C121117.7 (5)N23—C23—H23B109.5
C122—O121—Ba1138.3 (4)H23A—C23—H23B109.5
C121—C123—C124114.3 (4)N23—C23—H23C109.5
C121—C123—H12A108.7H23A—C23—H23C109.5
C124—C123—H12A108.7H23B—C23—H23C109.5
C121—C123—H12B108.7O24—C24—N23120.6 (4)
C124—C123—H12B108.7O24—C24—C25123.9 (5)
H12A—C123—H12B107.6N23—C24—C25115.6 (4)
C125—C124—C123114.0 (5)N25—C25—C26128.0 (4)
C125—C124—H12C108.8N25—C25—C24113.7 (4)
C123—C124—H12C108.8C26—C25—C24118.2 (4)
C125—C124—H12D108.8O25—N25—C25118.1 (4)
C123—C124—H12D108.8N26—C26—N21117.4 (4)
H12C—C124—H12D107.7N26—C26—C25119.9 (4)
O123—C125—O124122.7 (5)N21—C26—C25122.7 (4)
O123—C125—C124124.3 (5)C26—N26—H26A120.0
O124—C125—C124112.9 (5)C26—N26—H26B120.0
C125—O124—H124109.5H26A—N26—H26B120.0
C12—N13—C14120.7 (4)Ba1—O1—H1A145.4
C12—N13—C13120.3 (4)Ba1—O1—H1B124.5
C14—N13—C13118.9 (4)H1A—O1—H1B88.2
N13—C13—H13A109.5Ba1—O5—H5A117.6
N13—C13—H13B109.5Ba1—O5—H5B114.7
H13A—C13—H13B109.5H5A—O5—H5B102.0
N13—C13—H13C109.5Ba1—O6—H6A131.6
H13A—C13—H13C109.5Ba1—O6—H6B100.3
H13B—C13—H13C109.5H6A—O6—H6B91.0
C16—N11—C12—N12179.7 (4)C26—N21—C22—N23−2.2 (7)
C16—N11—C12—N13−1.7 (8)N21—C22—N22—C221−0.7 (7)
N11—C12—N12—C1212.0 (8)N23—C22—N22—C221−179.6 (4)
N13—C12—N12—C121−176.7 (4)C22—N22—C221—C222−162.3 (4)
C12—N12—C121—C122−162.3 (5)N22—C221—C222—O221−10.6 (7)
N12—C121—C122—O121−174.2 (5)C221—C222—O221—Ba1143.9 (4)
C121—C122—O121—Ba1−141.9 (4)C22—N22—C221—C22375.4 (6)
C12—N12—C121—C12374.2 (6)N22—C221—C223—C22461.6 (6)
N12—C121—C123—C12461.8 (6)C221—C223—C224—C225−63.7 (6)
C121—C123—C124—C125−61.2 (7)C223—C224—C225—O223126.0 (6)
C123—C124—C125—O123111.2 (6)C223—C221—C222—O222−67.1 (6)
C123—C121—C122—O121−50.8 (6)C223—C221—C222—O221113.5 (5)
N12—C121—C122—O1227.7 (7)O222—C222—O221—Ba1−35.5 (8)
C123—C121—C122—O122131.1 (5)N22—C221—C222—O222168.9 (5)
O122—C122—O121—Ba136.1 (9)O1—Ba1—O221—C222103.8 (5)
O1—Ba1—O121—C12291.6 (5)O2—Ba1—O221—C222−134.9 (5)
O2—Ba1—O121—C122−147.4 (5)O121—Ba1—O221—C22287.8 (5)
O3—Ba1—O121—C122104.5 (5)O3—Ba1—O221—C222−118.3 (5)
O4—Ba1—O121—C12225.6 (6)O4—Ba1—O221—C222−28.2 (5)
O221—Ba1—O121—C122−98.1 (5)O5—Ba1—O221—C22218.5 (5)
O5—Ba1—O121—C122−25.8 (5)O6—Ba1—O221—C222162.3 (5)
O6—Ba1—O121—C122165.6 (5)O223i—Ba1—O221—C222−68.7 (5)
O223i—Ba1—O121—C122−61.7 (6)C222—C221—C223—C224−59.4 (6)
C122—C121—C123—C124−59.2 (6)C223—C224—C225—O224−55.4 (6)
C123—C124—C125—O124−67.8 (6)O224—C225—O223—Ba1ii−126.6 (4)
N12—C12—N13—C14−177.1 (5)C224—C225—O223—Ba1ii51.9 (7)
N11—C12—N13—C144.2 (8)N21—C22—N23—C244.7 (7)
N12—C12—N13—C134.9 (7)N22—C22—N23—C24−176.5 (4)
N11—C12—N13—C13−173.7 (5)N21—C22—N23—C23−174.6 (5)
C12—N13—C14—O14178.4 (5)N22—C22—N23—C234.2 (7)
C13—N13—C14—O14−3.6 (7)C22—N23—C24—O24177.5 (4)
C12—N13—C14—C15−3.2 (7)C23—N23—C24—O24−3.2 (7)
C13—N13—C14—C15174.8 (4)C22—N23—C24—C25−3.1 (6)
O14—C14—C15—N15−1.5 (8)C23—N23—C24—C25176.2 (4)
N13—C14—C15—N15−179.9 (4)O24—C24—C25—N25−1.3 (7)
O14—C14—C15—C16178.5 (5)N23—C24—C25—N25179.4 (4)
N13—C14—C15—C160.1 (7)O24—C24—C25—C26179.0 (5)
C16—C15—N15—O15−3.1 (7)N23—C24—C25—C26−0.3 (6)
C14—C15—N15—O15176.9 (4)C26—C25—N25—O25−1.2 (7)
C12—N11—C16—N16−179.8 (5)C24—C25—N25—O25179.2 (4)
C12—N11—C16—C15−1.6 (7)C22—N21—C26—N26179.3 (4)
N15—C15—C16—N160.5 (8)C22—N21—C26—C25−1.6 (7)
C14—C15—C16—N16−179.5 (5)N25—C25—C26—N262.2 (8)
N15—C15—C16—N11−177.7 (5)C24—C25—C26—N26−178.2 (4)
C14—C15—C16—N112.3 (7)N25—C25—C26—N21−176.8 (5)
C26—N21—C22—N22179.0 (4)C24—C25—C26—N212.8 (7)
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N16—H16A···O14iii0.882.042.888 (5)161
N16—H16B···O150.881.982.625 (5)129
N26—H26A···O24iv0.882.062.892 (5)159
N26—H26B···O250.881.982.629 (5)129
O124—H124···N15v0.842.102.936 (5)174
O224—H224···N25vi0.842.052.886 (5)174
O1—H1A···O15vii0.901.952.853 (5)175
O1—H1B···O123viii0.831.922.743 (6)169
O5—H5A···O1220.931.862.709 (5)151
O5—H5B···O2220.941.942.746 (5)142
O6—H6A···O122iii0.812.332.987 (5)139
O6—H6B···O222iii1.041.942.794 (5)137
Symmetry codes: (iii) x−1, y, z; (iv) x+1, y, z; (v) −x+2, y−1/2, −z; (vi) −x+1, y−1/2, −z+1; (vii) −x+1, y+1/2, −z; (viii) x−1, y+1, z.

Experimental details

Crystal data
Chemical formula[Ba(C10H12N5O6)2(H2O)6]
Mr841.92
Crystal system, space groupMonoclinic, P21
Temperature (K)120
a, b, c (Å)7.5404 (2), 6.5754 (2), 31.4285 (10)
β (°) 94.6675 (15)
V (Å3)1553.09 (8)
Z2
Radiation typeMo Kα
µ (mm−1)1.38
Crystal size (mm)0.30 × 0.20 × 0.20
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
Tmin, Tmax0.676, 0.763
No. of measured, independent and
observed [I > 2σ(I)] reflections		15610, 6791, 5620
Rint0.063
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.083, 1.00
No. of reflections6791
No. of parameters445
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)1.49, −0.96
Absolute structureFlack (1983), with 2923 Friedel pairs
Absolute structure parameter−0.034 (14)

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top
N11—C121.333 (6)N21—C221.326 (6)
C12—N131.380 (6)C22—N231.387 (6)
N13—C141.398 (6)N23—C241.388 (6)
C14—C151.461 (7)C24—C251.465 (6)
C15—C161.453 (7)C25—C261.440 (7)
C16—N111.338 (6)C26—N211.340 (6)
C12—N121.316 (6)C22—N221.329 (6)
C14—O141.223 (6)C24—O241.225 (6)
C15—N151.335 (6)C25—N251.328 (6)
N15—O151.279 (5)N25—O251.291 (5)
C16—N161.312 (6)C26—N261.317 (6)
C122—O1211.255 (7)C222—O2211.256 (6)
C122—O1221.262 (7)C222—O2221.255 (7)
C125—O1231.213 (6)C225—O2231.212 (6)
C125—O1241.334 (6)C225—O2241.320 (6)
Ba1—O12.715 (3)Ba1—O62.910 (4)
Ba1—O22.777 (4)Ba1—O1212.788 (4)
Ba1—O32.796 (4)Ba1—O2212.881 (3)
Ba1—O42.806 (4)Ba1—O223i2.939 (4)
Ba1—O52.887 (3)
N13—C12—N12—C121−176.7 (4)N23—C22—N22—C221−179.6 (4)
C12—N12—C121—C122−162.3 (5)C22—N22—C221—C222−162.3 (4)
N12—C121—C122—O121−174.2 (5)N22—C221—C222—O221−10.6 (7)
C121—C122—O121—Ba1−141.9 (4)C221—C222—O221—Ba1143.9 (4)
C12—N12—C121—C12374.2 (6)C22—N22—C221—C22375.4 (6)
N12—C121—C123—C12461.8 (6)N22—C221—C223—C22461.6 (6)
C121—C123—C124—C125−61.2 (7)C221—C223—C224—C225−63.7 (6)
C123—C124—C125—O123111.2 (6)C223—C224—C225—O223126.0 (6)
C14—C15—N15—O15176.9 (4)C24—C25—N25—O25179.2 (4)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N16—H16A···O14ii0.882.042.888 (5)161
N16—H16B···O150.881.982.625 (5)129
N26—H26A···O24iii0.882.062.892 (5)159
N26—H26B···O250.881.982.629 (5)129
O124—H124···N15iv0.842.102.936 (5)174
O224—H224···N25v0.842.052.886 (5)174
O1—H1A···O15vi0.901.952.853 (5)175
O1—H1B···O123vii0.831.922.743 (6)169
O5—H5A···O1220.931.862.709 (5)151
O5—H5B···O2220.941.942.746 (5)142
O6—H6A···O122ii0.812.332.987 (5)139
O6—H6B···O222ii1.041.942.794 (5)137
Symmetry codes: (ii) x−1, y, z; (iii) x+1, y, z; (iv) −x+2, y−1/2, −z; (v) −x+1, y−1/2, −z+1; (vi) −x+1, y+1/2, −z; (vii) x−1, y+1, z.
 

Acknowledgements

The X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice.

References

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ISSN: 2053-2296
Volume 61| Part 5| May 2005| Pages m224-m227
doi:10.1107/S0108270105008474
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