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The crystal structure of the title melaminium salt, bis(2,4,6-tri­amino-1,3,5-triazin-1-ium) DL-malate tetrahydrate, 2C3H7N6+·C4H4O52−·4H2O, consists of singly protonated melaminium residues, DL-malate dianions and water mol­ecules. The melaminium residues are connected into chains by four N—H...N hydrogen bonds, and these chains form a stacking structure along the c axis. The DL-malate dianions form hydrogen-bonded chains and, together with hydrogen-bonded water mol­ecules, form a layer parallel to the (100) plane. The conformation of the malate ion is compared with an ab initio molecular-orbital calculation. The oppositely charged moieties, i.e. the stacks of melaminium chains and hydrogen-bonded DL-malate anions and water mol­ecules, form a three-dimensional polymeric structure, in which N—H...O hydrogen bonds stabilize the stacking.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103010047/na1613sup1.cif
Contains datablocks mejab, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103010047/na1613Isup2.hkl
Contains datablock I

CCDC reference: 214415

Comment top

This study is a continuation of our investigations characterizing the hydrogen bonds formed by triazine derivatives in the solid state (Janczak & Kubiak, 1999; Janczak & Perpétuo, 2001a,b,c,d; Perpétuo & Janczak, 2002a,b; Janczak & Perpétuo, 2002a,b). Melamine and its organic and inorganic complexes or salts can develop well defined supramolecular structures via multiple hydrogen bonds by self-assembly of components that contain complementary arrays of hydrogen-bonding sites (Desiraju, 1990; MacDonald & Whitesides, 1994; Row, 1999; Krische & Lehn, 2000; Sherrington & Taskinen, 2001). To expand the understanding of the solid-state physical-organic chemistry of compounds containing multiple hydrogen-bonding systems, we present here the solid-state structure of the title compound, (I). Additionally, the geometries of both oppositely charged parts, i.e. the singly protonated melaminium cation and the DL-malate dianion, are compared with ab initio fully optimized parameters calculated at the HF/6–31 G(d,p) level (Frisch et al. 1995). The ab initio molecular orbital calculations were carried out on isolated ions, and the results are illustrated in Fig. 1.

The asymmetric unit of (I) consists of two melaminium cations, singly protonated at one of the ring N atoms, a DL-malate dianion and four water molecules (Fig. 2). The six-membered rings of the singly protonated melaminium residues exhibit significant distortions from the ideal hexagonal form. The internal C—N—C angle at the protonated N atom in both independent melaminium cations is greater than the other two C—N—C angles within the ring. This increase is a result of the steric effect of a lone-pair electron, predicted by the valence-shell electron-pair repulsion theory (VSEPR; Gillespie, 1963, 1992). As a result of the protonation of the melamine ring at one of the three ring N atoms, the internal N—C—N angle involving only the non-protonated N atoms is significantly greater than the N—C—N angles involving both protonated and non-protonated N atoms. The ab initio optimized geometry calculated for the singly protonated melaminium residue shows a correlation between the C—N—C and N—C—N angles within the ring similar to that seen in the crystal. Thus, the ring distortion of the singly protonated malaminium residue results mainly from the protonation and, to a lesser degree, from the hydrogen-bonding system and the crystal packing. The C—N bond lengths in the optimized melaminium residue are slightly shorter than those in the crystal. The lengthening of the C—N bonds of the melaminium rings in the crystal is likely to be due to the interaction of the ππ clouds between the rings in the stacks and the hydrogen-bonding system. A similar correlation between the internal C—N—C and N—C—N angles within the melaminium ring is reported for crystals of barbituric acid with melamine (Zerkowski et al. 1994), melaminium phthalate (Janczak & Perpétuo, 2001a), melaminium chloride hemihydrate (Janczak & Perpétuo, 2001c), bis(melaminium) sulfate dihydrate (Janczak & Perpétuo, 2001 d), melaminium acetate (Perpétuo & Janczak, 2002a), melaminium glutarate monohydrate (Janczak & Perpétuo, 2002a) and melaminium phosphate (Janczak & Perpétuo, 2002b), i.e. those singly protonated melaminium salts that have been previously structurally characterized.

Each melaminium residue is involved in nine hydrogen bonds; in seven of them it acts as a donor and in the remaining two it acts as an acceptor. The two pairs of almost linear N—H···N hydrogen bonds link the melaminium moieties to form chains, which in turn form stacks along the [001] direction. Within one stack, the melaminium residues are separated by 3.196 (3) Å. This distance is shorter than that between the π-aromatic ring systems (3.4 Å; Pauling, 1960) and indicates a ππ interactions between the melaminium rings within the stack. The remaining five N—H···O hydrogen bonds (see Table 2), which are more bent, link the chains of melaminium residues with DL-malate ions and water molecules (see Fig. 3). These N—H···O hydrogen bonds stabilize the stacking structure. One of the melaminium moieties forms three hydrogen bonds with two malate ions (with atoms O1 and O2 of one malate ion and with atom O5 of the other malate ion), while the other melaminium residue forms only two hydrogen bonds with two malate ions (with atom O3 of one malate ion and with atom O5 of the second). Atom H12 at the protonated N atom of one melamine residue is involved in a hydrogen bond with atom O1 of the COO group, while atom H22 on the protonated N atom of the second melaminium residue forms a hydrogen bond with atom O3 of the other COO group. Additionally, the first melaminium residue is involved in hydrogen bonds with two water molecules (O2W and O4W), and the other melaminium cation is involved in hydrogen bonds with three water molecules (O2W, O3W and O4W).

The conformation of the carbon skeleton of the malate anion is extended [ψ = −170.5 (3)°], with the C3-carboxyl group almost planar with atoms C3 and O5 [ϕ2 = 7.3 (4)°] because of the intramolecular O5—H5···O4 hydrogen bonding interaction, with a relatively short O5···O4 distance. The conformation of the C2-carboxyl group (COO) around the C—C bond is clinal [χ = 17.3 (4)°]. The C1—C2—C3—C4 (ψ), O4—C4—C3—O5 (ϕ2) and C3—C2—C1—O1 (χ) torsion angles describe well the conformation of the malate ion and the conformation of malic acid (Sluis & Kron, 1985; 1989). In the optimized malate dianion, the values of ψ, ϕ2 and χ are −166.3, 4.2 and 36.9°, respectively. The greatest difference between the angles in the optimized ion and in the crystal malate ion is found for angle χ, which describes the orientation of the COO group at atom C2 as a result of the formation of the relatively strong O···H—N hydrogen bonds with the melaminium moiety. The optimized O—C—O angles in both dissociated carboxyl groups are greater than those in the crystal, probably because of the diminishing steric effect of lone pairs of electrons on the O atoms, resulting from the O···H—-N and O···H—O hydrogen-bonding interactions. The C—O bonds in both COO groups are intermediate between single Csp2—O (1.308–1.320 Å) and double Csp2O (1.214–1.224 Å; Allen et al., 1987; Allen, 2002) indicating delocalization of the charge on both O atoms of the COO groups. The slight difference between the C1—O1 and C1—O2 bonds in one COO group and between the C4—O3 and C4—O4 bonds in the other COO group correlates well with the strength of the hydrogen bonds in which the O atoms are involved (Table 2). The C3—O5 bond length is slightly longer in the crystal than in the ab initio calculation, since, in the crystal, the hydroxyl group is involved in four hydrogen bonds, viz. in two as a donor and in two as an acceptor. Thus, hydroxyl atom H5 of the malate ion forms bifurcated hydrogen bond. The malate ions form hydrogen-bonded chains via O5—H5···O2vi interactions and, together with hydrogen-bonded water molecules, form a two-dimensional layer parallel to the (100) plane.

Two pairs of water molecules (O1W and O4W) related by an inversion centre form a hydrogen-bonded cyclic tetramer in which atom O4W is a donor and atom O1W is an acceptor. Additionally, water molecule O3W interacts as an acceptor with atom H21W, and water molecule O2W interacts via atom H22W to form an O2W—H22W···O4Wix hydrogen bond.

Experimental top

Melamine was added to a solution of (DL)-malic acid (10%) and the resulting solution was slowly evaporated. After several days, colourless crystals of (I) appeared.

Computing details top

Data collection: KM-4 Software (Kuma, 2000); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The results of the optimized molecular orbital calculations (Å, °) for (a) the melaminium cation and (b) the malate(2-) ion.
[Figure 2] Fig. 2. A view of the molecular structure, showing displacement ellipsoids at the 50% probability level. H atoms are shown as spheres of arbitrary radii.
[Figure 3] Fig. 3. A view of the crystal packing, showing the stacking structure of hydrogen-bonded melaminium residues that stabilize the N—H···O hydrogen bonds, and the layer of O—H···O hydrogen- bonded malate ions with water molecules. Dashed lines represent hydrogen bonds and H atoms have been omited for clarity.
Bis(1,3,5-triamine-2,4,6-trianine-1-ium) DL-malate tetrahydrate top
Crystal data top
2C3H7N6+·C4H4O52·4H2OF(000) = 1936
Mr = 458.43Dx = 1.519 Mg m3
Dm = 1.52 Mg m3
Dm measured by floatation
Monoclinic, C2/cMelting point: decomposition K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 26.533 (5) ÅCell parameters from 3878 reflections
b = 12.297 (2) Åθ = 3.2–28.4°
c = 13.079 (3) ŵ = 0.13 mm1
β = 110.00 (3)°T = 293 K
V = 4010.0 (16) Å3Parallelepiped, colourless
Z = 80.28 × 0.24 × 0.16 mm
Data collection top
KUMA KM-4 with area CCD detector
diffractometer
4986 independent reflections
Radiation source: fine-focus sealed tube3878 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1θmax = 28.4°, θmin = 3.2°
ω scanh = 2435
Absorption correction: analytical
face-indexed, SHEXLTL (Sheldrick, 1990)
k = 1616
Tmin = 0.961, Tmax = 0.968l = 1717
15560 measured reflections
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)] = 0.040H-atom parameters constrained
wR(F2) = 0.041 w = 1/[σ2(Fo2) + (0.0061P)2 + 0.0402P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.009
4986 reflectionsΔρmax = 0.36 e Å3
305 parametersΔρmin = 0.28 e Å3
12 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.000227 (7)
Crystal data top
2C3H7N6+·C4H4O52·4H2OV = 4010.0 (16) Å3
Mr = 458.43Z = 8
Monoclinic, C2/cMo Kα radiation
a = 26.533 (5) ŵ = 0.13 mm1
b = 12.297 (2) ÅT = 293 K
c = 13.079 (3) Å0.28 × 0.24 × 0.16 mm
β = 110.00 (3)°
Data collection top
KUMA KM-4 with area CCD detector
diffractometer
4986 independent reflections
Absorption correction: analytical
face-indexed, SHEXLTL (Sheldrick, 1990)
3878 reflections with I > 2σ(I)
Tmin = 0.961, Tmax = 0.968Rint = 0.034
15560 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04012 restraints
wR(F2) = 0.041H-atom parameters constrained
S = 1.07Δρmax = 0.36 e Å3
4986 reflectionsΔρmin = 0.28 e Å3
305 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N110.46949 (9)0.79460 (18)0.11303 (15)0.0465 (6)
N120.54955 (7)0.8903 (2)0.14109 (14)0.0506 (6)
H120.58330.88880.15130.061*
N130.47021 (9)0.99027 (18)0.11278 (16)0.0516 (6)
C110.44537 (11)0.8942 (3)0.1040 (2)0.0548 (8)
C120.52339 (12)0.9864 (3)0.1336 (2)0.0529 (8)
C130.52136 (12)0.7964 (3)0.13210 (19)0.0524 (8)
N140.54929 (7)0.70549 (16)0.14191 (14)0.0556 (6)
H14A0.53350.64360.13580.067*
H14B0.58330.70830.15440.067*
N150.39330 (7)0.89640 (15)0.08354 (14)0.0610 (6)
H15A0.37680.95770.07650.073*
H15B0.37570.83660.07720.073*
N160.55240 (7)1.07418 (16)0.14903 (15)0.0610 (7)
H16A0.53761.13690.14600.073*
H16B0.58641.06950.16220.073*
N210.49878 (9)1.29636 (17)0.12272 (15)0.0475 (6)
N220.41808 (7)1.3887 (2)0.09778 (15)0.0567 (6)
H220.38421.38680.08620.068*
N230.49610 (9)1.49190 (17)0.12158 (15)0.0488 (6)
C210.44599 (12)1.2963 (3)0.1055 (2)0.0493 (8)
C220.44388 (13)1.4845 (3)0.1084 (2)0.0534 (8)
C230.52030 (10)1.3943 (3)0.12682 (19)0.0485 (7)
N240.42017 (7)1.20374 (17)0.09932 (14)0.0666 (7)
H24A0.43721.14310.10630.080*
H24B0.38631.20390.08830.080*
N250.41570 (7)1.57432 (16)0.10462 (15)0.0679 (7)
H25A0.43101.63680.11060.082*
H25B0.38221.57010.09620.082*
N260.57250 (7)1.39923 (15)0.14086 (14)0.0601 (6)
H26A0.59071.34030.14680.072*
H26B0.58791.46130.14390.072*
O10.64947 (6)0.87657 (15)0.14596 (14)0.0750 (6)
O20.66539 (6)1.04170 (14)0.21407 (14)0.0685 (5)
C10.67678 (10)0.9611 (3)0.1664 (2)0.0627 (9)
C20.72465 (8)0.97206 (18)0.12886 (19)0.0574 (7)
H2A0.75720.96150.19090.069*
H2B0.72541.04540.10220.069*
C30.72458 (8)0.8922 (2)0.0400 (2)0.0529 (7)
H30.71930.81880.06380.063*
O50.68117 (5)0.91631 (12)0.05737 (13)0.0636 (5)
H50.69290.93020.10630.095*
C40.77711 (11)0.8947 (2)0.0204 (3)0.0621 (8)
O30.81856 (6)0.86354 (14)0.09722 (14)0.0718 (6)
O40.77891 (6)0.92749 (14)0.06762 (15)0.0780 (6)
O1W0.76915 (9)1.15316 (16)0.0965 (2)0.0964 (6)
H11W0.772241.084840.102300.147*
H21W0.785031.183910.135190.147*
O2W0.64867 (5)0.58852 (18)0.18184 (15)0.0760 (6)
H12W0.670630.575370.148920.114*
H22W0.666330.615740.243440.114*
O3W0.66949 (9)1.26100 (15)0.20657 (15)0.0809 (6)
H13W0.666781.192230.200720.119*
H23W0.673051.277450.271800.119*
O4W0.82101 (8)1.21342 (19)0.11737 (18)0.1097 (7)
H14W0.794221.207480.0589800.166*
H24W0.815601.268200.1518800.166*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0438 (14)0.0396 (17)0.0646 (16)0.0039 (13)0.0294 (13)0.0037 (12)
N120.0383 (13)0.0460 (16)0.0757 (15)0.0043 (15)0.0303 (12)0.0057 (14)
N130.0452 (15)0.0478 (18)0.0664 (16)0.0016 (13)0.0249 (13)0.0034 (12)
C110.0492 (19)0.057 (2)0.068 (2)0.003 (2)0.0323 (17)0.0048 (19)
C120.059 (2)0.040 (2)0.070 (2)0.0006 (19)0.036 (2)0.0029 (17)
C130.058 (2)0.036 (2)0.068 (2)0.001 (2)0.0275 (19)0.0024 (17)
N140.0541 (14)0.0363 (15)0.0816 (16)0.0008 (12)0.0301 (12)0.0011 (13)
N150.0412 (12)0.0422 (14)0.0930 (17)0.0004 (13)0.0144 (13)0.0036 (12)
N160.0495 (14)0.0473 (16)0.0966 (18)0.0001 (13)0.0385 (13)0.0004 (14)
N210.0421 (14)0.0403 (16)0.0596 (16)0.0038 (13)0.0167 (12)0.0023 (12)
N220.0437 (13)0.0455 (15)0.0811 (17)0.0071 (16)0.0218 (13)0.0018 (15)
N230.0365 (14)0.0526 (19)0.0623 (16)0.0038 (13)0.0235 (13)0.0043 (12)
C210.045 (2)0.042 (2)0.060 (2)0.0003 (18)0.0169 (17)0.0009 (16)
C220.063 (2)0.046 (2)0.056 (2)0.0082 (19)0.0255 (18)0.0059 (16)
C230.0369 (17)0.046 (2)0.0647 (19)0.003 (2)0.0200 (16)0.0048 (18)
N240.0607 (15)0.0488 (16)0.0951 (19)0.0003 (13)0.0327 (14)0.0001 (14)
N250.0585 (15)0.0441 (16)0.1035 (19)0.0040 (13)0.0307 (14)0.0037 (14)
N260.0552 (14)0.0364 (14)0.0905 (16)0.0041 (12)0.0271 (13)0.0087 (12)
O10.0628 (13)0.0622 (15)0.1129 (16)0.0080 (11)0.0465 (12)0.0150 (12)
O20.0633 (12)0.0612 (13)0.0910 (14)0.0058 (10)0.0395 (11)0.0110 (11)
C10.0451 (19)0.067 (2)0.077 (2)0.0063 (18)0.0227 (18)0.001 (2)
C20.0514 (16)0.0487 (17)0.068 (2)0.0053 (15)0.0144 (15)0.0010 (17)
C30.0373 (15)0.0522 (18)0.072 (2)0.0027 (16)0.0217 (16)0.0095 (17)
O50.0454 (10)0.0773 (14)0.0734 (12)0.0044 (10)0.0272 (10)0.0034 (11)
C40.067 (2)0.0494 (19)0.086 (3)0.0051 (19)0.047 (2)0.006 (2)
O30.0469 (11)0.0835 (16)0.0860 (14)0.0065 (11)0.0242 (10)0.0143 (12)
O40.0629 (12)0.0928 (16)0.0954 (16)0.0094 (10)0.0490 (12)0.0126 (12)
O1W0.1077 (16)0.0800 (13)0.1187 (17)0.0054 (15)0.0610 (14)0.0135 (16)
O2W0.0554 (12)0.0910 (15)0.0857 (14)0.0027 (12)0.0292 (11)0.0006 (15)
O3W0.0823 (13)0.0660 (15)0.0931 (16)0.0110 (13)0.0286 (15)0.0055 (13)
O4W0.0873 (15)0.0985 (19)0.153 (2)0.0055 (12)0.0537 (17)0.0147 (17)
Geometric parameters (Å, º) top
N11—C131.312 (3)N24—H24A0.8600
N11—C111.368 (3)N24—H24B0.8600
N12—C121.357 (3)N25—H25A0.8600
N12—C131.359 (3)N25—H25B0.8600
N12—H120.8600N26—H26A0.8600
N13—C111.339 (3)N26—H26B0.8600
N13—C121.343 (3)O1—C11.243 (3)
C11—N151.315 (2)O2—C11.261 (3)
C12—N161.301 (3)C1—C21.516 (3)
C13—N141.323 (3)C2—C31.521 (3)
N14—H14A0.8600C2—H2A0.9700
N14—H14B0.8600C2—H2B0.9700
N15—H15A0.8600C3—O51.426 (2)
N15—H15B0.8600C3—C41.501 (3)
N16—H16A0.8600C3—H30.9800
N16—H16B0.8600O5—H50.8200
N21—C231.326 (3)C4—O41.236 (3)
N21—C211.341 (3)C4—O31.269 (3)
N22—C211.341 (3)O1W—H11W0.85
N22—C221.345 (3)O1W—H21W0.85
N22—H220.8600O2W—H12W0.85
N23—C221.340 (3)O2W—H22W0.85
N23—C231.351 (3)O3W—H13W0.85
C21—N241.316 (2)O3W—H23W0.85
C22—N251.326 (3)O4W—H14W0.85
C23—N261.335 (2)O4W—H24W0.85
C13—N11—C11115.5 (2)N21—C23—N23127.9 (2)
C12—N12—C13118.8 (2)N26—C23—N23114.8 (3)
C12—N12—H12120.6C21—N24—H24A120.0
C13—N12—H12120.6C21—N24—H24B120.0
C11—N13—C12116.0 (2)H24A—N24—H24B120.0
N15—C11—N13116.8 (3)C22—N25—H25A120.0
N15—C11—N11117.7 (3)C22—N25—H25B120.0
N13—C11—N11125.5 (2)H25A—N25—H25B120.0
N16—C12—N13121.8 (3)C23—N26—H26A120.0
N16—C12—N12116.8 (3)C23—N26—H26B120.0
N13—C12—N12121.4 (3)H26A—N26—H26B120.0
N11—C13—N14121.4 (3)O1—C1—O2122.9 (3)
N11—C13—N12122.8 (3)O1—C1—C2119.7 (3)
N14—C13—N12115.9 (3)O2—C1—C2117.4 (3)
C13—N14—H14A120.0C1—C2—C3114.1 (2)
C13—N14—H14B120.0C1—C2—H2A108.7
H14A—N14—H14B120.0C3—C2—H2A108.7
C11—N15—H15A120.0C1—C2—H2B108.7
C11—N15—H15B120.0C3—C2—H2B108.7
H15A—N15—H15B120.0H2A—C2—H2B107.6
C12—N16—H16A120.0O5—C3—C4110.9 (2)
C12—N16—H16B120.0O5—C3—C2109.7 (2)
H16A—N16—H16B120.0C4—C3—C2111.1 (2)
C23—N21—C21114.7 (2)O5—C3—H3108.4
C21—N22—C22119.1 (2)C4—C3—H3108.4
C21—N22—H22120.5C2—C3—H3108.4
C22—N22—H22120.5C3—O5—H5109.5
C22—N23—C23113.5 (2)O4—C4—O3122.5 (3)
N24—C21—N21120.2 (3)O4—C4—C3120.0 (3)
N24—C21—N22117.8 (3)O3—C4—C3117.5 (3)
N21—C21—N22122.0 (3)H11W—O1W—H21W107.7
N25—C22—N23119.5 (3)H12W—O2W—H22W107.4
N25—C22—N22117.7 (3)H13W—O3W—H23W107.7
N23—C22—N22122.7 (3)H14W—O4W—H24W107.7
N21—C23—N26117.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N12—H12···O10.861.792.635 (3)169
N14—H14A···N23i0.862.092.950 (3)179
N14—H14B···O2W0.862.212.890 (3)136
N15—H15A···O5ii0.862.142.977 (3)165
N15—H15B···O4Wiii0.862.283.085 (3)156
N16—H16A···N210.862.193.045 (3)175
N16—H16B···O20.862.002.851 (3)170
N22—H22···O3iv0.861.822.656 (3)164
N24—H24A···N130.862.062.920 (3)174
N24—H24B···O5ii0.862.252.950 (3)139
N25—H25A···N11v0.862.193.046 (3)176
N25—H25B···O4Wiv0.862.473.091 (3)129
N26—H26A···O3W0.862.192.956 (3)148
N26—H26B···O2Wv0.862.183.008 (3)162
O5—H5···O40.822.162.646 (3)118
O5—H5···O2vi0.822.242.919 (3)141
O1W—H11W···O40.851.982.801 (3)162
O1W—H21W···O3Wvii0.851.892.728 (3)170
O2W—H12W···O4viii0.851.972.815 (3)170
O2W—H22W···O4Wix0.852.112.908 (3)156
O3W—H13W···O20.851.862.702 (3)170
O3W—H23W···O3x0.851.962.778 (3)161
O4W—H14W···O1W0.852.022.763 (3)145
O4W—H24W···O1Wvii0.852.322.836 (3)119
Symmetry codes: (i) x, y1, z; (ii) x+1, y+2, z; (iii) x1/2, y1/2, z; (iv) x1/2, y+1/2, z; (v) x, y+1, z; (vi) x, y+2, z1/2; (vii) x+3/2, y+5/2, z; (viii) x+3/2, y+3/2, z; (ix) x+3/2, y1/2, z+1/2; (x) x+3/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula2C3H7N6+·C4H4O52·4H2O
Mr458.43
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)26.533 (5), 12.297 (2), 13.079 (3)
β (°) 110.00 (3)
V3)4010.0 (16)
Z8
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.28 × 0.24 × 0.16
Data collection
DiffractometerKUMA KM-4 with area CCD detector
diffractometer
Absorption correctionAnalytical
face-indexed, SHEXLTL (Sheldrick, 1990)
Tmin, Tmax0.961, 0.968
No. of measured, independent and
observed [I > 2σ(I)] reflections
15560, 4986, 3878
Rint0.034
(sin θ/λ)max1)0.669
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.041, 1.07
No. of reflections4986
No. of parameters305
No. of restraints12
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.36, 0.28

Computer programs: KM-4 Software (Kuma, 2000), KM-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1990).

Selected geometric parameters (Å, º) top
N11—C131.312 (3)N23—C221.340 (3)
N11—C111.368 (3)N23—C231.351 (3)
N12—C121.357 (3)O1—C11.243 (3)
N12—C131.359 (3)O2—C11.261 (3)
N13—C111.339 (3)C1—C21.516 (3)
N13—C121.343 (3)C2—C31.521 (3)
N21—C231.326 (3)C3—O51.426 (2)
N21—C211.341 (3)C3—C41.501 (3)
N22—C211.341 (3)C4—O41.236 (3)
N22—C221.345 (3)C4—O31.269 (3)
C13—N11—C11115.5 (2)N21—C23—N23127.9 (2)
C12—N12—C13118.8 (2)O1—C1—O2122.9 (3)
C11—N13—C12116.0 (2)O1—C1—C2119.7 (3)
N13—C11—N11125.5 (2)O2—C1—C2117.4 (3)
N13—C12—N12121.4 (3)C1—C2—C3114.1 (2)
N11—C13—N12122.8 (3)O5—C3—C4110.9 (2)
C23—N21—C21114.7 (2)O5—C3—C2109.7 (2)
C21—N22—C22119.1 (2)C4—C3—C2111.1 (2)
C22—N23—C23113.5 (2)O4—C4—O3122.5 (3)
N21—C21—N22122.0 (3)O4—C4—C3120.0 (3)
N23—C22—N22122.7 (3)O3—C4—C3117.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N12—H12···O10.861.792.635 (3)169
N14—H14A···N23i0.862.092.950 (3)179
N14—H14B···O2W0.862.212.890 (3)136
N15—H15A···O5ii0.862.142.977 (3)165
N15—H15B···O4Wiii0.862.283.085 (3)156
N16—H16A···N210.862.193.045 (3)175
N16—H16B···O20.862.002.851 (3)170
N22—H22···O3iv0.861.822.656 (3)164
N24—H24A···N130.862.062.920 (3)174
N24—H24B···O5ii0.862.252.950 (3)139
N25—H25A···N11v0.862.193.046 (3)176
N25—H25B···O4Wiv0.862.473.091 (3)129
N26—H26A···O3W0.862.192.956 (3)148
N26—H26B···O2Wv0.862.183.008 (3)162
O5—H5···O40.822.162.646 (3)118
O5—H5···O2vi0.822.242.919 (3)141
O1W—H11W···O40.851.982.801 (3)162
O1W—H21W···O3Wvii0.851.892.728 (3)170
O2W—H12W···O4viii0.851.972.815 (3)170
O2W—H22W···O4Wix0.852.112.908 (3)156
O3W—H13W···O20.851.862.702 (3)170
O3W—H23W···O3x0.851.962.778 (3)161
O4W—H14W···O1W0.852.022.763 (3)145
O4W—H24W···O1Wvii0.852.322.836 (3)119
Symmetry codes: (i) x, y1, z; (ii) x+1, y+2, z; (iii) x1/2, y1/2, z; (iv) x1/2, y+1/2, z; (v) x, y+1, z; (vi) x, y+2, z1/2; (vii) x+3/2, y+5/2, z; (viii) x+3/2, y+3/2, z; (ix) x+3/2, y1/2, z+1/2; (x) x+3/2, y+1/2, z+1/2.
 

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