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In the title compound, NH4+·C7H8N5O4-·H2O, the independent components are linked into bilayers by an extensive series of two-centre N-H...O hydrogen bonds [H...O = 1.85-1.96 Å, N...O = 2.776 (2)-2.840 (2) Å and N-H...O = 149-172°], and by asymmetric three-centre N-H...(O)2, O-H...(N,O) and O-H...(O)2 hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103009181/sk1636sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103009181/sk1636Isup2.hkl
Contains datablock I

CCDC reference: 214406

Comment top

The structure of N-(6-amino-3,4-dihydro-3-methyl-5-nitroso-4-oxopyrimidin-2-yl)glycine was determined, as the dihydrate, several years ago (Low et al., 1997), and more recently, we have reported the structures of a number of hydrated complexes formed by the N-(6-amino-3,4-dihydro-3-methyl-5-nitroso-4-oxopyrimidin-2-yl)glycinate anion with monopositive cations, including Li+, Na+ and K+ (Low et al., 2000). In addition, the structures of the simple salts of the [Mg(H2O)6]2+ and [Zn(H2O)6]2+ cations have recently been reported (Arranz Mascarós et al., 1999, 2000). Continuing with this study, we now report the molecular and supramolecular structure of the hydrated ammonium salt NH4+·C7H8N5O4·H2O, (I).

The bond distances within the substituted pyrimidine ring and its immediate substituents (Table 1) show the usual evidence for a highly polarized molecular–electronic structure. In particular, the four C—N bonds in the sequence from N2 to N6 are all rather similar in length, the bond distances C4—C5 and C5—C6 being almost identical, and the C5—N5 and N5—O5 distances differing by only ca 0.055 Å; these observations all indicate the importance of the polarized form (II).

There are two N—H···O hydrogen bonds (Table 2) within the anion, forming S(6) motifs (Bernstein et al., 1995), and these may have some influence in controlling the overall molecular conformation of the anion, where the non-H atoms are almost coplanar (Table 1 and Fig. 1). Two further hydrogen bonds link the three independent components within the selected asymmetric unit, where N11 acts as hydrogen-bond donor, via H11D, to O22, and O1 acts as donor, via H1A, primarily to nitroso atom N5 (Fig. 1). However, this H atom makes a second short contact, to O4, which may be adventitious; however, since the sum of angles at H1A is 360°, these two interactions may alternatively be considered as forming an asymmetric three-centre O—H···(N,O) system (Table 1).

There are two other asymmetric three-centre hydrogen bonds in the crystal structure of (I) formed by H1B in an O—H···(O)2 system and by H6B in an N—H···(O)2 system. In all, there are five hydrogen bonds, three of the two-centre type and two of the three-centre type, linking together the three-component aggregates (Fig. 1) into a bilayer structure, whose formation is readily analysed using the substructure approach (Gregson et al., 2000).

The anions alone form hydrogen-bonded chains running parallel to the [010] direction; atom N6 in the anion at (x, y, z) acts as donor, via H6A, to O4 in the anion at (x, 1 + y, z), so forming a C(6) chain by translation (Fig. 2). This chain is reinforced by the ammonium ions; atom N11 at (x, y, z) acts as hydrogen-bond donor, via H11A, to carboxylate atom O21 in the anion at (x, −1 + y, z); in combination with the N11—H11D···O22 hydrogen bond, a C22(6) chain is generated by translation. The C(6) and C22(6) chains thus act as the uprights of a [010] molecular ladder in which the body of the anion provides the rungs: between the rungs there are R33(20) rings (Fig. 2).

Adjacent ladders, related by translation along [101], are linked into sheets by the water molecules and by the ammonium ions. The water O1 at (x, y, z) acts as hydrogen-bond donor, via H1B, to both O21 and O22 in the anion at (1 + x, −1 + y, −1 + z), while ammonium atom N11 at (x, y, z) acts as donor, via H11C, to nitroso atom O5 in the anion at (−1 + x, y, 1 + z). The combination of the resulting [111] and [101] motifs with the [010] ladders generates a (101) sheet (Fig. 3). The (101) sheet is generated solely by translation and two such sheets, related to one another by inversion, pass through each unit cell; pairs of inversion-related sheets linked by one further hydrogen bond to form bilayers. Ammonium atom N11 at (x, y, z) acts as donor, via H11B, to water atom O1 at (-x, −y, −z), so generating a centrosymmetric R66(26) ring (Fig. 4) which links the sheets in pairs.

The only direction-specific interaction between the adjacent bilayers is provided by an anti-parallel carbonyl motif (Allen et al. 1998). The carboxyl bonds C22—O22 in the anions at (x, y, z) and (-x, 1 − y, 1 − z), which lie in different bilayers, form an almost exactly rectangular motif, with an O22···C22i distance of 2.898 (2) Å and a C22—O22···C22i angle of 89.9 (2)° [symmetry code: (i) −x, 1 − y, 1 − z].

Experimental top

Compound (I) was an adventitious by-product from an attempt to prepare the corresponding rubidium salt. Rubidium chloride (0.5 mmol in 20 ml water) was added to a mixture containing equimolar quantities (0.5 mmol) of N-(6-amino-3,4-dihydro-3-methyl-5-nitroso-4-oxopyrimidin-2-yl)glycine and ammonium hydroxide, contained in water (10 ml). After 3 d at ambient temperature, pink crystals of (I) had formed. These were collected by filtration and washed with ethanol. Analysis found: C 32.1, H 5.5, N 32.1%; C7H14N6O4 requires: C 32.1, H 5.4, N 32.1%.

Refinement top

Crystals of (I) are triclinic; space group P1 was selected and confirmed by the successful structure analysis. H atoms bonded to C atoms were treated as riding atoms, with C—H distances of 0.98 (CH3) or 0.99 Å (CH2). All H atoms bonded to N or O atoms were located from difference maps and allowed to ride on their parent atoms at the distances deduced from the maps: the resulting distances were N—H = 0.88 (in the anion) and 0.96–0.98 Å (in the ammonium ion), and O—H = 0.80–0.88 Å.

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: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: 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.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing the formation of a molecular ladder by the ionic components only. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, 1 + y, z) and (x, −1 + y, z), respectively.
[Figure 3] Fig. 3. Stereoview of part of the crystal structure of (I), showing the formation of a (101) sheet. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 4] Fig. 4. Part of the crystal structure of (I), showing the formation of the R66(26) ring motif which links pairs of (101) sheets. For the sake of clarity, the unit-cell box and H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (-x, −y, −z).
Ammonium N-(6-amino-3,4-dihydro-3-methyl-5-nitroso-4-oxopyrimidin-2-yl)glycinate monohydrate top
Crystal data top
NH4+·C7H8N5O4·H2OZ = 2
Mr = 262.24F(000) = 276
Triclinic, P1Dx = 1.584 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2451 (1) ÅCell parameters from 2508 reflections
b = 7.3772 (2) Åθ = 2.9–27.4°
c = 11.1339 (3) ŵ = 0.13 mm1
α = 88.416 (1)°T = 120 K
β = 78.695 (1)°Block, pink
γ = 70.527 (1)°0.20 × 0.20 × 0.10 mm
V = 549.71 (2) Å3
Data collection top
Nonius KappaCCD
diffractometer
2508 independent reflections
Radiation source: rotating anode2328 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
ϕ scans, and ω scans with κ offsetsθmax = 27.4°, θmin = 2.9°
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
h = 98
Tmin = 0.967, Tmax = 0.987k = 99
9766 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0683P)2 + 0.332P]
where P = (Fo2 + 2Fc2)/3
2508 reflections(Δ/σ)max < 0.001
164 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
NH4+·C7H8N5O4·H2Oγ = 70.527 (1)°
Mr = 262.24V = 549.71 (2) Å3
Triclinic, P1Z = 2
a = 7.2451 (1) ÅMo Kα radiation
b = 7.3772 (2) ŵ = 0.13 mm1
c = 11.1339 (3) ÅT = 120 K
α = 88.416 (1)°0.20 × 0.20 × 0.10 mm
β = 78.695 (1)°
Data collection top
Nonius KappaCCD
diffractometer
2508 independent reflections
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
2328 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.987Rint = 0.043
9766 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.118H-atom parameters constrained
S = 1.00Δρmax = 0.39 e Å3
2508 reflectionsΔρmin = 0.42 e Å3
164 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.17995 (16)0.54573 (15)0.07904 (10)0.0134 (2)
C20.12457 (18)0.41689 (18)0.14928 (11)0.0129 (3)
N20.02742 (17)0.47242 (16)0.26354 (10)0.0156 (2)
C210.00691 (19)0.66261 (18)0.31595 (11)0.0148 (3)
C220.13345 (18)0.68649 (18)0.44558 (11)0.0136 (3)
O210.14059 (15)0.82811 (13)0.50999 (9)0.0190 (2)
O220.22148 (14)0.56868 (13)0.47891 (9)0.0172 (2)
N30.15741 (16)0.22946 (15)0.11155 (10)0.0142 (2)
C30.0832 (2)0.09854 (19)0.19365 (12)0.0170 (3)
C40.25795 (19)0.16153 (18)0.00748 (12)0.0152 (3)
O40.28110 (17)0.00203 (14)0.04211 (10)0.0248 (3)
C50.32973 (19)0.29652 (18)0.08441 (12)0.0138 (3)
N50.43020 (16)0.22414 (16)0.19680 (10)0.0163 (2)
O50.49779 (15)0.33512 (14)0.27046 (9)0.0198 (2)
C60.28448 (18)0.48943 (18)0.03524 (11)0.0128 (3)
N60.34445 (17)0.61639 (16)0.10237 (10)0.0151 (2)
O10.51577 (15)0.17036 (15)0.30240 (9)0.0213 (2)
N110.31764 (15)0.23017 (15)0.48612 (9)0.0124 (2)
H20.01790.39130.30930.019*
H21A0.07670.76280.26390.018*
H21B0.12260.67840.31880.018*
H3A0.13960.08500.26790.026*
H3B0.12340.02770.15170.026*
H3C0.06280.15120.21610.026*
H6A0.31580.73370.07210.018*
H6B0.41320.58400.17760.018*
H1A0.47870.06150.25980.026*
H1B0.61300.16860.35050.026*
H11A0.21360.10470.48410.015*
H11B0.38890.22240.42280.015*
H11C0.40520.26250.56490.015*
H11D0.25110.32640.46520.015*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0149 (5)0.0124 (5)0.0124 (5)0.0046 (4)0.0014 (4)0.0011 (4)
C20.0123 (5)0.0132 (6)0.0131 (6)0.0038 (4)0.0029 (4)0.0013 (4)
N20.0200 (5)0.0141 (5)0.0127 (5)0.0077 (4)0.0009 (4)0.0015 (4)
C210.0181 (6)0.0142 (6)0.0122 (6)0.0071 (5)0.0002 (5)0.0019 (4)
C220.0140 (6)0.0124 (6)0.0127 (6)0.0025 (5)0.0025 (4)0.0007 (4)
O210.0260 (5)0.0140 (5)0.0152 (5)0.0062 (4)0.0002 (4)0.0040 (3)
O220.0186 (5)0.0167 (5)0.0161 (5)0.0076 (4)0.0003 (4)0.0004 (4)
N30.0175 (5)0.0124 (5)0.0130 (5)0.0062 (4)0.0015 (4)0.0000 (4)
C30.0224 (6)0.0151 (6)0.0150 (6)0.0091 (5)0.0018 (5)0.0014 (5)
C40.0176 (6)0.0128 (6)0.0148 (6)0.0045 (5)0.0025 (5)0.0019 (5)
O40.0381 (6)0.0148 (5)0.0205 (5)0.0118 (4)0.0027 (4)0.0051 (4)
C50.0150 (6)0.0131 (6)0.0130 (6)0.0043 (5)0.0022 (5)0.0018 (4)
N50.0169 (5)0.0171 (5)0.0141 (5)0.0057 (4)0.0009 (4)0.0017 (4)
O50.0234 (5)0.0213 (5)0.0142 (5)0.0101 (4)0.0023 (4)0.0010 (4)
C60.0118 (5)0.0133 (6)0.0128 (6)0.0033 (4)0.0032 (4)0.0004 (4)
N60.0189 (5)0.0124 (5)0.0135 (5)0.0059 (4)0.0004 (4)0.0009 (4)
O10.0218 (5)0.0229 (5)0.0178 (5)0.0088 (4)0.0026 (4)0.0067 (4)
N110.0136 (5)0.0122 (5)0.0111 (5)0.0054 (4)0.0006 (4)0.0025 (4)
Geometric parameters (Å, º) top
N1—C21.329 (2)C21—H21B0.99
C2—N31.385 (2)C22—O221.2485 (16)
N3—C41.398 (2)C22—O211.2647 (16)
C4—C51.456 (2)N3—C31.4704 (16)
C5—C61.447 (2)C3—H3A0.98
C6—N11.344 (2)C3—H3B0.98
C2—N21.329 (2)C3—H3C0.98
C4—O41.224 (2)N6—H6A0.88
C5—N51.342 (2)N6—H6B0.88
N5—O51.287 (2)O1—H1A0.88
C6—N61.315 (2)O1—H1B0.80
N2—C211.4583 (16)N11—H11A0.98
N2—H20.88N11—H11B0.96
C21—C221.5304 (17)N11—H11C0.96
C21—H21A0.99N11—H11D0.98
C2—N1—C6118.34 (11)H3A—C3—H3C109.5
N1—C2—N2117.79 (11)H3B—C3—H3C109.5
N1—C2—N3124.80 (11)O4—C4—N3120.49 (12)
N2—C2—N3117.41 (11)O4—C4—C5123.64 (12)
C2—N2—C21122.53 (11)N3—C4—C5115.87 (11)
C2—N2—H2118.7N5—C5—C6127.36 (12)
C21—N2—H2118.7N5—C5—C4114.04 (11)
N2—C21—C22109.84 (10)C6—C5—C4118.59 (11)
N2—C21—H21A109.7O5—N5—C5117.74 (11)
C22—C21—H21A109.7N6—C6—N1117.77 (11)
N2—C21—H21B109.7N6—C6—C5120.45 (11)
C22—C21—H21B109.7N1—C6—C5121.78 (11)
H21A—C21—H21B108.2C6—N6—H6A120.0
O22—C22—O21125.46 (12)C6—N6—H6B120.0
O22—C22—C21118.62 (11)H6A—N6—H6B120.0
O21—C22—C21115.92 (11)H1A—O1—H1B103.5
C2—N3—C4120.49 (11)H11A—N11—H11B106.0
C2—N3—C3121.29 (10)H11A—N11—H11C112.1
C4—N3—C3118.19 (10)H11B—N11—H11C111.6
N3—C3—H3A109.5H11A—N11—H11D107.6
N3—C3—H3B109.5H11B—N11—H11D109.3
H3A—C3—H3B109.5H11C—N11—H11D110.2
N3—C3—H3C109.5
C6—N1—C2—N2177.67 (11)C3—N3—C4—C5179.46 (11)
C6—N1—C2—N33.57 (19)O4—C4—C5—N52.0 (2)
N1—C2—N2—C214.47 (19)N3—C4—C5—N5178.25 (11)
N3—C2—N2—C21176.68 (11)O4—C4—C5—C6176.89 (13)
C2—N2—C21—C22176.50 (11)N3—C4—C5—C62.88 (18)
N2—C21—C22—O2214.22 (16)C6—C5—N5—O51.0 (2)
N2—C21—C22—O21166.40 (11)C4—C5—N5—O5179.73 (11)
N1—C2—N3—C41.02 (19)C2—N1—C6—N6177.67 (11)
N2—C2—N3—C4179.78 (11)C2—N1—C6—C52.70 (18)
N1—C2—N3—C3177.24 (11)N5—C5—C6—N60.4 (2)
N2—C2—N3—C31.52 (18)C4—C5—C6—N6179.13 (11)
C2—N3—C4—O4177.55 (12)N5—C5—C6—N1179.19 (12)
C3—N3—C4—O40.76 (19)C4—C5—C6—N10.49 (19)
C2—N3—C4—C52.23 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O220.882.282.655 (2)105
N6—H6B···O50.881.982.627 (2)129
O1—H1A···N50.882.132.990 (2)165
O1—H1A···O40.882.533.113 (2)125
N11—H11D···O220.981.882.803 (2)155
N6—H6A···O4i0.881.912.776 (2)167
N6—H6B···O1i0.882.473.000 (2)119
O1—H1B···O21ii0.802.122.917 (2)175
O1—H1B···O22ii0.802.563.043 (2)120
N11—H11A···O21iii0.981.962.840 (2)149
N11—H11B···O1iv0.961.882.840 (2)172
N11—H11C···O5v0.961.852.782 (2)162
Symmetry codes: (i) x, y+1, z; (ii) x+1, y1, z1; (iii) x, y1, z; (iv) x, y, z; (v) x1, y, z+1.

Experimental details

Crystal data
Chemical formulaNH4+·C7H8N5O4·H2O
Mr262.24
Crystal system, space groupTriclinic, P1
Temperature (K)120
a, b, c (Å)7.2451 (1), 7.3772 (2), 11.1339 (3)
α, β, γ (°)88.416 (1), 78.695 (1), 70.527 (1)
V3)549.71 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.20 × 0.20 × 0.10
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
Tmin, Tmax0.967, 0.987
No. of measured, independent and
observed [I > 2σ(I)] reflections
9766, 2508, 2328
Rint0.043
(sin θ/λ)max1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.118, 1.00
No. of reflections2508
No. of parameters164
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.39, 0.42

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

Selected geometric parameters (Å, º) top
N1—C21.329 (2)C2—N21.329 (2)
C2—N31.385 (2)C4—O41.224 (2)
N3—C41.398 (2)C5—N51.342 (2)
C4—C51.456 (2)N5—O51.287 (2)
C5—C61.447 (2)C6—N61.315 (2)
C6—N11.344 (2)
N1—C2—N2—C214.47 (19)N2—C21—C22—O2214.22 (16)
C2—N2—C21—C22176.50 (11)O4—C4—C5—N52.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O220.882.282.655 (2)105
N6—H6B···O50.881.982.627 (2)129
O1—H1A···N50.882.132.990 (2)165
O1—H1A···O40.882.533.113 (2)125
N11—H11D···O220.981.882.803 (2)155
N6—H6A···O4i0.881.912.776 (2)167
N6—H6B···O1i0.882.473.000 (2)119
O1—H1B···O21ii0.802.122.917 (2)175
O1—H1B···O22ii0.802.563.043 (2)120
N11—H11A···O21iii0.981.962.840 (2)149
N11—H11B···O1iv0.961.882.840 (2)172
N11—H11C···O5v0.961.852.782 (2)162
Symmetry codes: (i) x, y+1, z; (ii) x+1, y1, z1; (iii) x, y1, z; (iv) x, y, z; (v) x1, y, z+1.
 

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