Potassium N-(6-amino-3,4-di­hydro-3-methyl-5-nitro­so-4-oxopyrimidin-2-yl)-(S)-aspartate N-(6-amino-3,4-di­hydro-3-methyl-5-nitro­so-4-oxo­pyrimidin-2-yl)-(S)-aspartic acid 4.88-hydrate: a two-dimensional coordination polymer

In the title compound, K⁺·C₉H₁₀N₅O₆⁻·C₉H₁₁N₅O₆·4.88H₂O, the cations are eight-coordinate. There is a one-dimensional coordination-polymer substructure, built from K and O atoms only, in the form of chains of distorted confacial octahedra, and these are linked into sheets by the neutral organic ligand. The sheets are linked into a single framework by a combination of N—H...O and O—H...O hydrogen bonds.

S1. Comment

We have reported recently the molecular and supramolecular structures of the hydrated potassium complexes derived from the anionic ligands L¹ and L² (Scheme). In [K(L¹)H₂O], chains of spiro-fused K₂O₂ rings are linked into sheets by means of the unusual η² coordination of the nitroso substituent, and the coordination-polymer sheets are linked into a three-dimensional framework by hydrogen bonds (Low et al., 2001b). In [K(L²)H₂O], by contrast, the coordination polymer is three-dimensional: K₂O₂ rings are again present, but they are isolated from one another and the nitroso substituent adopts the more usual η¹ coordination mode (Low et al., 2001a).

Continuing this investigation, we have now turned to an analogous ligand, L³, containing a dicarboxylic acid side chain, and we report here the structure of the hydrated potassium complex, (I). The constitution of (I) is that of an acid salt, [K(L³)(HL³)(H₂O)_4.88], in which the carboxyl group of the HL³ unit is not ionized. There are three fully occupied water sites (viz. those containing atoms O1–O3, including one molecule that is directly coordinated to the cation) and three partially occupied sites (viz. those containing atoms O4–O6 (Fig. 1). The anionic ligand (containing atoms N11, C12 etc.) is coordinated to the K⁺ cation via both atom O14 and atom N15, while atom O14 is also coordinated to the cation at (0.5 + x, 1.5 − y, 1 − z). The neutral organic HL³ ligand is directly coordinated to the cation only via atom O24, which also coordinates to the K⁺ cation at (0.5 + x, 1.5 − y, 1 − z); likewise water atom O1 at (x, y, z) is coordinated to cations at both (x, y, z) and (0.5 + x, 1.5 − y, 1 − z). The eight-coordination of the cation is completed by carboxyl atom O224 at (x, −1 + y, z), and a hydrogen bond formed between atoms O1 and N25 effectively prevents this N atom from coordinating to the cation (Fig. 1), so that the coordination behaviour of the neutral HL³ ligand differs from that of the anionic (L³)⁻ ligand. The remaining water molecules are linked to the coordination complex by means of hydrogen bonds, primarily of O—H···O type but including one of N—H···O type (Fig. 1 and Table 2).

In both organic ligands, the ring dimensions (Table 1) display to an extreme degree the electronic polarization that is now a familiar feature of compounds containing this type of substituted oxopyrimidinyl ring (Low et al., 2000; Low et al., 2001a; Low et al., 2001b). In particular, the exocyclic Cn6—Nn6 bonds (n = 1 or 2) are both shorter than those typically found in metal complexes of ligands of this general type (Low et al., 2001b). Overall, the ring dimensions point to the importance of the polarized form (A) at the expense of the classically localized form of L³ (see Scheme).

The C—O distances in the carboxyl groups are consistent with the H-atom locations deduced from difference map. Thus, at both atom C124 and atom C224, the C—O distances are typical of those in unionized carboxyl groups (Allen et al., 1987), while the two distances at atom C122 are very similar and are consistent with the presence of a fully ionized carboxylate unit. At atom C222, on the other hand, the difference between the two C—O distances is less than that typically found in unionized carboxyl groups [mean value 0.122 Å; Allen et al., 1987). Although, in both organic ligands, there is complete synclinal staggering about the Cn21—Cn23 bonds (n = 1 or 2), the skeletal conformations about the Nn1—Cn21 bonds are quite different, being synclinal in the anionic ligand and anticlinal in the neutral ligand; this latter conformation may be influenced by the intramolecular N22—H22···O223 hydrogen bond.

Since atoms O1, O14 and O24 at (x, y, z) all bridge the pair of cations at (x, y, z) and (0.5 + x, 1.5 − y, 1 − z), these interactions give rise to a one-dimensional coordination polymer, which takes the form of a chain of distorted confacial octahedra (Fig. 2) that runs parallel to the [100] direction and is generated by the 2₁ screw axis along (x, 3/4, 1/2). There is a second such chain passing through the unit cell, this time generated by the 2₁ screw axis along (x, 1/4, 0). Within each domain of z, the [100] chains are linked into (001) sheets. The final coordination site of the cation at (x, y, z) is occupied by carboxyl atom O224 from the neutral organic ligand at (x, −1 + y, z), so forming by translation a C¹₂(10) motif (Starbuck et al., 1999) running parallel to the [010] direction (Fig. 3). The combination of the [100] and [010] chains generates a (001) sheet, two of which pass through each unit cell.

In addition to three intramolecular N—H···O hydrogen bonds, each of which forms an S(6) motif (Bernstein et al., 1995), there are intermolecular O—H···O, O—H···N and N—H···O hydrogen bonds in the asymmetric unit (Fig. 1 and Table 2). There are also a substantial number of hydrogen bonds linking these molecular aggregates together, and we discuss here just three points concerning these which are of structural significance. First, the three O—H···O hydrogen bonds having carboxyl donors are characterized by short O···O distances, in every case less than 2.60 Å. In particular, the hydrogen bond having anionic nitroso atom O15 as acceptor has an O···O distance of only 2.502 (3) Å, which is comparable with those observed for such hydrogen bonds in neutral N-(6-amino-3,4-dihydro-3-methyl-5-nitroso-4-oxopyrimidin-2-yl)amino acids; moreover the C15—N15 and N15—O15 distances associated with this hydrogen bond fit well with the correlation established previously between such distances and the O···O hydrogen bond distances (Low et al., 2000). Secondly, despite the number of unionized carboxyl groups present in the structure, these generate neither of the two hydrogen-bonded motifs [C(4) and R²₂(8)] that are so characteristic of simple carboxylic acids; indeed, there is no hydrogen bond present in which both donor and acceptor are components of neutral carboxyl groups. There is, however, a single example, namely O124—H124···O121(1 + x, y, z), in which the ionized carboxylate unit provides the acceptor. Thirdly, a number of the hydrogen bonds serve to link the (001) sheets into a single continuous framework, and just two examples suffice to demonstrate this behaviour. Atom N16 at (x, y, z) lies in the (001) sheet containing the 2₁ screw axes at z = 0.5 and acts as a hydrogen-bond donor, via atom H16A, to water atom O2 at (1 − x, −0.5 + y, 0.5 − z), which lies in the sheet containing the 2₁ axes at z = 0. A t the same time, atom N26 at (x, y, z) acts as a hydrogen-bond donor, via H26A, to carboxylate atom O121 at (0.5 − x, 2 − y, 0.5 + z), which lies in the sheet containing the 2₁ axes at z = 1.0. Two O—H···O hydrogen bonds, involving water atoms O2 and O5 as donors, reinforce the linking of the (001) sheets (Table 2).

S2. Experimental

The title compound was obtained by adding 6-amino-3,4-dihydro-3-methyl-2-methoxy-5-nitroso-4-oxopyrimidine (3.5 mmol) to a solution of potassium (S)-aspartate (3.5 mmol) in methanol (40 cm³). The mixture was stirred at 315 K for 2 d, and a pink solid was removed by filtration. The filtrate was evaporated to dryness, the residue was dissolved in water, and the pH of the resulting solution was adjusted to 2.15 by dropwise addition of aqueous HCl. After two weeks at room temperature, red crystals of the product were collected by filtration and washed with ethanol. Analysis found: C 31.3, H 4.9, N 20.3%; C₁₈H_30.76KN₁₀O_16.88 requires: C 31.0, H 4.5, N 20.1%. Crystals suitable for single-crystal X-ray diffraction were selected directly from the prepared sample.

S3. Refinement

Crystals of (I) are orthorhombic and the space group P2₁2₁2₁ was uniquely assigned from the systematic absences. H atoms bonded to C or N atoms were treated as riding atoms, with C—H distances of 0.98 (CH₃), 0.99 (CH₂) and 1.00 Å (CH), and N—H distances of 0.88 Å. Water H atoms were located from difference maps and were initially constrained, with O—H distances in each molecule set to the average distance found for that molecule from the difference maps, and finally treated as riding atoms using AFIX 3, giving O—H distances of 0.90–0.98 Å. Carboxyl H atoms were treated as riding atoms, the C—H distances of 0.99–1.12 Å being deduced from difference maps. At a late stage in the refinement, it became apparent that there was a partially occupied water O-atom site, denoted O6, whose distances from the sites denoted O4 and O5 meant that site O6 could not be occupied at the same time as either O4 and O5; sites O4 and O5 could themselves be concurrently occupied, provided that site O6 was unoccupied. This situation was modelled by assigning a common site occupancy to sites O4 and O5 while tying the occupancy of site O6 to this common occupancy. The resulting occupancy factors are 0.883 (5) for O4 and O5, and 0.117 (5) for O6, and these occupancy values are associated with satisfactory displacement parameters.

Computing details

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

	Fig. 1. The independent components of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. The water molecules based on atoms O4 and O5 have occupancies of 0.883 (5), and atom O6 has an occupancy of 0.117 (5). The H atoms bonded to atom O6 could not be located (see text).
	Fig. 2. Part of the crystal structure of (I), showing the formation of the coordination polymer along [100] built from K and O atoms only. For clarity, the unit-cell box has been omitted. Atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (−0.5 + x, 1.5 − y, 1 − z), (0.5 + x, 1.5 − y, 1 − z) and (1 + x, y, z), respectively.
	Fig. 3. Part of the crystal structure of (I), showing the formation of a chain along [010] built from cations and neutral organic ligands only. For 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.

Potassium N-(6-amino-3,4-dihydro-3-methyl-5-nitroso- 4-oxopyrimidin-2-yl)-(S)-aspartate N-(6-amino-3,4-dihydro-3-methyl- 5-nitroso-4-oxopyrimidin-2-yl)-(S)-aspartic acid 4.88(hydrate)

Crystal data

K^+·C9H10N5O6^−·C9H11N5O6·4.88H2O	F(000) = 1451.32
Mr = 696.52	Dx = 1.591 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6543 reflections
a = 7.4986 (1) Å	θ = 3.1–27.5°
b = 13.0997 (2) Å	µ = 0.28 mm^−1
c = 29.5866 (6) Å	T = 120 K
V = 2906.27 (8) Å^3	Needle, red
Z = 4	0.35 × 0.10 × 0.06 mm

Data collection

NONIUS KappaCCD diffractometer	6543 independent reflections
Radiation source: rotating anode	5256 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −9→9
Tmin = 0.941, Tmax = 0.986	k = −17→14
21931 measured reflections	l = −37→38

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0292P)^2 + 1.9469P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
6543 reflections	Δρmax = 0.66 e Å^−3
422 parameters	Δρmin = −0.58 e Å^−3
0 restraints	Absolute structure: Flack (1983), 2893 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (5)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
K1	0.14017 (9)	0.69196 (5)	0.49688 (2)	0.02062 (16)
N11	0.3778 (3)	0.65195 (19)	0.30134 (8)	0.0143 (5)
C12	0.4557 (4)	0.7391 (2)	0.31210 (10)	0.0145 (6)
N12	0.5311 (3)	0.79242 (19)	0.27860 (8)	0.0150 (5)
C122	0.3275 (4)	0.7430 (2)	0.21636 (10)	0.0171 (7)
C121	0.5214 (4)	0.7566 (2)	0.23173 (10)	0.0151 (6)
O121	0.2171 (3)	0.81012 (17)	0.23024 (7)	0.0192 (5)
O122	0.2938 (3)	0.67396 (17)	0.18868 (7)	0.0210 (5)
C123	0.6364 (4)	0.6633 (2)	0.22258 (10)	0.0165 (6)
C124	0.8327 (4)	0.6805 (2)	0.22802 (9)	0.0171 (6)
O123	0.9349 (3)	0.61502 (19)	0.24087 (8)	0.0262 (6)
O124	0.8846 (3)	0.77407 (18)	0.21657 (8)	0.0252 (5)
N13	0.4647 (4)	0.77896 (19)	0.35544 (8)	0.0171 (6)
C13	0.5460 (5)	0.8791 (2)	0.36356 (11)	0.0239 (8)
C14	0.3952 (4)	0.7251 (2)	0.39206 (10)	0.0167 (7)
O14	0.4085 (3)	0.75943 (17)	0.43065 (7)	0.0225 (5)
C15	0.3107 (4)	0.6273 (2)	0.38114 (10)	0.0163 (7)
O15	0.1630 (3)	0.49228 (16)	0.40951 (7)	0.0222 (5)
N15	0.2417 (4)	0.5793 (2)	0.41642 (8)	0.0187 (6)
C16	0.3076 (4)	0.5941 (2)	0.33406 (10)	0.0163 (7)
N16	0.2360 (4)	0.5066 (2)	0.32266 (9)	0.0198 (6)
N21	0.1753 (4)	1.08915 (19)	0.62104 (8)	0.0183 (6)
C22	0.1359 (4)	1.0934 (2)	0.57742 (10)	0.0169 (6)
N22	0.0645 (4)	1.1782 (2)	0.56070 (8)	0.0201 (6)
C221	0.0660 (5)	1.2746 (2)	0.58422 (11)	0.0244 (8)
C222	−0.1177 (5)	1.3121 (3)	0.59578 (10)	0.0257 (8)
O221	−0.2291 (4)	1.2415 (2)	0.60677 (10)	0.0453 (8)
O222	−0.1500 (4)	1.40394 (18)	0.59728 (9)	0.0371 (7)
C223	0.1699 (5)	1.3538 (3)	0.55727 (11)	0.0267 (8)
C224	0.0916 (5)	1.3735 (3)	0.51116 (11)	0.0234 (8)
O223	−0.0138 (3)	1.31679 (18)	0.49232 (7)	0.0296 (6)
O224	0.1570 (3)	1.45686 (17)	0.49261 (7)	0.0283 (6)
N23	0.1665 (4)	1.0155 (2)	0.54696 (8)	0.0179 (6)
C23	0.1254 (5)	1.0283 (2)	0.49871 (10)	0.0236 (7)
C24	0.2493 (4)	0.9257 (2)	0.56066 (10)	0.0189 (7)
O24	0.2923 (3)	0.86121 (17)	0.53267 (7)	0.0229 (5)
C25	0.2813 (4)	0.9159 (2)	0.60906 (10)	0.0184 (7)
N25	0.3485 (4)	0.8254 (2)	0.62120 (9)	0.0205 (6)
O25	0.3798 (3)	0.81102 (18)	0.66367 (7)	0.0240 (5)
C26	0.2463 (4)	1.0029 (2)	0.63769 (10)	0.0167 (7)
N26	0.2848 (4)	1.0009 (2)	0.68087 (8)	0.0201 (6)
O1	0.4270 (3)	0.66524 (18)	0.55405 (8)	0.0297 (6)
O2	0.7524 (3)	0.96926 (16)	0.27425 (7)	0.0206 (5)
O3	1.0547 (3)	0.86206 (17)	0.31114 (7)	0.0252 (5)
O4	0.5677 (4)	0.5247 (2)	0.61381 (9)	0.0295 (8)	0.883 (5)
O5	0.4768 (3)	0.3244 (2)	0.62752 (8)	0.0282 (8)	0.883 (5)
O6	0.482 (3)	0.4608 (15)	0.6348 (7)	0.025 (6)*	0.117 (5)
H12	0.5872	0.8498	0.2848	0.018*
H121	0.5719	0.8128	0.2127	0.018*
H12A	0.5993	0.6080	0.2433	0.020*
H12B	0.6133	0.6397	0.1913	0.020*
H124	1.0325	0.7855	0.2202	0.038*
H13A	0.6747	0.8750	0.3581	0.036*
H13B	0.5244	0.8997	0.3949	0.036*
H13C	0.4932	0.9295	0.3431	0.036*
H16A	0.2350	0.4874	0.2942	0.024*
H16B	0.1889	0.4670	0.3435	0.024*
H22	0.0138	1.1754	0.5339	0.024*
H221	0.1310	1.2640	0.6133	0.029*
H21E	−0.3430	1.2771	0.6131	0.054*
H22A	0.1724	1.4186	0.5745	0.032*
H22B	0.2945	1.3301	0.5537	0.032*
H224	0.1427	1.4760	0.4574	0.034*
H23A	0.1708	0.9695	0.4818	0.035*
H23B	0.1821	1.0908	0.4875	0.035*
H23C	−0.0040	1.0333	0.4947	0.035*
H26A	0.2638	1.0548	0.6978	0.024*
H26B	0.3315	0.9456	0.6929	0.024*
H1A	0.3933	0.7158	0.5728	0.036*
H1B	0.4535	0.6115	0.5718	0.036*
H2A	0.8628	0.9476	0.2813	0.025*
H2B	0.7449	1.0340	0.2842	0.025*
H3A	1.1437	0.8425	0.2885	0.030*
H3B	1.0059	0.7971	0.3220	0.030*
H4A	0.6697	0.4900	0.6093	0.035*	0.883 (5)
H4B	0.5861	0.5639	0.6384	0.035*	0.883 (5)
H5A	0.4013	0.3083	0.6536	0.034*	0.883 (5)
H5B	0.4671	0.3987	0.6242	0.034*	0.883 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0223 (4)	0.0216 (3)	0.0180 (3)	−0.0003 (3)	0.0002 (3)	−0.0044 (3)
N11	0.0151 (14)	0.0150 (12)	0.0128 (12)	−0.0032 (11)	0.0019 (10)	0.0003 (10)
C12	0.0130 (16)	0.0182 (15)	0.0124 (14)	0.0049 (13)	0.0006 (12)	0.0006 (12)
N12	0.0151 (13)	0.0156 (13)	0.0144 (12)	−0.0028 (11)	−0.0003 (10)	0.0002 (10)
C122	0.0190 (17)	0.0183 (15)	0.0140 (14)	−0.0021 (13)	0.0002 (13)	0.0076 (12)
C121	0.0155 (16)	0.0165 (15)	0.0134 (15)	−0.0018 (13)	0.0012 (12)	0.0018 (12)
O121	0.0160 (11)	0.0184 (11)	0.0231 (11)	0.0023 (10)	0.0029 (9)	0.0045 (10)
O122	0.0217 (12)	0.0251 (12)	0.0160 (11)	−0.0013 (10)	−0.0011 (9)	0.0012 (10)
C123	0.0182 (16)	0.0199 (16)	0.0115 (14)	0.0016 (13)	0.0011 (13)	0.0004 (11)
C124	0.0145 (16)	0.0242 (16)	0.0127 (14)	0.0027 (14)	0.0050 (12)	0.0022 (13)
O123	0.0185 (13)	0.0309 (14)	0.0291 (13)	0.0073 (11)	0.0052 (10)	0.0114 (11)
O124	0.0181 (13)	0.0239 (12)	0.0336 (13)	−0.0009 (10)	−0.0003 (11)	0.0046 (10)
N13	0.0210 (15)	0.0164 (13)	0.0139 (13)	−0.0020 (11)	0.0009 (11)	−0.0009 (10)
C13	0.033 (2)	0.0173 (17)	0.0212 (17)	−0.0100 (15)	0.0040 (15)	−0.0040 (13)
C14	0.0148 (17)	0.0201 (16)	0.0152 (15)	0.0021 (13)	0.0021 (13)	0.0027 (12)
O14	0.0283 (14)	0.0258 (13)	0.0134 (11)	−0.0026 (10)	0.0002 (9)	−0.0030 (9)
C15	0.0194 (18)	0.0174 (15)	0.0122 (14)	0.0025 (13)	−0.0011 (12)	−0.0003 (12)
O15	0.0287 (13)	0.0188 (11)	0.0190 (11)	−0.0055 (10)	0.0037 (10)	0.0003 (9)
N15	0.0214 (15)	0.0163 (13)	0.0186 (13)	0.0012 (12)	0.0027 (12)	0.0030 (11)
C16	0.0166 (17)	0.0173 (15)	0.0148 (15)	0.0019 (13)	−0.0013 (12)	0.0009 (12)
N16	0.0259 (16)	0.0194 (14)	0.0141 (13)	−0.0057 (12)	0.0033 (12)	−0.0015 (11)
N21	0.0244 (16)	0.0162 (13)	0.0141 (13)	0.0020 (12)	0.0003 (11)	−0.0008 (10)
C22	0.0174 (17)	0.0163 (15)	0.0170 (15)	−0.0041 (13)	0.0031 (13)	−0.0005 (12)
N22	0.0319 (16)	0.0163 (14)	0.0122 (12)	−0.0012 (13)	−0.0036 (11)	−0.0006 (11)
C221	0.046 (2)	0.0145 (16)	0.0124 (15)	0.0007 (15)	−0.0020 (15)	0.0017 (13)
C222	0.043 (2)	0.0199 (16)	0.0144 (15)	0.0063 (16)	0.0046 (15)	0.0051 (13)
O221	0.0403 (18)	0.0273 (15)	0.068 (2)	0.0030 (13)	0.0226 (15)	0.0006 (14)
O222	0.0456 (17)	0.0220 (13)	0.0436 (16)	0.0090 (12)	−0.0072 (14)	−0.0034 (11)
C223	0.037 (2)	0.0231 (17)	0.0203 (17)	−0.0030 (16)	−0.0030 (15)	0.0028 (14)
C224	0.0235 (19)	0.0244 (17)	0.0222 (17)	0.0001 (14)	0.0044 (14)	0.0009 (14)
O223	0.0373 (14)	0.0290 (13)	0.0224 (12)	−0.0109 (12)	−0.0083 (11)	0.0051 (11)
O224	0.0414 (15)	0.0254 (12)	0.0180 (11)	−0.0124 (11)	−0.0013 (11)	0.0078 (10)
N23	0.0193 (15)	0.0185 (14)	0.0160 (13)	0.0005 (11)	0.0009 (11)	−0.0044 (10)
C23	0.031 (2)	0.0244 (16)	0.0151 (15)	0.0016 (15)	−0.0033 (15)	−0.0027 (13)
C24	0.0187 (18)	0.0203 (16)	0.0177 (15)	−0.0059 (14)	0.0022 (13)	−0.0035 (13)
O24	0.0283 (14)	0.0202 (12)	0.0203 (12)	0.0010 (10)	0.0016 (10)	−0.0070 (10)
C25	0.0208 (18)	0.0162 (16)	0.0184 (15)	−0.0031 (14)	0.0009 (13)	−0.0028 (13)
N25	0.0231 (15)	0.0180 (13)	0.0204 (13)	−0.0017 (12)	−0.0014 (12)	−0.0012 (11)
O25	0.0332 (14)	0.0201 (11)	0.0187 (11)	0.0043 (11)	−0.0016 (10)	−0.0009 (10)
C26	0.0163 (17)	0.0155 (15)	0.0183 (15)	−0.0034 (13)	0.0007 (13)	0.0006 (12)
N26	0.0308 (17)	0.0142 (13)	0.0153 (13)	0.0060 (12)	−0.0001 (12)	−0.0018 (11)
O1	0.0371 (15)	0.0257 (13)	0.0261 (13)	0.0121 (12)	−0.0029 (11)	−0.0066 (10)
O2	0.0202 (12)	0.0177 (11)	0.0240 (12)	0.0010 (10)	−0.0004 (10)	0.0012 (9)
O3	0.0285 (14)	0.0225 (12)	0.0245 (12)	−0.0007 (11)	0.0042 (10)	0.0001 (10)
O4	0.0360 (18)	0.0270 (16)	0.0254 (15)	0.0130 (13)	0.0018 (12)	−0.0008 (12)
O5	0.0247 (16)	0.0342 (17)	0.0256 (15)	0.0034 (13)	0.0062 (11)	0.0033 (12)

Geometric parameters (Å, º)

K1—O1	2.758 (2)	N12—C121	1.466 (4)
K1—O14	2.944 (2)	N12—H12	0.88
K1—O24	2.709 (2)	C122—C121	1.534 (4)
K1—N15	2.902 (3)	C121—C123	1.519 (4)
N11—C12	1.321 (4)	C121—H121	1.00
C12—N13	1.386 (4)	C123—C124	1.498 (4)
N13—C14	1.394 (4)	C123—H12A	0.99
C14—C15	1.466 (4)	C123—H12B	0.99
C15—C16	1.459 (4)	O124—H124	1.12
C16—N11	1.338 (4)	C13—H13A	0.98
C12—N12	1.338 (4)	C13—H13B	0.98
N13—C13	1.466 (4)	C13—H13C	0.98
C14—O14	1.231 (4)	N16—H16A	0.88
C15—N15	1.324 (4)	N16—H16B	0.88
O15—N15	1.300 (3)	N22—C221	1.442 (4)
C16—N16	1.309 (4)	N22—H22	0.88
C122—O121	1.275 (4)	C221—C222	1.502 (5)
C122—O122	1.246 (4)	C221—C223	1.523 (5)
C124—O123	1.211 (4)	C221—H221	1.00
C124—O124	1.330 (4)	O221—H21E	0.99
K1—O1^i	2.885 (3)	C223—C224	1.507 (5)
K1—O14^i	2.832 (2)	C223—H22A	0.99
K1—O24^i	2.838 (2)	C223—H22B	0.99
K1—O224^ii	3.085 (2)	O224—H224	1.08
N21—C22	1.325 (4)	C23—H23A	0.98
C22—N23	1.381 (4)	C23—H23B	0.98
N23—C24	1.390 (4)	C23—H23C	0.98
C24—C25	1.458 (4)	N26—H26A	0.88
C25—C26	1.445 (4)	N26—H26B	0.88
C26—N21	1.342 (4)	O1—H1A	0.90
C22—N22	1.329 (4)	O1—H1B	0.90
N23—C23	1.470 (4)	O2—H2A	0.90
C24—O24	1.226 (4)	O2—H2B	0.90
C25—N25	1.337 (4)	O3—H3A	0.98
N25—O25	1.292 (3)	O3—H3B	0.98
C26—N26	1.310 (4)	O4—H4A	0.90
C222—O221	1.287 (4)	O4—H4B	0.90
C222—O222	1.228 (4)	O5—H5A	0.98
C224—O223	1.220 (4)	O5—H5B	0.98
C224—O224	1.316 (4)
O24—K1—O1	62.35 (7)	O15—N15—K1	117.13 (17)
O24—K1—O14^i	77.19 (7)	C15—N15—K1	120.5 (2)
O1—K1—O14^i	92.44 (7)	N16—C16—N11	118.1 (3)
O24—K1—O24^i	135.10 (7)	N16—C16—C15	120.9 (3)
O1—K1—O24^i	150.98 (8)	N11—C16—C15	121.0 (3)
O14^i—K1—O24^i	74.02 (7)	C16—N16—H16A	120.0
O24—K1—O1^i	84.65 (7)	C16—N16—H16B	120.0
O1—K1—O1^i	146.56 (5)	H16A—N16—H16B	120.0
O14^i—K1—O1^i	84.82 (7)	C22—N21—C26	118.8 (3)
O24^i—K1—O1^i	59.27 (7)	N21—C22—N22	119.2 (3)
O24—K1—N15	128.78 (7)	N21—C22—N23	124.6 (3)
O1—K1—N15	103.53 (7)	N22—C22—N23	116.2 (3)
O14^i—K1—N15	153.65 (8)	C22—N22—C221	123.4 (3)
O24^i—K1—N15	82.16 (7)	C22—N22—H22	118.3
O1^i—K1—N15	92.67 (7)	C221—N22—H22	118.3
O24—K1—O14	74.14 (6)	N22—C221—C222	112.9 (3)
O1—K1—O14	85.03 (7)	N22—C221—C223	110.4 (3)
O14^i—K1—O14	148.82 (3)	C222—C221—C223	111.5 (3)
O24^i—K1—O14	119.78 (7)	N22—C221—H221	107.3
O1^i—K1—O14	80.58 (7)	C222—C221—H221	107.3
N15—K1—O14	55.08 (7)	C223—C221—H221	107.3
O24—K1—O224^ii	144.68 (7)	O222—C222—O221	124.5 (4)
O1—K1—O224^ii	82.33 (7)	O222—C222—C221	120.6 (3)
O14^i—K1—O224^ii	106.30 (7)	O221—C222—C221	114.7 (3)
O24^i—K1—O224^ii	77.29 (7)	C222—O221—H21E	105.6
O1^i—K1—O224^ii	130.43 (7)	C224—C223—C221	113.1 (3)
N15—K1—O224^ii	56.50 (7)	C224—C223—H22A	109.0
O14—K1—O224^ii	104.15 (7)	C221—C223—H22A	109.0
C12—N11—C16	119.3 (3)	C224—C223—H22B	109.0
N11—C12—N12	117.3 (3)	C221—C223—H22B	109.0
N11—C12—N13	124.8 (3)	H22A—C223—H22B	107.8
N12—C12—N13	117.9 (3)	O223—C224—O224	123.8 (3)
C12—N12—C121	120.8 (3)	O223—C224—C223	124.1 (3)
C12—N12—H12	119.6	O224—C224—C223	112.0 (3)
C121—N12—H12	119.6	C224—O224—K1^iv	142.7 (2)
O122—C122—O121	125.5 (3)	C224—O224—H224	124.0
O122—C122—C121	118.1 (3)	K1^iv—O224—H224	78.6
O121—C122—C121	116.1 (3)	C22—N23—C24	120.6 (3)
N12—C121—C123	113.5 (2)	C22—N23—C23	121.0 (3)
N12—C121—C122	111.4 (2)	C24—N23—C23	118.3 (2)
C123—C121—C122	113.1 (3)	N23—C23—H23A	109.5
N12—C121—H121	106.1	N23—C23—H23B	109.5
C123—C121—H121	106.1	H23A—C23—H23B	109.5
C122—C121—H121	106.1	N23—C23—H23C	109.5
C124—C123—C121	114.7 (3)	H23A—C23—H23C	109.5
C124—C123—H12A	108.6	H23B—C23—H23C	109.5
C121—C123—H12A	108.6	O24—C24—N23	120.2 (3)
C124—C123—H12B	108.6	O24—C24—C25	124.0 (3)
C121—C123—H12B	108.6	N23—C24—C25	115.8 (3)
H12A—C123—H12B	107.6	C24—O24—K1	135.8 (2)
O123—C124—O124	123.2 (3)	C24—O24—K1^iii	128.2 (2)
O123—C124—C123	123.4 (3)	K1—O24—K1^iii	93.77 (7)
O124—C124—C123	113.5 (3)	N25—C25—C26	127.6 (3)
C124—O124—H124	112.7	N25—C25—C24	113.8 (3)
C12—N13—C14	120.7 (3)	C26—C25—C24	118.4 (3)
C12—N13—C13	120.6 (3)	O25—N25—C25	117.3 (3)
C14—N13—C13	118.7 (3)	N26—C26—N21	117.6 (3)
N13—C13—H13A	109.5	N26—C26—C25	121.0 (3)
N13—C13—H13B	109.5	N21—C26—C25	121.4 (3)
H13A—C13—H13B	109.5	C26—N26—H26A	120.0
N13—C13—H13C	109.5	C26—N26—H26B	120.0
H13A—C13—H13C	109.5	H26A—N26—H26B	120.0
H13B—C13—H13C	109.5	K1—O1—K1^iii	91.69 (7)
O14—C14—N13	120.4 (3)	K1—O1—H1A	93.7
O14—C14—C15	124.0 (3)	K1^iii—O1—H1A	90.0
N13—C14—C15	115.6 (3)	K1—O1—H1B	129.0
C14—O14—K1^iii	146.5 (2)	K1^iii—O1—H1B	133.5
C14—O14—K1	116.9 (2)	H1A—O1—H1B	106.2
K1^iii—O14—K1	89.02 (6)	H2A—O2—H2B	106.2
N15—C15—C16	127.2 (3)	H3A—O3—H3B	104.5
N15—C15—C14	114.2 (3)	H4A—O4—H4B	106.1
C16—C15—C14	118.6 (3)	H5A—O5—H5B	104.5
O15—N15—C15	118.0 (3)
N11—C12—N12—C121	2.0 (4)	C14—C15—C16—N16	179.0 (3)
C12—N12—C121—C122	57.6 (4)	N15—C15—C16—N11	177.8 (3)
C12—N12—C121—C123	−71.3 (4)	C14—C15—C16—N11	−1.0 (4)
N12—C121—C122—O121	38.6 (4)	C26—N21—C22—N22	179.6 (3)
N12—C121—C123—C124	−64.1 (3)	C26—N21—C22—N23	−1.6 (5)
C121—C123—C124—O123	147.8 (3)	N21—C22—N22—C221	15.5 (5)
C16—N11—C12—N12	177.1 (3)	C22—N22—C221—C222	−116.6 (3)
C16—N11—C12—N13	−2.9 (5)	C22—N22—C221—C223	117.9 (3)
N13—C12—N12—C121	−177.9 (3)	N22—C221—C222—O221	36.3 (4)
O122—C122—C121—N12	−147.5 (3)	N22—C221—C223—C224	60.5 (4)
O122—C122—C121—C123	−18.3 (4)	C221—C223—C224—O223	−17.3 (5)
O121—C122—C121—C123	167.7 (2)	N23—C22—N22—C221	−163.4 (3)
C122—C121—C123—C124	167.9 (2)	N22—C221—C222—O222	−148.5 (3)
C121—C123—C124—O124	−33.3 (3)	C223—C221—C222—O222	−23.6 (4)
N11—C12—N13—C14	2.7 (5)	C223—C221—C222—O221	161.2 (3)
N12—C12—N13—C14	−177.4 (3)	C222—C221—C223—C224	−65.9 (4)
N11—C12—N13—C13	−176.7 (3)	C221—C223—C224—O224	165.7 (3)
N12—C12—N13—C13	3.3 (4)	O223—C224—O224—K1^iv	108.3 (4)
C12—N13—C14—O14	177.7 (3)	C223—C224—O224—K1^iv	−74.7 (4)
C13—N13—C14—O14	−2.9 (5)	N21—C22—N23—C24	−2.2 (5)
C12—N13—C14—C15	−1.4 (4)	N22—C22—N23—C24	176.6 (3)
C13—N13—C14—C15	178.0 (3)	N21—C22—N23—C23	−177.4 (3)
N13—C14—O14—K1^iii	−68.2 (5)	N22—C22—N23—C23	1.5 (4)
C15—C14—O14—K1^iii	110.9 (4)	C22—N23—C24—O24	−172.6 (3)
N13—C14—O14—K1	154.8 (2)	C23—N23—C24—O24	2.7 (5)
C15—C14—O14—K1	−26.2 (4)	C22—N23—C24—C25	6.6 (4)
O24—K1—O14—C14	−162.7 (2)	C23—N23—C24—C25	−178.0 (3)
O1—K1—O14—C14	134.7 (2)	N23—C24—O24—K1	−92.8 (4)
O14^i—K1—O14—C14	−138.8 (2)	C25—C24—O24—K1	88.0 (4)
O24^i—K1—O14—C14	−29.4 (2)	N23—C24—O24—K1^iii	108.6 (3)
O1^i—K1—O14—C14	−75.6 (2)	C25—C24—O24—K1^iii	−70.6 (4)
N15—K1—O14—C14	24.4 (2)	O1—K1—O24—C24	−110.0 (3)
O224^ii—K1—O14—C14	53.9 (2)	O14^i—K1—O24—C24	−10.3 (3)
O24—K1—O14—K1^iii	39.42 (6)	O24^i—K1—O24—C24	40.8 (3)
O1—K1—O14—K1^iii	−23.22 (7)	O1^i—K1—O24—C24	75.6 (3)
O14^i—K1—O14—K1^iii	63.28 (16)	N15—K1—O24—C24	164.7 (3)
O24^i—K1—O14—K1^iii	172.72 (7)	O14—K1—O24—C24	157.3 (3)
O1^i—K1—O14—K1^iii	126.49 (7)	O224^ii—K1—O24—C24	−110.5 (3)
N15—K1—O14—K1^iii	−133.53 (10)	O1—K1—O24—K1^iii	53.29 (7)
O224^ii—K1—O14—K1^iii	−104.00 (7)	O14^i—K1—O24—K1^iii	152.99 (8)
O14—C14—C15—N15	2.6 (5)	O24^i—K1—O24—K1^iii	−155.93 (9)
N13—C14—C15—N15	−178.3 (3)	O1^i—K1—O24—K1^iii	−121.12 (7)
O14—C14—C15—C16	−178.4 (3)	N15—K1—O24—K1^iii	−31.99 (11)
N13—C14—C15—C16	0.7 (4)	O14—K1—O24—K1^iii	−39.42 (6)
C16—C15—N15—O15	0.7 (5)	O224^ii—K1—O24—K1^iii	52.80 (13)
C14—C15—N15—O15	179.5 (3)	O24—C24—C25—N25	−5.6 (5)
C16—C15—N15—K1	−155.3 (2)	N23—C24—C25—N25	175.2 (3)
C14—C15—N15—K1	23.5 (4)	O24—C24—C25—C26	171.7 (3)
O24—K1—N15—O15	170.80 (18)	N23—C24—C25—C26	−7.5 (4)
O1—K1—N15—O15	105.6 (2)	C26—C25—N25—O25	3.2 (5)
O14^i—K1—N15—O15	−20.2 (3)	C24—C25—N25—O25	−179.8 (3)
O24^i—K1—N15—O15	−45.4 (2)	C22—N21—C26—N26	179.7 (3)
O1^i—K1—N15—O15	−103.9 (2)	C22—N21—C26—C25	0.4 (5)
O14—K1—N15—O15	179.5 (2)	N25—C25—C26—N26	1.9 (5)
O224^ii—K1—N15—O15	34.47 (18)	C24—C25—C26—N26	−175.0 (3)
O24—K1—N15—C15	−33.0 (3)	N25—C25—C26—N21	−178.9 (3)
O1—K1—N15—C15	−98.3 (2)	C24—C25—C26—N21	4.2 (5)
O14^i—K1—N15—C15	136.0 (2)	O24—K1—O1—K1^iii	−51.92 (7)
O24^i—K1—N15—C15	110.7 (2)	O14^i—K1—O1—K1^iii	−126.08 (7)
O1^i—K1—N15—C15	52.2 (2)	O24^i—K1—O1—K1^iii	173.34 (11)
O14—K1—N15—C15	−24.3 (2)	O1^i—K1—O1—K1^iii	−41.78 (13)
O224^ii—K1—N15—C15	−169.4 (3)	N15—K1—O1—K1^iii	75.04 (7)
C12—N11—C16—N16	−178.0 (3)	O14—K1—O1—K1^iii	22.77 (6)
C12—N11—C16—C15	2.1 (4)	O224^ii—K1—O1—K1^iii	127.80 (7)
N15—C15—C16—N16	−2.2 (5)

Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x, y−1, z; (iii) x+1/2, −y+3/2, −z+1; (iv) x, y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12···O2	0.88	2.02	2.852 (3)	157
O124—H124···O121^v	1.12	1.45	2.570 (3)	172
N16—H16A···O2^vi	0.88	2.04	2.910 (3)	170
N16—H16B···O15	0.88	1.99	2.634 (3)	129
N22—H22···O223	0.88	2.23	2.781 (3)	120
O221—H21E···O5^vii	0.99	1.55	2.534 (4)	174
O224—H224···O15^iv	1.08	1.44	2.502 (3)	167
N26—H26A···O121^viii	0.88	2.02	2.875 (3)	164
N26—H26B···O25	0.88	2.00	2.637 (3)	129
N26—H26B···O123^i	0.88	2.25	2.989 (3)	141
O1—H1A···N25	0.90	2.06	2.949 (3)	172
O1—H1B···O4	0.90	1.89	2.762 (3)	163
O2—H2A···O3	0.90	2.03	2.881 (3)	158
O2—H2B···O122^ix	0.90	2.02	2.918 (3)	174
O3—H3A···O121^v	0.98	1.86	2.771 (3)	154
O3—H3B···O25^iii	0.98	1.76	2.723 (3)	169
O4—H4A···O222^x	0.90	1.80	2.687 (4)	171
O4—H4B···O3^i	0.90	1.80	2.672 (3)	164
O5—H5A···O122^xi	0.98	1.81	2.719 (3)	153
O5—H5B···O4	0.98	1.84	2.741 (4)	151

Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (iii) x+1/2, −y+3/2, −z+1; (iv) x, y+1, z; (v) x+1, y, z; (vi) −x+1, y−1/2, −z+1/2; (vii) x−1, y+1, z; (viii) −x+1/2, −y+2, z+1/2; (ix) −x+1, y+1/2, −z+1/2; (x) x+1, y−1, z; (xi) −x+1/2, −y+1, z+1/2.