Stoichiometry-dependent structures: an X-ray and neutron single-crystal diffraction study of the effect of reaction stoichiometry on the crystalline products formed in the potassium–cyanurate system

Reaction of cyanuric acid (C₃H₃N₃O₃; neutral form CYH₃; anionic form CYH; dianionic form CYH²⁻) with K₂CO₃ or KOH in aqueous solution gave three different crystalline products, according to the reaction stoichiometry used. The structures of two products were easily determined by single-crystal X-ray diffraction: [K(CYH₂)(H₂O)], (1), of which the crystal structure is already known [Marsh, R. E. et al. (2002). Acta Cryst. B58, 62–77], and [K₂(CYH)], (2), a highly symmetrical and dense structure. Further stoichiometric variation produced another new complex, (3), and reaction of Rb₂CO₃ with CYH₃ yielded a further product, (4), which was found to be isostructural with (3). Determination of the structures of (3) and (4) by X-ray diffraction gave a result that was chemically unreasonable owing to a charge imbalance, with the asymmetric unit apparently containing 2− against 1.5+ (partial charges as the result of crystallographic mirror symmetry). A single-crystal neutron diffraction analysis carried out on a fully deuterated sample of (3) revealed the presence of a supercell, with the c axis doubled compared with the X-ray result. Subsequent refinement of the structure with this supercell showed that it is the result of just two D atoms breaking crystallographically imposed mirror symmetry, which is otherwise essentially observed by the rest of the structure. This minor deviation from pseudo-symmetry could not be identified by X-ray diffraction. Thus, single-crystal neutron diffraction data revealed that the true chemical formula of the structure of (3) [and presumably also of the isostructural (4) with Rb instead of K and H instead of D], is [K₃(C₃D₂N₃O₃)₃(C₃D₃N₃O₃)(D₂O)₄], the deuterated form of [K₃(CYH₂)₃(CYH₃)(H₂O)₄].

1. Introduction

Cyanuric acid (C₃H₃N₃O₃; neutral form CYH₃; anionic form CYH; dianionic form CYH²⁻) is a sturdy, robust and relatively unreactive small molecule which nevertheless has had a diverse role to play in chemistry, particular with regard to commercial or industrial use, for many years. It has featured in products ranging from flame retardants (Blount, 2000) and plant growth feed (Hudec et al., 1987) to a catalyst for NO_x removal from exhaust gases (Siebers & Caton, 1990) and lavatory cleaning blocks (Barford et al., 1989). It is a mildly acidic compound with pK_a values of 6.85, 10.91 and >12 for the generation of the mono-, di- and trianionic forms, respectively (Aoki et al., 2000); whilst mono-deprotonation is easily achieved and double deprotonation can be achieved by careful control of the reaction equilibrium, triple deprotonation is much more uncommon and forms unstable complexes.

Despite the relative ease with which CYH₃ can be singly deprotonated its use as an anionic ligand in coordination chemistry has so far been surprisingly restricted. With a few exceptions, reported coordination complexes have largely been confined to the first-row transition elements (Falvello et al., 1999, 1995, 1997; Server-Carrio et al., 1998; Slade et al., 1973) with the notable exception of work on silver complexes (Brunner et al., 2001; Munakata et al., 2001a,b; Rao et al., 2000). Of particular interest is work by Aoki et al. (2000) detailing the synthesis and structural characterization of macrocycle-stabilized zinc complexes of CYH₃ in all three anionic forms.

By contrast to its coordination chemistry, the use of CYH₃ in organic supramolecular chemistry has been investigated to a far deeper level. The molecule has D_3h symmetry and is a complementary hydrogen-bond partner for melamine, which also has D_3h symmetry, forming very strong hydrogen bonds. The formation of these bonds is predictable and reliable and has been well exploited in the formation of supramolecular compounds (Arduini et al., 2003; Berl et al., 2002; Felix et al., 2003; Mascal et al., 1999; Seto et al., 1993; Seto & Whitesides, 1993; Whitesides et al., 1995; Zerkowski et al., 1994). One-dimensional and two-dimensional motifs predominate throughout.

We became interested in the coordination chemistry of CYH₃ as part of our work on s-block metal complexes of pyridones, barbiturates and related ligands (Nichol & Clegg, 2006a,b). Whilst the composition of coordination complexes of all the alkaline-earth metals, and most of the alkali metals, is independent of the reaction stoichiometry used, we found that the potassium and caesium reaction systems were sensitive to the relative amounts of acid and base used. In particular, three different potassium cyanurate complexes can by obtained by simple variation of the amount of base used in the reaction. Whilst two of these complexes are straightforward with metal–ligand ratios of 1:1 {[K(CYH₂)(H₂O)]_∞, compound (1)} and 2:1 {[K₂(CYH)]_∞, compound (2)}, the initial formulation of a third complex, [K₃(CYD₂)₃(CYD₃)(D₂O)₄]_∞, (3), exhibited charge balance problems as the number of potassium cations did not equal the number of cyanurate anions in the asymmetric unit. The equivalent rubidium analogue, [Rb₃(CYH₂)₃(CYH₃)(H₂O)₄]_∞, (4), was found to be isostructural with (3).

A single-crystal neutron diffraction data set was collected on a fully deuterated form of (3) in order to study the H-atom behaviour and hence to try to solve the charge balance problem. Crystals of (4) could not be grown large enough to permit neutron diffraction.

2. Experimental

2.1. Synthesis

2.1.1. Compound (1)

CYH₃ (0.132 g, 1 mmol, 1 equivalent) was dissolved in 30 ml of distilled water, with heating and stirring. Solid K₂CO₃ (0.142 g, 1 mmol, 2 equivalents) was added to the reaction solution, resulting in instant effervescence. The solution was boiled until ca 15 ml remained, when the hot solution was transferred to a fresh sample vial, sealed and allowed to stand at room temperature. Large colourless crystals of (1) grew over a period of 2–3 d (0.076 g, 40%). CHN analysis found: C 19.59, H 1.92, N 22.18%; calc.: C 19.46, H 2.18, N 22.69%.

2.1.2. Compound (2)

CYH₃ (0.134 g, 1 mmol, 1 equivalent) was dissolved in 30 ml of water along with KOH (0.27 g, 4.8 mmol, 4.8 equivalents). The reaction mixture was boiled until everything had dissolved. Slow evaporation of a small portion of the solution on a watchglass at room temperature yielded colourless crystals of (2). The amount of product obtained was too small to permit calculation of the yield or CHN analysis.

2.1.3. Compound (3)

Under an atmosphere of dry nitrogen, CYH₃ (0.134 g, 1 mmol, 1 equivalent) was dissolved in 30 ml of deuterated water, with heating. Solid K₂CO₃ (0.071 g, 0.5 mmol, 0.5 equivalents) was added; the solution was boiled until all the solid reagents had dissolved and was then allowed to stand, undisturbed, at room temperature. Very large colourless block crystals of (3) formed over a period of around 1 week (0.059 g, 17%). CDN analysis found: C 19.91, D 4.51, N 22.88%; calc.: C 20.02, D 4.74, N 23.36%.

2.1.4. Compound (4)

Rb₂CO₃ (0.309 g, 1.3 mmol, 1 equivalent) and CYH₃ (0.356 g, 2.75 mmol, 2.1 equivalent) were dissolved in 40 ml of boiling water. After 5 min of boiling the heat was removed and the flask sealed. A crop of large colourless crystals of (4) grew over a period of 2 d (0.111 g, 10.16%). CHN analysis found: C 17.25, H 1.91, N 20.40%; calc.: C 17.12, H 2.03, N 19.97%.

2.2. Crystallography

2.2.1. Single-crystal X-ray diffraction

Crystallographic experimental parameters for all data collections are summarized in Table 1.¹ Tables 2–5 give details of selected geometric and hydrogen-bonding parameters. Details of the single-crystal neutron data collection are given in the following paragraph. For the X-ray data sets, data collection and reduction was by COLLECT (Nonius, 1999) and EvalCCD (Duisenberg et al., 2003) for (1), or SMART and SAINT (Bruker, 2001) for (2)–(4). For all four structures semi-empirical absorption correction from symmetry-equivalent and repeated reflections was by SADABS (Sheldrick, 2003); structure solution (direct methods) and refinement was by SHELXTL (Sheldrick, 2001), using all unique F² values. DIAMOND3 (Brandenburg & Putz, 2004) and WinGX (Farrugia, 1999) were used to produce the molecular graphics.

Table 1
Summary of crystallographic experimental parameters for all data collections

	(1)	(2)	(3) X-ray	(3) neutron	(4)
Crystal data
Chemical formula	C3H4KN3O4	C3HK2N3O3	C12D17K3N12O16	C12D17K3N12O16	C12H16N12O16Rb3
Mr	185.19	205.27	719.71	719.71	840.78
Cell setting, space group	Monoclinic, C2/m	Orthorhombic, Cmcm	Monoclinic, C2/m	Monoclinic, I2/a	Monoclinic, C2/m
Temperature (K)	150 (2)	150 (2)	150 (2)	150 (2)	150 (2)
a, b, c (Å)	11.037 (2), 16.419 (3), 7.1497 (14)	13.062 (4), 6.620 (2), 6.817 (2)	12.8143 (15), 16.3214 (19), 11.8498 (14)	12.824 (2), 16.332 (3), 23.713 (4)	13.1499 (15), 16.6185 (19), 11.8444 (13)
α, β, γ (°)	90.00, 103.68 (3), 90.00	90.00, 90.00, 90.00	90.00, 97.520 (2), 90.00	90.00, 97.514 (3), 90.00	90.00, 99.584 (2), 90.00
V (Å^3)	1258.9 (4)	589.4 (3)	2457.0 (5)	4923.8 (15)	2552.2 (5)
Z	8	4	4	8	4
Dx (Mg m^−3)	1.954	2.313	1.946	1.942	2.188
Radiation type	Mo Kα	Mo Kα	Mo Kα	Neutron	Mo Kα
μ (mm^−1)	0.81	1.55	0.66	0.0652 + 0.00475	5.83
Crystal form, colour	Block, colourless	Block, colourless	Plate, colourless	Block, colourless	Plate, colourless
Crystal size (mm)	0.22 × 0.16 × 0.11	0.23 × 0.21 × 0.18	0.70 × 0.20 × 0.05	2.00 × 2.00 × 1.00	0.20 × 0.20 × 0.05
Data collection
Diffractometer	Nonius KappaCCD diffractometer	Bruker SMART 1K CCD diffractometer	Bruker SMART 1K CCD diffractometer	SXD at ISIS neutron source	Bruker SMART 1K CCD diffractometer
Data collection method	φ and ω scans	Thin-slice ω scans	Thin-slice ω scans	Time-of-flight Laue diffraction	Thin-slice ω scans
Absorption correction	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)	Numerical	Multi-scan (based on symmetry-related measurements)
Tmin	0.842	0.716	0.655	0.123	0.388
Tmax	0.916	0.767	0.968	0.497	0.759
No. of measured, independent and observed reflections	10 612, 1216, 982	2536, 412, 370	10 491, 2926, 2425	8194, 2545, 2535	9291, 2324, 1898
Criterion for observed reflections	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)
Rint	0.088	0.028	0.029	0.091	0.045
θmax (°)	25.5	28.3	28.5	Resolution 0.37 Å	25.0
Refinement
Refinement on	F^2	F^2	F^2	F^2	F^2
R[F^2> 2σ(F^2)], wR(F^2), S	0.058, 0.151, 1.06	0.024, 0.064, 1.15	0.034, 0.095, 1.07	0.068, 0.182, 1.03	0.034, 0.077, 1.14
No. of reflections	1216	412	2926	8194	2324
No. of parameters	121	38	232	651	229
H/D-atom treatment	Only coordinates refined	Refined independently	Only coordinates refined	Anisotropic	Constrained to parent site
Weighting scheme	w = 1/[σ^2(Fo^2) + (0.1091P)^2] where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0329P)^2 + 0.7482P] where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0557P)^2 + 1.2767P] where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.1144P)^2 + 438.2559P] where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0253P)^2 + 9.2128P] where P = (Fo^2 + 2Fc^2)/3
(Δ/σ)max	<0.0001	<0.0001	0.001	0.048	<0.0001
Δρmax, Δρmin (e Å^−3)	0.85, −0.93	0.26, −0.48	0.64, −0.45	2.01, −2.20	0.97, −0.98
Extinction method	None	None	None	SHELXL97	None
Extinction coefficient	–	–	–	8.3 (3) × 10^−5	–
Computer programs: COLLECT (Nonius, 1999), SMART (Bruker, 2001), SXD2001 (Gutmann & Wilson, 2001), EvalCCD (Duisenberg et al., 2003), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2001) and local programs.

Table 2
Selected bond lengths (Å) for (1)

K1—O1	2.780 (2)	K1—O4^ii	2.726 (18)
K1—O5	2.855 (4)	K1—O6	2.696 (4)
K1—O6^i	3.079 (4)	K2—O3	2.932 (2)
K2—O5	2.738 (3)	K2—O5^iii	2.979 (4)
K2—O6	2.859 (4)	K2—N2^iv	3.014 (2)
K2—N3	3.010 (3)	O1—C1	1.218 (5)
O2—C2	1.258 (4)	O3—C3	1.250 (3)
O4—C4	1.228 (5)
Symmetry codes: (i) -x, -y, -z; (ii) ; (iii) -x+1, -y, -z+1; (iv) .

Table 3
Selected bond lengths (Å) in (2)

K—O1	2.7688 (13)	K—O1^i	2.8773 (14)
K—N2^ii	3.0390 (15)	K—O2^iii	2.9058 (8)
O1—C1	1.263 (2)	O2—C2	1.278 (4)
Symmetry codes: (i) ; (ii) ; (iii) .

Table 4
Selected bond lengths (Å) in the neutron-determined structure of (3)

K1—O1	2.965 (15)	K1—O1^i	2.91 (2)	O1—C1	1.240 (9)
K1—O4	3.01 (2)	K1—O4^i	2.975 (13)	O2—C2	1.244 (12)
K1—O9^ii	2.863 (16)	K1—O12^iii	2.857 (17)	O3—C3	1.207 (12)
K1—O15	2.762 (9)	K1—O16	2.841 (15)	O4—C4	1.209 (9)
K2—O8^iv	2.751 (16)	K2—O7	2.84 (2)	O5—C5	1.262 (14)
K2—O11^v	2.853 (19)	K2—O10	2.800 (15)	O6—C6	1.240 (12)
K2—O15	2.761 (14)	K2—O14	2.816 (12)	O7—C7	1.256 (11)
K3—O3^vi	2.831 (16)	K3—O11^v	2.748 (18)	O8—C8	1.213 (11)
K3—O7	2.833 (18)	K3—O13	2.707 (16)	O9—C9	1.230 (11)
O10—C10	1.278 (12)	O11—C11	1.209 (9)	O12—C12	1.255 (12)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) -x+1, -y+2, -z+1; (v) -x+1, -y+1, -z+1; (vi) .

Table 5
Hydrogen-bonding geometry (Å, °) in the neutron-determined structure of (3)

D—D⋯A	D—D	D⋯A	D⋯A	D—D⋯A
N1—D1⋯O9^ii	1.017 (11)	1.796 (11)	2.809 (10)	174 (1)
N3—D3⋯O10^i	1.054 (12)	1.701 (13)	2.734 (12)	165 (2)
N4—D4⋯O8^iv	1.027 (11)	1.787 (11)	2.807 (10)	171 (2)
N5—D5⋯O16^vii	1.059 (7)	1.654 (11)	2.690 (12)	165 (1)
N6—D6⋯O12^viii	1.060 (10)	1.681 (11)	2.738 (11)	175 (1)
N7—D7⋯O5^iv	1.043 (12)	1.708 (12)	2.746 (12)	173 (1)
N9—D9⋯O2^vii	1.034 (11)	1.736 (12)	2.763 (11)	172 (1)
N10—D10⋯O3^i	1.022 (10)	1.804 (11)	2.825 (10)	178 (1)
N11—D11⋯O6^ix	1.022 (11)	1.821 (13)	2.828 (11)	168 (1)
O13—D13A⋯N8^vii	0.968 (12)	1.866 (12)	2.830 (12)	174 (1)
O14—D14A⋯O2^vii	0.964 (12)	1.838(12)	2.756(13)	158 (1)
O14—D14B⋯O6^vi	0.959 (11)	1.866 (12)	2.768(13)	156 (1)
O15—D15A⋯N12^iii	0.945 (11)	2.123 (12)	3.042(12)	164 (1)
O15—D15B⋯N8^ii	0.946 (12)	2.190 (15)	3.098(11)	160 (1)
O16—D16A⋯N2^x	0.964 (10)	1.771 (8)	2.733(12)	175 (1)
O16—D16A⋯O3^x	0.964 (10)	2.705 (11)	3.293(13)	120 (1)
O16—D16B⋯O13^xi	0.969 (6)	1.895 (7)	2.864(6)	178 (1)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) -x+1, -y+2, -z+1; (vi) ; (vii) ; (viii) ; (ix) ; (x) ; (xi) x-1,y,z.

2.2.2. Single-crystal neutron diffraction

Very large deuterated crystals (by normal X-ray diffraction standards) of compound (3) were prepared for the collection of a single-crystal neutron diffraction data set on instrument SXD at the ISIS spallation neutron source, Rutherford Appleton Laboratories, Oxfordshire, UK (https://www.isis.rl.ac.uk/crystallography/sxd/ ). SXD uses the time-of-flight Laue technique to obtain reflections from large amounts of reciprocal space in a single measurement with a stationary crystal (Wilson, 2005; Keen et al., 2006). Data were collected from eight crystal orientations to a resolution of 0.37 Å, each experiment taking around 10 h, giving a total data collection time of just over 3 d.

The program SXD-2001 (Gutmann & Wilson, 2001) was used to collect and process the neutron diffraction data. The structure was determined by using trial structures determined by X-ray analysis as a starting point and the remaining atoms located by carrying out successive Fourier and least-squares refinements with SHELXTL.

Carrying out the reaction using D₂O as the solvent allows for deuterium–hydrogen exchange and incorporation of D₂O in the structure. Deuterated samples have three important advantages over standard samples. Firstly, deuterium scatters neutrons over twice as strongly as hydrogen, giving an improvement in the intensity of the diffracted neutron beams. Secondly, hydrogen is one of the few nuclei which scatters neutrons out-of-phase, giving holes rather than peaks in a difference map. This property allows for easy checking that full deuteration has taken place, and makes difference map analysis more straightforward. Finally, hydrogen contributes significantly to incoherent and background scattering; using deuterium significantly reduces this problem.

3. Results and discussion

3.1. Compound (1)

As noted in the Experimental section this compound was synthesized using equimolar amounts of K₂CO₃ and CYH₃. Thus, the K:CYH₃ ratio was 2:1. The crystal structure of this compound was first reported by Sysoeva et al. (1990) in space group Cm, subsequently corrected to C2/m by Marsh et al. (2002). We present here a low-temperature redetermination, for the purpose of comparison with the other compounds. The compound does indeed crystallize in space group C2/m and shows no structural effect as a result of the cooling, other than a slight reduction in unit-cell volume, consistent with the effect of reduced temperature. The structure is shown in Fig. 1. There are two crystallographically independent K⁺ cations and two crystallographically independent CYH anions in the asymmetric unit, along with two molecules of water. Both cations and both water molecules are located on crystallographic mirror planes, and both anions are located on twofold rotation axes, so there are few unique atoms in this highly symmetrical structure. The two independent potassium cations have rather different coordination environments. Atom K1 is coordinated exclusively by O atoms from the carbonyl groups of both anions, and also by both water molecules. By contrast K2 is coordinated by an even combination of N and O atoms (four each). Atoms K1 and K2 are bridged by both water molecules, whilst K1 is bridged to its symmetry equivalents via carbonyl O atoms only and K2 is bridged to its symmetry equivalents via N atoms only. Both K1 and K2 are related to their symmetry equivalents by twofold rotation axes, the same axes which also pass through the CYH anions. K—O and K—N bond lengths are unexceptional, as is the geometry of the CYH anions. Table 2 gives selected geometrical parameters for compound (1).

Figure 1 A partial packing diagram of (1). Displacement ellipsoids are drawn at the 50% probability level, and dashed lines indicate hydrogen bonding [symmetry codes (twofold rotation): (v) −x, y, −z; (vi) −x + 1, y, −z +1]. In all graphical representations of structures in the on-line version of the journal, bonds within ligands are orange, and bonds to metals are semi-transparent grey.

Alongside this extensive coordination is a degree of predictable hydrogen bonding. The R₂²(8) motif (Bernstein et al., 1995) linking the CYH₂⁻ anions together via N—H⋯O interactions is one of the most regular and persistent motifs in cyanuric structural chemistry (Falvello et al., 1997), so its appearance here, linking the anions into a tape, is unsurprising.

3.2. Compound (2)

As CYH₃ can be potentially deprotonated at all three NH sites we experimented with the reaction conditions to see if we could doubly deprotonate the acid and observe the effect on the coordination chemistry. The instability of CY³⁻ complexes has already been mentioned so we considered that a [K₃(CY)] complex would be difficult or impossible to synthesize. The relatively high pK_a of the second deprotonation meant that hydroxide was preferable to carbonate as base. Double deprotonation and the formation of [K₂(CYH)·xH₂O] was achieved using approximately 5:1 KOH:CYH in aqueous solution. Somewhat surprisingly, there is no water present in this compound and the structure is highly symmetrical, crystallizing in the orthorhombic space group Cmcm with only seven unique atoms in the asymmetric unit (Fig. 2).

Figure 2 The structure of (2). Displacement ellipsoids are drawn at the 50% probability level, and the unique hydrogen bond is marked by a dashed line. [Symmetry codes: (i) −x, y, −z + ; (ii) −x, −y + 1, z − .

Removal of the second proton means that the R₂²(8) motif is not formed and, as a result, this is one of only a handful of cyanuric structures not to feature this hydrogen-bonding motif. Instead there is a lone N—H⋯O interaction forming a C6 motif which, because of the crystallographic symmetry, links the anions into linear chains. As hydrogen bonding is of little importance now, the structure is held together by a very dense network of coordination bonds. The calculated crystal density is 2.313 Mg m⁻³ and there are only 30 other compounds which contain potassium as the only metal in the Cambridge Structural Database (version 5.27 with January 2006 update; Allen, 2002) with a higher density. Atom O1 links four potassium centres and N2 bridges across two potassium centres, whilst atom O2, as the hydrogen-bond acceptor, does not coordinate to the metal at all. The unique potassium centre is thus six-coordinate and its geometry can best be described as distorted pentagonal bipyramidal with one of the equatorial points removed. As with (1), the bond lengths and angles in this structure are unexceptional; selected bond lengths are given in Table 3.

A c-axis projection of the crystal packing (Fig. 3) shows quite neatly both the dense coordination bonding and its symmetrical nature in this structure. The CYH²⁻ rings are stacked along the c axis with a lateral displacement between adjacent rings of approximately 1/3 of a ring along the b axis. The stacking distance between the rings is approximately 3.4 Å; this distance and the ring displacement are good indicators of ring-stacking stabilization. However, given the extent of metal–ligand coordination in this structure, it is unlikely that the ring stacking is a significant directing influence in the crystal packing. The lone hydrogen bond runs parallel to the b axis but is omitted from Fig. 3.

Figure 3 The crystal packing of (2), projected along the c axis.

3.3. Compounds (3) and (4)

Our experiments with the reaction stoichiometry thus far yielded two different chemical compounds. We experimented with this ratio further by using 0.5 equivalents of K₂CO₃ with 1 equivalent of CYH₃ to give a K:CYH₃ ratio of 1:1. This change in reaction stoichiometry yielded a third complex, compound (3), this time with coordinated water. To be sure that this was not a one-off observation the reaction was repeated many times at both 1:1 and 2:1 K:CYH₃ with the same two results being achieved each time.

Compound (4), the rubidium analogue of (3), was also prepared. Unlike potassium, rubidium showed no change in the structure of the product as a result of varying the stoichoimetries and the same product resulted after many experiments with different reaction stoichoiometries. Compound (4) is isostructural with compound (3) but the crystals grown were not large enough for neutron diffraction, so only the X-ray structure was determined. Thus, the following discussion relates to (3) but the conclusions are equally applicable to (4). Table 1 contains a summary of the experimental parameters for (4).

The crystal structure of (3) as determined by X-ray diffraction is presented in Fig. 4. [The structure and subsequent discussions hereafter relate to a deuterated sample which was prepared especially for neutron diffraction and investigated also by X-ray diffraction to confirm that deuteration did not change the structure; although the initial discovery was made using data collected from a non-deuterated sample, it is the X-ray data pertaining to this deuterated structure which are reported.] The space group was determined as C2/m and three potassium cations and four water molecules lie on a crystallographic mirror plane. The atoms of the two CYH ligands all lie on general positions. It was quickly realized that the structure as determined did not make chemical sense. If all the cations are lying on a mirror plane, then they each can be considered to have a charge of 0.5+ in the asymmetric unit, giving an overall positive charge of 1.5+. By contrast each anion is singly deprotonated and so gives a total negative charge of 2−. Thus, the charges do not balance and there is 0.5+ missing somewhere. The difference-Fourier map contained no large peaks indicating a fourth unassigned potassium ion, so attention focused on the only other atoms that could affect the charge of the compound, the D atoms.

Figure 4 The apparent asymmetric unit of (3), as determined by X-ray diffraction. Displacement ellipsoids are drawn at the 50% probability level and the dashed line indicates a bond to a disordered D atom.

A difference-Fourier map of the environment around atoms N3 and N6 was examined for any indication of a missed H atom. As can be seen in Fig. 5, the residual electron density surrounding atom N3 is insignificant and is no greater than the electron density found within the bonds of the cyanurate ring. On the other hand, the residual electron density around the N6 atom is much clearer and more concentrated, more so than that around N3 and more so than the residual bonding electron density of the ligand. This indicated that an H atom might be located here. However, whilst selection of this peak as an H atom and refinement of its coordinates may improve the refinement result, it does not solve the chemical problem with the charges. Placing an H atom here results in a charge imbalance with 0.5+ in excess. In order to resolve this problem we tried two different approaches.

Figure 5 Difference-Fourier maps of both cyanurate rings in the X-ray-determined structure of (3), showing the residual electron density about N3 (top) and N6 (bottom).

(1) Assume that the mirror plane is only a pseudo-symmetry element and remove it, assigning the structure to space group C2. This assumption doubles the size of the asymmetric unit such that it contains three potassium centres (now in general positions), four cyanuric ligands and four water molecules, also in general positions. The strategy was then to examine difference Fourier maps for every cyanuric ligand to determine if one of the four definitely showed three strong N—D deuterium peaks whilst the other three showed only two strong N—D deuterium peaks.

This approach failed for two important reasons. Firstly, it was not overwhelmingly clear from any of the difference maps which ligand was C₃D₃N₃O₃ and which were C₃D₂N₃O₃. Secondly, the refinement of at least half the non-D atoms in the asymmetric unit was unstable, with many becoming `non-positive definite', indicating that the inversion centre should be present in the structural model to fit this set of data. Given the unconvincing Fourier analyses, and poor refinement of the anisotropic displacement parameters of several atoms that should be well defined, this model was rejected.

(2) Assume the mirror plane is a genuine symmetry element, requiring the additional `missing' H atom to be disordered on either side of it, with an occupancy of 50% on each site. This approach makes chemical sense, as the charges balance properly and no restraints were needed on any of the anisotropic displacement parameters. The final R1 value of 0.0335 implies that the problem had been resolved. However, this was not the case. Fig. 6 shows the result of applying the mirror plane on which the potassium cations and water molecules reside. Because of the mirror symmetry, water D atoms must be symmetry-equivalent and either both lie on the mirror plane or each lies on one side of it. The latter is apparently the case for all water molecules in this structure. However, as shown in Fig. 6, this brings D7 within a very close distance (1.31 Å) of the disordered D6N and its symmetry equivalent. No two D atoms can be brought this close in a correct structure; one would expect some sort of twisting of the water molecule to relieve the steric strain. However, such twisting would necessitate breaking the mirror symmetry and, as was noted above, a model in which the mirror symmetry is removed does not refine satisfactorily.

Figure 6 The result of applying the mirror symmetry element in the initial X-ray-determined structure of (3). The unacceptable steric interaction between atoms D6N and D7 is represented by a dashed line.

A more complicated model containing disordered water H atoms could also be constructed. Unfortunately, as the positions and occupancies of H atoms are unreliable when determined by X-ray diffraction, such a model would be unsuccessful.

In order to investigate further the behaviour of these D atoms we collected a full single-crystal neutron diffraction data set, with the aim of refining the occupancies of the D atoms. Several independent batches of deuterated complexes of (3) were prepared and taken to the ISIS neutron source for single-crystal neutron diffraction experiments. A crystal with a total volume of approximately 4 mm³ was selected and mounted. Initial tests showed good diffraction recorded on each detector, and even a relatively intense back-scattering was detected. To determine the unit cell, around 100 strong reflections were collected by each detector and the data were then indexed to automatically give a unit cell that matched that determined by X-ray analysis. When a sufficient amount of data had been collected to facilitate an attempt to refine the structure, a trial model was used based on the atomic coordinates from the X-ray structure. Starting without the D atoms, initial least-squares refinement was rather unsatisfactory, not particularly unusual since deuterium is the second strongest neutron scatter in this compound. As D atoms bonded to N1, N2, N4, N5 and all the water molecules, except for those on O7, were located in successive Fourier maps the refinement improved markedly to a respectable R1 = 0.1039. There remained, however, a lot of residual diffraction density around the O7 atom, with two very large peaks about 0.96 Å away from O7, subtending an angle of 113° at O7. One of these peaks was located exactly on the mirror plane; the second was not. Selection of these peaks as D atoms, followed by anisotropic least-squares refinement, further improved the result to R1 = 0.0756. This was, however, the best result that could be obtained with this unit cell and space group. The anisotropic displacement parameters of the D atoms attached to atom O7 remained rather unstable during further refinement cycles.

Aside from the steric crowding around this water molecule the charge balance problem still remained to be dealt with. Difference maps did show a relatively strong peak corresponding to a D atom bonded to N6. This peak was selected as deuterium and refined, with the site occupation factor for the atom freely refined. Rather than refining to give an occupancy of ∼0.5 and a sensible displacement ellipsoid, the occupancy refined to ∼1 with a rather large and elongated ellipsoid. Thus, simply using the trial model determined by X-ray analysis coupled with the data integrated so far did not as yet offer an acceptable explanation of the problem.

As data collection proceeded further it was noticed that there were many rather weak unindexed reflections with half-integer values of l. These suggest a supercell, corresponding to the unit cell with the c axis doubled in length. The data were thus reindexed on this supercell, and re-integrated. Examination of the new reflection data suggested that the space group could be either Ia or I2/a. Trial models without D atoms were created in both space groups then refined using this second set of neutron data. Refinement in Ia was very poor; however, refinement in I2/a was rather more satisfactory and, with the addition of D atoms, quickly converged. Least-squares restraints were used on some of the C and O atoms to control their anisotropic displacement parameters. The model now contained three potassium cations, four water molecules and four cyanuric ligands. Each cyanuric ligand was examined in turn using observed and difference-Fourier maps to identify which one was in fact neutral. As shown in Fig. 7, the ligand containing N4, N5 and N6 showed three distinct peaks corresponding to deuterium in the observed Fourier map, identifying this ligand as CYD₃. The remaining three ligands showed no significant unaccounted diffraction density in either observed or difference maps, so we were confident that we had located the CYD₃ ligand as distinct from the remaining three CYD ligands, and the charges now balanced, as the chemical formula is [K₃(CYD₂)₃(CYD₃)(D₂O)₄].

Figure 7 An Fobs Fourier map of the CYD3 ligand as determined by neutron diffraction with the second model. The locations of all 12 atoms in the molecule are clear.

With the charge balance problem solved our attention then turned to the question of the unfavourable steric interactions between the D atoms of one water molecule and the CYD₃ ligand. As noted above the first model (in C2/m) used in the analysis of the neutron diffraction data showed that one of the water molecules did not obey the mirror symmetry of that space group, instead placing one D atom exactly on the crystallographic mirror plane. In this new model all atoms lie in general positions and the relative orientation of all water D atoms is the same as in the first model, with three water molecules obeying pseudo-mirror symmetry and one molecule breaking it. As Fig. 8 shows, the presence of D5 causes D16A and D16B to twist away, allowing an N—D⋯O interaction to form, and breaking the pseudo-symmetry. The D atoms attached to atom O15 suffer no such steric hindrance from their deprotonated CYD₂⁻ neighbours and thus can form two pseudo-symmetrical O—D⋯N interactions.

Figure 8 Part of the correct structure of (3) determined by neutron diffraction. The pseudo-mirror symmetry of the structure is approximately observed by all atoms except D5 and D16B. Their positions break the symmetry and result in extra weak reflections in the diffraction pattern which were not identified by X-ray diffraction.

To summarize: the crystallographic mirror symmetry determined by X-ray diffraction is actually false, broken by the presence of D5 within the structure, which, to minimize steric hindrance and maximize hydrogen-bonding interactions, causes a twist of the water molecule O16, which in turn breaks the mirror symmetry observed by the remaining water molecules. Atom D5 also causes atoms N2 and N5 to be symmetry-inequivalent and these thus also break the mirror pseudo-symmetry. This breaking of the symmetry results in the formation of a supercell, caused only by the difference in D-atom positions. It is thus no surprise that this supercell was not detected at all by X-ray diffraction, given the poor scattering of X-rays by the electron density associated with D atoms. This supercell turned out to be the true unit cell. The correct structure of (3), as determined by neutron diffraction, is shown in Fig. 9. The structures of (3) and (4) determined by X-ray diffraction are not completely correct, as they have been determined in a sub-cell with the incorrect space group as a consequence of the very weak scattering of X-rays by H or D atoms. Although the results are shown here for comparison with the true structure determined with neutrons, and the CIFs are available as supplementary material, these have not been deposited in the Cambridge Structural Database since it is considered inappropriate to include in the database structures that are known to be strictly incorrect.

Figure 9 The asymmetric unit of (3) as correctly determined by neutron diffraction. Displacement ellipsoids are drawn at the 50% probability level; atom labelling has been restricted for clarity.

The asymmetric unit contains three crystallographically independent potassium cations, three CYD₂⁻ anions, one neutral CYD₃ molecule and four water molecules, all on general positions. The coordination environments of all three metal centres are shown in Fig. 10. Atoms K1 and K3 are both eight-coordinate but their coordination geometries are rather different, with K1 having a typical square-antiprismatic coordination environment whilst K3 has a square-antiprismatic environment that is rather more distorted, as if one side of the antiprism has been flattened out, such that the O14—K3—O13 angle is approximately 143° and the O3—K3—O5 angle is approximately 121°; ideally these would be 90° for undistorted geometry. The environment of seven-coordinate K2 is rather more difficult to describe quantitatively, as it does not have a typical seven-coordinate geometry. Five of the coordinating O atoms form an approximate pentagon, to which addition of an apical coordinated O atom generates a pentagonal-based pyramid. The seventh O atom, rather than occupying the second axial site (which would give a regular pentagonal-based bipyramid), is distorted well away from this ideal position to bridge atoms K2 and K3 (this is the bridging water molecule in Fig. 10). It is worthy of note that, unlike compounds (1) and (2), there is no K—N coordination in this structure; with four water molecules in the structure the N atoms are used as hydrogen-bonding acceptors and so cannot coordinate to the metal. The crystal packing of (3) is rather unexceptional for a cyanurate complex. Polymeric water coordination to the potassium centres forms a thin two-dimensional sheet; tapes of R₂²(8) hydrogen-bonded CYD₂ and CYD₃ ligands are linked to this sheet via coordination and hydrogen bonding to form an overall three-dimensional structure. Such crystal packing is very common in cyanurate complexes.

Figure 10 The coordination environments of the three independent potassium centres in the neutron-determined structure of (3).

4. Conclusion

The potassium–cyanuric acid reaction in aqueous solution was found to be particularly sensitive to stoichiometry, with three different complexes formed depending on the relative amount and type of base used. Using equimolar amounts of CYH₃ and K₂CO₃ (and so an effective K:CYH₃ ratio of 2:1) always resulted in the product [K⁺(CYH₂⁻)(H₂O)], (1), which was first reported some 15 years ago. By using a large excess of KOH we synthesized a new compound, [K⁺₂(CYH²⁻)], (2). This compact dense structure features doubly deprotonated cyanuric acid and, surprisingly, no water is present. A direct result of the double deprotonation is the loss of the R₂²(8) hydrogen-bonding motif, which is almost always found in cyanuric structural chemistry. The most interesting compound formed, however, was (3). Single-crystal X-ray diffraction gave a result which, although crystallographically largely sound, did not make chemical sense as a result of a charge imbalance between three cations and two anions and, in an attempt to rectify this by inclusion of a disordered H atom, an impossibly short contact between two H-atom sites. Resolution of these issues was achieved through a single-crystal neutron diffraction study carried out on a deuterated sample of this compound, leading to a supercell model with all atoms in general positions, the assignment of one neutral and three deprotonated organic ligands, and an ordered arrangement of D atoms with sensible interactions; the true structure has only pseudo-mirror symmetry, which is significantly broken by only two D atoms, an effect essentially invisible to X-ray diffraction.

Supporting information

Computing details

Data collection: Nonius COLLECT for (1); Bruker SMART for (2), 3_Xray, (4); SXD2001 for 3_neutron. Cell refinement: EVALCCD for (1); Bruker SAINT for (2), 3_Xray, (4); SXD2001 for 3_neutron. Data reduction: EVALCCD for (1); Bruker SAINT for (2), 3_Xray, (4); SXD2001 for 3_neutron. Program(s) used to solve structure: Bruker SHELXTL for (1), (2), 3_Xray, (4); using coords of known structure for 3_neutron. For all compounds, program(s) used to refine structure: Bruker SHELXTL; molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL and local programs.

Figures

(1)

Crystal data

C3H4KN3O4	F(000) = 752
Mr = 185.19	Dx = 1.954 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 5462 reflections
a = 11.037 (2) Å	θ = 2.5–27.5°
b = 16.419 (3) Å	µ = 0.81 mm^−1
c = 7.1497 (14) Å	T = 150 K
β = 103.68 (3)°	Block, colourless
V = 1258.9 (4) Å^3	0.22 × 0.16 × 0.11 mm
Z = 8

Data collection

Nonius KappaCCD diffractometer	1216 independent reflections
Radiation source: sealed tube	982 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.088
ϕ and ω scans	θmax = 25.5°, θmin = 4.8°
Absorption correction: multi-scan SADABS; Sheldrick, 2003	h = −13→13
Tmin = 0.842, Tmax = 0.916	k = −19→19
10612 measured reflections	l = −8→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	Hydrogen site location: difference Fourier map
wR(F^2) = 0.151	Only H-atom coordinates refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1091P)^2] where P = (Fo^2 + 2Fc^2)/3
1216 reflections	(Δ/σ)max < 0.001
121 parameters	Δρmax = 0.85 e Å^−3
0 restraints	Δρmin = −0.93 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
K1	0.07998 (8)	0.0000	0.25778 (12)	0.0248 (4)
K2	0.42367 (8)	0.0000	0.25455 (12)	0.0230 (4)
O1	0.0000	0.12659 (15)	0.0000	0.0269 (7)
O2	0.19766 (18)	0.36493 (11)	0.1904 (3)	0.0253 (6)
O3	0.30627 (18)	0.15675 (12)	0.2989 (3)	0.0273 (6)
O4	0.5000	0.39576 (16)	0.5000	0.0260 (7)
O5	0.3059 (3)	0.0000	0.5514 (5)	0.0269 (7)
H5	0.295 (3)	0.0334 (18)	0.616 (4)	0.032*
O6	0.1953 (3)	0.0000	−0.0351 (5)	0.0274 (8)
H6	0.220 (3)	0.0300 (19)	−0.087 (5)	0.033*
N1	0.0995 (2)	0.24638 (15)	0.0967 (3)	0.0217 (6)
H1N	0.164 (3)	0.217 (2)	0.149 (4)	0.026*
N2	0.0000	0.37320 (19)	0.0000	0.0211 (8)
N3	0.5000	0.14879 (19)	0.5000	0.0214 (8)
N4	0.4011 (2)	0.27577 (15)	0.4039 (3)	0.0230 (6)
H4N	0.336 (3)	0.305 (2)	0.344 (4)	0.028*
C1	0.0000	0.2008 (2)	0.0000	0.0224 (9)
C2	0.1003 (3)	0.33052 (17)	0.0964 (4)	0.0217 (7)
C3	0.4005 (3)	0.19107 (17)	0.3995 (4)	0.0218 (7)
C4	0.5000	0.3210 (2)	0.5000	0.0207 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0283 (6)	0.0195 (5)	0.0307 (6)	0.000	0.0151 (4)	0.000
K2	0.0237 (6)	0.0175 (5)	0.0313 (6)	0.000	0.0135 (4)	0.000
O1	0.0268 (16)	0.0143 (15)	0.0399 (17)	0.000	0.0085 (13)	0.000
O2	0.0206 (11)	0.0183 (11)	0.0385 (13)	−0.0032 (8)	0.0103 (9)	−0.0015 (9)
O3	0.0215 (11)	0.0195 (11)	0.0415 (13)	−0.0005 (9)	0.0088 (9)	0.0005 (9)
O4	0.0272 (16)	0.0186 (15)	0.0356 (16)	0.000	0.0145 (13)	0.000
O5	0.0346 (18)	0.0181 (16)	0.0343 (18)	0.000	0.0207 (14)	0.000
O6	0.0330 (18)	0.0184 (16)	0.0380 (19)	0.000	0.0229 (15)	0.000
N1	0.0206 (14)	0.0183 (13)	0.0288 (14)	0.0025 (10)	0.0111 (11)	0.0015 (10)
N2	0.0176 (17)	0.0216 (18)	0.0280 (18)	0.000	0.0131 (14)	0.000
N3	0.0169 (17)	0.0191 (17)	0.0312 (19)	0.000	0.0118 (15)	0.000
N4	0.0199 (14)	0.0190 (13)	0.0320 (14)	0.0023 (10)	0.0099 (11)	0.0017 (10)
C1	0.020 (2)	0.020 (2)	0.029 (2)	0.000	0.0111 (17)	0.000
C2	0.0237 (15)	0.0184 (15)	0.0278 (16)	−0.0014 (12)	0.0155 (13)	0.0001 (12)
C3	0.0240 (16)	0.0178 (15)	0.0280 (16)	−0.0011 (12)	0.0148 (12)	−0.0028 (12)
C4	0.020 (2)	0.022 (2)	0.024 (2)	0.000	0.0142 (17)	0.000

Geometric parameters (Å, º)

K1—O1	2.780 (2)	O4—K1^viii	2.7260 (18)
K1—O1^i	2.780 (2)	O4—C4	1.228 (5)
K1—O4^ii	2.7260 (18)	O5—K2^v	2.979 (4)
K1—O4^iii	2.7260 (18)	O5—H5	0.74 (3)
K1—O5	2.855 (4)	O6—K1^i	3.079 (4)
K1—O6	2.696 (4)	O6—H6	0.71 (3)
K1—O6^i	3.079 (4)	N1—H1N	0.87 (3)
K2—O3	2.932 (2)	N1—C1	1.374 (3)
K2—O3^iv	2.932 (2)	N1—C2	1.382 (4)
K2—O5	2.738 (3)	N2—K2^ix	3.014 (2)
K2—O5^v	2.979 (4)	N2—K2^vii	3.014 (2)
K2—O6	2.859 (4)	N2—C2	1.353 (3)
K2—N2^vi	3.014 (2)	N2—C2^x	1.353 (3)
K2—N2^vii	3.014 (2)	N3—K2^v	3.010 (3)
K2—N3	3.010 (3)	N3—C3	1.353 (3)
K2—N3^v	3.010 (3)	N3—C3^xi	1.353 (3)
O1—K1^i	2.780 (2)	N4—H4N	0.88 (3)
O1—C1	1.218 (5)	N4—C3	1.391 (4)
O2—C2	1.258 (4)	N4—C4	1.364 (3)
O3—C3	1.250 (3)	C1—N1^x	1.374 (3)
O4—K1^ii	2.7260 (18)	C4—N4^xi	1.364 (3)
O1—K1—O1^i	96.79 (8)	N2^vii—K2—N3	73.24 (5)
O1^i—K1—O4^ii	142.27 (4)	N3—K2—N3^v	108.53 (8)
O1^i—K1—O4^iii	81.49 (5)	K1—O1—K1^i	83.21 (8)
O1—K1—O4^ii	81.49 (5)	K1—O1—C1	138.40 (4)
O1—K1—O4^iii	142.27 (4)	K1^i—O1—C1	138.40 (4)
O1—K1—O5	124.94 (5)	K2—O3—C3	97.41 (17)
O1^i—K1—O5	124.94 (5)	K1^ii—O4—K1^viii	102.21 (9)
O1—K1—O6	67.62 (5)	K1^ii—O4—C4	128.89 (5)
O1^i—K1—O6	67.62 (5)	K1^viii—O4—C4	128.89 (5)
O1^i—K1—O6^i	62.44 (5)	K1—O5—K2	85.53 (10)
O1—K1—O6^i	62.44 (5)	K1—O5—K2^v	161.30 (14)
O4^ii—K1—O4^iii	77.78 (9)	K1—O5—H5	102 (2)
O4^ii—K1—O5	83.72 (6)	K2—O5—K2^v	75.77 (9)
O4^iii—K1—O5	83.72 (6)	K2—O5—H5	131 (3)
O4^ii—K1—O6	140.98 (5)	K2^v—O5—H5	90 (3)
O4^iii—K1—O6	140.98 (5)	K1—O6—K1^i	79.16 (9)
O4^ii—K1—O6^i	84.27 (6)	K1—O6—K2	86.25 (11)
O4^iii—K1—O6^i	84.27 (6)	K1^i—O6—K2	165.41 (14)
O5—K1—O6	94.61 (10)	K1—O6—H6	136 (3)
O5—K1—O6^i	164.56 (12)	K1^i—O6—H6	100 (3)
O6—K1—O6^i	100.84 (9)	K2—O6—H6	90 (3)
O3—K2—O3^iv	122.74 (8)	H1N—N1—C1	113 (2)
O3—K2—O5	67.25 (5)	H1N—N1—C2	124 (2)
O3^iv—K2—O5	67.25 (5)	C1—N1—C2	123.3 (3)
O3^iv—K2—O5^v	111.67 (5)	K2^ix—N2—K2^vii	92.60 (9)
O3—K2—O5^v	111.67 (5)	K2^ix—N2—C2	111.24 (14)
O3—K2—O6	75.05 (5)	K2^ix—N2—C2^x	110.69 (14)
O3^iv—K2—O6	75.05 (5)	K2^vii—N2—C2	110.69 (14)
O3^iv—K2—N2^vi	69.68 (6)	K2^vii—N2—C2^x	111.23 (14)
O3—K2—N2^vi	149.94 (6)	C2—N2—C2^x	117.6 (3)
O3^iv—K2—N2^vii	149.94 (6)	K2—N3—K2^v	71.47 (8)
O3—K2—N2^vii	69.68 (6)	K2—N3—C3	91.53 (14)
O3—K2—N3	45.12 (5)	K2^v—N3—C3^xi	91.53 (14)
O3^iv—K2—N3^v	45.12 (5)	K2^v—N3—C3	143.74 (16)
O3—K2—N3^v	135.99 (6)	K2—N3—C3^xi	143.74 (16)
O3^iv—K2—N3	136.00 (6)	C3—N3—C3^xi	118.3 (3)
O5—K2—O5^v	104.23 (9)	H4N—N4—C3	122 (2)
O5—K2—O6	93.61 (10)	H4N—N4—C4	114 (2)
O5^v—K2—O6	162.16 (12)	C3—N4—C4	123.7 (3)
O5—K2—N2^vi	136.04 (5)	O1—C1—N1	123.05 (18)
O5^v—K2—N2^vi	83.62 (6)	O1—C1—N1^x	123.05 (18)
O5—K2—N2^vii	136.04 (5)	N1—C1—N1^x	113.9 (4)
O5^v—K2—N2^vii	83.62 (6)	O2—C2—N1	116.9 (3)
O5—K2—N3	70.53 (4)	O2—C2—N2	122.1 (3)
O5—K2—N3^v	70.53 (4)	N1—C2—N2	120.9 (3)
O5^v—K2—N3^v	67.48 (4)	K2—C3—O3	60.75 (14)
O5^v—K2—N3	67.48 (4)	K2—C3—N3	64.53 (15)
O6—K2—N2^vi	83.51 (6)	K2—C3—N4	161.45 (19)
O6—K2—N2^vii	83.51 (6)	O3—C3—N3	122.3 (3)
O6—K2—N3	119.98 (4)	O3—C3—N4	117.5 (3)
O6—K2—N3^v	119.98 (4)	N3—C3—N4	120.2 (3)
N2^vi—K2—N2^vii	87.39 (9)	O4—C4—N4	122.97 (18)
N2^vi—K2—N3^v	73.24 (5)	O4—C4—N4^xi	122.98 (18)
N2^vi—K2—N3	146.43 (4)	N4—C4—N4^xi	114.0 (4)
N2^vii—K2—N3^v	146.43 (4)
O1^i—K1—O1—K1^i	0.0	O5^v—K2—O6—K1	180.0
O1^i—K1—O1—C1	180.0	O5—K2—O6—K1^i	0.0
O4^ii—K1—O1—K1^i	−141.96 (4)	O5^v—K2—O6—K1^i	180.0
O4^iii—K1—O1—K1^i	−84.85 (9)	N2^vi—K2—O6—K1	135.95 (5)
O4^ii—K1—O1—C1	38.04 (4)	N2^vii—K2—O6—K1	−135.95 (5)
O4^iii—K1—O1—C1	95.15 (9)	N2^vi—K2—O6—K1^i	135.95 (5)
O5—K1—O1—K1^i	141.90 (10)	N2^vii—K2—O6—K1^i	−135.95 (5)
O5—K1—O1—C1	−38.10 (10)	N3—K2—O6—K1	−69.57 (5)
O6—K1—O1—K1^i	62.37 (7)	N3^v—K2—O6—K1	69.57 (5)
O6^i—K1—O1—K1^i	−54.01 (7)	N3^v—K2—O6—K1^i	69.57 (5)
O6—K1—O1—C1	−117.63 (7)	N3—K2—O6—K1^i	−69.57 (5)
O6^i—K1—O1—C1	125.99 (7)	O3^iv—K2—N3—K2^v	43.59 (7)
O3^iv—K2—O3—C3	135.28 (15)	O3—K2—N3—K2^v	137.46 (7)
O5—K2—O3—C3	95.47 (18)	O3—K2—N3—C3	−9.86 (13)
O5^v—K2—O3—C3	−1.43 (19)	O3^iv—K2—N3—C3^xi	109.4 (2)
O6—K2—O3—C3	−164.00 (18)	O3—K2—N3—C3^xi	−156.7 (3)
N2^vi—K2—O3—C3	−118.05 (18)	O3^iv—K2—N3—C3	−103.73 (15)
N2^vii—K2—O3—C3	−75.49 (16)	O5—K2—N3—K2^v	60.58 (7)
N3—K2—O3—C3	10.77 (15)	O5^v—K2—N3—K2^v	−54.81 (7)
N3^v—K2—O3—C3	78.09 (18)	O5—K2—N3—C3	−86.75 (14)
O3—K2—O5—K1	72.13 (5)	O5—K2—N3—C3^xi	126.4 (3)
O3^iv—K2—O5—K1	−72.13 (5)	O5^v—K2—N3—C3^xi	11.0 (3)
O3^iv—K2—O5—K2^v	107.87 (5)	O5^v—K2—N3—C3	157.86 (15)
O3—K2—O5—K2^v	−107.87 (5)	O6—K2—N3—K2^v	143.29 (10)
O5^v—K2—O5—K1	180.0	O6—K2—N3—C3	−4.03 (16)
O5^v—K2—O5—K2^v	0.0	O6—K2—N3—C3^xi	−150.9 (3)
O6—K2—O5—K1	0.0	N2^vi—K2—N3—K2^v	−87.42 (10)
O6—K2—O5—K2^v	180.0	N2^vii—K2—N3—K2^v	−144.77 (4)
N2^vi—K2—O5—K1	−84.39 (8)	N2^vi—K2—N3—C3^xi	−21.6 (3)
N2^vii—K2—O5—K1	84.39 (8)	N2^vii—K2—N3—C3^xi	−78.9 (3)
N2^vi—K2—O5—K2^v	95.61 (8)	N2^vi—K2—N3—C3	125.25 (15)
N2^vii—K2—O5—K2^v	−95.61 (8)	N2^vii—K2—N3—C3	67.91 (13)
N3—K2—O5—K1	120.58 (4)	N3^v—K2—N3—K2^v	0.0
N3^v—K2—O5—K1	−120.58 (4)	N3^v—K2—N3—C3^xi	65.8 (3)
N3^v—K2—O5—K2^v	59.42 (4)	N3^v—K2—N3—C3	−147.33 (13)
N3—K2—O5—K2^v	−59.42 (4)	K1—O1—C1—N1	40.28 (12)
C3—K2—O5—K1	95.20 (6)	K1^i—O1—C1—N1	−139.72 (12)
C3^iv—K2—O5—K1	−95.20 (6)	K1^i—O1—C1—N1^x	40.28 (12)
C3^iv—K2—O5—K2^v	84.80 (6)	K1—O1—C1—N1^x	−139.72 (12)
C3—K2—O5—K2^v	−84.80 (6)	C2—N1—C1—O1	179.63 (19)
O1—K1—O5—K2	−65.81 (6)	C2—N1—C1—N1^x	−0.37 (19)
O1^i—K1—O5—K2	65.81 (6)	K2^ix—N2—C2—O2	−50.7 (3)
O1^i—K1—O5—K2^v	65.81 (6)	K2^vii—N2—C2—O2	50.8 (3)
O1—K1—O5—K2^v	−65.81 (6)	K2^ix—N2—C2—N1	128.8 (2)
O4^ii—K1—O5—K2	−140.83 (5)	K2^vii—N2—C2—N1	−129.8 (2)
O4^iii—K1—O5—K2	140.83 (5)	C2^x—N2—C2—O2	−179.8 (3)
O4^ii—K1—O5—K2^v	−140.83 (5)	C2^x—N2—C2—N1	−0.36 (18)
O4^iii—K1—O5—K2^v	140.83 (5)	C1—N1—C2—O2	−179.8 (2)
O6—K1—O5—K2	0.0	C1—N1—C2—N2	0.8 (4)
O6^i—K1—O5—K2	180.0	K2—O3—C3—N3	−20.4 (3)
O6—K1—O5—K2^v	0.0	K2—O3—C3—N4	159.0 (2)
O6^i—K1—O5—K2^v	180.0	K2^v—N3—C3—K2	−59.9 (2)
O1^i—K1—O6—K1^i	53.97 (4)	K2—N3—C3—O3	19.7 (3)
O1—K1—O6—K1^i	−53.97 (4)	K2^v—N3—C3—O3	−40.2 (4)
O1—K1—O6—K2	126.03 (4)	K2—N3—C3—N4	−159.7 (2)
O1^i—K1—O6—K2	−126.03 (4)	K2^v—N3—C3—N4	140.4 (2)
O4^ii—K1—O6—K1^i	−94.29 (10)	C3^xi—N3—C3—K2	158.45 (7)
O4^iii—K1—O6—K1^i	94.29 (10)	C3^xi—N3—C3—O3	178.1 (3)
O4^ii—K1—O6—K2	85.71 (10)	C3^xi—N3—C3—N4	−1.23 (18)
O4^iii—K1—O6—K2	−85.71 (10)	C4—N4—C3—K2	−97.0 (6)
O5—K1—O6—K1^i	180.0	C4—N4—C3—O3	−176.8 (2)
O5—K1—O6—K2	0.0	C4—N4—C3—N3	2.6 (4)
O6^i—K1—O6—K1^i	0.0	K1^ii—O4—C4—N4	88.16 (12)
O6^i—K1—O6—K2	180.0	K1^viii—O4—C4—N4	−91.84 (12)
O3—K2—O6—K1	−65.30 (5)	K1^ii—O4—C4—N4^xi	−91.85 (12)
O3^iv—K2—O6—K1	65.30 (5)	K1^viii—O4—C4—N4^xi	88.16 (12)
O3^iv—K2—O6—K1^i	65.30 (5)	C3—N4—C4—O4	178.71 (19)
O3—K2—O6—K1^i	−65.30 (5)	C3—N4—C4—N4^xi	−1.29 (19)
O5—K2—O6—K1	0.0

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O2^ii	0.74 (3)	2.16 (3)	2.892 (3)	169 (4)
O6—H6···O2^vii	0.71 (3)	2.16 (3)	2.858 (3)	168 (3)
N1—H1N···O3	0.87 (3)	1.95 (3)	2.811 (3)	172 (3)
N4—H4N···O2	0.88 (3)	1.93 (3)	2.809 (3)	175 (3)

Symmetry codes: (ii) −x+1/2, −y+1/2, −z+1; (vii) −x+1/2, −y+1/2, −z.

(2)

Crystal data

C3HK2N3O3	F(000) = 408
Mr = 205.27	Dx = 2.313 Mg m^−3
Orthorhombic, Cmcm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2c 2	Cell parameters from 1837 reflections
a = 13.062 (4) Å	θ = 3.0–28.2°
b = 6.620 (2) Å	µ = 1.56 mm^−1
c = 6.817 (2) Å	T = 150 K
V = 589.4 (3) Å^3	Block, colourless
Z = 4	0.23 × 0.21 × 0.18 mm

Data collection

Bruker SMART 1K CCD diffractometer	412 independent reflections
Radiation source: sealed tube	370 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
thin–slice ω scans	θmax = 28.3°, θmin = 3.1°
Absorption correction: multi-scan SADABS; Sheldrick, 2003	h = −17→16
Tmin = 0.716, Tmax = 0.767	k = −8→8
2536 measured reflections	l = −9→9

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.024	Hydrogen site location: difference Fourier map
wR(F^2) = 0.064	All H-atom parameters refined
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0329P)^2 + 0.7482P] where P = (Fo^2 + 2Fc^2)/3
412 reflections	(Δ/σ)max < 0.001
38 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.48 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
K	0.32199 (3)	0.5000	0.5000	0.01181 (19)
O1	0.17320 (10)	0.6499 (2)	0.2500	0.0110 (3)
N1	0.0000	0.6430 (4)	0.2500	0.0103 (5)
N2	0.09318 (13)	0.3413 (2)	0.2500	0.0094 (4)
O2	0.0000	0.0552 (3)	0.2500	0.0150 (5)
C1	0.09272 (15)	0.5441 (3)	0.2500	0.0076 (4)
C2	0.0000	0.2483 (4)	0.2500	0.0104 (6)
H1N	0.0000	0.766 (8)	0.2500	0.032 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K	0.0116 (3)	0.0122 (3)	0.0116 (3)	0.000	0.000	0.00027 (14)
O1	0.0060 (7)	0.0115 (7)	0.0154 (7)	−0.0021 (5)	0.000	0.000
N1	0.0089 (12)	0.0036 (11)	0.0185 (13)	0.000	0.000	0.000
N2	0.0082 (8)	0.0075 (8)	0.0125 (8)	0.0015 (6)	0.000	0.000
O2	0.0149 (11)	0.0047 (9)	0.0255 (12)	0.000	0.000	0.000
C1	0.0076 (9)	0.0071 (8)	0.0081 (8)	0.0006 (7)	0.000	0.000
C2	0.0136 (14)	0.0094 (13)	0.0080 (12)	0.000	0.000	0.000

Geometric parameters (Å, º)

K—O1	2.7688 (13)	N1—C1^ix	1.377 (2)
K—O1^i	2.7688 (13)	N1—H1N	0.81 (5)
K—O1^ii	2.8773 (14)	N2—K^x	3.0390 (15)
K—O1^iii	2.8774 (14)	N2—K^v	3.0390 (15)
K—N2^iv	3.0390 (15)	N2—C1	1.343 (3)
K—N2^v	3.0390 (15)	N2—C2	1.364 (2)
K—O2^vi	2.9058 (8)	O2—K^xi	2.9059 (8)
K—O2^v	2.9058 (8)	O2—K^v	2.9059 (8)
O1—K^vii	2.7688 (13)	O2—K^xii	2.9059 (8)
O1—K^ii	2.8773 (14)	O2—K^x	2.9059 (8)
O1—K^viii	2.8773 (14)	O2—C2	1.278 (4)
O1—C1	1.263 (2)	C2—N2^ix	1.364 (2)
N1—C1	1.377 (2)
O1—K—O1^i	90.83 (5)	K—O1—K^viii	129.63 (5)
O1^i—K—O1^ii	86.53 (3)	K^ii—O1—K^viii	72.64 (4)
O1—K—O1^ii	95.23 (3)	K—O1—C1	112.67 (9)
O1^i—K—O1^iii	95.23 (3)	K^vii—O1—C1	112.67 (9)
O1—K—O1^iii	86.53 (3)	K^ii—O1—C1	117.70 (9)
O1^ii—K—O1^iii	177.50 (6)	K^viii—O1—C1	117.70 (9)
O1^i—K—N2^iv	150.17 (5)	C1—N1—C1^ix	123.2 (2)
O1—K—N2^iv	69.17 (4)	C1—N1—H1N	118.39 (12)
O1^ii—K—N2^iv	74.06 (4)	C1^ix—N1—H1N	118.40 (13)
O1^iii—K—N2^iv	104.99 (4)	K^x—N2—K^v	68.21 (4)
O1^i—K—N2^v	69.17 (4)	K^x—N2—C1	138.16 (8)
O1—K—N2^v	150.17 (5)	K^v—N2—C1	138.16 (8)
O1^ii—K—N2^v	104.99 (4)	K^x—N2—C2	89.42 (11)
O1^iii—K—N2^v	74.06 (4)	K^v—N2—C2	89.42 (11)
O1^i—K—O2^vi	165.40 (5)	C1—N2—C2	116.58 (19)
O1—K—O2^vi	98.95 (3)	K^xi—O2—K^v	165.54 (9)
O1^ii—K—O2^vi	103.21 (5)	K^xi—O2—K^xii	71.81 (3)
O1^iii—K—O2^vi	74.73 (4)	K^v—O2—K^xii	106.29 (3)
O1^i—K—O2^v	98.95 (3)	K^xi—O2—K^x	106.29 (3)
O1—K—O2^v	165.40 (5)	K^v—O2—K^x	71.81 (3)
O1^ii—K—O2^v	74.73 (4)	K^xii—O2—K^x	165.54 (9)
O1^iii—K—O2^v	103.21 (5)	K^xi—O2—C2	97.23 (4)
N2^iv—K—N2^v	137.23 (7)	K^v—O2—C2	97.23 (4)
N2^iv—K—O2^vi	44.43 (5)	K^xii—O2—C2	97.23 (4)
N2^iv—K—O2^v	97.51 (5)	K^x—O2—C2	97.23 (4)
N2^v—K—O2^vi	97.51 (5)	O1—C1—N1	117.93 (18)
N2^v—K—O2^v	44.43 (5)	O1—C1—N2	123.42 (18)
K—O1—K^vii	75.97 (4)	N1—C1—N2	118.65 (19)
K^vii—O1—K^ii	129.63 (5)	N2—C2—N2^ix	126.3 (3)
K—O1—K^ii	84.77 (3)	N2—C2—O2	116.83 (13)
K^vii—O1—K^viii	84.77 (3)	N2^ix—C2—O2	116.83 (13)
O1^i—K—O1—K^vii	−140.32 (5)	K^vii—O1—C1—N1	−138.16 (5)
O1^ii—K—O1—K^vii	133.09 (4)	K^ii—O1—C1—N1	41.98 (5)
O1^iii—K—O1—K^vii	−45.13 (4)	K^viii—O1—C1—N1	−41.98 (5)
O1^i—K—O1—K^ii	86.59 (3)	K—O1—C1—N2	−41.84 (5)
O1^ii—K—O1—K^ii	0.001 (2)	K^vii—O1—C1—N2	41.84 (5)
O1^iii—K—O1—K^ii	−178.22 (4)	K^ii—O1—C1—N2	−138.02 (5)
O1^i—K—O1—K^viii	148.88 (7)	K^viii—O1—C1—N2	138.02 (5)
O1^ii—K—O1—K^viii	62.29 (5)	K^x—N2—C1—O1	−57.21 (14)
O1^iii—K—O1—K^viii	−115.93 (7)	K^v—N2—C1—O1	57.21 (14)
O1^i—K—O1—C1	−31.29 (7)	K^x—N2—C1—N1	122.79 (14)
O1^ii—K—O1—C1	−117.88 (9)	K^v—N2—C1—N1	−122.79 (14)
O1^iii—K—O1—C1	63.90 (7)	C2—N2—C1—O1	180.0
N2^iv—K—O1—K^vii	62.35 (3)	C2—N2—C1—N1	0.0
N2^v—K—O1—K^vii	−93.92 (6)	C1^ix—N1—C1—O1	180.0
N2^iv—K—O1—K^ii	−70.74 (4)	C1^ix—N1—C1—N2	0.0
N2^v—K—O1—K^ii	132.99 (6)	K^xi—O2—C2—N2^ix	36.238 (13)
N2^iv—K—O1—K^viii	−8.45 (4)	K^v—O2—C2—N2^ix	−143.762 (14)
N2^v—K—O1—K^viii	−164.72 (5)	K^xii—O2—C2—N2^ix	−36.238 (13)
N2^iv—K—O1—C1	171.38 (9)	K^x—O2—C2—N2^ix	143.762 (14)
N2^v—K—O1—C1	15.11 (11)	K^xi—O2—C2—N2	−143.762 (14)
O2^vi—K—O1—K^vii	28.80 (5)	K^v—O2—C2—N2	36.238 (13)
O2^v—K—O1—K^vii	87.36 (10)	K^xii—O2—C2—N2	143.762 (14)
O2^vi—K—O1—K^ii	−104.28 (5)	K^x—O2—C2—N2	−36.238 (13)
O2^v—K—O1—K^ii	−45.73 (10)	K^x—N2—C2—N2^ix	−145.89 (2)
O2^vi—K—O1—K^viii	−41.99 (6)	K^v—N2—C2—N2^ix	145.89 (2)
O2^v—K—O1—K^viii	16.56 (12)	K^x—N2—C2—O2	34.11 (2)
O2^vi—K—O1—C1	137.84 (9)	K^v—N2—C2—O2	−34.11 (2)
O2^v—K—O1—C1	−163.61 (9)	C1—N2—C2—N2^ix	0.0
K—O1—C1—N1	138.16 (5)	C1—N2—C2—O2	180.0

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^xiii	0.81 (5)	1.91 (6)	2.729 (3)	180

Symmetry code: (xiii) x, y+1, z.

(3_Xray)

Crystal data

C12D17K3N12O16	F(000) = 1432
Mr = 719.71	Dx = 1.946 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 12.8143 (15) Å	Cell parameters from 7146 reflections
b = 16.3214 (19) Å	θ = 2.5–28.1°
c = 11.8498 (14) Å	µ = 0.66 mm^−1
β = 97.520 (2)°	T = 150 K
V = 2457.0 (5) Å^3	Plate, colourless
Z = 4	0.70 × 0.20 × 0.05 mm

Data collection

Bruker SMART 1K CCD diffractometer	2926 independent reflections
Radiation source: sealed tube	2425 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
thin–slice ω scans	θmax = 28.5°, θmin = 1.7°
Absorption correction: multi-scan SADABS	h = −16→17
Tmin = 0.655, Tmax = 0.968	k = −20→20
10491 measured reflections	l = −15→15

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.034	Secondary atom site location: difference Fourier map
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0557P)^2 + 1.2767P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2926 reflections	Δρmax = 0.64 e Å^−3
232 parameters	Δρmin = −0.45 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
K1	0.57585 (4)	0.5000	0.87603 (4)	0.01848 (14)
K2	0.28021 (4)	0.5000	0.65303 (5)	0.02235 (15)
K3	0.03827 (4)	0.5000	0.34925 (5)	0.02167 (14)
O1	0.36192 (9)	0.34845 (7)	0.60425 (9)	0.0162 (3)
O2	0.38952 (9)	0.10816 (7)	0.41946 (9)	0.0170 (3)
O3	0.37484 (10)	0.34798 (7)	0.22327 (9)	0.0181 (3)
O4	0.11489 (10)	0.34507 (7)	0.27492 (9)	0.0187 (3)
O5	0.10581 (10)	0.10292 (7)	0.08414 (9)	0.0197 (3)
O6	0.14092 (11)	0.34212 (8)	−0.10245 (9)	0.0224 (3)
O7	0.79380 (16)	0.5000	0.86355 (17)	0.0213 (4)
D7	0.8155 (18)	0.5334 (13)	0.8793 (18)	0.026*
O8	0.49315 (15)	0.5000	0.64870 (16)	0.0215 (4)
D8	0.5180 (16)	0.5384 (12)	0.6209 (17)	0.026*
O9	−0.13646 (18)	0.5000	0.18744 (15)	0.0290 (5)
D9	−0.1413 (18)	0.5385 (13)	0.1479 (18)	0.035*
O10	0.24823 (14)	0.5000	0.37824 (16)	0.0203 (4)
D10	0.2829 (17)	0.4618 (12)	0.3935 (17)	0.024*
N1	0.37629 (10)	0.22902 (8)	0.51198 (11)	0.0124 (3)
D1N	0.3771 (15)	0.2066 (12)	0.5762 (17)	0.015*
N2	0.37868 (11)	0.22837 (9)	0.31979 (11)	0.0146 (3)
D2N	0.3774 (15)	0.2035 (13)	0.2561 (18)	0.018*
N3	0.37088 (11)	0.35545 (8)	0.41406 (10)	0.0135 (3)
N4	0.11454 (11)	0.22362 (8)	0.18226 (11)	0.0145 (3)
D4N	0.1159 (15)	0.2005 (12)	0.2479 (18)	0.017*
N5	0.12358 (11)	0.22276 (9)	−0.01043 (11)	0.0145 (3)
D5N	0.1220 (15)	0.2002 (13)	−0.0720 (17)	0.017*
N6	0.12729 (12)	0.34764 (9)	0.08610 (11)	0.0169 (3)
D6N	0.142 (3)	0.395 (3)	0.093 (3)	0.020*	0.50
C1	0.36941 (12)	0.31380 (10)	0.51209 (12)	0.0115 (3)
C2	0.38181 (12)	0.18288 (10)	0.41726 (12)	0.0122 (3)
C3	0.37456 (12)	0.31315 (10)	0.31680 (12)	0.0129 (3)
C4	0.11879 (13)	0.30779 (10)	0.18513 (13)	0.0145 (3)
C5	0.11459 (12)	0.17721 (10)	0.08533 (13)	0.0142 (3)
C6	0.13108 (13)	0.30684 (10)	−0.01222 (12)	0.0147 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0256 (3)	0.0164 (3)	0.0146 (2)	0.000	0.00713 (19)	0.000
K2	0.0193 (3)	0.0146 (3)	0.0344 (3)	0.000	0.0082 (2)	0.000
K3	0.0186 (3)	0.0191 (3)	0.0289 (3)	0.000	0.0089 (2)	0.000
O1	0.0275 (7)	0.0141 (6)	0.0077 (5)	0.0018 (5)	0.0049 (4)	−0.0018 (4)
O2	0.0229 (6)	0.0136 (6)	0.0152 (5)	0.0015 (5)	0.0051 (5)	−0.0014 (4)
O3	0.0286 (7)	0.0185 (6)	0.0080 (5)	0.0008 (5)	0.0056 (4)	0.0025 (4)
O4	0.0327 (7)	0.0158 (6)	0.0089 (5)	0.0002 (5)	0.0071 (5)	−0.0011 (4)
O5	0.0296 (7)	0.0156 (6)	0.0149 (5)	−0.0022 (5)	0.0071 (5)	−0.0015 (4)
O6	0.0415 (8)	0.0192 (6)	0.0078 (5)	0.0044 (5)	0.0090 (5)	0.0029 (5)
O7	0.0311 (11)	0.0087 (9)	0.0239 (9)	0.000	0.0028 (8)	0.000
O8	0.0233 (9)	0.0147 (9)	0.0278 (10)	0.000	0.0080 (7)	0.000
O9	0.0505 (13)	0.0205 (10)	0.0157 (9)	0.000	0.0035 (8)	0.000
O10	0.0189 (9)	0.0122 (9)	0.0297 (10)	0.000	0.0027 (7)	0.000
N1	0.0181 (7)	0.0132 (7)	0.0066 (6)	0.0011 (5)	0.0039 (5)	0.0006 (5)
N2	0.0234 (8)	0.0145 (7)	0.0064 (6)	0.0013 (5)	0.0041 (5)	−0.0026 (5)
N3	0.0196 (7)	0.0131 (7)	0.0086 (6)	0.0010 (5)	0.0038 (5)	−0.0003 (5)
N4	0.0240 (7)	0.0143 (7)	0.0062 (6)	−0.0011 (5)	0.0054 (5)	0.0013 (5)
N5	0.0220 (7)	0.0160 (7)	0.0060 (6)	0.0002 (5)	0.0037 (5)	−0.0022 (5)
N6	0.0314 (8)	0.0120 (7)	0.0084 (6)	−0.0010 (6)	0.0066 (5)	−0.0001 (5)
C1	0.0125 (7)	0.0134 (8)	0.0087 (7)	0.0007 (6)	0.0024 (5)	0.0001 (6)
C2	0.0120 (7)	0.0147 (8)	0.0101 (7)	−0.0002 (6)	0.0025 (5)	−0.0014 (6)
C3	0.0140 (8)	0.0155 (8)	0.0094 (7)	0.0004 (6)	0.0025 (6)	0.0001 (6)
C4	0.0179 (8)	0.0156 (8)	0.0107 (7)	−0.0011 (6)	0.0044 (6)	−0.0006 (6)
C5	0.0150 (8)	0.0169 (8)	0.0112 (7)	−0.0011 (6)	0.0038 (6)	−0.0009 (6)
C6	0.0201 (8)	0.0158 (8)	0.0081 (7)	0.0017 (6)	0.0016 (6)	−0.0003 (6)

Geometric parameters (Å, º)

K1—O3^i	2.8520 (12)	O3—C3	1.2461 (18)
K1—O3^ii	2.8520 (12)	O4—C4	1.2323 (19)
K1—O5^iii	2.9583 (13)	O5—K1^iii	2.9582 (13)
K1—O5^iv	2.9583 (13)	O5—K1^xii	2.9669 (12)
K1—O5^v	2.9669 (12)	O5—C5	1.218 (2)
K1—O5^vi	2.9669 (12)	O6—C6	1.2353 (19)
K1—O7	2.816 (2)	O7—D7	0.63 (2)
K1—O8	2.7627 (19)	O8—D8	0.794 (19)
K2—O1	2.7761 (12)	O9—K2^viii	2.807 (2)
K2—O1^vii	2.7762 (12)	O9—D9	0.78 (2)
K2—O2^iii	2.8453 (13)	O10—D10	0.773 (19)
K2—O2^iv	2.8453 (13)	N1—D1N	0.84 (2)
K2—O8	2.736 (2)	N1—C1	1.387 (2)
K2—O9^viii	2.807 (2)	N1—C2	1.3611 (19)
K2—O10	3.228 (2)	N2—D2N	0.85 (2)
K3—O2^ix	2.8030 (12)	N2—C2	1.369 (2)
K3—O2^x	2.8030 (12)	N2—C3	1.385 (2)
K3—O2^iii	3.2895 (12)	N3—C1	1.3482 (19)
K3—O2^iv	3.2895 (12)	N3—C3	1.3496 (19)
K3—O4	2.8914 (12)	N4—D4N	0.86 (2)
K3—O4^vii	2.8914 (12)	N4—C4	1.375 (2)
K3—O9	2.751 (2)	N4—C5	1.376 (2)
K3—O10	2.6674 (19)	N5—D5N	0.81 (2)
O1—C1	1.2446 (18)	N5—C5	1.374 (2)
O2—K2^iii	2.8453 (13)	N5—C6	1.376 (2)
O2—K3^xi	2.8030 (12)	N6—D6N	0.80 (4)
O2—K3^iii	3.2895 (12)	N6—C4	1.359 (2)
O2—C2	1.224 (2)	N6—C6	1.348 (2)
O3—K1^ii	2.8521 (12)
O3^i—K1—O3^ii	120.91 (5)	O2^ix—K3—O10	132.49 (3)
O3^i—K1—O5^iii	78.07 (3)	O2^x—K3—O10	132.49 (3)
O3^ii—K1—O5^iii	141.37 (4)	O2^iii—K3—O10	73.96 (4)
O3^i—K1—O5^iv	141.37 (4)	O2^iv—K3—O10	73.96 (4)
O3^ii—K1—O5^iv	78.07 (3)	O4—K3—O4^vii	121.98 (5)
O3^i—K1—O5^v	80.72 (3)	O4—K3—O9	93.76 (3)
O3^ii—K1—O5^v	145.48 (4)	O4^vii—K3—O9	93.76 (3)
O3^i—K1—O5^vi	145.48 (4)	O4—K3—O10	70.26 (3)
O3^ii—K1—O5^vi	80.72 (3)	O4^vii—K3—O10	70.26 (3)
O3^i—K1—O7	72.76 (3)	O9—K3—O10	143.62 (6)
O3^ii—K1—O7	72.76 (3)	K2—O1—C1	131.46 (10)
O3^i—K1—O8	71.04 (3)	K2^iii—O2—K3^xi	92.43 (4)
O3^ii—K1—O8	71.04 (3)	K2^iii—O2—K3^iii	92.24 (3)
O5^iii—K1—O5^iv	69.20 (5)	K2^iii—O2—C2	123.75 (10)
O5^iii—K1—O5^v	64.20 (5)	K3^xi—O2—K3^iii	77.36 (3)
O5^iv—K1—O5^v	101.99 (3)	K3^xi—O2—C2	132.66 (10)
O5^iii—K1—O5^vi	101.99 (3)	K3^iii—O2—C2	124.45 (9)
O5^iv—K1—O5^vi	64.20 (5)	K1^ii—O3—C3	142.22 (10)
O5^v—K1—O5^vi	68.97 (5)	K3—O4—C4	138.47 (11)
O5^iii—K1—O7	144.58 (3)	K1^iii—O5—K1^xii	78.01 (3)
O5^iv—K1—O7	144.58 (3)	K1^iii—O5—C5	129.57 (11)
O5^v—K1—O7	91.28 (4)	K1^xii—O5—C5	125.11 (10)
O5^vi—K1—O7	91.28 (4)	K1—O7—D7	113 (2)
O5^iii—K1—O8	86.91 (4)	K1—O8—K2	103.77 (6)
O5^iv—K1—O8	86.91 (4)	K1—O8—D8	106.4 (15)
O5^v—K1—O8	143.31 (3)	K2—O8—D8	117.5 (15)
O5^vi—K1—O8	143.31 (3)	K2^viii—O9—K3	94.39 (6)
O7—K1—O8	101.85 (6)	K2^viii—O9—D9	113.4 (17)
O1—K2—O1^vii	125.99 (5)	K3—O9—D9	114.3 (17)
O1—K2—O2^iii	71.25 (4)	K2—O10—K3	97.04 (6)
O1^vii—K2—O2^iii	141.64 (4)	K2—O10—D10	76.8 (15)
O1—K2—O2^iv	141.65 (4)	K3—O10—D10	124.7 (16)
O1^vii—K2—O2^iv	71.25 (4)	D1N—N1—C1	115.2 (14)
O1—K2—O8	65.91 (3)	D1N—N1—C2	120.5 (14)
O1^vii—K2—O8	65.91 (3)	C1—N1—C2	124.28 (13)
O1—K2—O9^viii	116.03 (3)	D2N—N2—C2	118.8 (14)
O1^vii—K2—O9^viii	116.03 (3)	D2N—N2—C3	117.1 (14)
O1—K2—O10	77.97 (3)	C2—N2—C3	124.06 (13)
O1^vii—K2—O10	77.97 (3)	C1—N3—C3	118.94 (14)
O2^iii—K2—O2^iv	76.70 (5)	D4N—N4—C4	114.8 (13)
O2^iii—K2—O8	135.99 (3)	D4N—N4—C5	120.6 (13)
O2^iv—K2—O8	135.99 (3)	C4—N4—C5	124.50 (13)
O2^iii—K2—O9^viii	70.13 (4)	D5N—N5—C5	120.0 (14)
O2^iv—K2—O9^viii	70.13 (4)	D5N—N5—C6	115.5 (14)
O2^iii—K2—O10	72.81 (3)	C5—N5—C6	124.47 (13)
O2^iv—K2—O10	72.81 (3)	D6N—N6—C4	115 (3)
O8—K2—O9^viii	139.17 (6)	D6N—N6—C6	122 (3)
O8—K2—O10	88.65 (5)	C4—N6—C6	121.74 (15)
O9^viii—K2—O10	132.18 (6)	O1—C1—N1	117.81 (13)
O2^ix—K3—O2^x	78.07 (5)	O1—C1—N3	122.57 (14)
O2^ix—K3—O2^iii	62.79 (4)	N1—C1—N3	119.62 (13)
O2^x—K3—O2^iii	102.64 (3)	O2—C2—N1	123.14 (14)
O2^ix—K3—O2^iv	102.64 (3)	O2—C2—N2	123.49 (14)
O2^x—K3—O2^iv	62.79 (4)	N1—C2—N2	113.37 (14)
O2^iii—K3—O2^iv	64.91 (4)	O3—C3—N2	118.29 (14)
O2^ix—K3—O4^vii	155.84 (4)	O3—C3—N3	122.05 (15)
O2^x—K3—O4^vii	79.10 (3)	N2—C3—N3	119.65 (13)
O2^ix—K3—O4	79.10 (3)	O4—C4—N4	120.58 (14)
O2^x—K3—O4	155.84 (4)	O4—C4—N6	121.76 (15)
O2^iii—K3—O4^vii	130.80 (4)	N4—C4—N6	117.66 (14)
O2^iii—K3—O4	73.43 (3)	O5—C5—N4	123.22 (14)
O2^iv—K3—O4^vii	73.43 (3)	O5—C5—N5	123.15 (14)
O2^iv—K3—O4	130.80 (4)	N4—C5—N5	113.62 (14)
O2^ix—K3—O9	71.56 (4)	O6—C6—N5	119.57 (14)
O2^x—K3—O9	71.56 (4)	O6—C6—N6	122.48 (15)
O2^iii—K3—O9	134.06 (4)	N5—C6—N6	117.96 (14)
O2^iv—K3—O9	134.06 (4)
O1^vii—K2—O1—C1	−66.54 (16)	O2^iv—K2—O10—K3	−40.50 (3)
O2^iii—K2—O1—C1	74.45 (13)	O8—K2—O10—K3	180.0
O2^iv—K2—O1—C1	39.59 (16)	O9^viii—K2—O10—K3	0.0
O8—K2—O1—C1	−95.21 (14)	K2—O1—C1—N1	−156.14 (10)
O9^viii—K2—O1—C1	130.03 (14)	K2—O1—C1—N3	23.8 (2)
O10—K2—O1—C1	−1.26 (13)	C3—N3—C1—O1	−177.13 (14)
O2^ix—K3—O4—C4	107.23 (16)	C3—N3—C1—N1	2.8 (2)
O2^x—K3—O4—C4	87.92 (18)	C2—N1—C1—O1	178.06 (14)
O2^iii—K3—O4—C4	171.86 (17)	C2—N1—C1—N3	−1.9 (2)
O2^iv—K3—O4—C4	−155.41 (15)	K2^iii—O2—C2—N1	103.99 (15)
O4^vii—K3—O4—C4	−59.98 (18)	K2^iii—O2—C2—N2	−76.52 (18)
O9—K3—O4—C4	36.82 (17)	K3^xi—O2—C2—N1	−122.79 (14)
O10—K3—O4—C4	−109.65 (17)	K3^iii—O2—C2—N1	−17.0 (2)
O1—K2—O8—K1	−102.58 (3)	K3^xi—O2—C2—N2	56.7 (2)
O1^vii—K2—O8—K1	102.58 (3)	K3^iii—O2—C2—N2	162.45 (11)
O2^iii—K2—O8—K1	−116.75 (5)	C1—N1—C2—O2	178.80 (15)
O2^iv—K2—O8—K1	116.75 (5)	C1—N1—C2—N2	−0.7 (2)
O9^viii—K2—O8—K1	0.0	C3—N2—C2—O2	−177.08 (15)
O10—K2—O8—K1	180.0	C3—N2—C2—N1	2.5 (2)
O3^i—K1—O8—K2	113.10 (3)	K1^ii—O3—C3—N2	−156.67 (12)
O3^ii—K1—O8—K2	−113.10 (3)	K1^ii—O3—C3—N3	23.0 (3)
O5^iii—K1—O8—K2	34.66 (2)	C1—N3—C3—O3	179.14 (15)
O5^iv—K1—O8—K2	−34.66 (2)	C1—N3—C3—N2	−1.2 (2)
O5^v—K1—O8—K2	71.36 (7)	C2—N2—C3—O3	178.10 (15)
O5^vi—K1—O8—K2	−71.36 (7)	C2—N2—C3—N3	−1.6 (2)
O7—K1—O8—K2	180.0	K3—O4—C4—N4	−148.45 (12)
O2^ix—K3—O9—K2^viii	41.60 (3)	K3—O4—C4—N6	31.5 (3)
O2^x—K3—O9—K2^viii	−41.60 (3)	C6—N6—C4—O4	−179.70 (16)
O2^iii—K3—O9—K2^viii	48.31 (4)	C6—N6—C4—N4	0.3 (2)
O2^iv—K3—O9—K2^viii	−48.31 (4)	C5—N4—C4—O4	177.57 (15)
O4^vii—K3—O9—K2^viii	−118.79 (3)	C5—N4—C4—N6	−2.4 (2)
O4—K3—O9—K2^viii	118.79 (3)	K1^iii—O5—C5—N4	66.6 (2)
O10—K3—O9—K2^viii	180.0	K1^xii—O5—C5—N4	171.19 (11)
O2^ix—K3—O10—K2	−58.66 (5)	K1^iii—O5—C5—N5	−112.16 (15)
O2^x—K3—O10—K2	58.66 (5)	K1^xii—O5—C5—N5	−7.6 (2)
O2^iii—K3—O10—K2	−33.95 (2)	C6—N5—C5—O5	178.37 (16)
O2^iv—K3—O10—K2	33.95 (2)	C6—N5—C5—N4	−0.5 (2)
O4—K3—O10—K2	−111.70 (3)	C4—N4—C5—O5	−176.44 (16)
O4^vii—K3—O10—K2	111.70 (3)	C4—N4—C5—N5	2.4 (2)
O9—K3—O10—K2	180.0	C4—N6—C6—O6	−178.51 (16)
O1—K2—O10—K3	114.36 (3)	C4—N6—C6—N5	1.5 (2)
O1^vii—K2—O10—K3	−114.36 (3)	C5—N5—C6—O6	178.63 (15)
O2^iii—K2—O10—K3	40.50 (3)	C5—N5—C6—N6	−1.4 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—D7···N6^ii	0.63 (2)	2.10 (2)	2.7211 (17)	172 (3)
O8—D8···N3^ii	0.79 (2)	2.31 (2)	3.0812 (18)	163 (2)
O10—D10···N3	0.77 (2)	2.07 (2)	2.8358 (17)	173 (2)
O9—D9···O6^xiii	0.78 (2)	2.02 (2)	2.7646 (14)	159 (2)
N2—D2N···O6^xiv	0.85 (2)	1.95 (2)	2.8019 (18)	172 (2)
N1—D1N···O4^iii	0.84 (2)	1.95 (2)	2.7889 (18)	178 (2)
N5—D5N···O3^xiv	0.81 (2)	1.96 (2)	2.7763 (18)	176 (2)
N4—D4N···O1^iii	0.86 (2)	1.91 (2)	2.7704 (17)	173 (2)
N6—D6N···O7^ii	0.80 (4)	1.94 (4)	2.7211 (17)	166 (4)

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+1/2, −y+1/2, −z+1; (xiii) −x, −y+1, −z; (xiv) −x+1/2, −y+1/2, −z.

(3_neutron)

Crystal data

C12D17K3N12O16	Z = 8
Mr = 719.71	F(000) = 3275
Monoclinic, I2/a	Dx = 1.942 Mg m^−3
Hall symbol: -I 2ya	Neutron radiation, λ = 0.5-7.0 Å
a = 12.824 (2) Å	Cell parameters from 11000 reflections
b = 16.332 (3) Å	µ = 0.07+0.00475 mm^−1
c = 23.713 (4) Å	T = 150 K
β = 97.514 (3)°	Block, colourless
V = 4923.8 (15) Å^3	2.00 × 2.00 × 1.00 mm

Data collection

SXD at ISIS neutron source diffractometer	2545 independent reflections
Radiation source: ISIS spallation neutron source	2535 reflections with I > 2σ(I)
None monochromator	Rint = 0.091
time–of–flight Laue diffraction scans	θmax = 83.2°, θmin = 8.7°
Absorption correction: numerical Mu = 0.7cm^-1 at 1.8A calculated using custom ISIS software program SXD-2001.	h = −19→17
Tmin = 0.123, Tmax = 0.497	k = −37→37
8194 measured reflections	l = −62→42

Refinement

Refinement on F^2	Primary atom site location: using coords of known structure
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.068	w = 1/[σ^2(Fo^2) + (0.1144P)^2 + 438.2559P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.182	(Δ/σ)max = 0.048
S = 1.03	Δρmax = 2.01 e Å^−3
8194 reflections	Δρmin = −2.20 e Å^−3
651 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
40 restraints	Extinction coefficient: 0.000083 (3)

Special details

Experimental. For peak integration a local UB matrix refined for each frame, using approximately 100 reflections per run from each of the 11 detectors. Hence _cell_measurement_reflns_used 11000

For final cell dimensions a weighted average of all local cells was calculated

Because of the nature of the experiment, it is not possible to give values of theta_min and theta_max for the cell determination.

The same applies for the wavelength used for the experiment. The range of wavelengths used was 0.48–7.0 Angstroms, BUT the bulk of the diffraction information is obtained from wavelengths in the range 0.7–2.5 Angstroms.

The data collection procedures on the SXD instrument used for the single-crystal neutron data collection are most recently summarized in the Appendix to the following paper Wilson, C·C. (1997). J. Mol. Struct. 405, 207–217

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. The variable wavelength nature of the data collection procedure means that sensible values of _diffrn_reflns_theta_min & _diffrn_reflns_theta_max cannot be given instead the following limits are given

_diffrn_reflns_sin(theta)/lambda_min 0.05 _diffrn_reflns_sin(theta)/lambda_max 1.31

_refine_diff_density_max/min is given in Fermi per per angstrom cubed not electons per angstrom cubed. Another way to consider the _refine_diff_density_ is as a percentage of the diffracted intensity of a given atom: _refine_diff_density_max = 5% of Carbon _refine_diff_density_min = −4% of Carbon

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 (Ų)

	x	y	z	Uiso*/Ueq
K1	0.1743 (8)	0.7470 (9)	0.3123 (2)	0.022 (2)
K2	0.4689 (7)	0.7496 (7)	0.4233 (2)	0.022 (2)
K3	0.7869 (8)	0.7466 (8)	0.4246 (2)	0.021 (2)
O1	0.1437 (14)	0.8506 (3)	0.2088 (4)	0.024 (3)
O2	0.1201 (12)	1.0890 (4)	0.3025 (4)	0.015 (3)
O3	0.1383 (12)	1.0958 (4)	0.1142 (4)	0.008 (2)
N1	0.1295 (8)	0.9712 (3)	0.2550 (2)	0.0150 (18)
N2	0.1261 (9)	1.0981 (2)	0.2095 (3)	0.018 (2)
N3	0.1363 (8)	0.9725 (3)	0.1588 (3)	0.016 (2)
C1	0.1364 (10)	0.9262 (3)	0.2083 (3)	0.010 (2)
C2	0.1253 (11)	1.0557 (3)	0.2557 (3)	0.0148 (18)
C3	0.1330 (11)	1.0566 (4)	0.1573 (3)	0.018 (3)
D1	0.1261 (15)	0.9408 (4)	0.2921 (4)	0.025 (3)
D3	0.1396 (12)	0.9431 (4)	0.1198 (4)	0.018 (3)
O4	0.3570 (12)	0.8549 (3)	0.2929 (3)	0.016 (2)
O5	0.3696 (15)	1.0946 (5)	0.3893 (4)	0.027 (4)
O6	0.4002 (13)	1.0961 (4)	0.1998 (4)	0.014 (2)
N4	0.3665 (8)	0.9744 (2)	0.3406 (2)	0.016 (2)
N5	0.3803 (9)	1.0979 (2)	0.2954 (3)	0.0148 (19)
N6	0.3777 (8)	0.9741 (3)	0.2442 (2)	0.0119 (17)
C4	0.3656 (11)	0.9289 (3)	0.2937 (3)	0.016 (2)
C5	0.3702 (11)	1.0588 (4)	0.3424 (3)	0.011 (3)
C6	0.3869 (10)	1.0582 (3)	0.2435 (3)	0.0090 (18)
D4	0.3677 (14)	0.9442 (5)	0.3791 (3)	0.030 (4)
D5	0.4018 (6)	1.1606 (2)	0.29823 (15)	0.0234 (17)
D6	0.3738 (15)	0.9450 (4)	0.2042 (4)	0.023 (3)
O7	0.6401 (15)	0.8588 (5)	0.4578 (4)	0.019 (2)
O8	0.6110 (13)	1.0994 (4)	0.5516 (4)	0.0129 (17)
O9	0.6248 (12)	1.1012 (4)	0.3623 (3)	0.0118 (19)
N7	0.6267 (10)	0.9789 (2)	0.5062 (3)	0.017 (2)
N8	0.6208 (9)	1.1058 (3)	0.4569 (2)	0.018 (3)
N9	0.6307 (10)	0.9807 (2)	0.4092 (2)	0.012 (2)
C7	0.6324 (12)	0.9346 (4)	0.4561 (3)	0.012 (2)
C8	0.6193 (12)	1.0635 (3)	0.5076 (3)	0.0130 (17)
C9	0.6254 (13)	1.0646 (3)	0.4082 (3)	0.0116 (19)
D7	0.6254 (10)	0.9478 (3)	0.5444 (3)	0.016 (3)
D9	0.6340 (14)	0.9505 (4)	0.3710 (4)	0.026 (3)
O10	0.3878 (14)	0.5968 (4)	0.4474 (4)	0.019 (3)
O11	0.3607 (13)	0.3577 (4)	0.5390 (3)	0.0114 (17)
O12	0.3750 (13)	0.5945 (4)	0.6389 (4)	0.021 (3)
N10	0.3743 (9)	0.4789 (2)	0.4940 (3)	0.0078 (14)
N11	0.3726 (12)	0.4753 (2)	0.5899 (3)	0.017 (2)
N12	0.3781 (8)	0.6043 (3)	0.5425 (2)	0.010 (2)
C10	0.3803 (11)	0.5637 (3)	0.4952 (3)	0.0076 (14)
C11	0.3678 (11)	0.4319 (4)	0.5391 (3)	0.0110 (17)
C12	0.3767 (13)	0.5618 (3)	0.5914 (3)	0.013 (2)
D10	0.3713 (12)	0.4507 (4)	0.4549 (3)	0.027 (4)
D11	0.3767 (13)	0.4455 (4)	0.6281 (4)	0.022 (3)
O13	0.9996 (5)	0.7486 (6)	0.43930 (15)	0.0242 (14)
D13A	1.0456 (11)	0.7965 (3)	0.4469 (3)	0.019 (3)
D13B	1.0423 (13)	0.6998 (5)	0.4456 (3)	0.033 (4)
O14	0.6125 (6)	0.7541 (6)	0.34356 (14)	0.0282 (16)
D14A	0.6116 (13)	0.8020 (5)	0.3207 (4)	0.040 (4)
D14B	0.6053 (13)	0.7073 (5)	0.3187 (3)	0.040 (4)
O15	0.2550 (5)	0.7476 (6)	0.42625 (14)	0.0225 (14)
D15A	0.2261 (10)	0.7002 (4)	0.4417 (3)	0.027 (3)
D15B	0.2266 (12)	0.7941 (4)	0.4419 (3)	0.041 (4)
O16	−0.0452 (5)	0.7505 (5)	0.31794 (12)	0.0237 (14)
D16A	−0.0771 (6)	0.6982 (2)	0.30659 (17)	0.0248 (17)
D16B	−0.0310 (5)	0.7485 (5)	0.35901 (12)	0.0287 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.036 (7)	0.013 (2)	0.0171 (19)	0.000 (7)	0.008 (3)	−0.003 (4)
K2	0.021 (7)	0.0107 (18)	0.038 (3)	0.011 (7)	0.012 (3)	0.011 (4)
K3	0.021 (7)	0.015 (2)	0.031 (2)	0.005 (7)	0.015 (3)	0.002 (4)
O1	0.041 (9)	0.0066 (18)	0.024 (3)	0.000 (3)	0.008 (4)	0.0012 (18)
O2	0.027 (8)	0.0085 (17)	0.010 (2)	0.004 (3)	0.005 (3)	0.0029 (14)
O3	0.007 (7)	0.009 (2)	0.007 (2)	0.004 (3)	−0.002 (3)	0.0033 (17)
N1	0.031 (5)	0.0100 (12)	0.0039 (14)	0.0017 (16)	0.0022 (19)	0.0012 (9)
N2	0.037 (7)	0.0090 (13)	0.0070 (17)	−0.006 (2)	0.004 (2)	0.0012 (10)
N3	0.023 (7)	0.0150 (19)	0.011 (2)	0.005 (3)	0.010 (3)	−0.0025 (16)
C1	0.006 (6)	0.0112 (17)	0.013 (2)	−0.004 (2)	0.001 (3)	0.0000 (16)
C2	0.031 (5)	0.0104 (12)	0.0030 (14)	0.0017 (17)	0.0023 (19)	0.0013 (10)
C3	0.034 (10)	0.010 (2)	0.014 (3)	−0.001 (3)	0.018 (4)	0.002 (2)
D1	0.038 (10)	0.019 (2)	0.019 (3)	0.001 (4)	0.003 (4)	0.005 (2)
D3	0.021 (9)	0.014 (2)	0.020 (3)	0.000 (3)	0.009 (4)	0.003 (2)
O4	0.033 (7)	0.0106 (17)	0.0050 (17)	−0.006 (2)	0.004 (3)	−0.0017 (13)
O5	0.056 (12)	0.019 (3)	0.008 (3)	0.008 (4)	0.009 (4)	0.001 (2)
O6	0.023 (7)	0.016 (2)	0.0025 (18)	−0.005 (3)	0.000 (2)	0.0010 (15)
N4	0.032 (7)	0.0074 (16)	0.006 (2)	0.005 (2)	−0.004 (3)	−0.0013 (13)
N5	0.030 (6)	0.0112 (14)	0.0033 (13)	−0.008 (2)	0.0015 (18)	0.0001 (9)
N6	0.010 (5)	0.0122 (14)	0.0145 (19)	−0.0007 (17)	0.006 (2)	0.0008 (12)
C4	0.033 (7)	0.0107 (17)	0.0054 (18)	−0.006 (2)	0.004 (3)	−0.0015 (13)
C5	0.015 (9)	0.011 (2)	0.006 (2)	−0.002 (3)	−0.005 (3)	0.0018 (19)
C6	0.004 (5)	0.0132 (17)	0.010 (2)	0.002 (2)	0.005 (2)	0.0022 (13)
D4	0.060 (12)	0.020 (3)	0.011 (3)	−0.001 (4)	0.009 (4)	0.007 (2)
D5	0.034 (5)	0.0171 (14)	0.0191 (15)	−0.003 (2)	0.0035 (19)	0.0014 (12)
D6	0.045 (10)	0.018 (2)	0.009 (2)	0.002 (3)	0.012 (3)	−0.0004 (17)
O7	0.022 (8)	0.015 (2)	0.024 (3)	0.006 (3)	0.013 (4)	−0.0007 (18)
O8	0.022 (5)	0.0115 (16)	0.0067 (18)	−0.006 (2)	0.006 (2)	−0.0009 (13)
O9	0.017 (6)	0.0120 (15)	0.006 (2)	−0.003 (2)	0.001 (3)	0.0001 (13)
N7	0.028 (6)	0.0120 (16)	0.011 (2)	−0.006 (2)	0.004 (3)	0.0011 (14)
N8	0.033 (8)	0.014 (2)	0.006 (2)	−0.004 (3)	0.005 (3)	0.0008 (14)
N9	0.023 (6)	0.0087 (12)	0.0038 (17)	0.0041 (19)	0.002 (2)	0.0000 (10)
C7	0.013 (6)	0.017 (2)	0.009 (2)	0.004 (2)	0.006 (2)	0.0026 (13)
C8	0.022 (5)	0.0114 (15)	0.0068 (18)	−0.007 (2)	0.005 (2)	−0.0012 (12)
C9	0.017 (6)	0.0118 (15)	0.006 (2)	−0.003 (2)	0.001 (3)	0.0001 (13)
D7	0.023 (9)	0.0087 (19)	0.018 (3)	0.004 (3)	0.007 (4)	−0.006 (2)
D9	0.039 (10)	0.020 (3)	0.019 (3)	0.000 (4)	0.009 (4)	−0.007 (2)
O10	0.033 (8)	0.011 (2)	0.016 (3)	−0.010 (3)	0.008 (3)	0.0014 (17)
O11	0.024 (5)	0.0056 (14)	0.0051 (15)	0.0008 (19)	0.002 (2)	0.0005 (10)
O12	0.046 (8)	0.0098 (19)	0.010 (2)	−0.006 (3)	0.010 (3)	0.0001 (15)
N10	0.011 (4)	0.0076 (12)	0.0055 (16)	−0.0055 (17)	0.0021 (19)	−0.0003 (11)
N11	0.028 (7)	0.0103 (14)	0.012 (2)	0.006 (2)	0.006 (3)	0.0015 (13)
N12	0.015 (7)	0.0058 (16)	0.011 (3)	−0.005 (3)	0.005 (3)	0.0010 (13)
C10	0.011 (4)	0.0072 (12)	0.0052 (16)	−0.0052 (17)	0.0016 (19)	0.0004 (10)
C11	0.023 (5)	0.0053 (13)	0.0044 (14)	0.0014 (18)	0.0022 (19)	0.0011 (9)
C12	0.020 (7)	0.0102 (17)	0.009 (2)	−0.007 (3)	0.006 (3)	−0.0027 (16)
D10	0.044 (11)	0.023 (3)	0.013 (3)	0.004 (4)	0.004 (4)	−0.008 (2)
D11	0.036 (10)	0.020 (2)	0.009 (3)	0.000 (3)	0.004 (4)	0.002 (2)
O13	0.030 (5)	0.0130 (13)	0.0303 (16)	0.000 (6)	0.006 (2)	−0.010 (3)
D13A	0.016 (8)	0.011 (2)	0.029 (3)	−0.002 (3)	0.004 (4)	−0.007 (2)
D13B	0.050 (12)	0.023 (3)	0.028 (4)	−0.001 (5)	0.009 (5)	−0.007 (2)
O14	0.055 (5)	0.0145 (18)	0.0154 (12)	−0.002 (4)	0.0040 (17)	−0.002 (3)
D14A	0.065 (12)	0.024 (3)	0.030 (4)	0.014 (4)	0.007 (5)	0.002 (2)
D14B	0.072 (11)	0.030 (3)	0.019 (3)	0.007 (4)	0.007 (4)	−0.008 (2)
O15	0.029 (4)	0.0112 (14)	0.0278 (14)	0.003 (5)	0.0049 (18)	−0.003 (3)
D15A	0.032 (10)	0.022 (2)	0.032 (4)	−0.006 (3)	0.015 (5)	0.005 (2)
D15B	0.069 (13)	0.0107 (19)	0.042 (5)	−0.001 (4)	−0.002 (6)	0.000 (2)
O16	0.041 (5)	0.0134 (12)	0.0163 (12)	0.005 (6)	0.0028 (17)	−0.005 (4)
D16A	0.031 (6)	0.0156 (14)	0.0266 (18)	0.000 (2)	0.001 (2)	−0.0021 (13)
D16B	0.036 (4)	0.0286 (15)	0.0220 (11)	0.006 (6)	0.0054 (15)	0.001 (4)

Geometric parameters (Å, º)

K1—O1	2.965 (13)	N5—C5	1.306 (10)
K1—O1^i	2.92 (2)	N5—C6	1.403 (10)
K1—O4	3.01 (2)	N5—D5	1.060 (6)
K1—O4^i	2.983 (11)	N6—C4	1.411 (9)
K1—O9^ii	2.856 (15)	N6—C6	1.380 (7)
K1—O12^iii	2.853 (16)	N6—D6	1.056 (9)
K1—O15	2.764 (6)	O7—C7	1.242 (10)
K1—O16	2.836 (12)	O8—K2^iv	2.765 (14)
K2—O7	2.86 (2)	O8—C8	1.214 (12)
K2—O8^iv	2.765 (14)	O9—K1^vii	2.856 (15)
K2—O10	2.791 (14)	O9—C9	1.239 (11)
K2—O11^v	2.852 (16)	N7—C7	1.401 (10)
K2—O14	2.808 (9)	N7—C8	1.385 (8)
K2—O15	2.753 (11)	N7—D7	1.042 (10)
K3—O3^vi	2.840 (16)	N8—C8	1.390 (9)
K3—O5^vii	2.964 (17)	N8—C9	1.345 (9)
K3—O7	2.812 (17)	N9—C7	1.340 (9)
K3—O11^v	2.768 (17)	N9—C9	1.372 (7)
K3—O13	2.704 (12)	N9—D9	1.039 (11)
K3—O14	2.755 (11)	O10—C10	1.269 (12)
O1—K1^i	2.92 (2)	O11—K2^v	2.852 (16)
O1—C1	1.239 (8)	O11—K3^v	2.768 (17)
O2—C2	1.244 (12)	O11—C11	1.215 (9)
O3—K3^viii	2.840 (16)	O12—K1^iii	2.853 (16)
O3—C3	1.216 (12)	O12—C12	1.248 (11)
N1—C1	1.342 (10)	N10—C10	1.387 (7)
N1—C2	1.381 (7)	N10—C11	1.329 (8)
N1—D1	1.014 (9)	N10—D10	1.030 (10)
N2—C2	1.299 (9)	N11—C11	1.391 (10)
N2—C3	1.424 (10)	N11—C12	1.413 (7)
N3—C1	1.397 (10)	N11—D11	1.024 (10)
N3—C3	1.374 (8)	N12—C10	1.308 (9)
N3—D3	1.046 (10)	N12—C12	1.353 (9)
O4—K1^i	2.983 (11)	O13—D13A	0.982 (12)
O4—C4	1.214 (8)	O13—D13B	0.968 (13)
O5—K3^ii	2.964 (17)	O14—D14A	0.952 (10)
O5—C5	1.255 (13)	O14—D14B	0.963 (10)
O6—C6	1.239 (12)	O15—D15A	0.952 (10)
N4—C4	1.336 (9)	O15—D15B	0.940 (11)
N4—C5	1.380 (8)	O16—D16A	0.969 (9)
N4—D4	1.036 (9)	O16—D16B	0.968 (4)
O1—K1—O1^i	101.1 (4)	K1^i—O4—C4	124.8 (7)
O1—K1—O4	64.0 (4)	K3^ii—O5—C5	134.5 (8)
O1^i—K1—O4^i	64.9 (3)	C4—N4—C5	125.3 (6)
O1—K1—O4^i	68.70 (13)	C4—N4—D4	117.8 (7)
O1^i—K1—O4	68.8 (2)	C5—N4—D4	116.9 (8)
O1^i—K1—O9^ii	140.4 (6)	C5—N5—C6	123.2 (4)
O1—K1—O9^ii	80.6 (4)	C5—N5—D5	118.2 (6)
O1^i—K1—O12^iii	79.5 (5)	C6—N5—D5	117.1 (7)
O1—K1—O12^iii	145.3 (5)	C4—N6—C6	123.3 (5)
O1—K1—O15	143.1 (6)	C4—N6—D6	121.0 (6)
O1^i—K1—O15	87.9 (4)	C6—N6—D6	115.5 (6)
O1—K1—O16	90.2 (4)	O4—C4—N4	123.8 (8)
O1^i—K1—O16	147.0 (6)	O4—C4—N6	121.8 (7)
O4—K1—O4^i	102.8 (3)	N4—C4—N6	114.3 (5)
O4^i—K1—O9^ii	145.0 (5)	O5—C5—N4	119.2 (7)
O4—K1—O9^ii	77.0 (5)	O5—C5—N5	122.7 (7)
O4^i—K1—O12^iii	80.8 (4)	N4—C5—N5	117.9 (6)
O4—K1—O12^iii	142.2 (6)	O6—C6—N5	122.3 (6)
O4—K1—O15	87.0 (4)	O6—C6—N6	122.0 (7)
O4^i—K1—O15	144.3 (6)	N5—C6—N6	115.7 (5)
O4—K1—O16	142.3 (6)	K2—O7—K3	91.8 (4)
O4^i—K1—O16	91.4 (4)	K2—O7—C7	123.9 (12)
O9^ii—K1—O12^iii	121.1 (3)	K3—O7—C7	133.9 (11)
O9^ii—K1—O15	70.5 (4)	K2^iv—O8—C8	133.8 (8)
O9^ii—K1—O16	71.7 (4)	K1^vii—O9—C9	143.8 (7)
O12^iii—K1—O15	71.4 (4)	C7—N7—C8	123.2 (6)
O12^iii—K1—O16	74.0 (5)	C7—N7—D7	119.6 (5)
O15—K1—O16	101.6 (3)	C8—N7—D7	117.2 (7)
O7—K2—O8^iv	71.0 (5)	C8—N8—C9	120.1 (5)
O7—K2—O10	142.3 (4)	C7—N9—C9	124.9 (6)
O7—K2—O11^v	76.4 (2)	C7—N9—D9	117.3 (6)
O7—K2—O14	68.3 (4)	C9—N9—D9	117.8 (7)
O7—K2—O15	136.8 (5)	O7—C7—N7	120.0 (6)
O8^iv—K2—O10	126.5 (3)	O7—C7—N9	125.4 (7)
O8^iv—K2—O11^v	140.4 (5)	N7—C7—N9	114.5 (6)
O8^iv—K2—O14	114.5 (5)	O8—C8—N7	121.1 (7)
O8^iv—K2—O15	66.8 (4)	O8—C8—N8	121.1 (6)
O10—K2—O11^v	71.2 (5)	N7—C8—N8	117.8 (6)
O10—K2—O14	117.2 (5)	O9—C9—N8	121.0 (6)
O10—K2—O15	65.5 (5)	O9—C9—N9	119.5 (7)
O11^v—K2—O14	71.6 (3)	N8—C9—N9	119.5 (6)
O11^v—K2—O15	135.3 (5)	K2—O10—C10	129.6 (7)
O14—K2—O15	139.5 (3)	K2^v—O11—K3^v	93.0 (4)
O3^vi—K3—O5^vii	121.3 (3)	K2^v—O11—C11	123.8 (11)
O3^vi—K3—O7	157.3 (6)	K3^v—O11—C11	131.9 (11)
O3^vi—K3—O11^v	80.8 (5)	K1^iii—O12—C12	140.4 (7)
O3^vi—K3—O13	71.0 (4)	C10—N10—C11	124.8 (6)
O3^vi—K3—O14	95.2 (4)	C10—N10—D10	117.4 (7)
O5^vii—K3—O7	77.7 (5)	C11—N10—D10	117.8 (6)
O5^vii—K3—O11^v	155.7 (6)	C11—N11—C12	122.0 (6)
O5^vii—K3—O13	68.5 (5)	C11—N11—D11	120.9 (6)
O5^vii—K3—O14	93.0 (4)	C12—N11—D11	117.1 (7)
O7—K3—O11^v	78.6 (3)	C10—N12—C12	118.7 (5)
O7—K3—O13	131.1 (6)	O10—C10—N10	114.7 (6)
O7—K3—O14	69.7 (4)	O10—C10—N12	124.3 (6)
O11^v—K3—O13	133.4 (5)	N10—C10—N12	121.0 (6)
O11^v—K3—O14	73.7 (4)	O11—C11—N10	125.9 (6)
O13—K3—O14	143.4 (3)	O11—C11—N11	120.4 (6)
K1—O1—K1^i	78.9 (4)	N10—C11—N11	113.6 (6)
K1—O1—C1	125.3 (7)	O12—C12—N11	116.5 (6)
K1^i—O1—C1	127.2 (11)	O12—C12—N12	123.8 (6)
K3^viii—O3—C3	142.0 (8)	N11—C12—N12	119.6 (6)
C1—N1—C2	124.3 (5)	K3—O13—D13A	127.2 (8)
C1—N1—D1	117.5 (7)	K3—O13—D13B	123.4 (10)
C2—N1—D1	118.2 (7)	D13A—O13—D13B	108.3 (8)
C2—N2—C3	119.2 (4)	K2—O14—K3	94.2 (3)
C1—N3—C3	124.0 (6)	K2—O14—D14A	116.5 (10)
C1—N3—D3	119.8 (6)	K2—O14—D14B	111.9 (10)
C3—N3—D3	116.2 (7)	K3—O14—D14A	112.5 (11)
O1—C1—N1	123.5 (8)	K3—O14—D14B	113.3 (10)
O1—C1—N3	122.6 (8)	D14A—O14—D14B	108.1 (5)
N1—C1—N3	113.9 (5)	K1—O15—K2	102.9 (3)
O2—C2—N1	117.0 (6)	K1—O15—D15A	105.0 (8)
O2—C2—N2	121.8 (6)	K1—O15—D15B	105.9 (8)
N1—C2—N2	121.2 (6)	K2—O15—D15A	117.3 (9)
O3—C3—N2	119.8 (6)	K2—O15—D15B	116.1 (11)
O3—C3—N3	122.9 (7)	D15A—O15—D15B	108.2 (7)
N2—C3—N3	117.4 (6)	K1—O16—D16A	110.8 (7)
K1—O4—K1^i	77.2 (3)	K1—O16—D16B	89.4 (5)
K1—O4—C4	130.6 (11)	D16A—O16—D16B	105.5 (8)
O1^i—K1—O1—K1^i	0.0	C7—N9—C9—O9	179.6 (19)
O1^i—K1—O1—C1	−128.0 (16)	C7—N9—C9—N8	−1 (2)
O4^i—K1—O1—K1^i	−57.3 (4)	D9—N9—C9—O9	0 (3)
O4—K1—O1—K1^i	59.7 (3)	D9—N9—C9—N8	180 (2)
O4—K1—O1—C1	−68.3 (15)	O7—K2—O10—C10	42 (2)
O4^i—K1—O1—C1	174.7 (18)	O8^iv—K2—O10—C10	−64.8 (15)
O9^ii—K1—O1—K1^i	139.8 (6)	O11^v—K2—O10—C10	74.8 (15)
O9^ii—K1—O1—C1	11.7 (15)	O14—K2—O10—C10	131.5 (14)
O12^iii—K1—O1—K1^i	−87.5 (11)	O15—K2—O10—C10	−93.7 (15)
O12^iii—K1—O1—C1	144.5 (14)	K2—O10—C10—N10	−156.7 (10)
O15—K1—O1—K1^i	101.4 (8)	K2—O10—C10—N12	23 (3)
O15—K1—O1—C1	−26.6 (19)	C12—N12—C10—O10	−175.8 (17)
O16—K1—O1—K1^i	−148.8 (6)	C12—N12—C10—N10	4 (2)
O16—K1—O1—C1	83.2 (15)	C11—N10—C10—O10	178.8 (15)
K1—O1—C1—N1	−8 (2)	C11—N10—C10—N12	−1.2 (18)
K1^i—O1—C1—N1	−111.8 (14)	D10—N10—C10—O10	−4 (2)
K1—O1—C1—N3	171.1 (10)	D10—N10—C10—N12	175.9 (17)
K1^i—O1—C1—N3	67.1 (16)	K2^v—O11—C11—N10	103.3 (13)
C2—N1—C1—O1	177.4 (15)	K2^v—O11—C11—N11	−75.1 (17)
C2—N1—C1—N3	−1.5 (19)	K3^v—O11—C11—N10	−123.5 (12)
D1—N1—C1—O1	−4 (3)	K3^v—O11—C11—N11	58 (2)
D1—N1—C1—N3	177.5 (15)	C10—N10—C11—O11	178.6 (16)
C3—N3—C1—O1	−177.0 (15)	C10—N10—C11—N11	−2.9 (19)
C3—N3—C1—N1	2.0 (18)	D10—N10—C11—O11	2 (2)
D3—N3—C1—O1	2 (2)	D10—N10—C11—N11	−179.9 (18)
D3—N3—C1—N1	−178.6 (16)	C12—N11—C11—O11	−177.4 (14)
C3—N2—C2—O2	179.5 (16)	C12—N11—C11—N10	4 (2)
C3—N2—C2—N1	−1 (2)	D11—N11—C11—O11	5 (3)
C1—N1—C2—O2	−179.2 (15)	D11—N11—C11—N10	−173.1 (18)
C1—N1—C2—N2	1 (2)	K1^iii—O12—C12—N11	−158.2 (13)
D1—N1—C2—O2	2 (2)	K1^iii—O12—C12—N12	19 (3)
D1—N1—C2—N2	−177.9 (19)	C10—N12—C12—O12	179.7 (17)
K3^viii—O3—C3—N2	30 (3)	C10—N12—C12—N11	−3 (2)
K3^viii—O3—C3—N3	−147.7 (12)	C11—N11—C12—O12	176.3 (19)
C1—N3—C3—O3	176.2 (16)	C11—N11—C12—N12	−1 (2)
C1—N3—C3—N2	−1.9 (18)	D11—N11—C12—O12	−7 (3)
D3—N3—C3—O3	−3 (2)	D11—N11—C12—N12	176 (2)
D3—N3—C3—N2	178.6 (16)	O3^vi—K3—O13—D13A	164.8 (7)
C2—N2—C3—O3	−176.9 (16)	O3^vi—K3—O13—D13B	−28.4 (6)
C2—N2—C3—N3	1.3 (19)	O5^vii—K3—O13—D13A	28.3 (7)
O1^i—K1—O4—K1^i	56.4 (4)	O5^vii—K3—O13—D13B	−164.9 (7)
O1—K1—O4—K1^i	−58.3 (3)	O7—K3—O13—D13A	−21.3 (8)
O1—K1—O4—C4	66.8 (9)	O7—K3—O13—D13B	145.4 (7)
O1^i—K1—O4—C4	−178.5 (11)	O11^v—K3—O13—D13A	−139.0 (8)
O4^i—K1—O4—K1^i	0.0	O11^v—K3—O13—D13B	27.7 (8)
O4^i—K1—O4—C4	125.2 (10)	O14—K3—O13—D13A	92.5 (10)
O9^ii—K1—O4—K1^i	−144.1 (5)	O14—K3—O13—D13B	−100.8 (11)
O9^ii—K1—O4—C4	−18.9 (9)	O3^vi—K3—O14—K2	118.1 (4)
O12^iii—K1—O4—K1^i	91.4 (8)	O3^vi—K3—O14—D14A	−121.0 (10)
O12^iii—K1—O4—C4	−143.4 (9)	O3^vi—K3—O14—D14B	2.1 (10)
O15—K1—O4—K1^i	145.3 (6)	O5^vii—K3—O14—K2	−120.1 (5)
O15—K1—O4—C4	−89.6 (9)	O5^vii—K3—O14—D14A	0.8 (10)
O16—K1—O4—K1^i	−109.6 (4)	O5^vii—K3—O14—D14B	123.8 (10)
O16—K1—O4—C4	15.6 (11)	O7—K3—O14—K2	−44.4 (4)
K1—O4—C4—N4	67.5 (17)	O7—K3—O14—D14A	76.5 (9)
K1^i—O4—C4—N4	171.4 (10)	O7—K3—O14—D14B	−160.5 (9)
K1—O4—C4—N6	−113.9 (13)	O11^v—K3—O14—K2	39.2 (4)
K1^i—O4—C4—N6	−10 (2)	O11^v—K3—O14—D14A	160.2 (9)
C5—N4—C4—O4	−176.1 (15)	O11^v—K3—O14—D14B	−76.8 (9)
C5—N4—C4—N6	5.1 (19)	O13—K3—O14—K2	−177.1 (9)
D4—N4—C4—O4	6 (2)	O13—K3—O14—D14A	−56.2 (14)
D4—N4—C4—N6	−172.3 (16)	O13—K3—O14—D14B	66.9 (14)
C6—N6—C4—O4	179.5 (14)	O7—K2—O14—K3	44.0 (4)
C6—N6—C4—N4	−1.7 (19)	O7—K2—O14—D14A	−73.8 (10)
D6—N6—C4—O4	5 (3)	O7—K2—O14—D14B	161.2 (10)
D6—N6—C4—N4	−176.5 (15)	O8^iv—K2—O14—K3	99.5 (5)
K3^ii—O5—C5—N4	−148.1 (11)	O8^iv—K2—O14—D14A	−18.3 (11)
K3^ii—O5—C5—N5	36 (3)	O8^iv—K2—O14—D14B	−143.3 (10)
C6—N5—C5—O5	176.3 (16)	O10—K2—O14—K3	−94.8 (5)
C6—N5—C5—N4	0 (2)	O10—K2—O14—D14A	147.4 (10)
D5—N5—C5—O5	11 (2)	O10—K2—O14—D14B	22.4 (10)
D5—N5—C5—N4	−165.2 (10)	O11^v—K2—O14—K3	−38.4 (4)
C4—N4—C5—O5	179.3 (17)	O11^v—K2—O14—D14A	−156.1 (11)
C4—N4—C5—N5	−4.6 (19)	O11^v—K2—O14—D14B	78.9 (10)
D4—N4—C5—O5	−3 (2)	O15—K2—O14—K3	−178.1 (8)
D4—N4—C5—N5	172.8 (17)	O15—K2—O14—D14A	64.2 (13)
C4—N6—C6—O6	178.1 (16)	O15—K2—O14—D14B	−60.9 (13)
C4—N6—C6—N5	−1.9 (17)	O7—K2—O15—K1	116.1 (6)
D6—N6—C6—O6	−7 (2)	O7—K2—O15—D15A	−129.2 (8)
D6—N6—C6—N5	173.2 (17)	O7—K2—O15—D15B	1.0 (9)
C5—N5—C6—O6	−177.4 (17)	O8^iv—K2—O15—K1	102.8 (5)
C5—N5—C6—N6	2.6 (19)	O8^iv—K2—O15—D15A	−142.5 (7)
D5—N5—C6—O6	−12 (2)	O8^iv—K2—O15—D15B	−12.4 (7)
D5—N5—C6—N6	168.3 (11)	O10—K2—O15—K1	−102.2 (5)
O3^vi—K3—O7—K2	−7.5 (11)	O10—K2—O15—D15A	12.5 (7)
O3^vi—K3—O7—C7	−151.0 (12)	O10—K2—O15—D15B	142.6 (7)
O5^vii—K3—O7—K2	141.1 (4)	O11^v—K2—O15—K1	−117.8 (6)
O5^vii—K3—O7—C7	−2.3 (12)	O11^v—K2—O15—D15A	−3.1 (9)
O11^v—K3—O7—K2	−33.4 (3)	O11^v—K2—O15—D15B	127.0 (9)
O11^v—K3—O7—C7	−176.8 (14)	O14—K2—O15—K1	1.6 (10)
O13—K3—O7—K2	−172.3 (4)	O14—K2—O15—D15A	116.2 (8)
O13—K3—O7—C7	44.2 (14)	O14—K2—O15—D15B	−113.6 (9)
O14—K3—O7—K2	43.3 (3)	O1—K1—O15—K2	−72.0 (9)
O14—K3—O7—C7	−100.2 (12)	O1^i—K1—O15—K2	33.7 (6)
O8^iv—K2—O7—K3	−170.3 (4)	O1—K1—O15—D15A	164.7 (11)
O8^iv—K2—O7—C7	−21.5 (7)	O1^i—K1—O15—D15A	−89.5 (9)
O10—K2—O7—K3	64.0 (8)	O1—K1—O15—D15B	50.3 (13)
O10—K2—O7—C7	−147.2 (8)	O1^i—K1—O15—D15B	156.1 (10)
O11^v—K2—O7—K3	32.6 (3)	O4—K1—O15—K2	−35.2 (5)
O11^v—K2—O7—C7	−178.6 (9)	O4^i—K1—O15—K2	72.7 (9)
O14—K2—O7—K3	−42.8 (3)	O4—K1—O15—D15A	−158.4 (9)
O14—K2—O7—C7	106.1 (7)	O4^i—K1—O15—D15A	−50.6 (12)
O15—K2—O7—K3	176.7 (4)	O4—K1—O15—D15B	87.1 (10)
O15—K2—O7—C7	−34.4 (10)	O4^i—K1—O15—D15B	−165.0 (12)
K2—O7—C7—N7	103.0 (12)	O9^ii—K1—O15—K2	−112.5 (5)
K2—O7—C7—N9	−78.2 (19)	O9^ii—K1—O15—D15A	124.3 (10)
K3—O7—C7—N7	−122.8 (12)	O9^ii—K1—O15—D15B	9.9 (11)
K3—O7—C7—N9	56 (2)	O12^iii—K1—O15—K2	113.3 (5)
C9—N9—C7—O7	−177.9 (15)	O12^iii—K1—O15—D15A	−9.9 (10)
C9—N9—C7—N7	1 (2)	O12^iii—K1—O15—D15B	−124.3 (11)
D9—N9—C7—O7	2 (3)	O16—K1—O15—K2	−178.1 (4)
D9—N9—C7—N7	−179.5 (16)	O16—K1—O15—D15A	58.6 (11)
C8—N7—C7—O7	179.3 (16)	O16—K1—O15—D15B	−55.8 (12)
C8—N7—C7—N9	0.3 (19)	O1—K1—O16—D16A	106.5 (5)
D7—N7—C7—O7	−3 (2)	O1^i—K1—O16—D16A	−4.4 (8)
D7—N7—C7—N9	178.2 (18)	O1—K1—O16—D16B	−147.2 (7)
K2^iv—O8—C8—N7	−156.2 (10)	O1^i—K1—O16—D16B	101.9 (9)
K2^iv—O8—C8—N8	23 (3)	O4—K1—O16—D16A	151.0 (5)
C7—N7—C8—O8	177.5 (17)	O4^i—K1—O16—D16A	37.8 (5)
C7—N7—C8—N8	−2.0 (18)	O4—K1—O16—D16B	−102.7 (8)
D7—N7—C8—O8	0 (2)	O4^i—K1—O16—D16B	144.1 (7)
D7—N7—C8—N8	−179.8 (17)	O9^ii—K1—O16—D16A	−173.5 (5)
C9—N8—C8—O8	−177.1 (17)	O9^ii—K1—O16—D16B	−67.1 (7)
C9—N8—C8—N7	2 (2)	O12^iii—K1—O16—D16A	−42.2 (5)
K1^vii—O9—C9—N8	26 (3)	O12^iii—K1—O16—D16B	64.2 (7)
K1^vii—O9—C9—N9	−154.5 (13)	O15—K1—O16—D16A	−108.7 (5)
C8—N8—C9—O9	178.6 (16)	O15—K1—O16—D16B	−2.4 (8)
C8—N8—C9—N9	−1 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—D1···O9^ii	1.02 (1)	1.80 (1)	2.809 (10)	174 (1)
N3—D3···O10^i	1.05 (1)	1.70 (1)	2.734 (12)	166 (2)
N4—D4···O8^iv	1.03 (1)	1.79 (1)	2.807 (10)	171 (2)
N5—D5···O16^vii	1.06 (1)	1.65 (1)	2.690 (12)	165 (1)
N6—D6···O12^ix	1.06 (1)	1.68 (1)	2.738 (11)	175 (1)
N7—D7···O5^iv	1.04 (1)	1.71 (1)	2.746 (12)	173 (1)
N9—D9···O2^vii	1.03 (1)	1.74 (1)	2.763 (11)	172 (1)
N10—D10···O3^i	1.02 (1)	1.80 (1)	2.825 (10)	178 (1)
N11—D11···O6^x	1.02 (1)	1.82 (1)	2.828 (11)	168 (2)
O13—D13A···N8^vii	0.97 (1)	1.87 (1)	2.830 (12)	174 (1)
O14—D14A···O2^vii	0.96 (1)	1.84 (1)	2.756 (13)	158 (1)
O14—D14B···O6^vi	0.96 (1)	1.87 (1)	2.768 (13)	156 (1)
O15—D15A···N12^iii	0.95 (1)	2.12 (1)	3.042 (12)	164 (1)
O15—D15B···N8^ii	0.95 (1)	2.19 (2)	3.098 (11)	160 (1)
O16—D16A···N2^xi	0.96 (1)	1.77 (1)	2.733 (12)	175 (1)
O16—D16A···O3^xi	0.96 (1)	2.71 (1)	3.293 (13)	120 (1)
O16—D16B···O13^xii	0.97 (1)	1.90 (1)	2.864 (6)	178 (1)

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

(4)

Crystal data

C12H16N12O16Rb3	F(000) = 1644
Mr = 840.78	Dx = 2.188 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 4184 reflections
a = 13.1499 (15) Å	θ = 2.5–28.1°
b = 16.6185 (19) Å	µ = 5.83 mm^−1
c = 11.8444 (13) Å	T = 150 K
β = 99.584 (2)°	Plate, colourless
V = 2552.2 (5) Å^3	0.20 × 0.20 × 0.05 mm
Z = 4

Data collection

Bruker SMART 1K CCD diffractometer	2324 independent reflections
Radiation source: sealed tube	1898 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
thin–slice ω scans	θmax = 25.0°, θmin = 2.8°
Absorption correction: multi-scan SADABS	h = −15→15
Tmin = 0.388, Tmax = 0.759	k = −19→19
9291 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: difference Fourier map
wR(F^2) = 0.077	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0253P)^2 + 9.2128P] where P = (Fo^2 + 2Fc^2)/3
2324 reflections	(Δ/σ)max < 0.001
229 parameters	Δρmax = 0.97 e Å^−3
4 restraints	Δρmin = −0.98 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Rb1	0.28616 (5)	0.5000	0.67207 (5)	0.02017 (17)
Rb2	0.58400 (5)	0.5000	0.88045 (5)	0.01854 (16)
Rb3	0.95888 (5)	0.5000	0.64691 (5)	0.01889 (16)
O1	0.3660 (2)	0.34729 (17)	0.6021 (2)	0.0179 (7)
O2	0.3732 (2)	0.34641 (18)	0.2202 (2)	0.0195 (7)
O3	0.3868 (2)	0.11087 (17)	0.4177 (2)	0.0154 (6)
O4	0.8842 (2)	0.65589 (17)	0.7222 (2)	0.0186 (7)
O5	0.8907 (2)	0.89393 (17)	0.9118 (2)	0.0183 (7)
O6	0.8620 (3)	0.65894 (18)	1.0995 (2)	0.0238 (7)
O7	0.8071 (4)	0.5000	0.8620 (4)	0.0225 (10)
H7	0.835 (3)	0.5439 (15)	0.873 (4)	0.027*
O8	0.7440 (3)	0.5000	0.6236 (4)	0.0226 (10)
H8	0.701 (3)	0.536 (2)	0.609 (4)	0.027*
O9	0.4961 (3)	0.5000	0.6408 (4)	0.0218 (10)
H9	0.523 (3)	0.5375 (19)	0.613 (4)	0.026*
O10	1.1346 (4)	0.5000	0.8270 (4)	0.0327 (12)
H10	1.142 (4)	0.465 (2)	0.876 (3)	0.039*
N1	0.3723 (3)	0.3541 (2)	0.4122 (3)	0.0129 (7)
N2	0.3775 (3)	0.2288 (2)	0.3180 (3)	0.0148 (8)
H2N	0.372 (4)	0.209 (3)	0.261 (4)	0.018*
N3	0.3767 (3)	0.2299 (2)	0.5097 (3)	0.0131 (8)
H3N	0.373 (3)	0.208 (3)	0.564 (4)	0.016*
N4	0.8846 (3)	0.7751 (2)	0.8149 (3)	0.0141 (8)
H4N	0.885 (3)	0.798 (3)	0.757 (4)	0.017*
N5	0.8770 (3)	0.7765 (2)	1.0074 (3)	0.0150 (8)
H5N	0.869 (3)	0.797 (3)	1.067 (4)	0.018*
N6	0.8746 (3)	0.6527 (2)	0.9110 (3)	0.0155 (8)
C1	0.3710 (3)	0.3132 (2)	0.5102 (3)	0.0108 (8)
C2	0.3739 (3)	0.3124 (2)	0.3146 (3)	0.0126 (9)
C3	0.3803 (3)	0.1841 (3)	0.4152 (3)	0.0103 (8)
C4	0.8815 (3)	0.6926 (2)	0.8121 (3)	0.0138 (9)
C5	0.8839 (3)	0.8207 (3)	0.9111 (3)	0.0132 (9)
C6	0.8707 (3)	0.6937 (2)	1.0090 (3)	0.0145 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rb1	0.0195 (3)	0.0137 (3)	0.0280 (4)	0.000	0.0057 (3)	0.000
Rb2	0.0292 (3)	0.0146 (3)	0.0131 (3)	0.000	0.0071 (2)	0.000
Rb3	0.0189 (3)	0.0158 (3)	0.0236 (3)	0.000	0.0081 (2)	0.000
O1	0.0310 (18)	0.0159 (16)	0.0072 (15)	0.0004 (13)	0.0040 (12)	−0.0023 (12)
O2	0.0336 (18)	0.0191 (17)	0.0061 (14)	0.0007 (14)	0.0039 (13)	0.0029 (13)
O3	0.0220 (16)	0.0116 (17)	0.0126 (15)	0.0021 (12)	0.0031 (12)	−0.0020 (12)
O4	0.0355 (18)	0.0134 (16)	0.0081 (15)	0.0007 (13)	0.0067 (13)	−0.0005 (12)
O5	0.0282 (18)	0.0122 (17)	0.0151 (16)	−0.0028 (13)	0.0053 (13)	−0.0050 (12)
O6	0.042 (2)	0.0224 (17)	0.0081 (15)	0.0061 (15)	0.0077 (14)	0.0029 (13)
O7	0.038 (3)	0.005 (2)	0.026 (3)	0.000	0.010 (2)	0.000
O8	0.020 (3)	0.012 (2)	0.033 (3)	0.000	−0.002 (2)	0.000
O9	0.023 (2)	0.014 (3)	0.029 (3)	0.000	0.007 (2)	0.000
O10	0.054 (3)	0.031 (3)	0.015 (3)	0.000	0.013 (2)	0.000
N1	0.0213 (19)	0.0100 (18)	0.0072 (17)	−0.0006 (14)	0.0021 (14)	0.0021 (14)
N2	0.022 (2)	0.016 (2)	0.0062 (18)	0.0009 (16)	0.0029 (15)	−0.0032 (15)
N3	0.0196 (19)	0.0114 (19)	0.0084 (18)	0.0007 (15)	0.0027 (15)	0.0047 (15)
N4	0.026 (2)	0.0106 (19)	0.0063 (18)	0.0000 (15)	0.0043 (15)	0.0018 (14)
N5	0.023 (2)	0.0150 (19)	0.0072 (17)	0.0013 (15)	0.0035 (15)	−0.0028 (15)
N6	0.026 (2)	0.0142 (19)	0.0069 (17)	0.0009 (15)	0.0051 (15)	−0.0015 (14)
C1	0.0088 (19)	0.011 (2)	0.012 (2)	−0.0006 (16)	0.0009 (16)	−0.0015 (17)
C2	0.013 (2)	0.014 (2)	0.010 (2)	0.0034 (17)	0.0007 (16)	−0.0004 (17)
C3	0.009 (2)	0.014 (2)	0.008 (2)	0.0012 (16)	0.0007 (15)	0.0002 (16)
C4	0.017 (2)	0.012 (2)	0.012 (2)	0.0002 (18)	0.0014 (17)	0.0018 (17)
C5	0.014 (2)	0.018 (3)	0.007 (2)	0.0010 (17)	−0.0010 (16)	0.0010 (17)
C6	0.016 (2)	0.015 (2)	0.012 (2)	0.0025 (18)	0.0011 (17)	0.0005 (18)

Geometric parameters (Å, º)

Rb1—O1	2.919 (3)	O3—Rb3^v	3.287 (3)
Rb1—O1^i	2.919 (3)	O3—C3	1.221 (5)
Rb1—O3^ii	2.982 (3)	O4—C4	1.232 (5)
Rb1—O3^iii	2.982 (3)	O5—Rb1^xiv	3.429 (3)
Rb1—O5^iv	3.429 (3)	O5—Rb2^ix	3.000 (3)
Rb1—O5^v	3.429 (3)	O5—Rb2^xiv	3.165 (3)
Rb1—O8^vi	3.458 (5)	O5—C5	1.220 (5)
Rb1—O9	2.845 (5)	O6—C6	1.239 (5)
Rb1—O10^vii	2.925 (5)	O7—H7	0.816 (10)
Rb2—O2^viii	2.912 (3)	O8—Rb1^vi	3.458 (5)
Rb2—O2^vi	2.912 (3)	O8—H8	0.820 (10)
Rb2—O5^ix	3.000 (3)	O9—H9	0.818 (10)
Rb2—O5^x	3.000 (3)	O10—Rb1^xv	2.925 (5)
Rb2—O5^v	3.165 (3)	O10—H10	0.821 (10)
Rb2—O5^iv	3.165 (3)	N1—C1	1.348 (5)
Rb2—O7	2.977 (5)	N1—C2	1.351 (5)
Rb2—O9	2.881 (5)	N2—H2N	0.74 (5)
Rb3—O3^xi	2.935 (3)	N2—C2	1.390 (5)
Rb3—O3^xii	2.935 (3)	N2—C3	1.365 (5)
Rb3—O3^xiii	3.287 (3)	N3—H3N	0.74 (5)
Rb3—O3^xiv	3.287 (3)	N3—C1	1.386 (5)
Rb3—O4	2.960 (3)	N3—C3	1.361 (5)
Rb3—O4^i	2.960 (3)	N4—H4N	0.78 (5)
Rb3—O7	3.488 (5)	N4—C4	1.372 (5)
Rb3—O8	2.793 (4)	N4—C5	1.370 (5)
Rb3—O10	2.873 (5)	N5—H5N	0.80 (5)
O1—C1	1.239 (5)	N5—C5	1.373 (5)
O2—Rb2^vi	2.912 (3)	N5—C6	1.378 (5)
O2—C2	1.251 (5)	N6—C4	1.362 (5)
O3—Rb1^ii	2.982 (3)	N6—C6	1.355 (5)
O3—Rb3^xii	2.935 (3)
O1—Rb1—O1^i	120.81 (11)	O3^xiii—Rb3—O7	118.80 (8)
O1—Rb1—O3^ii	69.55 (8)	O3^xiv—Rb3—O7	118.80 (8)
O1^i—Rb1—O3^ii	136.46 (8)	O3^xi—Rb3—O8	134.92 (7)
O1—Rb1—O3^iii	136.46 (8)	O3^xii—Rb3—O8	134.92 (7)
O1^i—Rb1—O3^iii	69.55 (8)	O3^xiii—Rb3—O8	76.73 (9)
O1—Rb1—O5^iv	124.64 (8)	O3^xiv—Rb3—O8	76.73 (9)
O1^i—Rb1—O5^iv	71.00 (7)	O3^xi—Rb3—O10	71.83 (9)
O1—Rb1—O5^v	71.00 (7)	O3^xii—Rb3—O10	71.83 (9)
O1^i—Rb1—O5^v	124.64 (8)	O3^xiii—Rb3—O10	134.35 (8)
O1—Rb1—O8^vi	72.46 (6)	O3^xiv—Rb3—O10	134.35 (8)
O1^i—Rb1—O8^vi	72.46 (6)	O4—Rb3—O4^i	122.14 (11)
O1—Rb1—O9	63.93 (6)	O4—Rb3—O7	61.39 (6)
O1^i—Rb1—O9	63.93 (6)	O4^i—Rb3—O7	61.39 (6)
O1—Rb1—O10^vii	119.53 (6)	O4—Rb3—O8	69.44 (7)
O1^i—Rb1—O10^vii	119.53 (6)	O4^i—Rb3—O8	69.44 (7)
O3^ii—Rb1—O3^iii	76.31 (11)	O4—Rb3—O10	92.44 (7)
O3^ii—Rb1—O5^iv	142.16 (7)	O4^i—Rb3—O10	92.44 (7)
O3^iii—Rb1—O5^iv	98.89 (7)	O7—Rb3—O8	51.66 (13)
O3^ii—Rb1—O5^v	98.89 (7)	O7—Rb3—O10	86.85 (13)
O3^iii—Rb1—O5^v	142.16 (7)	O8—Rb3—O10	138.51 (14)
O3^ii—Rb1—O8^vi	71.74 (8)	Rb1—O1—C1	136.2 (3)
O3^iii—Rb1—O8^vi	71.74 (8)	Rb2^vi—O2—C2	142.1 (3)
O3^ii—Rb1—O9	130.72 (8)	Rb1^ii—O3—Rb3^xii	92.21 (8)
O3^iii—Rb1—O9	130.72 (8)	Rb1^ii—O3—Rb3^v	92.64 (8)
O3^ii—Rb1—O10^vii	70.43 (9)	Rb1^ii—O3—C3	124.1 (2)
O3^iii—Rb1—O10^vii	70.43 (9)	Rb3^xii—O3—Rb3^v	75.33 (7)
O5^iv—Rb1—O5^v	61.87 (9)	Rb3^xii—O3—C3	132.0 (2)
O5^iv—Rb1—O8^vi	143.23 (6)	Rb3^v—O3—C3	126.1 (2)
O5^v—Rb1—O8^vi	143.23 (6)	Rb3—O4—C4	138.7 (3)
O5^iv—Rb1—O9	81.02 (9)	Rb1^xiv—O5—Rb2^ix	110.58 (9)
O5^v—Rb1—O9	81.02 (9)	Rb1^xiv—O5—Rb2^xiv	80.55 (7)
O5^iv—Rb1—O10^vii	72.64 (10)	Rb1^xiv—O5—C5	119.2 (2)
O5^v—Rb1—O10^vii	72.64 (10)	Rb2^ix—O5—Rb2^xiv	77.73 (7)
O8^vi—Rb1—O9	79.54 (12)	Rb2^ix—O5—C5	126.1 (2)
O8^vi—Rb1—O10^vii	131.31 (13)	Rb2^xiv—O5—C5	127.9 (3)
O9—Rb1—O10^vii	149.15 (14)	Rb2—O7—Rb3	138.09 (16)
O2^viii—Rb2—O2^vi	122.47 (11)	Rb2—O7—H7	114 (4)
O2^viii—Rb2—O5^ix	148.04 (8)	Rb3—O7—H7	80 (3)
O2^vi—Rb2—O5^ix	79.53 (8)	Rb1^vi—O8—Rb3	92.51 (13)
O2^viii—Rb2—O5^x	79.53 (8)	Rb1^vi—O8—H8	80 (3)
O2^vi—Rb2—O5^x	148.04 (8)	Rb3—O8—H8	132 (3)
O2^viii—Rb2—O5^v	76.92 (8)	Rb1—O9—Rb2	96.35 (14)
O2^vi—Rb2—O5^v	138.60 (8)	Rb1—O9—H9	124 (3)
O2^viii—Rb2—O5^iv	138.60 (8)	Rb2—O9—H9	106 (3)
O2^vi—Rb2—O5^iv	76.92 (8)	Rb1^xv—O10—Rb3	94.69 (13)
O2^viii—Rb2—O7	73.13 (7)	Rb1^xv—O10—H10	116 (4)
O2^vi—Rb2—O7	73.13 (7)	Rb3—O10—H10	121 (4)
O2^viii—Rb2—O9	70.72 (6)	C1—N1—C2	118.8 (4)
O2^vi—Rb2—O9	70.72 (6)	H2N—N2—C2	115 (4)
O5^ix—Rb2—O5^x	71.96 (11)	H2N—N2—C3	121 (4)
O5^ix—Rb2—O5^v	102.27 (7)	C2—N2—C3	124.3 (4)
O5^x—Rb2—O5^v	63.78 (10)	H3N—N3—C1	118 (4)
O5^ix—Rb2—O5^iv	63.78 (10)	H3N—N3—C3	117 (4)
O5^x—Rb2—O5^iv	102.27 (7)	C1—N3—C3	124.8 (4)
O5^v—Rb2—O5^iv	67.68 (11)	H4N—N4—C4	118 (3)
O5^ix—Rb2—O7	94.83 (9)	H4N—N4—C5	117 (3)
O5^x—Rb2—O7	94.83 (9)	C4—N4—C5	124.7 (4)
O5^v—Rb2—O7	145.97 (5)	H5N—N5—C5	123 (3)
O5^iv—Rb2—O7	145.97 (5)	H5N—N5—C6	113 (3)
O5^ix—Rb2—O9	141.22 (7)	C5—N5—C6	123.9 (4)
O5^x—Rb2—O9	141.22 (7)	C4—N6—C6	120.7 (4)
O5^v—Rb2—O9	85.24 (9)	O1—C1—N1	122.5 (4)
O5^iv—Rb2—O9	85.24 (9)	O1—C1—N3	118.1 (4)
O7—Rb2—O9	99.58 (13)	N1—C1—N3	119.4 (4)
O3^xi—Rb3—O3^xii	77.77 (11)	O2—C2—N1	122.2 (4)
O3^xi—Rb3—O3^xiii	104.67 (7)	O2—C2—N2	118.2 (4)
O3^xii—Rb3—O3^xiii	63.22 (10)	N1—C2—N2	119.6 (4)
O3^xi—Rb3—O3^xiv	63.22 (9)	O3—C3—N2	123.7 (4)
O3^xii—Rb3—O3^xiv	104.67 (7)	O3—C3—N3	123.3 (4)
O3^xiii—Rb3—O3^xiv	68.18 (10)	N2—C3—N3	113.0 (4)
O3^xi—Rb3—O4^i	155.01 (8)	O4—C4—N4	120.7 (4)
O3^xii—Rb3—O4^i	78.91 (8)	O4—C4—N6	121.2 (4)
O3^xi—Rb3—O4	78.91 (8)	N4—C4—N6	118.1 (4)
O3^xii—Rb3—O4	155.01 (8)	O5—C5—N4	123.2 (4)
O3^xiii—Rb3—O4^i	72.16 (7)	O5—C5—N5	122.9 (4)
O3^xiii—Rb3—O4	132.44 (8)	N4—C5—N5	113.9 (4)
O3^xiv—Rb3—O4^i	132.44 (8)	O6—C6—N5	119.5 (4)
O3^xiv—Rb3—O4	72.16 (7)	O6—C6—N6	121.9 (4)
O3^xi—Rb3—O7	134.03 (7)	N5—C6—N6	118.6 (4)
O3^xii—Rb3—O7	134.03 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···N1^vi	0.82 (1)	2.06 (2)	2.860 (4)	164 (5)
O9—H9···N1^vi	0.82 (1)	2.31 (2)	3.103 (4)	163 (5)
O10—H10···O6^xvi	0.82 (1)	2.08 (3)	2.779 (3)	143 (5)
N2—H2N···O6^xvii	0.74 (5)	2.07 (5)	2.813 (5)	176 (5)
N3—H3N···O4^v	0.74 (5)	2.05 (5)	2.788 (4)	172 (5)
N4—H4N···O1^xiv	0.78 (5)	1.99 (5)	2.765 (4)	172 (5)
N5—H5N···O2^xviii	0.80 (5)	1.99 (5)	2.783 (4)	171 (5)
O7—H7···N6	0.82 (1)	1.92 (2)	2.720 (4)	168 (5)

Symmetry codes: (v) x−1/2, y−1/2, z; (vi) −x+1, −y+1, −z+1; (xiv) x+1/2, y+1/2, z; (xvi) −x+2, −y+1, −z+2; (xvii) x−1/2, y−1/2, z−1; (xviii) x+1/2, y+1/2, z+1.

 

Footnotes

¹Supplementary data for this paper are available from the IUCr electronic archives (Reference: BS5033 ). Services for accessing these data are described at the back of the journal.