Coordination polymeric structures in the sodium salt of 4-chloro-3-nitro­benzoic acid and the sodium and potassium salts of 4-nitro­anthranilic acid

The structures of the hydrated sodium salts of 4-chloro-3-nitro­benzoic acid {poly[aqua­([mu]₄-4-chloro-3-nitro­ben­zoato)sodium(I)], [Na(C₇H₃ClNO₄)(H₂O)]_n, (I)} and 2-amino-4-nitro­benzoic acid {poly[[mu]-aqua-aqua­([mu]₃-2-amino-4-nitro­benzo­ato)sodium(I)], [Na(C₇H₅N₂O₄)(H₂O)₂]_n, (II)}, and the hydrated potassium salt of 2-amino-4-nitro­benzoic acid {poly[[mu]-aqua-aqua­([mu]₅-2-amino-4-nitro­benzoato)potassium(I)], [K(C₇H₅N₂O₄)(H₂O)]_n, (III)} have been determined and their complex polymeric structures described. All three structures are stabilized by intra- and inter­molecular hydrogen bonding and strong [pi]-[pi] ring inter­actions. In the structure of (I), the distorted trigonal bipyrimidal NaO₅ coordination polyhedron comprises a monodentate water mol­ecule and four bridging carboxyl­ate O-atom donors, generating a two-dimensional polymeric structure lying parallel to (001). Intra-layer hydrogen-bonding associations and strong inter-ring [pi]-[pi] inter­actions are present. Structure (II) has a distorted octa­hedral NaO₆ stereochemistry, with four bridging O-atom donors, two from a single carboxyl­ate group and two from a single nitro group and three from the two water mol­ecules, one of which is bridging. Na centres are linked through centrosymmetric four-membered duplex water bridges and through 18-membered duplex head-to-tail ligand bridges. Similar centrosymmetric bridges are found in the structure of (III), and in both (II) and (III) strong inter-ring [pi]-[pi] inter­actions are found. A two-dimensional layered structure lying parallel to (010) is generated in (II), whereas in (III) the structure is three-dimensional. With (III), the irregular KO₇ coordination polyhedron comprises a doubly bridging water mol­ecule, a single bidentate bridging carboxyl­ate O-atom donor and three bridging O-atom donors from the two nitro groups. A three-dimensional structure is generated. These coordination polymer structures are among the few examples of metal complexes of any type with either 4-chloro-3-nitro­benzoic acid or 4-nitro­anthranilic acid.

S1. Introduction

The structures of the alkali metal salts with aromatic carb­oxy­lic acids are of inter­est because of their ability to form polymeric systems. With the lighter Group 1 metals Na and K in particular, despite the simple chemical formulae of the salts, they display extensive polymeric complex structures in the solid state, e.g. sodium 4-hy­droxy­benzoate (Dinnebier, Von Dreele et al., 2002) and potassium 2-hy­droxy­benzoate (Dinnebier, Jelonek et al., 2002). These structures are usually based on regular although commonly distorted six- or seven-coordination centres about the metals with the carboxyl and often water O-atom donors giving metal–metal bridging. Hydrogen-bonding involving the coordinated water molecules when present result in two- and three-dimensional structures in which π–π aromatic ring inter­actions may also be found, e.g. with sodium and potassium anthranilate (Wiesbrock & Schmidbaur, 2002). The nitro-substituted benzoic acid analogues have proved to be particularly useful as ligands for the formation of stable complexes with the alkali metals, often having nitro-O as well as water involvement in the coordination which along with the carboxyl O-atom donors, commonly form single or multiple bridges between metal centres. A number of structures of sodium and potassium complexes with these nitro­benzoates are known, e.g. for sodium: with 4-nitro­benzoic acid (a trihydrate) (Turowska-Tyrk et al., 1988); 2,4-di­chloro-5-nitro­benzoic acid (a dihydrate) (Morales et al., 1999); 3,5-di­nitro­benzoic acid (anhydrous) (Jones et al., 2005; Yang & Ng, 2007); 2-methyl-3,5-di­nitro­benzoic acid (anhydrous) (Danish et al., 2010) and for potassium: with 3,5-di­nitro­benzoic acid (anhydrous) (Du & Hu, 2006); 2-methyl-3,5-di­nitro­benzoic acid (anhydrous) (Danish et al., 2010). Anhydrous (1:1) 3,5-di­nitro­benzoate–3,5-di­nitro­benzoic acid complex adducts with both Na (Tiekink et al., 1990) and K (Askarinejad et al., 2007) as well as a 1:1 potassium complex adduct with 4-nitro­benzoic acid (Srivastava & Speakman, 1961), are also known.

S2. Experimental

S2.1. Synthesis and crystallization

The title salts were prepared by the addition of solid NaHCO₃ (1 mmol, 94 mg) to a hot solution of either 4-chloro-3-nitro­benzoic acid (1 mmol, 200 mg) [for (I)] or 2-amino-4-nitro­benzoic acid (4-nitro­anthranilic acid) (1 mmol, 180 mg) [for (II)] in an ethanol–water mixture (15 ml, 1:2 v/v). With (III), a similar procedure was used but with 4-nitro­anthranilic acid and K₂CO₃ (1 mmol, 140 mg). Partial room-temperature evaporation of the solutions gave large colourless needle prisms of (I), orange prisms of (II) and small red single-crystal plates of (III) from which, for (I) and (II), suitable specimens were cleaved for the X-ray analyses.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The amine and water H atoms were located in difference Fourier maps but were allowed to ride in the refinement, with U_iso(H) = 1.2U_eq(N) or 1.5U_eq(O). Other H atoms were included in the refinement in calculated positions, with C—H = 0.95 Å, and were also allowed to ride, with U_iso(H) = 1.2U_eq(C).

S3. Results and discussion

The general coordination chemistry of the two nitro­benzoic acids involved in this work, 4-chloro-3-nitro­benzoic acid (CLNBA) and 4-nitro­anthranilic acid (4-NAA), is not extensive. There were no reported structures of alkali metal complexes of either acid until that of the polymeric Cs complex with 4-NAA, [Cs₂(C₇H₅N₂O₄)₂(H₂O)₂]_n (Smith & Wermuth, 2011), while no metal complex structures with CLNBA are known, although the structure of the analogous sodium 3,5-di­chloro-3-nitro­benzoate trihydrate is known (Morales et al., 1999). This paucity of structural data on alkali metal complexes with these two ligands prompted the present study giving the structures reported here, the hydrated sodium salts with 4-chloro-3-nitro­benzoic acid, (I), and 2-amino-4-nitro­benzoic acid, (II), and the hydrated potassium salt of 2-amino-4-nitro­benzoic acid, (III). The basic asymmetric units for (I)–(III) are shown in Figs. 1, 4 and 5.

In the structure of (I) (Fig. 1), the NaO₅ coordination polyhedron has a very distorted trigonal bipyramidal stereochemistry, comprising O-atom donors from a monodentate water molecule and four O-atom donors from bridging carboxyl­ate groups [Na–O = 2.3115 (18)–2.4532 (16) Å; Table 2]. The nitro group is not involved in coordination. Sodium more commonly assumes a slightly distorted o­cta­hedral stereochemistry such as with complex (II). In (I), one of the carboxyl­ate O atoms (O12) links Na centres, giving a centrosymmetric cyclic bridge, with an Na···Naⁱⁱ separation of 3.5343 (17) Å [symmetry code: (ii) -x+1, -y+1, -z+1; Table 2]. The other carboxyl­ate O-atom donor (O11) provides a second bridging linkage to another Na centre through an O:O' association, enclosing a series of eight-membered ring systems lying parallel to (001), with additional Na···Na separations of 4.0333 and 3.7083 (17) Å [for Na···Na^vii and Na···Na^ix, respectively; symmetry codes: (vii) x+1/2, -y+1/2, -z+1; (ix) -x, -y, -z+1] (Fig. 2). The two-dimensional layered structure generated is stabilized by intra­molecular water O—H···O and C—H···O hydrogen-bonding inter­actions to carboxyl­ate and nitro O-atom acceptors, as well as a weak C2—H···O1W hydrogen bond (Table 3). In addition, π–π inter­actions between the benzene rings are present [minimum ring-centroid separation for Cg···Cgⁱⁱⁱ = 3.5062 (12) Å; symmetry code: (iii) -x+3/2, y-1/2, z+1] (Fig. 3).

In the CLNBA ligand, the carboxyl­ate group is essentially coplanar with the benzene ring [torsion angle C2—C1—C11—O11 = 179.69 (19)°], while the nitro group is rotated well out of the plane [C2—C3—N3—O32 = -137.8 (2)°]. In the parent acid CLNBA (Ferguson & Sim, 1959; Ishida & Fukunaga, 2003), the corresponding torsion angles are -174.02 (17) and -132.61 (18)°, respectively.

With the sodium 4-nitro­anthanilate dihydrate complex, (II), the common distorted o­cta­hedral NaO₆ stereochemistry for sodium is found (Fig. 4) [Na—O = 2.3919 (14)–2.5947 (18) Å; Table 4]. The donors comprise a monodentate water molecule (O2W), a bridging water (O1W), a bridging carboxyl­ate O atom (O12) and a bridging nitro O atom (O42). Both the second carboxyl­ate O atom (O11) and the N atom of the 2-amino group are uncoordinated. The features of the centrosymmetric cyclic duplex carboxyl­ate bridge are similar to those found in (III) [Na···Naⁱⁱ and Na···Naⁱⁱⁱ = 3.6687 (14) and 3.5889 (14) Å, respectively] and link the Na centres down a (Fig. 5) [symmetry codes: (ii) -x, -y, -z; (ii) -x+1, -y, -z; Table 4]. However, linking the Na centres across c are a pair of inversion-related ligand molecules through carboxyl­ate atom O12 at one end and nitro atom O42 at the other, giving a cyclic 18-membered duplex bridge. Present within these linking structures are π–π inter­actions between the benzene rings [ring centroid separation Cg···Cg^vii = 3.5436 (13) Å; symmetry code: (vii) -x+1, -y, -z+1]. The resulting coordination polymeric structure is a two-dimensional sheet lying parallel to (010). Extensive intra- and inter­molecular hydrogen-bonding inter­actions (Table 5) stabilize the structure.

The coordination mode in (II) is quite different from those found in the polymeric sodium anthranilate structure (seven-coordinate, carboxyl­ate O:O'-bridged but involving the amine and carboxyl groups in a bidentate chelate mode) (Wiesbrock & Schmidbaur, 2002) or in the polymeric sodium 3,5-di­chloro­anthranilate hexahydrate structure (two independent and different o­cta­hedral NaO₆ centres, with bis-aqua and carboxyl­ate O:O'-bridges, but also with bidentate chelate carboxyl­ate O,O' inter­actions (Rzaczyńska et al., 2000). The difference between (I) and (II) (NaO₅ cf. NaO₆ coordination) would appear to be because of the stereochemical crowding of the meta-related nitro group by the para-chloro group, preventing its participation in coordination to the metal or giving polymer extension such as that present with the para-related nitro substituent in (II).

In the structure of the potassium 4-nitro­anthranilate monohydrate salt, (III), the KO₇ coordination polyhedron has irregular stereochemistry: two O-atom donors from a bridging water molecule, two O-atom donors from a bidentate bridging carboxyl­ate O atom (O12) and three O-atom donors from bridging nitro groups [one singly bridging (O41) and the other doubly bridging (O42)] (Fig. 6). The K—O bond length range is 2.7062 (14)–3.0459 (16) Å (Table 6). The water molecule, together with carboxyl­ate atom O12 and the two carboxyl­ate O:O'-bridging O atoms, give a triple bridge between K centres, forming chains which extend down b (Fig. 7). The K···K separation is 4.0432 (4) Å. The links across a are provided by duplex centrosymmetric head-to-tail 4-NBA ligands through atoms O12 and O41, giving 18-membered cyclic bridges similar to those found in (II). Present also are the inter-ring π–π inter­actions [minimum Cg···Cg^ix = 3.6528 (10) Å; symmetry code: (ix) -x+1, -y+1, -z+1]. These linkages give a three-dimensional framework coordination polymer structure in which there are a number of inter­molecular O—H···O and N—H···O hydrogen-bonding inter­actions (Table 7). The seven-coordination in (III) is also found in the structure of potassium anthranilate monohydrate (Wiesbrock & Schmidbaur, 2002; Rzaczyńska et al., 2004), but the coordination mode in that polymeric structure is quite different, involving along with the common bridging water, a bidentate O,O'-chelate and a bridging carboxyl­ate inter­action.

The comparative conformational features of the 4-nitro­anthranilate ligands in (II) and (III) are similar, with the carboxyl­ate and nitro groups close to being coplanar with the benzene ring [C2—C1—C11—O11 = -171.9 (2)° in (I) and -179.68 (16)° in (II); C3—C4—N4—O42 = 179.3 (2)° in (I) and 178.18 (16)° in (II)]. The intra­molecular N—H···O12 hydrogen bond is present in both structures [N···O = 2.7022 (19) Å in (II) and 2.656 (2) Å in (III)], these structural features being similar to those found in the parent acid 4-NAA and its adducts (Wardell & Tiekink, 2011) and in the Cs complex with 4-NAA (Smith & Wermuth, 2011).

The structures reported here, while being uncommon examples of metal complexes of either 4-chloro-3-nitro­benzoic acid or 4-nitro­anthranilic acid, also indicate the utility of the nitro-substituted benzoic acids for the formation of stable crystalline coordination polymeric complexes with the alkali metals.

Related literature

For related literature, see: Askarinejad et al. (2007); Danish et al. (2010); Dinnebier, Jelonek, Seiler & Stephens (2002); Dinnebier, Von Dreele, Stephens, Jelonek & Seiler (2002); Ferguson & Sim (1959); Ishida & Fukunaga (2003); Jones et al. (2005); Morales et al. (1999); Rzaczyńska et al. (2000, 2004); Smith & Wermuth (2011); Srivastava & Speakman (1961); Tiekink et al. (1990); Wardell & Tiekink (2011); Yang & Ng (2007).

Computing details

For all compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I), (II); SIR92 (Altomare et al., 1993) for (III). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular configuration and atom-numbering scheme for the basic repeat unit of (I), with non-H atoms drawn as 40% probability displacement ellipsoids. [Symmetry codes: (i) x-1/2, -y+1/2, -z+1; (ii) -x+1, -y+1, -z+1; (iii) -x+3/2, y-1/2, z.]
	Fig. 2. The partial cyclic-bridged polymer extension in the structure of (I). Non-associative H atoms have been omitted. [Symmetry codes: (vii) x+1/2, -y+1/2, -z+1; (viii) -x+1/2, y+1/2, -z; for other codes, see Fig. 1.]
	Fig. 3. The two-dimensional polymeric structure of (I) in the unit cell viewed down a. Non-associative H atoms have been omitted and hydrogen bonds are shown as dashed lines.
	Fig. 4. The molecular configuration and atom-numbering scheme for the repeat unit of (II), with non-H atoms drawn as 40% probability displacement ellipsoids. [Symmetry codes: (i) x, y, z-1; (ii) -x, -y, -z; (iii) -x+1, -y, -z.]
	Fig. 5. The polymeric structure of (II) in the unit cell viewed down b. Non-associative H atoms have been omitted. [Symmetry codes: (i) x, y, z-1; (ii) -x, -y, -z; (iii) -x+1, -y, -z.]
	Fig. 6. The molecular configuration and atom-numbering scheme for the repeat unit of (III), with non-H atoms drawn as 40% probability displacement ellipsoids. [Symmetry codes: (i) -x, y-1/2, -z+1/2; (ii) -x, y+1/2, -z+1/2; (iii) -x+1, y-1/2, -z+1/2; (iv) -x+1, -y, -z+1; (v) x-1, -y+1/2, z-1.2.]
	Fig. 7. The polymeric structure of (III) in the unit cell viewed down c. Non-associative H atoms have been omitted. [Symmetry codes: (i) -x, y-1/2, -z+1/2; (ii) -x, y+1/2, -z+1/2; (iii) -x+1, y-1/2, -z+1/2; (iv) -x+1, -y, -z+1; (v) x-1, -y+1/2, z-1.2.]

(I) Poly[aqua(µ₄-4-chloro-3-nitrobenzoato)sodium(I)]

Crystal data

[Na(C7H3ClNO4)(H2O)]	F(000) = 976
Mr = 241.56	Dx = 1.786 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3227 reflections
a = 7.9406 (4) Å	θ = 3.5–28.4°
b = 6.8025 (4) Å	µ = 0.47 mm^−1
c = 33.2700 (17) Å	T = 200 K
V = 1797.11 (17) Å^3	Plate, colourless
Z = 8	0.35 × 0.23 × 0.16 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	1762 independent reflections
Radiation source: Enhance (Mo) X-ray source	1643 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.6°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −5→8
Tmin = 0.963, Tmax = 0.990	l = −41→41
11239 measured reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.037P)^2 + 1.4996P] where P = (Fo^2 + 2Fc^2)/3
1762 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
Cl4	0.61917 (8)	0.65133 (10)	0.27191 (2)	0.0424 (2)
Na1	0.43553 (10)	0.25681 (12)	0.48941 (2)	0.0281 (3)
O1W	0.2368 (2)	0.3161 (3)	0.44011 (5)	0.0400 (5)
O11	0.92659 (17)	0.4788 (2)	0.45590 (4)	0.0255 (4)
O12	0.65361 (17)	0.4655 (2)	0.46968 (4)	0.0267 (4)
O31	0.2537 (2)	0.6340 (3)	0.36052 (5)	0.0408 (5)
O32	0.3141 (2)	0.4742 (3)	0.30652 (5)	0.0483 (6)
N3	0.3541 (2)	0.5563 (3)	0.33740 (5)	0.0292 (6)
C1	0.7337 (2)	0.5188 (3)	0.40189 (5)	0.0175 (5)
C2	0.5677 (2)	0.5251 (3)	0.38922 (6)	0.0187 (5)
C3	0.5321 (2)	0.5583 (3)	0.34907 (6)	0.0203 (5)
C4	0.6591 (3)	0.5901 (3)	0.32095 (6)	0.0235 (6)
C5	0.8247 (3)	0.5830 (3)	0.33389 (6)	0.0259 (6)
C6	0.8609 (2)	0.5461 (3)	0.37387 (6)	0.0226 (6)
C11	0.7742 (2)	0.4845 (3)	0.44583 (6)	0.0183 (5)
H2	0.47880	0.50680	0.40800	0.0220*
H5	0.91370	0.60350	0.31530	0.0310*
H6	0.97510	0.53930	0.38230	0.0270*
H11W	0.14440	0.36210	0.44260	0.0600*
H12W	0.23520	0.25090	0.41960	0.0600*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl4	0.0510 (4)	0.0600 (4)	0.0163 (3)	−0.0006 (3)	0.0002 (2)	0.0076 (2)
Na1	0.0310 (5)	0.0262 (4)	0.0270 (5)	0.0026 (4)	0.0087 (3)	0.0021 (3)
O1W	0.0293 (8)	0.0461 (10)	0.0446 (10)	0.0045 (7)	−0.0029 (7)	−0.0136 (8)
O11	0.0211 (7)	0.0315 (8)	0.0239 (8)	0.0011 (6)	−0.0062 (6)	−0.0030 (6)
O12	0.0260 (7)	0.0353 (8)	0.0189 (7)	−0.0041 (6)	0.0026 (6)	0.0008 (6)
O31	0.0223 (7)	0.0608 (11)	0.0394 (9)	0.0062 (8)	−0.0008 (7)	0.0040 (8)
O32	0.0469 (10)	0.0687 (13)	0.0294 (9)	−0.0151 (9)	−0.0177 (8)	−0.0014 (9)
N3	0.0277 (9)	0.0354 (10)	0.0244 (10)	−0.0037 (8)	−0.0058 (8)	0.0073 (8)
C1	0.0189 (9)	0.0145 (9)	0.0190 (9)	−0.0001 (7)	0.0001 (7)	−0.0004 (7)
C2	0.0197 (9)	0.0172 (9)	0.0191 (10)	−0.0004 (8)	0.0017 (7)	0.0000 (7)
C3	0.0202 (9)	0.0206 (9)	0.0202 (10)	0.0010 (8)	−0.0032 (8)	−0.0002 (8)
C4	0.0331 (11)	0.0227 (10)	0.0148 (9)	0.0009 (9)	0.0011 (8)	0.0000 (7)
C5	0.0280 (10)	0.0265 (11)	0.0233 (10)	−0.0014 (9)	0.0083 (9)	−0.0003 (8)
C6	0.0194 (10)	0.0218 (10)	0.0267 (11)	−0.0010 (8)	0.0012 (8)	0.0003 (8)
C11	0.0204 (9)	0.0141 (9)	0.0204 (10)	−0.0002 (7)	−0.0018 (8)	−0.0026 (7)

Geometric parameters (Å, º)

Na1—O1W	2.3115 (18)	N3—C3	1.466 (2)
Na1—O12	2.3334 (16)	C1—C11	1.515 (3)
Na1—O11^i	2.4258 (15)	C1—C2	1.385 (2)
Na1—O12^ii	2.4335 (16)	C1—C6	1.387 (2)
Na1—O11^iii	2.4532 (16)	C2—C3	1.384 (3)
Cl4—C4	1.714 (2)	C3—C4	1.393 (3)
O11—C11	1.256 (2)	C4—C5	1.385 (3)
O12—C11	1.250 (2)	C5—C6	1.384 (3)
O31—N3	1.227 (2)	C2—H2	0.9500
O32—N3	1.212 (2)	C5—H5	0.9500
O1W—H11W	0.8000	C6—H6	0.9500
O1W—H12W	0.8100
O1W—Na1—O12	101.59 (6)	C2—C1—C6	118.98 (16)
O1W—Na1—O11^i	128.87 (7)	C2—C1—C11	120.04 (15)
O1W—Na1—O12^ii	93.60 (6)	C1—C2—C3	119.56 (16)
O1W—Na1—O11^iii	96.70 (6)	N3—C3—C2	116.81 (15)
O11^i—Na1—O12	129.40 (6)	N3—C3—C4	121.45 (18)
O12—Na1—O12^ii	84.32 (5)	C2—C3—C4	121.73 (16)
O11^iii—Na1—O12	90.57 (5)	Cl4—C4—C3	122.92 (17)
O11^i—Na1—O12^ii	94.87 (5)	Cl4—C4—C5	118.71 (17)
O11^i—Na1—O11^iii	81.06 (5)	C3—C4—C5	118.26 (18)
O11^iii—Na1—O12^ii	169.24 (6)	C4—C5—C6	120.17 (19)
Na1^iv—O11—C11	104.40 (12)	C1—C6—C5	121.27 (17)
Na1—O12—C11	144.08 (13)	O11—C11—O12	124.42 (18)
Na1—O12—Na1^ii	95.69 (5)	O11—C11—C1	117.82 (16)
Na1^ii—O12—C11	119.83 (13)	O12—C11—C1	117.76 (15)
Na1—O1W—H11W	128.00	C1—C2—H2	120.00
Na1—O1W—H12W	121.00	C3—C2—H2	120.00
H11W—O1W—H12W	107.00	C4—C5—H5	120.00
O31—N3—O32	124.02 (17)	C6—C5—H5	120.00
O31—N3—C3	117.15 (17)	C1—C6—H6	119.00
O32—N3—C3	118.79 (17)	C5—C6—H6	119.00
C6—C1—C11	120.97 (15)
O1W—Na1—O12—C11	−79.2 (2)	O31—N3—C3—C2	40.1 (3)
O1W—Na1—O12—Na1^ii	92.53 (7)	O32—N3—C3—C2	−137.8 (2)
O11^i—Na1—O12—C11	96.7 (2)	O31—N3—C3—C4	−140.6 (2)
O11^i—Na1—O12—Na1^ii	−91.64 (7)	O32—N3—C3—C4	41.6 (3)
O12^ii—Na1—O12—C11	−171.7 (2)	C11—C1—C2—C3	179.42 (19)
O12^ii—Na1—O12—Na1^ii	0.02 (9)	C2—C1—C6—C5	1.2 (3)
O11^iii—Na1—O12—C11	17.8 (2)	C6—C1—C2—C3	0.0 (3)
O11^iii—Na1—O12—Na1^ii	−170.51 (5)	C6—C1—C11—O12	178.38 (19)
O1W—Na1—O11^i—C11^i	−34.83 (15)	C2—C1—C11—O11	179.60 (19)
O12—Na1—O11^i—C11^i	150.41 (12)	C2—C1—C11—O12	−1.0 (3)
O1W—Na1—O12^ii—Na1^ii	−101.30 (6)	C11—C1—C6—C5	−178.16 (19)
O1W—Na1—O12^ii—C11^ii	84.32 (14)	C6—C1—C11—O11	−1.0 (3)
O12—Na1—O12^ii—Na1^ii	0.00 (7)	C1—C2—C3—N3	177.91 (19)
O12—Na1—O12^ii—C11^ii	−174.38 (14)	C1—C2—C3—C4	−1.4 (3)
O1W—Na1—O11^iii—C11^iii	118.41 (15)	N3—C3—C4—Cl4	6.1 (3)
O12—Na1—O11^iii—C11^iii	16.67 (15)	N3—C3—C4—C5	−177.73 (19)
Na1^iv—O11—C11—O12	34.0 (2)	C2—C3—C4—Cl4	−174.54 (16)
Na1^iv—O11—C11—C1	−146.67 (15)	C2—C3—C4—C5	1.6 (3)
Na1—O12—C11—O11	−109.7 (2)	Cl4—C4—C5—C6	175.97 (16)
Na1—O12—C11—C1	70.9 (3)	C3—C4—C5—C6	−0.3 (3)
Na1^ii—O12—C11—O11	79.8 (2)	C4—C5—C6—C1	−1.1 (3)
Na1^ii—O12—C11—C1	−99.50 (18)

Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+3/2, y−1/2, z; (iv) 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
O1W—H11W···O11^v	0.80	1.95	2.751 (2)	173
O1W—H12W···O31^vi	0.81	2.12	2.924 (2)	169
C2—H2···O1W	0.95	2.55	3.434 (2)	154
C6—H6···O31^vii	0.95	2.42	3.207 (2)	141

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

(II) Poly[µ-aqua-aqua(µ₃-2-amino-4-nitrobenzoato)sodium(I)]

Crystal data

[Na(C7H5N2O4)(H2O)2]	Z = 2
Mr = 240.15	F(000) = 248
Triclinic, P1	Dx = 1.660 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6110 (6) Å	Cell parameters from 1629 reflections
b = 6.9443 (7) Å	θ = 3.3–28.4°
c = 11.7453 (11) Å	µ = 0.18 mm^−1
α = 75.054 (8)°	T = 200 K
β = 85.243 (7)°	Prism, orange-yellow
γ = 67.249 (9)°	0.40 × 0.20 × 0.18 mm
V = 480.35 (8) Å^3

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	1889 independent reflections
Radiation source: fine-focus sealed tube	1552 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.3°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −8→8
Tmin = 0.95, Tmax = 0.98	l = −14→14
5509 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0545P)^2 + 0.0795P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1889 reflections	Δρmax = 0.22 e Å^−3
146 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.088 (9)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
Na1	0.22849 (11)	0.08204 (11)	−0.05787 (6)	0.0250 (2)
O1W	0.1586 (2)	−0.2406 (2)	0.01889 (11)	0.0270 (4)
O2W	0.2115 (2)	0.4538 (2)	−0.10897 (11)	0.0281 (4)
O11	0.3889 (2)	−0.3339 (2)	0.22854 (11)	0.0259 (4)
O12	0.3942 (2)	−0.0138 (2)	0.13256 (10)	0.0236 (4)
O41	0.1397 (3)	0.2885 (3)	0.66462 (13)	0.0437 (6)
O42	0.2066 (3)	−0.0423 (3)	0.75486 (12)	0.0427 (6)
N2	0.2218 (3)	0.3142 (2)	0.23966 (13)	0.0263 (5)
N4	0.1882 (2)	0.0988 (3)	0.66469 (14)	0.0292 (5)
C1	0.3060 (3)	−0.0682 (3)	0.33713 (15)	0.0178 (5)
C2	0.2484 (3)	0.1489 (3)	0.34038 (15)	0.0200 (5)
C3	0.2092 (3)	0.1986 (3)	0.45054 (16)	0.0229 (6)
C4	0.2282 (3)	0.0385 (3)	0.55096 (15)	0.0230 (6)
C5	0.2816 (3)	−0.1750 (3)	0.55064 (16)	0.0239 (5)
C6	0.3179 (3)	−0.2229 (3)	0.44170 (15)	0.0209 (5)
C11	0.3652 (3)	−0.1422 (3)	0.22390 (15)	0.0196 (5)
H3	0.16960	0.34300	0.45570	0.0270*
H5	0.29270	−0.28260	0.62140	0.0290*
H6	0.35240	−0.36730	0.43810	0.0250*
H11W	0.24570	−0.29620	0.08820	0.0410*
H12W	0.20120	−0.34430	−0.01800	0.0410*
H21	0.30210	0.26910	0.17910	0.0320*
H21W	0.07740	0.52590	−0.15240	0.0420*
H22	0.26100	0.42100	0.25950	0.0320*
H22W	0.34220	0.42040	−0.14980	0.0420*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0278 (4)	0.0255 (4)	0.0225 (4)	−0.0113 (3)	0.0019 (3)	−0.0060 (3)
O1W	0.0334 (8)	0.0233 (7)	0.0256 (7)	−0.0103 (6)	−0.0012 (6)	−0.0084 (6)
O2W	0.0279 (7)	0.0268 (7)	0.0305 (7)	−0.0095 (6)	0.0024 (6)	−0.0106 (6)
O11	0.0355 (8)	0.0217 (7)	0.0247 (7)	−0.0135 (6)	0.0029 (6)	−0.0093 (6)
O12	0.0296 (7)	0.0243 (7)	0.0178 (6)	−0.0118 (6)	0.0030 (5)	−0.0050 (6)
O41	0.0490 (10)	0.0455 (10)	0.0387 (9)	−0.0096 (8)	0.0023 (7)	−0.0274 (8)
O42	0.0511 (10)	0.0605 (11)	0.0189 (8)	−0.0240 (8)	0.0028 (7)	−0.0101 (8)
N2	0.0371 (9)	0.0191 (8)	0.0232 (8)	−0.0115 (7)	0.0043 (7)	−0.0060 (7)
N4	0.0209 (8)	0.0458 (11)	0.0238 (9)	−0.0115 (7)	0.0020 (6)	−0.0156 (8)
C1	0.0148 (8)	0.0208 (9)	0.0186 (9)	−0.0071 (7)	−0.0003 (6)	−0.0057 (7)
C2	0.0177 (9)	0.0215 (9)	0.0218 (9)	−0.0085 (7)	−0.0002 (7)	−0.0053 (8)
C3	0.0205 (9)	0.0243 (10)	0.0273 (10)	−0.0089 (7)	0.0020 (7)	−0.0121 (8)
C4	0.0179 (9)	0.0344 (11)	0.0205 (9)	−0.0102 (8)	0.0026 (7)	−0.0135 (9)
C5	0.0238 (9)	0.0292 (10)	0.0179 (9)	−0.0113 (8)	0.0002 (7)	−0.0024 (8)
C6	0.0207 (9)	0.0212 (9)	0.0217 (9)	−0.0096 (7)	0.0005 (7)	−0.0044 (8)
C11	0.0195 (9)	0.0200 (9)	0.0195 (9)	−0.0071 (7)	−0.0011 (7)	−0.0053 (8)

Geometric parameters (Å, º)

Na1—O1W	2.3950 (15)	N2—C2	1.388 (2)
Na1—O2W	2.4546 (15)	N4—C4	1.474 (2)
Na1—O12	2.3917 (14)	N2—H21	0.9000
Na1—O42^i	2.5949 (18)	N2—H22	0.9600
Na1—O1W^ii	2.4201 (16)	C1—C11	1.515 (3)
Na1—O12^iii	2.4806 (16)	C1—C2	1.415 (3)
O11—C11	1.266 (2)	C1—C6	1.392 (3)
O12—C11	1.260 (2)	C2—C3	1.402 (3)
O41—N4	1.229 (3)	C3—C4	1.372 (3)
O42—N4	1.221 (2)	C4—C5	1.386 (3)
O1W—H12W	0.8800	C5—C6	1.383 (3)
O1W—H11W	0.9400	C3—H3	0.9500
O2W—H21W	0.9500	C5—H5	0.9500
O2W—H22W	0.9300	C6—H6	0.9500
O1W—Na1—O2W	164.89 (6)	O41—N4—C4	118.58 (16)
O1W—Na1—O12	82.78 (5)	O42—N4—C4	118.51 (18)
O1W—Na1—O42^i	76.59 (6)	O41—N4—O42	122.91 (18)
O1W—Na1—O1W^ii	80.75 (5)	C2—N2—H21	113.00
O1W—Na1—O12^iii	113.21 (5)	C2—N2—H22	108.00
O2W—Na1—O12	95.32 (5)	H21—N2—H22	110.00
O2W—Na1—O42^i	111.20 (6)	C6—C1—C11	118.04 (17)
O1W^ii—Na1—O2W	85.08 (5)	C2—C1—C6	119.50 (16)
O2W—Na1—O12^iii	81.43 (5)	C2—C1—C11	122.42 (16)
O12—Na1—O42^i	146.57 (6)	N2—C2—C1	122.98 (16)
O1W^ii—Na1—O12	102.61 (5)	N2—C2—C3	118.99 (17)
O12—Na1—O12^iii	85.13 (5)	C1—C2—C3	117.99 (16)
O1W^ii—Na1—O42^i	99.72 (6)	C2—C3—C4	119.93 (18)
O12^iii—Na1—O42^i	79.34 (6)	C3—C4—C5	123.48 (17)
O1W^ii—Na1—O12^iii	165.03 (5)	N4—C4—C3	117.79 (17)
Na1—O1W—Na1^ii	99.25 (6)	N4—C4—C5	118.74 (16)
Na1—O12—C11	127.11 (13)	C4—C5—C6	116.39 (17)
Na1—O12—Na1^iii	94.87 (5)	C1—C6—C5	122.69 (18)
Na1^iii—O12—C11	119.00 (13)	O11—C11—C1	117.11 (16)
Na1^ii—O1W—H12W	118.00	O12—C11—C1	118.83 (17)
Na1—O1W—H12W	122.00	O11—C11—O12	124.02 (17)
H11W—O1W—H12W	106.00	C2—C3—H3	120.00
Na1—O1W—H11W	99.00	C4—C3—H3	120.00
Na1^ii—O1W—H11W	112.00	C4—C5—H5	122.00
Na1—O2W—H21W	100.00	C6—C5—H5	122.00
Na1—O2W—H22W	94.00	C1—C6—H6	119.00
H21W—O2W—H22W	119.00	C5—C6—H6	119.00
O12—Na1—O1W—Na1^ii	104.10 (5)	Na1—O12—C11—O11	53.5 (3)
O42^i—Na1—O1W—Na1^ii	−102.39 (6)	Na1—O12—C11—C1	−128.72 (16)
O1W^ii—Na1—O1W—Na1^ii	0.00 (6)	Na1^iii—O12—C11—O11	−69.2 (2)
O12^iii—Na1—O1W—Na1^ii	−174.38 (5)	Na1^iii—O12—C11—C1	108.53 (18)
O1W—Na1—O12—C11	−18.24 (16)	O41—N4—C4—C3	0.1 (3)
O1W—Na1—O12—Na1^iii	114.17 (5)	O41—N4—C4—C5	−179.6 (2)
O2W—Na1—O12—C11	146.68 (15)	O42—N4—C4—C3	−179.3 (2)
O2W—Na1—O12—Na1^iii	−80.90 (5)	O42—N4—C4—C5	1.0 (3)
O42^i—Na1—O12—C11	−70.2 (2)	C6—C1—C2—N2	−176.5 (2)
O42^i—Na1—O12—Na1^iii	62.23 (13)	C6—C1—C2—C3	1.2 (3)
O1W^ii—Na1—O12—C11	60.55 (16)	C11—C1—C2—N2	6.1 (3)
O1W^ii—Na1—O12—Na1^iii	−167.03 (5)	C11—C1—C2—C3	−176.2 (2)
O12^iii—Na1—O12—C11	−132.42 (16)	C2—C1—C6—C5	−1.9 (3)
O12^iii—Na1—O12—Na1^iii	0.00 (5)	C11—C1—C6—C5	175.6 (2)
O1W—Na1—O42^i—N4^i	165.67 (16)	C2—C1—C11—O11	−171.9 (2)
O2W—Na1—O42^i—N4^i	−0.75 (17)	C2—C1—C11—O12	10.2 (3)
O12—Na1—O42^i—N4^i	−140.90 (14)	C6—C1—C11—O11	10.7 (3)
O1W—Na1—O1W^ii—Na1^ii	0.00 (6)	C6—C1—C11—O12	−167.25 (19)
O2W—Na1—O1W^ii—Na1^ii	−174.75 (5)	N2—C2—C3—C4	178.1 (2)
O12—Na1—O1W^ii—Na1^ii	−80.39 (6)	C1—C2—C3—C4	0.3 (3)
O1W—Na1—O12^iii—Na1^iii	−79.99 (6)	C2—C3—C4—N4	179.18 (18)
O1W—Na1—O12^iii—C11^iii	142.32 (13)	C2—C3—C4—C5	−1.2 (3)
O2W—Na1—O12^iii—Na1^iii	96.14 (5)	N4—C4—C5—C6	−179.87 (18)
O2W—Na1—O12^iii—C11^iii	−41.55 (13)	C3—C4—C5—C6	0.5 (3)
O12—Na1—O12^iii—Na1^iii	0.00 (6)	C4—C5—C6—C1	1.1 (3)
O12—Na1—O12^iii—C11^iii	−137.69 (14)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O11	0.94	1.88	2.7995 (19)	165
O1W—H12W···O2W^iv	0.88	1.95	2.8043 (19)	165
O2W—H21W···N2^v	0.95	2.06	3.007 (2)	177
O2W—H22W···O11^iii	0.93	1.89	2.816 (2)	176
N2—H21···O12	0.90	2.03	2.7022 (19)	131
N2—H22···O11^vi	0.96	2.12	3.018 (2)	156

Symmetry codes: (iii) −x+1, −y, −z; (iv) x, y−1, z; (v) −x, −y+1, −z; (vi) x, y+1, z.

(III) Poly[µ-aqua-aqua(µ₅-2-amino-4-nitrobenzoato)potassium(I)]

Crystal data

[K(C7H5N2O4)(H2O)]	F(000) = 488
Mr = 238.25	Dx = 1.745 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2641 reflections
a = 11.0753 (6) Å	θ = 3.4–28.1°
b = 7.3693 (4) Å	µ = 0.59 mm^−1
c = 11.8371 (7) Å	T = 200 K
β = 110.144 (6)°	Plate, red
V = 907.01 (9) Å^3	0.18 × 0.15 × 0.05 mm
Z = 4

Data collection

Oxford Diffracrion Gemini-S CCD-detector diffractometer	1784 independent reflections
Radiation source: Enhance (Mo) X-ray source	1548 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 26.0°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −13→13
Tmin = 0.947, Tmax = 0.990	k = −9→9
5706 measured reflections	l = −14→14

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0342P)^2 + 0.4145P] where P = (Fo^2 + 2Fc^2)/3
1784 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.04598 (4)	−0.02480 (6)	0.20840 (4)	0.0254 (1)
O1W	−0.01985 (13)	−0.34549 (19)	0.09198 (11)	0.0284 (4)
O11	0.21947 (12)	0.48661 (19)	0.11597 (11)	0.0260 (4)
O12	0.14981 (12)	0.31343 (19)	0.23408 (12)	0.0282 (4)
O41	0.78821 (14)	0.2735 (2)	0.62154 (12)	0.0378 (5)
O42	0.84330 (13)	0.4274 (2)	0.49229 (14)	0.0382 (5)
N2	0.31821 (16)	0.1797 (2)	0.43506 (15)	0.0301 (6)
N4	0.76222 (15)	0.3509 (2)	0.52435 (14)	0.0262 (5)
C1	0.37410 (16)	0.3759 (2)	0.29538 (15)	0.0159 (5)
C2	0.40710 (17)	0.2735 (2)	0.40320 (15)	0.0182 (5)
C3	0.53702 (17)	0.2670 (2)	0.47784 (15)	0.0199 (5)
C4	0.62746 (17)	0.3567 (2)	0.44387 (16)	0.0195 (5)
C5	0.59843 (18)	0.4570 (3)	0.33925 (17)	0.0225 (6)
C6	0.47081 (17)	0.4645 (3)	0.26716 (16)	0.0205 (5)
C11	0.23735 (17)	0.3931 (3)	0.20897 (15)	0.0184 (5)
H3	0.56190	0.20100	0.55120	0.0240*
H5	0.66320	0.51770	0.31810	0.0270*
H6	0.44790	0.53320	0.19490	0.0250*
H11W	−0.08040	−0.37910	0.02030	0.0430*
H12W	0.05610	−0.39820	0.09870	0.0430*
H21	0.33100	0.13400	0.50730	0.0360*
H22	0.23980	0.19940	0.39330	0.0360*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0215 (2)	0.0242 (2)	0.0282 (2)	−0.0018 (2)	0.0057 (2)	−0.0008 (2)
O1W	0.0235 (7)	0.0319 (8)	0.0260 (7)	0.0066 (6)	0.0037 (6)	−0.0075 (6)
O11	0.0168 (6)	0.0396 (9)	0.0197 (7)	0.0017 (6)	0.0037 (5)	0.0060 (6)
O12	0.0139 (6)	0.0329 (8)	0.0355 (8)	−0.0045 (6)	0.0055 (6)	0.0067 (6)
O41	0.0299 (8)	0.0483 (10)	0.0252 (7)	0.0091 (7)	−0.0031 (6)	0.0052 (7)
O42	0.0170 (7)	0.0505 (10)	0.0425 (9)	−0.0058 (7)	0.0044 (6)	−0.0024 (7)
N2	0.0227 (9)	0.0400 (11)	0.0290 (9)	−0.0013 (8)	0.0108 (7)	0.0137 (8)
N4	0.0190 (8)	0.0269 (9)	0.0271 (9)	0.0047 (7)	0.0008 (7)	−0.0060 (7)
C1	0.0143 (8)	0.0151 (9)	0.0179 (8)	0.0008 (7)	0.0052 (7)	−0.0022 (7)
C2	0.0191 (9)	0.0176 (9)	0.0186 (8)	0.0013 (7)	0.0074 (7)	−0.0015 (7)
C3	0.0226 (9)	0.0204 (10)	0.0163 (8)	0.0042 (8)	0.0061 (7)	−0.0001 (7)
C4	0.0147 (9)	0.0194 (10)	0.0212 (9)	0.0024 (7)	0.0020 (7)	−0.0044 (7)
C5	0.0155 (9)	0.0244 (10)	0.0270 (10)	−0.0026 (8)	0.0065 (8)	0.0002 (8)
C6	0.0192 (9)	0.0218 (10)	0.0194 (9)	0.0004 (8)	0.0054 (7)	0.0027 (7)
C11	0.0160 (9)	0.0198 (9)	0.0190 (9)	0.0018 (8)	0.0056 (7)	−0.0034 (7)

Geometric parameters (Å, º)

K1—O1W	2.7062 (14)	N4—C4	1.469 (3)
K1—O12	2.7178 (15)	N2—H21	0.8800
K1—O12^i	2.7575 (15)	N2—H22	0.8500
K1—O1W^ii	2.8079 (14)	C1—C2	1.418 (2)
K1—O42^iii	3.0459 (16)	C1—C6	1.390 (3)
K1—O41^iv	2.8701 (15)	C1—C11	1.513 (3)
K1—O42^v	2.8536 (16)	C2—C3	1.406 (3)
O11—C11	1.255 (2)	C3—C4	1.371 (3)
O12—C11	1.254 (2)	C4—C5	1.382 (3)
O41—N4	1.226 (2)	C5—C6	1.378 (3)
O42—N4	1.226 (2)	C3—H3	0.9500
O1W—H12W	0.9000	C5—H5	0.9500
O1W—H11W	0.9200	C6—H6	0.9500
N2—C2	1.358 (3)
O1W—K1—O12	152.53 (5)	H11W—O1W—H12W	109.00
O1W—K1—O12^i	69.59 (4)	K1—O1W—H11W	134.00
O1W—K1—O1W^ii	138.74 (5)	K1^i—O1W—H11W	113.00
O1W—K1—O42^iii	67.18 (4)	O41—N4—C4	118.67 (16)
O1W—K1—O41^iv	78.15 (4)	O42—N4—C4	118.35 (15)
O1W—K1—O42^v	76.84 (4)	O41—N4—O42	122.96 (17)
O12—K1—O12^i	135.01 (5)	C2—N2—H21	125.00
O1W^ii—K1—O12	68.69 (4)	C2—N2—H22	116.00
O12—K1—O42^iii	85.69 (4)	H21—N2—H22	115.00
O12—K1—O41^iv	111.30 (4)	C2—C1—C6	119.03 (17)
O12—K1—O42^v	92.38 (4)	C2—C1—C11	122.74 (16)
O1W^ii—K1—O12^i	71.21 (4)	C6—C1—C11	118.23 (15)
O12^i—K1—O42^iii	134.80 (4)	N2—C2—C1	122.27 (17)
O12^i—K1—O41^iv	85.32 (4)	N2—C2—C3	119.40 (15)
O12^i—K1—O42^v	83.53 (4)	C1—C2—C3	118.32 (16)
O1W^ii—K1—O42^iii	153.72 (4)	C2—C3—C4	119.48 (15)
O1W^ii—K1—O41^iv	86.37 (4)	N4—C4—C5	117.89 (17)
O1W^ii—K1—O42^v	111.03 (4)	C3—C4—C5	123.56 (18)
O41^iv—K1—O42^iii	98.10 (4)	N4—C4—C3	118.53 (15)
O42^iii—K1—O42^v	74.55 (4)	C4—C5—C6	116.68 (19)
O41^iv—K1—O42^v	154.85 (5)	C1—C6—C5	122.92 (18)
K1—O1W—K1^i	94.03 (4)	O11—C11—C1	117.24 (17)
K1—O12—C11	137.31 (13)	O12—C11—C1	118.45 (16)
K1—O12—K1^ii	94.92 (5)	O11—C11—O12	124.31 (17)
K1^ii—O12—C11	126.46 (13)	C2—C3—H3	120.00
K1^iv—O41—N4	147.33 (13)	C4—C3—H3	120.00
K1^vi—O42—N4	146.01 (12)	C4—C5—H5	122.00
K1^vii—O42—N4	105.79 (11)	C6—C5—H5	122.00
K1^vi—O42—K1^vii	105.45 (5)	C1—C6—H6	119.00
K1^i—O1W—H12W	95.00	C5—C6—H6	119.00
K1—O1W—H12W	105.00
O12—K1—O1W—K1^i	161.91 (8)	K1—O12—C11—C1	−83.8 (2)
O12^i—K1—O1W—K1^i	−41.11 (4)	K1^ii—O12—C11—O11	−67.4 (2)
O1W^ii—K1—O1W—K1^i	−22.03 (8)	K1^ii—O12—C11—C1	112.93 (17)
O42^iii—K1—O1W—K1^i	152.43 (6)	K1^iv—O41—N4—O42	−47.3 (3)
O41^iv—K1—O1W—K1^i	48.27 (4)	K1^iv—O41—N4—C4	134.40 (19)
O42^v—K1—O1W—K1^i	−129.02 (5)	K1^vi—O42—N4—O41	130.88 (19)
O1W—K1—O12—C11	−30.6 (2)	K1^vi—O42—N4—C4	−50.8 (3)
O1W—K1—O12—K1^ii	135.96 (9)	K1^vii—O42—N4—O41	−25.28 (19)
O12^i—K1—O12—C11	−179.42 (16)	K1^vii—O42—N4—C4	153.03 (12)
O12^i—K1—O12—K1^ii	−12.81 (8)	O42—N4—C4—C3	178.18 (16)
O1W^ii—K1—O12—C11	152.15 (18)	O41—N4—C4—C5	174.80 (17)
O1W^ii—K1—O12—K1^ii	−41.25 (4)	O42—N4—C4—C5	−3.6 (2)
O42^iii—K1—O12—C11	−21.88 (17)	O41—N4—C4—C3	−3.4 (2)
O42^iii—K1—O12—K1^ii	144.72 (5)	C11—C1—C2—C3	−179.61 (16)
O41^iv—K1—O12—C11	75.15 (18)	C11—C1—C6—C5	−179.68 (19)
O41^iv—K1—O12—K1^ii	−118.25 (5)	C2—C1—C11—O11	−179.68 (16)
O42^v—K1—O12—C11	−96.19 (17)	C2—C1—C6—C5	0.3 (3)
O42^v—K1—O12—K1^ii	70.42 (5)	C6—C1—C11—O11	0.3 (3)
O1W—K1—O12^i—K1^i	42.85 (4)	C6—C1—C11—O12	−180.00 (18)
O1W—K1—O12^i—C11^i	−148.42 (15)	C11—C1—C2—N2	1.7 (3)
O12—K1—O12^i—K1^i	−151.94 (5)	C2—C1—C11—O12	0.1 (3)
O12—K1—O12^i—C11^i	16.80 (16)	C6—C1—C2—N2	−178.31 (17)
O1W—K1—O1W^ii—K1^ii	−135.90 (6)	C6—C1—C2—C3	0.4 (2)
O12—K1—O1W^ii—K1^ii	42.15 (4)	C1—C2—C3—C4	−0.9 (2)
O1W—K1—O42^iii—N4^iii	−74.2 (2)	N2—C2—C3—C4	177.86 (15)
O12—K1—O42^iii—N4^iii	110.1 (2)	C2—C3—C4—N4	178.85 (14)
O1W—K1—O41^iv—N4^iv	−109.9 (2)	C2—C3—C4—C5	0.7 (3)
O12—K1—O41^iv—N4^iv	97.1 (2)	N4—C4—C5—C6	−178.15 (17)
O1W—K1—O42^v—N4^v	123.97 (12)	C3—C4—C5—C6	0.0 (3)
O12—K1—O42^v—N4^v	−81.58 (11)	C4—C5—C6—C1	−0.5 (3)
K1—O12—C11—O11	96.0 (2)

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, −y, −z+1; (v) x−1, −y+1/2, z−1/2; (vi) −x+1, y+1/2, −z+1/2; (vii) 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
O1W—H11W···O11^viii	0.92	1.97	2.8775 (18)	169
O1W—H12W···O11^ix	0.90	1.94	2.849 (2)	179
N2—H21···O11^x	0.88	2.25	2.983 (2)	140
N2—H22···O12	0.85	1.99	2.656 (2)	134
N2—H22···O1W^ii	0.85	2.52	3.214 (2)	139

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