Tetra­aqua-1[kappa]O,2[kappa]³O-([mu]-2,4-dinitro­phenolato-1[kappa]²O¹,O²:2[kappa]O¹)(2,4-dinitro­phenolato-1[kappa]²O¹,O²)dilithium(I): a dinuclear lithium(I) complex

The title complex, [Li₂(C₆H₃N₂O₅)₂(H₂O)₄], contains two kinds of Li atoms, viz. five-coordinated and four-coordinated. The five-coordinated Li ion has a tetra­gonal-pyramidal geometry, with a water mol­ecule in the apical position and four O atoms from two 2,4-dinitro­phenolate (2,4-DNP) ligands in the basal plane. The four-coordinated Li ion has a tetra­hedral geometry, with three water mol­ecules and one phenolate O atom of a 2,4-DNP ligand. The Li ions are bridged by a phenolate O atom, giving the complex a dinuclear structure. The crystal packing is stabilized by O-H...O hydrogen-bonding inter­actions involving the water mol­ecules and nitro O atoms.

S1. Comment

Nitrophenols and their metal salts have been investigated extensively because they have useful properties as highly energetic materials. The thermal and combustion properties (Stammler, 1969; Brill et al., 2000) and molecular structures and coordination behaviour (Harrowfield et al., 1995a,b) of 2,4,6-trinitrophenol metal salts have been thoroughly studied. In our studies of the crystal structures and thermal properties of lithium 2,6-dinitrophenol (Yun et al., 2004), yttrium 2,6-dinitrophenol (Suh et al., 2002a), lanthanide 2,6-dinitrophenol (Suh et al., 2002b; Yun et al., 2006) and lanthanide 2,4,6-trinitrophenol (Yun et al., 2005) salts, we have found that the coordination behaviour of the 2,6-dinitrophenol ligand is quite different from that of the 2,4,6-trinitrophenol ligand, in keeping with the electronic effect of the nitro substituent at the para position. As an extension of this study, we have also employed the 2,4-dinitrophenol (2,4-DNP) ligand (Iwasaki & Kawano, 1977; Kagawa et al., 1976). Here, we report the preparation and crystal structure of the title lithium(I) 2,4-DNP complex, (I).

As shown in Fig. 1, compound (I) is a unique dinuclear complex with two kinds of Li atoms and two kinds of 2,4-DNP ligands. The geometries of the Li atoms are tetragonal pyramidal (Li1) and tetrahedral (Li2), while the coordination modes of the 2,4-DNP ligands are chelation and chelation/bridging. The Li1 ion has a five-coordinate geometry, with a water molecule in the apical position and four O atoms from two 2,4-DNP ligands in the basal plane. As expected, the Li—O distances are slightly longer in the pyramid than in the tetrahedron (Table 1). Each of the 2,4-DNP ligands forms a six-membered chelation ring with Li1 through the O atoms of the phenolate and nitro groups. Ion Li2 has a four-coordinate geometry, with three water molecules and one phenolate O atom of a 2,4-DNP ligand. The phenolate O atom serves as the bridge between the Li1 and Li2 atoms. There is no metal-to-metal interaction, since the Li1···Li2 distance is 3.172 (1) Å. The dinuclear complexes are linked in three-dimensions by numerous O_water—H···O_2,4-DNP and O_water—H···O_water intermolecular hydrogen bonds (Fig. 2, Table 2).

Although lithium is now known in at least 20 coordination geometries with coordination numbers ranging from 1 to 12 (Greenwood & Earnshaw, 1998), this dinuclear lithium 2,4-DNP complex with both four- and five-coordinate Li is unique. To our knowledge, only lithium o-phenylenedioxydiacetate trihydrate, [Li₂(C₁₀H₈O₆)(H₂O)₃]₂ (Smith et al., 1986), has a similar geometry combination. However this complex is dimeric, with four Li atoms bridged by the two o-phenylenedioxydiacetate ligands.

The structural features of (I) are very different from those of the dinuclear lithium 2,6-DNP complex, [Li(2,6-DNP)(H₂O)]₂·2H₂O, which we have studied recently (Yun et al., 2004). Ions Li1 and Li2 of the lithium 2,6-DNP complex are both coordinated to five O atoms in a square-pyramidal geometry, and there are both coordinated and free water molecules.

Related literature

For related literature, see: Brill et al. (2000); Greenwood & Earnshaw (1998); Harrowfield et al. (1995a, 1995b); Iwasaki & Kawano (1977); Kagawa et al. (1976); Nakamoto (1997); Smith et al. (1986); Stammler (1969); Suh et al. (2002a, 2002b); Yun et al. (2004, 2005, 2006).

S2. Experimental

The lithium(I) 2,4-DNP complex, (I), was prepared in a manner similar to that used for the lithium(I) 2,6-DNP complex (Yun et al., 2004). Pale-yellow crystals of (I) suitable for single-crystal X-ray diffraction were obtained and characterized by EDS [Please give technique name in full], FT–IR and elemental analysis. Analysis, calculated for C₁₂H₁₄N₄O₁₄Li₂: C 31.87, H 3.12, N 12.39, Li 3.07%; found: C 31.94, H 3.14, N 12.38, Li 3.05%. The 2,4-DNP ligand was confirmed by assignment of the relevant FT–IR absorption bands (Nakamoto, 1997).

S3. Refinement

The H atoms on the 2,4-DNP ligand were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The water H atoms were located in a difference electron-density map and refined with U_iso(H) = 1.5U_eq(O) and with O—H constrained to 0.82 (2) Å.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of complex (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing diagram of complex (I), viewed along the b axis. Hydrogen-bonding interactions are shown as dashed lines.

Tetraaqua-1κO,2κ³O-(µ-2,4-dinitrophenolato-1κ²O¹,O²:2κO¹)(2,4-dinitrophenolato-1κ²O¹,O²)dilithium(I)

Crystal data

[Li2(C6H3N2O5)2(H2O)4]	Z = 2
Mr = 452.15	F(000) = 464
Triclinic, P1	Dx = 1.652 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3038 (2) Å	Cell parameters from 6863 reflections
b = 10.1267 (3) Å	θ = 2.5–28.2°
c = 11.2984 (3) Å	µ = 0.15 mm^−1
α = 76.733 (2)°	T = 296 K
β = 79.565 (2)°	Block, pale yellow
γ = 86.276 (2)°	0.39 × 0.23 × 0.14 mm
V = 909.16 (4) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4473 independent reflections
Radiation source: fine-focus sealed tube	3497 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ϕ and ω scans	θmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.944, Tmax = 0.979	k = −13→13
18045 measured reflections	l = −14→15

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.0613P)^2 + 0.1182P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
4473 reflections	Δρmax = 0.22 e Å^−3
314 parameters	Δρmin = −0.29 e Å^−3
5 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.033 (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
Li1	0.5445 (3)	0.2226 (2)	1.00546 (18)	0.0398 (4)
Li2	0.1638 (3)	0.2790 (2)	1.00809 (18)	0.0407 (5)
C1	0.69795 (13)	0.41651 (11)	0.78588 (10)	0.0316 (2)
C2	0.63323 (12)	0.36442 (10)	0.69642 (10)	0.0286 (2)
C3	0.67057 (13)	0.41919 (11)	0.57024 (10)	0.0298 (2)
H3A	0.6263	0.3833	0.5148	0.036*
C4	0.77371 (13)	0.52690 (11)	0.52873 (9)	0.0303 (2)
C5	0.84491 (13)	0.58049 (11)	0.61070 (10)	0.0334 (2)
H5A	0.9158	0.6527	0.5810	0.040*
C6	0.80926 (14)	0.52582 (12)	0.73376 (10)	0.0352 (3)
H6A	0.8593	0.5609	0.7868	0.042*
O7	0.66451 (12)	0.37518 (9)	0.90208 (7)	0.0468 (2)
N8	0.52188 (11)	0.25229 (9)	0.73355 (9)	0.0321 (2)
O9	0.47853 (12)	0.20118 (10)	0.84440 (8)	0.0513 (3)
O10	0.47307 (11)	0.20941 (9)	0.65440 (8)	0.0462 (2)
N11	0.80795 (12)	0.58774 (10)	0.39890 (9)	0.0351 (2)
O12	0.89293 (12)	0.68978 (9)	0.36511 (8)	0.0495 (2)
O13	0.75335 (12)	0.53746 (10)	0.32602 (8)	0.0503 (3)
C21	0.29630 (12)	0.10166 (10)	1.20904 (9)	0.0281 (2)
C22	0.36945 (12)	0.13986 (10)	1.30145 (9)	0.0275 (2)
C23	0.33269 (12)	0.07838 (10)	1.42602 (10)	0.0285 (2)
H23A	0.3793	0.1082	1.4839	0.034*
C24	0.22604 (12)	−0.02741 (11)	1.46216 (9)	0.0295 (2)
C25	0.15124 (13)	−0.07154 (11)	1.37696 (10)	0.0332 (2)
H25A	0.0801	−0.1438	1.4029	0.040*
C26	0.18394 (14)	−0.00734 (12)	1.25562 (10)	0.0340 (2)
H26A	0.1308	−0.0356	1.2003	0.041*
O27	0.32281 (10)	0.15692 (8)	1.09383 (7)	0.0373 (2)
N28	0.48406 (11)	0.24949 (9)	1.27040 (9)	0.0316 (2)
O29	0.53924 (13)	0.29831 (10)	1.16129 (8)	0.0513 (3)
O30	0.52299 (11)	0.29239 (9)	1.35338 (8)	0.0455 (2)
N31	0.19131 (11)	−0.09370 (10)	1.59087 (9)	0.0344 (2)
O32	0.24377 (12)	−0.04677 (10)	1.66680 (8)	0.0476 (2)
O33	0.10765 (12)	−0.19619 (9)	1.62011 (8)	0.0498 (3)
OW1	0.71159 (15)	0.07466 (12)	1.04332 (12)	0.0625 (3)
HW1A	0.732 (3)	0.063 (2)	1.1105 (16)	0.094*
HW1B	0.708 (3)	−0.003 (2)	1.033 (2)	0.094*
OW2	0.25595 (13)	0.46125 (10)	0.94962 (9)	0.0494 (3)
HW2A	0.312 (2)	0.4746 (19)	0.8869 (14)	0.074*
HW2B	0.287 (2)	0.5076 (19)	0.9930 (17)	0.074*
OW3	0.06174 (15)	0.20399 (13)	0.89693 (10)	0.0609 (3)
HW3A	0.074 (3)	0.228 (2)	0.820 (2)	0.091*
HW3B	−0.034 (3)	0.188 (2)	0.9181 (19)	0.091*
OW4	−0.03338 (13)	0.30573 (12)	1.12200 (9)	0.0549 (3)
HW4A	−0.094 (2)	0.3676 (17)	1.1022 (18)	0.082*
HW4B	−0.062 (2)	0.274 (2)	1.1961 (14)	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li1	0.0424 (10)	0.0405 (10)	0.0332 (10)	−0.0102 (8)	−0.0033 (8)	−0.0017 (8)
Li2	0.0467 (11)	0.0397 (10)	0.0366 (10)	−0.0082 (9)	−0.0149 (8)	−0.0024 (8)
C1	0.0353 (5)	0.0313 (5)	0.0286 (5)	−0.0063 (4)	−0.0056 (4)	−0.0061 (4)
C2	0.0295 (5)	0.0273 (5)	0.0293 (5)	−0.0046 (4)	−0.0041 (4)	−0.0066 (4)
C3	0.0315 (5)	0.0311 (5)	0.0283 (5)	−0.0020 (4)	−0.0058 (4)	−0.0091 (4)
C4	0.0315 (5)	0.0327 (5)	0.0253 (5)	−0.0016 (4)	−0.0028 (4)	−0.0049 (4)
C5	0.0340 (5)	0.0325 (5)	0.0329 (6)	−0.0097 (4)	−0.0036 (4)	−0.0051 (4)
C6	0.0407 (6)	0.0372 (6)	0.0302 (6)	−0.0124 (5)	−0.0074 (5)	−0.0080 (4)
O7	0.0681 (6)	0.0479 (5)	0.0254 (4)	−0.0275 (4)	−0.0075 (4)	−0.0032 (3)
N8	0.0347 (5)	0.0311 (5)	0.0317 (5)	−0.0067 (4)	−0.0049 (4)	−0.0085 (4)
O9	0.0651 (6)	0.0551 (6)	0.0324 (5)	−0.0332 (5)	−0.0018 (4)	−0.0035 (4)
O10	0.0565 (5)	0.0465 (5)	0.0413 (5)	−0.0194 (4)	−0.0123 (4)	−0.0134 (4)
N11	0.0381 (5)	0.0381 (5)	0.0275 (5)	−0.0049 (4)	−0.0042 (4)	−0.0037 (4)
O12	0.0603 (6)	0.0481 (5)	0.0358 (5)	−0.0218 (4)	−0.0065 (4)	0.0039 (4)
O13	0.0659 (6)	0.0579 (6)	0.0290 (4)	−0.0161 (5)	−0.0110 (4)	−0.0074 (4)
C21	0.0267 (5)	0.0304 (5)	0.0258 (5)	−0.0008 (4)	−0.0040 (4)	−0.0038 (4)
C22	0.0272 (5)	0.0255 (5)	0.0286 (5)	−0.0051 (4)	−0.0025 (4)	−0.0042 (4)
C23	0.0298 (5)	0.0293 (5)	0.0267 (5)	−0.0027 (4)	−0.0052 (4)	−0.0062 (4)
C24	0.0304 (5)	0.0301 (5)	0.0250 (5)	−0.0033 (4)	−0.0020 (4)	−0.0013 (4)
C25	0.0323 (5)	0.0323 (5)	0.0339 (6)	−0.0100 (4)	−0.0025 (4)	−0.0048 (4)
C26	0.0344 (5)	0.0395 (6)	0.0302 (6)	−0.0104 (4)	−0.0068 (4)	−0.0084 (4)
O27	0.0362 (4)	0.0467 (5)	0.0258 (4)	−0.0075 (3)	−0.0063 (3)	0.0009 (3)
N28	0.0343 (5)	0.0285 (4)	0.0317 (5)	−0.0072 (4)	−0.0026 (4)	−0.0068 (4)
O29	0.0675 (6)	0.0483 (5)	0.0344 (5)	−0.0320 (5)	0.0074 (4)	−0.0057 (4)
O30	0.0525 (5)	0.0463 (5)	0.0427 (5)	−0.0192 (4)	−0.0094 (4)	−0.0138 (4)
N31	0.0338 (5)	0.0360 (5)	0.0290 (5)	−0.0042 (4)	−0.0023 (4)	0.0002 (4)
O32	0.0583 (6)	0.0554 (6)	0.0282 (4)	−0.0129 (4)	−0.0094 (4)	−0.0027 (4)
O33	0.0586 (6)	0.0450 (5)	0.0388 (5)	−0.0221 (4)	−0.0033 (4)	0.0066 (4)
OW1	0.0728 (7)	0.0472 (6)	0.0668 (7)	0.0074 (5)	−0.0183 (6)	−0.0088 (5)
OW2	0.0613 (6)	0.0465 (5)	0.0370 (5)	−0.0203 (4)	0.0006 (4)	−0.0044 (4)
OW3	0.0660 (7)	0.0854 (8)	0.0337 (5)	−0.0307 (6)	−0.0108 (5)	−0.0084 (5)
OW4	0.0515 (6)	0.0674 (7)	0.0373 (5)	−0.0004 (5)	−0.0040 (4)	0.0025 (5)

Geometric parameters (Å, º)

Li1—O7	1.923 (2)	C21—O27	1.2782 (13)
Li1—OW1	2.001 (3)	C21—C22	1.4333 (14)
Li1—O27	2.004 (2)	C21—C26	1.4336 (15)
Li1—O9	2.053 (2)	C22—C23	1.3887 (14)
Li1—O29	2.068 (2)	C22—N28	1.4487 (13)
Li2—OW4	1.936 (2)	C23—C24	1.3749 (14)
Li2—OW3	1.944 (2)	C23—H23A	0.9300
Li2—OW2	1.967 (2)	C24—C25	1.4008 (15)
Li2—O27	1.978 (2)	C24—N31	1.4400 (13)
C1—O7	1.2675 (13)	C25—C26	1.3619 (15)
C1—C6	1.4364 (15)	C25—H25A	0.9300
C1—C2	1.4376 (14)	C26—H26A	0.9300
C2—C3	1.3912 (15)	N28—O30	1.2196 (12)
C2—N8	1.4483 (13)	N28—O29	1.2325 (12)
C3—C4	1.3727 (15)	N31—O32	1.2251 (13)
C3—H3A	0.9300	N31—O33	1.2338 (12)
C4—C5	1.4045 (15)	OW1—HW1A	0.788 (15)
C4—N11	1.4384 (14)	OW1—HW1B	0.82 (2)
C5—C6	1.3587 (15)	OW2—HW2A	0.763 (14)
C5—H5A	0.9300	OW2—HW2B	0.833 (15)
C6—H6A	0.9300	OW3—HW3A	0.84 (2)
N8—O10	1.2186 (12)	OW3—HW3B	0.80 (2)
N8—O9	1.2367 (12)	OW4—HW4A	0.797 (14)
N11—O13	1.2249 (12)	OW4—HW4B	0.821 (15)
N11—O12	1.2359 (13)
O7—Li1—OW1	105.87 (11)	O12—N11—C4	118.04 (9)
O7—Li1—O27	144.96 (13)	O27—C21—C22	125.51 (9)
OW1—Li1—O27	109.11 (10)	O27—C21—C26	120.12 (10)
O7—Li1—O9	84.53 (8)	C22—C21—C26	114.36 (9)
OW1—Li1—O9	105.18 (11)	C23—C22—C21	122.99 (9)
O27—Li1—O9	88.33 (9)	C23—C22—N28	115.48 (9)
O7—Li1—O29	91.78 (9)	C21—C22—N28	121.51 (9)
OW1—Li1—O29	96.56 (10)	C24—C23—C22	118.68 (10)
O27—Li1—O29	82.37 (8)	C24—C23—H23A	120.7
O9—Li1—O29	158.14 (13)	C22—C23—H23A	120.7
OW4—Li2—OW3	97.58 (10)	C23—C24—C25	121.56 (10)
OW4—Li2—OW2	103.81 (11)	C23—C24—N31	118.74 (9)
OW3—Li2—OW2	118.93 (11)	C25—C24—N31	119.71 (9)
OW4—Li2—O27	111.11 (10)	C26—C25—C24	119.19 (9)
OW3—Li2—O27	115.48 (11)	C26—C25—H25A	120.4
OW2—Li2—O27	108.59 (10)	C24—C25—H25A	120.4
O7—C1—C6	119.58 (10)	C25—C26—C21	123.16 (10)
O7—C1—C2	126.02 (10)	C25—C26—H26A	118.4
C6—C1—C2	114.40 (10)	C21—C26—H26A	118.4
C3—C2—C1	122.60 (9)	C21—O27—Li2	123.91 (9)
C3—C2—N8	116.01 (9)	C21—O27—Li1	121.88 (9)
C1—C2—N8	121.38 (9)	Li2—O27—Li1	105.60 (9)
C4—C3—C2	119.08 (10)	O30—N28—O29	121.28 (9)
C4—C3—H3A	120.5	O30—N28—C22	118.98 (9)
C2—C3—H3A	120.5	O29—N28—C22	119.74 (9)
C3—C4—C5	121.34 (10)	N28—O29—Li1	130.37 (9)
C3—C4—N11	119.52 (9)	O32—N31—O33	122.56 (10)
C5—C4—N11	119.13 (9)	O32—N31—C24	119.60 (9)
C6—C5—C4	119.35 (10)	O33—N31—C24	117.84 (9)
C6—C5—H5A	120.3	Li1—OW1—HW1A	113.9 (17)
C4—C5—H5A	120.3	Li1—OW1—HW1B	125.4 (17)
C5—C6—C1	123.16 (10)	HW1A—OW1—HW1B	103 (2)
C5—C6—H6A	118.4	Li2—OW2—HW2A	116.2 (15)
C1—C6—H6A	118.4	Li2—OW2—HW2B	126.2 (14)
C1—O7—Li1	132.25 (9)	HW2A—OW2—HW2B	108 (2)
O10—N8—O9	121.07 (9)	Li2—OW3—HW3A	127.9 (16)
O10—N8—C2	119.12 (9)	Li2—OW3—HW3B	116.5 (15)
O9—N8—C2	119.80 (9)	HW3A—OW3—HW3B	104 (2)
N8—O9—Li1	135.09 (9)	Li2—OW4—HW4A	119.3 (14)
O13—N11—O12	122.34 (10)	Li2—OW4—HW4B	132.0 (15)
O13—N11—C4	119.62 (9)	HW4A—OW4—HW4B	107.5 (19)
O7—C1—C2—C3	177.16 (11)	C22—C23—C24—C25	−1.68 (16)
C6—C1—C2—C3	−2.42 (16)	C22—C23—C24—N31	178.31 (9)
O7—C1—C2—N8	−1.67 (18)	C23—C24—C25—C26	−0.56 (17)
C6—C1—C2—N8	178.74 (10)	N31—C24—C25—C26	179.45 (10)
C1—C2—C3—C4	0.27 (16)	C24—C25—C26—C21	2.07 (18)
N8—C2—C3—C4	179.16 (9)	O27—C21—C26—C25	179.35 (10)
C2—C3—C4—C5	1.51 (16)	C22—C21—C26—C25	−1.24 (16)
C2—C3—C4—N11	−177.54 (9)	C22—C21—O27—Li2	−106.58 (13)
C3—C4—C5—C6	−0.91 (17)	C26—C21—O27—Li2	72.75 (14)
N11—C4—C5—C6	178.14 (10)	C22—C21—O27—Li1	36.52 (16)
C4—C5—C6—C1	−1.53 (18)	C26—C21—O27—Li1	−144.14 (11)
O7—C1—C6—C5	−176.55 (11)	OW4—Li2—O27—C21	1.10 (15)
C2—C1—C6—C5	3.07 (17)	OW3—Li2—O27—C21	−108.81 (13)
C6—C1—O7—Li1	−172.02 (13)	OW2—Li2—O27—C21	114.67 (11)
C2—C1—O7—Li1	8.4 (2)	OW4—Li2—O27—Li1	−146.95 (10)
OW1—Li1—O7—C1	94.52 (15)	OW3—Li2—O27—Li1	103.15 (12)
O27—Li1—O7—C1	−88.9 (2)	OW2—Li2—O27—Li1	−33.38 (13)
O9—Li1—O7—C1	−9.75 (17)	O7—Li1—O27—C21	−126.17 (19)
O29—Li1—O7—C1	−168.14 (12)	OW1—Li1—O27—C21	50.31 (14)
C3—C2—N8—O10	2.78 (15)	O9—Li1—O27—C21	155.81 (9)
C1—C2—N8—O10	−178.31 (10)	O29—Li1—O27—C21	−44.03 (12)
C3—C2—N8—O9	−177.59 (10)	O7—Li1—O27—Li2	22.7 (2)
C1—C2—N8—O9	1.32 (16)	OW1—Li1—O27—Li2	−160.84 (10)
O10—N8—O9—Li1	171.94 (13)	O9—Li1—O27—Li2	−55.34 (10)
C2—N8—O9—Li1	−7.7 (2)	O29—Li1—O27—Li2	104.83 (9)
O7—Li1—O9—N8	10.01 (17)	C23—C22—N28—O30	−9.63 (15)
OW1—Li1—O9—N8	−94.99 (15)	C21—C22—N28—O30	168.52 (10)
O27—Li1—O9—N8	155.66 (13)	C23—C22—N28—O29	170.96 (10)
O29—Li1—O9—N8	91.1 (3)	C21—C22—N28—O29	−10.89 (16)
C3—C4—N11—O13	−4.70 (16)	O30—N28—O29—Li1	163.26 (12)
C5—C4—N11—O13	176.24 (10)	C22—N28—O29—Li1	−17.34 (18)
C3—C4—N11—O12	175.54 (10)	O7—Li1—O29—N28	−176.91 (12)
C5—C4—N11—O12	−3.52 (16)	OW1—Li1—O29—N28	−70.71 (15)
O27—C21—C22—C23	178.26 (10)	O27—Li1—O29—N28	37.77 (15)
C26—C21—C22—C23	−1.11 (15)	O9—Li1—O29—N28	103.4 (3)
O27—C21—C22—N28	0.25 (16)	C23—C24—N31—O32	7.19 (16)
C26—C21—C22—N28	−179.12 (9)	C25—C24—N31—O32	−172.82 (10)
C21—C22—C23—C24	2.54 (16)	C23—C24—N31—O33	−173.38 (10)
N28—C22—C23—C24	−179.34 (9)	C25—C24—N31—O33	6.61 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
OW1—HW1A···O32^i	0.79 (2)	2.53 (2)	3.3083 (15)	171 (2)
OW1—HW1B···O27^ii	0.82 (2)	2.41 (2)	3.1461 (15)	151 (2)
OW1—HW1B···O9^ii	0.82 (2)	2.59 (2)	3.1821 (15)	130.3 (19)
OW2—HW2A···O29^iii	0.76 (1)	2.58 (2)	2.9592 (12)	113 (2)
OW2—HW2A···O13^iv	0.76 (1)	2.59 (2)	3.1262 (13)	129 (2)
OW2—HW2B···O7^iii	0.83 (2)	1.96 (2)	2.7936 (13)	174 (2)
OW3—HW3A···O12^iv	0.84 (2)	2.04 (2)	2.8725 (14)	173 (2)
OW3—HW3B···OW1^v	0.80 (2)	2.50 (2)	3.2655 (17)	159 (2)
OW4—HW4A···OW2^vi	0.80 (1)	2.16 (1)	2.9560 (16)	178 (2)
OW4—HW4B···O33^vii	0.82 (2)	2.02 (2)	2.8381 (13)	174 (2)

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