Hydro­gen bonding in proton-transfer compounds of 8-quinolinol (oxine) with aromatic sulfonic acids

The crystal structures of the proton-transfer compounds of 8-quinolinol (oxine) with the aromatic sulfonic acids 2-amino­benzene­sulfonic acid (orthanilic acid) and 8-hydroxy-7-iodo­quinoline-5-sulfonic acid (ferron) have been determined. In both 8-hydroxy­quinolinium 2-amino­benzene­sulfonate, C₉H₈NO⁺·C₆H₆NO₃S^-, (I), and 8-hydroxyquino­linium 8-hydroxy-7-iodo­quinoline-5-sulfonate ses­qui­hydrate, C₉H₈NO⁺·C₉H₅INO₄S^-·1.5H₂O, (II), extensive hydrogen-bonding interactions, together with significant cation-cation [in (I)] and cation-anion [in (II)] [pi]-[pi] stacking associations, give rise to layered polymer structures.

S1. Comment

8-Quinolinol (8-hydroxyquinoline, 8-HQ) is a particularly useful reagent (oxine) for metal complex formation, achieved through bidentate N,O interaction, giving bis- and tris-chelate compounds, e.g. [Pd(8—HQ⁻)₂] (Prout & Wheeler, 1966). Oxine will react with most metal types, but the values of the dissociation constants for the phenol O and the heterocyclic N-donor groups (pK_a1,2 = 4.9, 10.8) provide the textbook example of a reagent that has wide interactive selectivity, particularly through pH control, giving numerous analytical chemical applications (Skoog et al., 1988). The molecule also readily forms adducts, both with metal complex species, e.g. [K⁺ (8-HQ⁻). (8-HQ)] and [K⁺ (8-HQ⁻). 2(8-HQ)] (Hughes & Truter, 1979), and with neutral compounds, e.g. chloranil (1:1) (Prout & Wheeler, 1967) and 1,3,5-trinitrobenzene (1:1) (Castellano & Prout, 1971). In the presence of relatively strong organic acids, protonation of the hetero-N atom of oxine occurs and the 8-HQ⁺ cation formed provides structure extension through hydrogen-bonding interactions. Known structures of this type are those with salicylic acid (SA, a discrete 2:2 dimer; Singh et al., 2000; Smith et al., 2003a), 2-nitrobenzoic acid (1:1 monohydrate), 3,5-dinitrobenzoic acid (1:1 trihydrate) and 3,5-dinitrosalicylic acid (1:1; Smith et al., 2001), with 5-sulfosalicylic acid (1:1 monohydrate; Smith et al., 2004a), and with Kemp's triacid (cis-cis- 1,3,5-trimethylhexane-1,3,5-tricarboxylic acid, a 1:1 anhydrate; Smith et al., 2000). Adduct salts with salicylic acid [(8-HQ)⁺(SA)⁻. (8-HQ); Jebamony & Muthiah, 1998] and 1,2,3-trihydroxybenzene [(8-HQ)⁺(THB)⁻. (8-HQ); Singh et al., 1994] are also known. It is also of interest that, with a number of these compounds, the formation reactions can proceed in the solid state (Rastogi et al., 1977; Singh et al., 1994, 1999, 2000).

8-Hydroxy-7-iodoquinoline-5-sulfonic acid (ferron) is chemically analogous to oxine, with potential for complex formation but with steric constraints because of the presence of the bulky 7-iodo substituent. Therefore, ferron gives a colour reaction with iron(III) but not with iron(II) (Vogel, 1964). The crystal structure determination of ferron (Merritt & Duffin, 1970; Balasubramanian & Muthiah, 1996) has confirmed the presence of a sulfonate–quinolinium group zwitterion. We have reported the structure of the bis(guanidinium) monohydrate salt of ferron, in which deprotonation of both the sulfonic acid and phenol groups has occurred (Smith et al., 2003b), while in the structure of the (1:1) salt with 4,4'-bipyridine (Hemamalini et al., 2004), only the sulfonate group is deprotonated. We have also determined the 1:1:1 ferron/urea/water adduct structure (Smith et al., 2004b).

The crystal structures reported here are those of the products of the reaction of of 8-hydroxyquinoline with 2-aminobenzenesulfonic acid (orthanilic acid), 8-hydroxyquinolinium 2-aminobenzenesulfonate [(C₉H₈NO)⁺ (C₆H₆NO₃S)⁻], (I), and with ferron, 8-hydroxyquinolinium 8-hydroxy-7-iodoquinoline-5-sulfonate 1.5 hydrate [(C₉H₈NO)⁺ (C₉H₆NIO₄S)⁻.1.5 H₂O], (II). As expected, in both compounds, proton transfer from the sulfonic acid group to the quinoline N atom of the oxine molecule occurs. Fig. 1 shows the atom-numbering scheme used for the 8-hydroxyquinolinium cation (8-HQ⁺) and the 2-amino benzenesulfonate anion (2-ABS⁻) in (I). A similar scheme is employed for the 8-HQ⁺ cation in (II) (Fig. 2). Tables 1 and 2 list the geometries for the hydrogen-bonding interactions in (I) and (II) and the symmetry codes used below.

The anhydrous (1:1) compound [(8-HQ)⁺ (2-ABS)⁻], (I) exhibits a direct N⁺—H···O⁻_sulfonate interaction [N11—H11···O11 = 2.745 (4) Å; Fig. 3]. The 8-hydroxy substituent group of the 8-HQ⁺ cation is strongly associated intermolecularly with a 2-ABS sulfonate O atom [O81···O13ⁱⁱ = 2.623 (3) Å]. As is usual for 8-HQ⁺ cations, there is an intramolecular association between the quinolinium proton and the phenol O atom [2.675 (4) Å], while in the 2-ABS⁻ anion, the conformation of the sulfonate group is stabilized by N_amine—H···O and C_ring—H···O interactions [2.937 (5) and 2.875 (4) Å respectively].

The inversion-related 8-HQ⁺ cation rings form stacks that extend approximately down the c direction, with approximate superimposition of the C5–C101 six-membered ring systems. These have perpendicular separations of 3.40 (1) (intra) and 3.39 (1) Å (inter), with a ring-centroid separation of 3.78 (1) Å, which is strongly indicative of π–π interaction. These `sandwich' dimers are similar to those found in the discrete dimeric 2:2 compound of oxine with salicylic acid (Smith et al., 2003a), in which the intra- and interdimer separations are 3.34 and 3.40 Å, respectively (ring centroid separation = 3.58 Å). In this salicylate compound, the oxine rings are edge-linked by bis-salicylato-O,O' cleats. In (I), the molecular pairs are peripherally linked to the sulfonate anions, forming sheets across the ac plane with only weak intersheet interactions [N2—H2B···O11ⁱ = 3.402 Å].

In the hydrated 1:1 compound [(8-HQ)⁺ (ferron)⁻]·1.5H₂O, (II), the protonated hetero N atom of the 8-HQ⁺ cation forms an intramolecular hydrogen bond with the phenol O atom, similar to that in (I) [N11···O81 = 2.694 (6) Å; Fig. 4]. However, the propagating interaction is with a water molecule [N11—H11 ···O1W^iv = 2.733 (5) Å] rather than with a sulfonate O atom as found in (I). Although the direct N⁺—H···O⁻_sulfonate interaction is also found in the monohydrated compound of oxine with 5-sulfosalicylic acid (5-SSA; Smith et al., 2004a), it is more usual that, in the hydrated 5-SSA compounds with the quinoline-type Lewis bases, this primary interaction is with a water molecule. The ferron anion molecules have an intramolecular aromatic C6—H6···O51_sulfonate contact [2.823 (6) Å], while a short intermolecular OW2···I7ⁱⁱ contact [3.17 (1) Å] is also present.

The molecules of (II) form stacks of alternating 8-HQ⁺ cations and ferron anions, having approximate superimposition of the six-membered ring systems N11–C91 and N1–C10, with perpendicular separations of 3.51 (1) (intra) and 3.40 (1) Å (inter), also indicative of significant π–π interaction. These stacks form down the c axis and are linked by the previously described hydrogen bonds as well as by a number of other associations involving the water molecules. This stacking phenomenon is consistent with the perfect crystal cleavage perpendicular to the short (6.977 Å) c axis. The presence of a hemihydrate molecule (O2W) is consistent with some lability in this molecule, although it is quite strongly associated in the crystal and only minor crystal decomposition (1.1%) was observed during data collection.

S2. Experimental

The title compounds were synthesized by heating, under reflux, 1 mmol quantities of 8-quinolinol (oxine) and either 2-aminobenzenesulfonic acid (orthanilic acid) [for (I)] or 8-hydroxy-7-iodonaphthalene-5-sulfonic acid (ferron) [for (II)] in 50% ethanol/water (50 ml) for 10 min. After concentration to ca 30 ml, partial room-temperature evaporation of the hot-filtered solutions gave large pale-brown crystal blocks of (I) (m.p. 454.6– 454.7 K) and large yellow prisms of (II) (m.p. 475.7–478.7 K).

S3. Refinement

H atoms potentially involved in hydrogen-bonding interactions were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were included in the respective refinements at calculated positions (C—H = 0.95 Å) as riding atoms, with U_iso(H) fixed at 1.2U_eq(C). The large difference electron density maximum and minimum for (II) (1.552–1.302 e Å⁻³) are adjacent to the I atom.

Computing details

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1999); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON for Windows (Spek, 1999); software used to prepare material for publication: PLATON for Windows.

Figures

	Fig. 1. The molecular configuration and atom-numbering scheme for the 8-HQ^+ cation and 2-ABS^− anion in (I). Non-H atoms are shown as 30% probability displacement ellipsoids.
	Fig. 2. The molecular configuration and atom-numbering scheme for (II), showing the 8-HQ^+ cation and ferron anion superimposition. Non-H atoms are shown as 30% probability displacement ellipsoids.
	Fig. 3. A perspective view of the packing of (I) in the unit cell, viewed down c, showing homomolecular stacks of oxine cations and hydrogen- bonding associations as broken lines.
	Fig. 4. A perspective view of the packing of (II) in the unit cell, viewed down c, showing the 8-HQ^+ cation–ferron anion stacks linked through hydrogen-bonding interactions also involving the water molecules.

(I) 8-hydroxyquinolinium 2-aminobenzenesulfonate

Crystal data

C9H8NO^+·C6H6NO3S^−	F(000) = 664
Mr = 318.34	Dx = 1.484 Mg m^−3
Monoclinic, P21/a	Melting point = 454.6–454.7 K
Hall symbol: -P 2yab	Mo Kα radiation, λ = 0.71069 Å
a = 16.030 (4) Å	Cell parameters from 25 reflections
b = 11.726 (3) Å	θ = 12.7–17.1°
c = 7.7024 (15) Å	µ = 0.25 mm^−1
β = 100.298 (17)°	T = 298 K
V = 1424.5 (6) Å^3	Fragment, pale brown
Z = 4	0.40 × 0.20 × 0.10 mm

Data collection

Rigaku AFC-7R diffractometer	2047 reflections with I > 2σ(I)
Radiation source: Rigaku rotating-anode	Rint = 0.053
Graphite monochromator	θmax = 27.5°, θmin = 2.6°
ω–2θ scans	h = −8→20
Absorption correction: ψ scan TEXSAN for Windows (Molecular Structure Corporation, 1999)	k = −15→6
Tmin = 0.942, Tmax = 0.976	l = −10→9
3780 measured reflections	3 standard reflections every 150 reflections
3265 independent reflections	intensity decay: 0.03%

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)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.163	w = 1/[σ^2(Fo^2) + (0.1P)^2 + 3.934P] where P = (Fo^2 + 2Fc^2)/3
S = 0.90	(Δ/σ)max < 0.001
3265 reflections	Δρmax = 0.34 e Å^−3
212 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (2)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'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
S1	0.12539 (5)	0.41652 (6)	0.36349 (11)	0.0375 (3)
O11	0.13124 (17)	0.3616 (2)	0.5349 (3)	0.0553 (9)
O12	0.03930 (15)	0.4380 (2)	0.2776 (4)	0.0606 (9)
O13	0.17789 (15)	0.51871 (18)	0.3759 (3)	0.0506 (8)
N2	0.1156 (2)	0.4258 (3)	−0.0414 (5)	0.0566 (11)
C1	0.17121 (18)	0.3208 (2)	0.2292 (4)	0.0334 (8)
C2	0.16245 (19)	0.3390 (2)	0.0457 (4)	0.0374 (9)
C3	0.2067 (2)	0.2643 (3)	−0.0475 (4)	0.0466 (10)
C4	0.2555 (2)	0.1767 (3)	0.0343 (5)	0.0471 (11)
C5	0.2629 (2)	0.1593 (3)	0.2140 (5)	0.0440 (10)
C6	0.22087 (19)	0.2320 (2)	0.3100 (4)	0.0372 (9)
O81	0.16548 (15)	0.08411 (19)	0.6226 (3)	0.0463 (8)
N11	0.02389 (16)	0.2021 (2)	0.6354 (3)	0.0388 (8)
C21	−0.0437 (2)	0.2659 (3)	0.6387 (5)	0.0466 (11)
C31	−0.1140 (2)	0.2206 (3)	0.6966 (5)	0.0494 (11)
C41	−0.1128 (2)	0.1095 (3)	0.7494 (5)	0.0474 (11)
C51	−0.0343 (2)	−0.0746 (3)	0.8047 (4)	0.0448 (10)
C61	0.0382 (2)	−0.1338 (3)	0.8006 (4)	0.0467 (10)
C71	0.1080 (2)	−0.0833 (3)	0.7428 (4)	0.0413 (9)
C81	0.10444 (19)	0.0278 (3)	0.6859 (4)	0.0353 (8)
C91	0.02915 (18)	0.0900 (2)	0.6885 (4)	0.0335 (8)
C101	−0.04046 (19)	0.0406 (3)	0.7491 (4)	0.0383 (9)
H2A	0.081 (2)	0.455 (3)	0.013 (5)	0.046 (11)*
H2B	0.110 (2)	0.427 (3)	−0.154 (5)	0.048 (10)*
H3	0.202600	0.275500	−0.172400	0.0540*
H4	0.284900	0.126800	−0.034300	0.0550*
H5	0.296900	0.098600	0.271000	0.0520*
H6	0.225600	0.220700	0.434400	0.0440*
H11	0.066 (2)	0.233 (3)	0.602 (5)	0.047 (10)*
H21	−0.044400	0.343800	0.598200	0.0540*
H31	−0.163100	0.267300	0.699300	0.0590*
H41	−0.162000	0.078200	0.787700	0.0560*
H51	−0.081100	−0.109900	0.845800	0.0530*
H61	0.041500	−0.212400	0.837400	0.0550*
H71	0.159000	−0.126400	0.743700	0.0490*
H81	0.211 (2)	0.048 (3)	0.622 (5)	0.051 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0368 (4)	0.0286 (4)	0.0498 (5)	−0.0013 (3)	0.0150 (3)	−0.0002 (3)
O11	0.0783 (18)	0.0439 (13)	0.0507 (14)	0.0022 (12)	0.0304 (13)	0.0031 (11)
O12	0.0363 (13)	0.0635 (16)	0.0823 (19)	0.0078 (11)	0.0117 (12)	−0.0072 (14)
O13	0.0503 (13)	0.0304 (11)	0.0757 (16)	−0.0062 (10)	0.0239 (12)	−0.0093 (11)
N2	0.066 (2)	0.0539 (19)	0.0479 (19)	0.0111 (16)	0.0050 (16)	0.0114 (15)
C1	0.0336 (14)	0.0262 (13)	0.0414 (15)	−0.0040 (11)	0.0091 (12)	−0.0006 (12)
C2	0.0372 (15)	0.0330 (15)	0.0409 (16)	−0.0042 (12)	0.0042 (12)	0.0044 (12)
C3	0.0531 (19)	0.0474 (19)	0.0401 (16)	−0.0063 (15)	0.0107 (14)	−0.0024 (14)
C4	0.0481 (18)	0.0401 (17)	0.056 (2)	0.0024 (14)	0.0173 (15)	−0.0096 (15)
C5	0.0441 (17)	0.0295 (15)	0.059 (2)	0.0043 (13)	0.0107 (15)	0.0017 (14)
C6	0.0414 (16)	0.0290 (14)	0.0421 (16)	−0.0013 (12)	0.0099 (13)	0.0072 (12)
O81	0.0422 (13)	0.0358 (12)	0.0652 (15)	0.0070 (10)	0.0214 (11)	0.0052 (11)
N11	0.0411 (14)	0.0315 (12)	0.0456 (14)	0.0022 (11)	0.0125 (11)	−0.0019 (11)
C21	0.0511 (19)	0.0375 (17)	0.0512 (19)	0.0117 (14)	0.0094 (15)	0.0006 (15)
C31	0.0420 (17)	0.0497 (19)	0.058 (2)	0.0128 (15)	0.0128 (15)	−0.0034 (16)
C41	0.0407 (17)	0.053 (2)	0.0502 (19)	−0.0007 (15)	0.0131 (14)	−0.0054 (15)
C51	0.0470 (18)	0.0402 (17)	0.0477 (18)	−0.0107 (14)	0.0100 (14)	−0.0009 (14)
C61	0.059 (2)	0.0309 (15)	0.0489 (19)	−0.0009 (14)	0.0062 (16)	0.0012 (14)
C71	0.0450 (17)	0.0321 (15)	0.0462 (17)	0.0076 (13)	0.0064 (14)	−0.0016 (13)
C81	0.0378 (15)	0.0345 (15)	0.0346 (14)	0.0018 (12)	0.0088 (12)	−0.0025 (12)
C91	0.0404 (15)	0.0288 (13)	0.0311 (13)	0.0003 (12)	0.0056 (11)	−0.0031 (11)
C101	0.0413 (16)	0.0371 (15)	0.0363 (15)	−0.0019 (13)	0.0068 (12)	−0.0061 (12)

Geometric parameters (Å, º)

S1—O11	1.457 (2)	C4—H4	0.9658
S1—O12	1.442 (3)	C5—H5	0.9544
S1—O13	1.458 (2)	C6—H6	0.9568
S1—C1	1.772 (3)	C21—C31	1.391 (5)
O81—C81	1.342 (4)	C31—C41	1.364 (5)
O81—H81	0.84 (3)	C41—C101	1.414 (5)
N2—C2	1.367 (4)	C51—C101	1.415 (5)
N2—H2B	0.86 (4)	C51—C61	1.359 (5)
N2—H2A	0.83 (3)	C61—C71	1.407 (5)
N11—C91	1.375 (3)	C71—C81	1.372 (5)
N11—C21	1.320 (4)	C81—C91	1.413 (4)
N11—H11	0.85 (3)	C91—C101	1.409 (4)
C1—C6	1.389 (4)	C21—H21	0.9637
C1—C2	1.411 (4)	C31—H31	0.9621
C2—C3	1.403 (4)	C41—H41	0.9628
C3—C4	1.374 (5)	C51—H51	0.9588
C4—C5	1.383 (5)	C61—H61	0.9629
C5—C6	1.380 (5)	C71—H71	0.9601
C3—H3	0.9615
O11—S1—O12	113.22 (17)	C1—C6—H6	119.28
O11—S1—O13	111.17 (14)	C5—C6—H6	119.47
O11—S1—C1	106.42 (14)	N11—C21—C31	120.3 (3)
O12—S1—O13	112.36 (14)	C21—C31—C41	119.5 (3)
O12—S1—C1	107.78 (15)	C31—C41—C101	120.9 (3)
O13—S1—C1	105.32 (14)	C61—C51—C101	119.6 (3)
C81—O81—H81	116 (2)	C51—C61—C71	121.6 (3)
C2—N2—H2B	117 (2)	C61—C71—C81	120.7 (3)
H2A—N2—H2B	123 (3)	O81—C81—C71	126.3 (3)
C2—N2—H2A	115 (3)	O81—C81—C91	115.5 (3)
C21—N11—C91	122.9 (3)	C71—C81—C91	118.2 (3)
C91—N11—H11	119 (2)	C81—C91—C101	121.4 (3)
C21—N11—H11	118 (2)	N11—C91—C81	119.8 (3)
C2—C1—C6	120.6 (3)	N11—C91—C101	118.8 (3)
S1—C1—C6	118.5 (2)	C41—C101—C51	123.9 (3)
S1—C1—C2	120.7 (2)	C41—C101—C91	117.7 (3)
C1—C2—C3	116.7 (3)	C51—C101—C91	118.4 (3)
N2—C2—C1	123.5 (3)	N11—C21—H21	119.62
N2—C2—C3	119.8 (3)	C31—C21—H21	120.12
C2—C3—C4	122.1 (3)	C21—C31—H31	120.18
C3—C4—C5	120.6 (3)	C41—C31—H31	120.35
C4—C5—C6	118.8 (3)	C31—C41—H41	119.13
C1—C6—C5	121.2 (3)	C101—C41—H41	119.98
C2—C3—H3	118.45	C61—C51—H51	120.67
C4—C3—H3	119.50	C101—C51—H51	119.71
C3—C4—H4	119.71	C51—C61—H61	118.97
C5—C4—H4	119.68	C71—C61—H61	119.41
C6—C5—H5	120.49	C61—C71—H71	120.04
C4—C5—H5	120.67	C81—C71—H71	119.26

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O12	0.83 (3)	2.26 (4)	2.937 (5)	139 (3)
N2—H2B···O11^i	0.86 (4)	2.60 (4)	3.402 (4)	157 (3)
N11—H11···O81	0.85 (3)	2.35 (4)	2.675 (4)	103 (3)
N11—H11···O11	0.85 (3)	1.95 (4)	2.745 (4)	155 (3)
O81—H81···O13^ii	0.84 (3)	1.81 (3)	2.623 (3)	161 (3)
C6—H6···O11	0.96	2.46	2.875 (4)	106

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

(II)

Crystal data

C9H5INO4S^+·C9H8NO^−·1.5H2O	F(000) = 1040
Mr = 523.30	Dx = 1.791 Mg m^−3
Monoclinic, P21/a	Melting point = 475.7–478.7 K
Hall symbol: -P 2yab	Mo Kα radiation, λ = 0.71069 Å
a = 15.857 (4) Å	Cell parameters from 25 reflections
b = 17.667 (7) Å	θ = 12.6–16.6°
c = 6.977 (4) Å	µ = 1.80 mm^−1
β = 95.78 (4)°	T = 298 K
V = 1944.5 (14) Å^3	Block, yellow
Z = 4	0.50 × 0.50 × 0.35 mm

Data collection

Rigaku AFC-7R diffractometer	3424 reflections with I > 2 σ(I)
Radiation source: Rigaku rotating anode	Rint = 0.068
Graphite monochromator	θmax = 27.5°, θmin = 2.6°
ω–2q scans	h = −9→20
Absorption correction: ψ scan TEXSAN for Windows (Molecular Structure Corporation, 1999)	k = 0→22
Tmin = 0.434, Tmax = 0.533	l = −9→9
5029 measured reflections	3 standard reflections every 150 reflections
4473 independent reflections	intensity decay: 1.1%

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)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.158	w = 1/[σ^2(Fo^2) + (0.1P)^2 + 7.5983P] where P = (Fo^2 + 2Fc^2)/3
S = 0.89	(Δ/σ)max = 0.002
4473 reflections	Δρmax = 1.55 e Å^−3
291 parameters	Δρmin = −1.30 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0024 (6)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'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	Occ. (<1)
I7	0.41943 (2)	0.454944 (19)	0.23168 (7)	0.0621 (2)
S5	0.77115 (6)	0.38886 (6)	0.39535 (17)	0.0410 (3)
O8	0.41795 (19)	0.2767 (2)	0.2473 (5)	0.0467 (11)
O51	0.7631 (2)	0.4696 (2)	0.3869 (7)	0.0583 (13)
O52	0.8200 (2)	0.3576 (2)	0.2478 (6)	0.0529 (11)
O53	0.8014 (2)	0.3616 (3)	0.5871 (6)	0.0638 (14)
N1	0.5416 (2)	0.1733 (2)	0.3148 (6)	0.0411 (11)
C2	0.6016 (3)	0.1226 (3)	0.3517 (7)	0.0456 (16)
C3	0.6873 (3)	0.1402 (3)	0.3914 (7)	0.0445 (14)
C4	0.7123 (3)	0.2143 (3)	0.3909 (7)	0.0409 (12)
C5	0.6670 (2)	0.3515 (2)	0.3505 (6)	0.0340 (11)
C6	0.6020 (3)	0.4015 (2)	0.3136 (6)	0.0379 (12)
C7	0.5173 (3)	0.3772 (2)	0.2797 (6)	0.0373 (11)
C8	0.4985 (3)	0.3008 (2)	0.2801 (6)	0.0353 (11)
C9	0.6510 (2)	0.2720 (2)	0.3536 (6)	0.0323 (11)
C10	0.5655 (3)	0.2474 (2)	0.3167 (5)	0.0317 (10)
O81	0.4576 (2)	0.1167 (2)	−0.2463 (6)	0.0579 (11)
N11	0.6265 (3)	0.1155 (2)	−0.1505 (5)	0.0434 (11)
C21	0.7085 (3)	0.1109 (3)	−0.1051 (7)	0.0507 (17)
C31	0.7580 (3)	0.1763 (3)	−0.0813 (7)	0.0552 (17)
C41	0.7192 (4)	0.2453 (3)	−0.1057 (7)	0.0528 (16)
C51	0.5885 (4)	0.3206 (3)	−0.1843 (7)	0.0514 (16)
C61	0.5032 (4)	0.3217 (3)	−0.2345 (9)	0.0629 (19)
C71	0.4570 (4)	0.2531 (4)	−0.2562 (8)	0.0545 (17)
C81	0.4960 (3)	0.1851 (3)	−0.2284 (7)	0.0449 (14)
C91	0.5841 (3)	0.1834 (3)	−0.1778 (6)	0.0401 (11)
C101	0.6318 (3)	0.2514 (3)	−0.1559 (6)	0.0456 (14)
O1W	0.9311 (3)	0.4709 (2)	0.1144 (7)	0.0699 (16)
O2W	0.7478 (6)	0.4515 (5)	0.8912 (14)	0.071 (3)	0.500
H2	0.585800	0.070900	0.349700	0.0540*
H3	0.727900	0.101100	0.418100	0.0540*
H4	0.770600	0.226900	0.415100	0.0490*
H6	0.614400	0.454200	0.309800	0.0460*
H8	0.414 (4)	0.228 (5)	0.238 (10)	0.060 (10)*
H11	0.588 (4)	0.074 (4)	−0.139 (10)	0.074 (15)*
H21	0.734700	0.062800	−0.086600	0.0610*
H31	0.817300	0.173100	−0.047500	0.0660*
H41	0.752600	0.289900	−0.088200	0.0640*
H51	0.619000	0.366900	−0.167700	0.0630*
H61	0.474600	0.368400	−0.256900	0.0760*
H71	0.397500	0.254900	−0.291300	0.0650*
H81	0.407 (4)	0.121 (3)	−0.303 (9)	0.056 (16)*
H1A	0.901 (4)	0.437 (3)	0.194 (9)	0.052 (10)*
H1B	0.879 (4)	0.465 (3)	0.031 (9)	0.056 (10)*
H2A	0.700 (4)	0.461 (4)	0.856 (9)	0.087 (12)*	0.500
H2B	0.765 (4)	0.423 (3)	0.795 (9)	0.076 (13)*	0.500

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I7	0.0394 (2)	0.0402 (2)	0.1035 (4)	0.0074 (1)	−0.0090 (2)	0.0023 (2)
S5	0.0309 (5)	0.0401 (6)	0.0512 (6)	−0.0060 (4)	0.0000 (4)	−0.0006 (5)
O8	0.0326 (16)	0.0386 (19)	0.067 (2)	−0.0046 (13)	−0.0048 (14)	0.0030 (16)
O51	0.0450 (19)	0.0380 (18)	0.091 (3)	−0.0096 (14)	0.0025 (18)	−0.0092 (18)
O52	0.0382 (17)	0.051 (2)	0.072 (2)	−0.0034 (14)	0.0172 (16)	−0.0061 (17)
O53	0.047 (2)	0.082 (3)	0.058 (2)	−0.0160 (19)	−0.0160 (17)	0.015 (2)
N1	0.0405 (19)	0.0344 (19)	0.048 (2)	−0.0030 (15)	0.0029 (15)	−0.0024 (15)
C2	0.050 (3)	0.033 (2)	0.054 (3)	−0.0016 (18)	0.006 (2)	−0.0012 (19)
C3	0.046 (2)	0.038 (2)	0.050 (3)	0.0110 (18)	0.0068 (19)	0.0042 (19)
C4	0.034 (2)	0.040 (2)	0.049 (2)	0.0023 (17)	0.0054 (17)	−0.0001 (19)
C5	0.0266 (17)	0.034 (2)	0.041 (2)	−0.0014 (14)	0.0016 (15)	−0.0006 (16)
C6	0.038 (2)	0.031 (2)	0.044 (2)	−0.0028 (16)	0.0007 (17)	−0.0025 (17)
C7	0.0322 (19)	0.035 (2)	0.044 (2)	0.0034 (15)	−0.0003 (16)	0.0035 (17)
C8	0.0301 (18)	0.039 (2)	0.036 (2)	−0.0036 (15)	−0.0005 (15)	−0.0003 (16)
C9	0.0319 (18)	0.0350 (19)	0.0298 (18)	−0.0009 (15)	0.0020 (14)	−0.0006 (15)
C10	0.0341 (18)	0.0324 (19)	0.0284 (17)	−0.0042 (15)	0.0018 (14)	−0.0028 (15)
O81	0.0410 (18)	0.056 (2)	0.073 (2)	−0.0013 (16)	−0.0123 (16)	0.0077 (18)
N11	0.049 (2)	0.041 (2)	0.0390 (19)	−0.0044 (17)	−0.0011 (16)	0.0013 (16)
C21	0.048 (3)	0.053 (3)	0.049 (3)	0.000 (2)	−0.006 (2)	0.008 (2)
C31	0.051 (3)	0.065 (3)	0.047 (3)	−0.010 (2)	−0.008 (2)	0.003 (2)
C41	0.061 (3)	0.054 (3)	0.042 (2)	−0.017 (2)	−0.001 (2)	−0.002 (2)
C51	0.078 (4)	0.038 (2)	0.040 (2)	−0.004 (2)	0.015 (2)	−0.0048 (19)
C61	0.082 (4)	0.052 (3)	0.056 (3)	0.017 (3)	0.014 (3)	−0.003 (2)
C71	0.051 (3)	0.066 (3)	0.047 (3)	0.009 (2)	0.008 (2)	0.000 (2)
C81	0.048 (2)	0.049 (3)	0.038 (2)	0.002 (2)	0.0057 (18)	0.0014 (19)
C91	0.045 (2)	0.045 (2)	0.0306 (19)	−0.0039 (18)	0.0054 (16)	−0.0003 (17)
C101	0.061 (3)	0.045 (2)	0.031 (2)	−0.008 (2)	0.0060 (19)	−0.0040 (18)
O1W	0.076 (3)	0.046 (2)	0.092 (3)	0.0027 (19)	0.030 (2)	0.009 (2)
O2W	0.073 (6)	0.069 (6)	0.069 (5)	0.031 (4)	−0.008 (4)	−0.012 (4)

Geometric parameters (Å, º)

I7—C7	2.074 (4)	C6—C7	1.407 (7)
S5—O51	1.433 (4)	C7—C8	1.382 (5)
S5—O52	1.458 (4)	C8—C10	1.425 (6)
S5—O53	1.457 (4)	C9—C10	1.422 (6)
S5—C5	1.777 (4)	C2—H2	0.9469
O8—C8	1.344 (6)	C3—H3	0.9498
O8—H8	0.86 (9)	C4—H4	0.9493
O81—C81	1.353 (6)	C6—H6	0.9525
O81—H81	0.86 (6)	C21—C31	1.397 (7)
O1W—H1A	0.97 (6)	C31—C41	1.368 (8)
O1W—H1B	0.97 (6)	C41—C101	1.399 (8)
O2W—H2A	0.79 (6)	C51—C61	1.363 (9)
O2W—H2B	0.90 (6)	C51—C101	1.406 (8)
N1—C10	1.363 (5)	C61—C71	1.416 (9)
N1—C2	1.313 (6)	C71—C81	1.356 (9)
N11—C91	1.379 (6)	C81—C91	1.406 (7)
N11—C21	1.309 (7)	C91—C101	1.420 (7)
N11—H11	0.96 (7)	C21—H21	0.9490
C2—C3	1.394 (7)	C31—H31	0.9478
C3—C4	1.368 (7)	C41—H41	0.9504
C4—C9	1.414 (6)	C51—H51	0.9514
C5—C9	1.428 (5)	C61—H61	0.9469
C5—C6	1.362 (6)	C71—H71	0.9511
O51—S5—O52	113.5 (2)	C3—C2—H2	117.98
O51—S5—O53	112.7 (3)	C2—C3—H3	120.30
O51—S5—C5	106.57 (19)	C4—C3—H3	120.37
O52—S5—O53	112.0 (2)	C3—C4—H4	120.08
O52—S5—C5	106.6 (2)	C9—C4—H4	120.17
O53—S5—C5	104.7 (2)	C7—C6—H6	119.32
C8—O8—H8	113 (4)	C5—C6—H6	119.00
C81—O81—H81	111 (4)	N11—C21—C31	120.6 (5)
H1A—O1W—H1B	81 (5)	C21—C31—C41	118.8 (5)
H2A—O2W—H2B	104 (6)	C31—C41—C101	121.4 (5)
C2—N1—C10	117.3 (4)	C61—C51—C101	120.4 (5)
C21—N11—C91	123.1 (4)	C51—C61—C71	120.3 (5)
C21—N11—H11	124 (4)	C61—C71—C81	121.3 (6)
C91—N11—H11	112 (4)	O81—C81—C71	125.7 (5)
N1—C2—C3	124.0 (5)	C71—C81—C91	118.8 (5)
C2—C3—C4	119.3 (5)	O81—C81—C91	115.5 (4)
C3—C4—C9	119.7 (4)	C81—C91—C101	120.9 (5)
C6—C5—C9	120.6 (3)	N11—C91—C101	118.3 (4)
S5—C5—C6	117.7 (3)	N11—C91—C81	120.8 (5)
S5—C5—C9	121.7 (3)	C41—C101—C91	117.7 (5)
C5—C6—C7	121.7 (3)	C41—C101—C51	124.0 (5)
C6—C7—C8	120.0 (4)	C51—C101—C91	118.2 (5)
I7—C7—C8	119.3 (3)	C31—C21—H21	119.43
I7—C7—C6	120.7 (3)	N11—C21—H21	119.93
O8—C8—C10	120.0 (3)	C21—C31—H31	120.77
O8—C8—C7	120.7 (4)	C41—C31—H31	120.43
C7—C8—C10	119.3 (4)	C31—C41—H41	119.00
C4—C9—C5	126.3 (3)	C101—C41—H41	119.57
C5—C9—C10	117.7 (3)	C101—C51—H51	119.69
C4—C9—C10	116.0 (4)	C61—C51—H51	119.88
C8—C10—C9	120.7 (3)	C51—C61—H61	120.09
N1—C10—C8	115.6 (4)	C71—C61—H61	119.60
N1—C10—C9	123.7 (4)	C81—C71—H71	119.52
N1—C2—H2	118.01	C61—C71—H71	119.20
O51—S5—C5—C6	1.5 (4)	C6—C7—C8—C10	0.5 (6)
O51—S5—C5—C9	−178.2 (4)	O8—C8—C10—N1	0.2 (6)
O52—S5—C5—C6	−120.1 (4)	O8—C8—C10—C9	−179.4 (4)
O52—S5—C5—C9	60.3 (4)	C7—C8—C10—C9	0.3 (6)
O53—S5—C5—C6	121.2 (4)	C7—C8—C10—N1	179.9 (4)
O53—S5—C5—C9	−58.5 (4)	C5—C9—C10—N1	179.8 (4)
C10—N1—C2—C3	−0.3 (7)	C4—C9—C10—C8	179.1 (4)
C2—N1—C10—C9	0.8 (6)	C5—C9—C10—C8	−0.7 (6)
C2—N1—C10—C8	−178.7 (4)	C4—C9—C10—N1	−0.4 (6)
C21—N11—C91—C101	0.1 (6)	N11—C21—C31—C41	0.2 (7)
C91—N11—C21—C31	0.1 (7)	C21—C31—C41—C101	−0.8 (7)
C21—N11—C91—C81	179.3 (4)	C31—C41—C101—C51	−179.5 (5)
N1—C2—C3—C4	−0.7 (8)	C31—C41—C101—C91	1.0 (7)
C2—C3—C4—C9	1.1 (7)	C101—C51—C61—C71	0.8 (8)
C3—C4—C9—C5	179.2 (4)	C61—C51—C101—C41	179.5 (5)
C3—C4—C9—C10	−0.6 (6)	C61—C51—C101—C91	−1.0 (7)
S5—C5—C9—C10	179.8 (3)	C51—C61—C71—C81	−0.2 (9)
S5—C5—C9—C4	0.0 (6)	C61—C71—C81—C91	−0.2 (8)
S5—C5—C6—C7	−178.9 (3)	C61—C71—C81—O81	−179.7 (5)
C6—C5—C9—C4	−179.6 (4)	O81—C81—C91—N11	0.4 (6)
C9—C5—C6—C7	0.8 (6)	O81—C81—C91—C101	179.6 (4)
C6—C5—C9—C10	0.1 (7)	C71—C81—C91—N11	−179.2 (4)
C5—C6—C7—I7	178.2 (3)	C71—C81—C91—C101	0.0 (7)
C5—C6—C7—C8	−1.1 (6)	N11—C91—C101—C41	−0.7 (6)
I7—C7—C8—C10	−178.8 (3)	C81—C91—C101—C41	−179.9 (4)
C6—C7—C8—O8	−179.8 (4)	N11—C91—C101—C51	179.8 (5)
I7—C7—C8—O8	0.9 (6)	C81—C91—C101—C51	0.6 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O52	0.97 (6)	1.96 (6)	2.882 (6)	156 (5)
O1W—H1B···O2W^i	0.97 (6)	2.22 (6)	3.175 (11)	169 (5)
O2W—H2A···I7^ii	0.79 (6)	2.44 (7)	3.169 (10)	155 (7)
O2W—H2B···O53	0.90 (6)	1.94 (6)	2.848 (11)	180 (6)
O8—H8···N1	0.86 (9)	2.26 (7)	2.687 (5)	111 (5)
O8—H8···O52^iii	0.86 (9)	2.13 (8)	2.836 (5)	139 (6)
N11—H11···O81	0.96 (7)	2.26 (7)	2.694 (6)	107 (5)
N11—H11···O1W^iv	0.96 (7)	1.86 (7)	2.733 (5)	150 (6)
O81—H81···O53^v	0.86 (6)	1.80 (6)	2.656 (5)	175 (5)
C6—H6···O51	0.95	2.38	2.823 (6)	108

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