Sulfonate pseudohalides of boron subphthalocyanine

The crystal structures of three sulfonate pseudo­halide derivatives of boron sub­phthalo­cyanine (BsubPc) are described and compared with four structures of three published sulfonate derivatives. Benzene­sulfonate boron sub­phthalo­cyanine [(benzene­sulfonato)­(sub­phthalo­cyaninato)­boron, C₃₀H₁₇BN₆O₃S, (I)] crystallizes in the space group P with Z = 2. The structure contains two centrosymmetric π-stacking inter­actions between the concave faces of the isoindoline units in the BsubPc ligands. 3-Nitro­benzene­sul­fonate boron sub­phthalo­cyanine [(3-nitro­benzene­sulfonato)­(sub­phthalo­cyaninato)­boron, C₃₀H₁₆BN₇O₅S, (II)] crystallizes in the space group P2₁/c with Z = 4. The structure contains an inter­molecular S—O...π inter­action from the sulfonate group to a five-membered N-containing ring of an isoindoline unit on the concave side of a neighbouring BsubPc ligand, at a distance of 3.151 (3) Å. The crystal of methane­sulfonate boron sub­phthalo­cyanine [(methane­sulfonato)­(sub­phthalo­cyaninato)­boron, C₂₅H₁₅BN₆O₃S, (III)] was produced via sublimation and it is not a solvate, in contrast with two previously published structures of the same compound. Compound (III) crystallizes in the space group P2₁/n with Z = 2, and its structure is similar to that of the more common compound Cl-BsubPc.

S1. Comment

Boron subphthalocyanine (Bsubpc) is magenta coloured and the only ring-reduced member of the phthalocyanine family of dyes and pigments. The three isoindoline units in the ring system are coordinated to a central B atom, which creates a bowl-shaped yet aromatic ligand. The most common and currently most efficient synthetic route to the formation of BsubPcs is the reaction of phthalonitrile with either BCl₃ or BBr₃ (which is also the boron source). In each of these cases, the central B atom forms two covalent bonds and one dative bond with N atoms in the phthalonitriles during cyclization, leaving one position open on the trivalent B atom. This open position is typically occupied by the halide of the boron source, which protrudes in what is referred to as the axial position, i.e. perpendicular to the molecular plane of the subPc ligand. The chemistry to replace the axial Cl or Br atom with other nucleophiles is well known (Zyskowski & Kennedy, 2000; Claessens et al., 2002, 2003; Gommans et al., 2009). However, these two starting materials have their drawbacks, viz. Br-BsubPc is susceptible to hydrolysis and Cl-BsubPc has a low reactivity to substitution.

Recently, our group reported the synthesis of sulfonic acid-based pseudohalides of BsubPc, which are a new family of BsubPc derivatives (Paton et al., 2012). These compounds were synthesized to act as alternative reagents for axial substitution. We have shown that the pseudohalides have similar reactivity and electrochemical properties to the halide-BsubPcs. However, due to the size and polarity difference of the sulfonate group over Cl^- or Br^-, it would be expected that the solid-state arrangement would be dramatically different. In this paper, we report the crystal structures of three sulfonate pseudohalide-BsubPcs and compare them with four structures we have published previously (Paton et al., 2012). We also compare the solid-state arrangements of the pseudohalides with the published crystal structures of Cl-BsubPcs and other halo-BsubPcs.

The three sulfonate–BsubPc derivatives, benzenesulfonate boron subphthalocyanine, (I), 3-nitrobenzenesulfonate boron subphthalocyanine, (II), and methanesulfonate boron subphthalocyanine, (III), were synthesized according to a previously published method (Paton et al., 2012). Previously, crystals of chlosylate-BsubPc (ClsO-BsubPc) and tosylate-BsubPc (TsO-BsubPc) were grown via vapour diffusion of heptane into a solution of the compound in benzene, and two different solvates of mesylate-BsubPc (MsO-BsubPc) were grown in one container by diffusing pentane into a solution of the compound in dichloromethane (DCM). The latter system of pentane/DCM was used in that case because crystals of MsO-BsubPc could not be grown using the benzene/heptane system. However, neither of these solvent systems was successful in producing crystals of (I) or (II) of suitable quality for diffraction, nor could a nonsolvated crystal of (III) be obtained. Many crystallization attempts were made, including multiple attempts at vapour diffusion in the two solvent systems described above, liquid layering using the same two solvent systems, evaporation from a variety of solvents, such as DCM, toluene, chlorobenzene, benzene and chloroform, and finally sublimation. Evaporation from chloroform produced crystals of (I) and evaporation from benzene produced crystals of (II). Sublimation of (III) produced a diffraction-quality nonsolvated crystal. It is also noted that sublimation of TsO-BsubPc produced crystals of the same structure as described previously for that compound (Paton et al., 2012).

The previously reported crystal structures can be grouped into two categories: ClsO-BsubPc and TsO-BsubPc, which contain a benzenesulfonate group, and the two solvates of MsO-BsubPc, which have a methanesulfonate group. The structures of these compounds are shown in Fig. 1, redrawn from the original crystallographic data (Paton et al., 2012). ClsO-BsubPc and TsO-BsubPc are isostructural, having P1 symmetry. Their structures are characterized by a centrosymmetric π-stacking interaction between the concave faces of the subPc ligand at centroid-to-centroid (Cg–Cg) distances of 3.5229 (12) and 3.521 (2) Å for ClsO-BsubPc and TsO-BsubPc, respectively. This interaction creates a pairing of molecules that is typically seen in phenoxy-BsubPc derivatives (Paton et al., 2011). In these derivatives, however, the polarity of the benzenesulfonate group produces an additional centrosymmetric π-stacking interaction between the benzenesulfonate groups at Cg–Cg distances of 3.6813 (13) and 3.701 (2) Å for ClsO-BsubPc and TsO-BsubPc, respectively. In contrast, the MsO-BsubPc crystal structures are both solvates. One structure, which crystallized into a rhombus of the space group Pna2₁, possesses two BsubPc molecules and one molecule of DCM in the asymmetric unit, stabilized by a weak C—H···Cl interaction at a Cl···H distance of 2.960 (2) Å between atoms H20B and Cl1, and a C—Cl···O interaction at 2.884 (4) Å between atoms Cl1 and O2A of the sulfonate. Instead of the typical concave–concave centrosymmetric π-stacking that creates pairs of molecules, this crystal has a concave–concave head-to-tail (Morse, Helander et al., 2010) π-stacking interaction, creating a ribbon of BsubPc ligands in the structure. The other, which crystallized into a needle shape of the space group C2/c, has disordered solvent of unknown identity incorporated into solvent-accessible voids. The structure is stabilized by three sets of π-stacking interactions: the typical concave–concave centrosymmetric stacking at a Cg–Cg distance of 3.7169 (19) Å, a convex–convex interaction at a Cg–Cg distance of 3.6405 (19) Å and an unusual convex–convex head-to-tail interaction, creating rows of BsubPc ligands. Furthermore, the sulfonate group in this structure is involved in several interactions, which include three C—H···O interactions and, more interestingly, an S—O···π interaction at an O···π distance of 3.630 (3) Å.

Compound (I) crystallizes in the space group P1 with Z = 2, and possesses 30.0 ų of solvent-accessible void space. The molecular structure is shown in Fig. 2(a) and the crystal structure in Fig. 2(b). The structure is stabilized by two pairs of π-stacking interactions. The closer of the two pairs is between isoindoline units through their convex faces. The pair of π-stacking interactions are centrosymmetric, and have a Cg–Cg distance of 3.5170 (10) Å. The other pair is between isoindoline units through their concave faces and is also centrosymmetric, with a Cg–Cg distance of 3.7528 (11) Å. The structure also contains three C—H···O hydrogen bonds, viz. C12—H12A···O2, C13—H13A···O2 and C26—H26A···O3, with H···O distances of 2.52, 2.57 and 2.43 Å, respectively. The last C—H···O hydrogen bond makes a pair of centrosymmetric interactions between sulfonate atom O3 and a C atom in the ring of the benzenesulfonate group.

Compound (II) crystallizes in the space group P2₁/c with Z = 4. The molecular structure is shown in Fig. 3(a) and the crystal structure in Fig. 3(b). Examination of the structure shows that the subPc ligands overlap one of their isoindole units with a π-stacking interaction through their convex faces. The isoindole units overlap with a slight angle between them, with the closest π-stacking interaction between the N3/C9/C10/C15/C16 and C2–C7 rings at a Cg–Cg distance of 3.537 (2) Å. The structure is also stabilized by two C—H···O hydrogen bonds (C5—H5A···O3 and C28—H28A···O3), with H···O distances of 2.56 and 2.32 Å, respectively. The structure also contains an intermolecular S—O···π interaction from the sulfonate group to a five-membered ring (N1/C1/C2/C7/C8) on the concave side of a neighbouring BsubPc ligand at an O···π distance of 3.151 (3) Å. This S—O···π contact stabilizes the sulfonate group positioned within the bowl of the adjacent subPc ligand, and defines a column of molecules approximately perpendicular to the plane of the subPc ligand.

Compound (III) upon sublimation crystallizes in the space group P2₁/n. The molecular structure is shown in Fig. 4(a) and the crystal structure in Fig. 4(b). This structure is stabilized by a concave–concave interaction between the centroid of the six-membered ring C10–C15 and atom N6, at a distance of 3.793 (7) Å. Interestingly, there are no π-stacking interactions shorter than 4.0 Å in the structure. There are two C—H···π interactions, with H···π distances of 2.91 and 2.90 Å, between C19—H19A and the C2–C7 ring, and between C22—H22A and the C10–C15 ring, respectively. There are also one C—H···N and two C—H···O hydrogen bonds in the structure, with H···A distances of 2.49 and 2.56/2.56 Å, respectively, with the C—H···O interactions being between the O atoms of the sulfonate and the BsubPc ligand, and the C—H···N interaction being between the mesylate methyl group and an imine N atom.

In terms of chemical and physical properties, the halo-BsubPc derivatives are the closest analogues of the sulfonate pseudohalides of BsubPc (Paton et al., 2012). Halo-BsubPcs form two crystal-structure motifs, which depend on whether their peripheral substituents are H (H₁₂) or F (F₁₂). The halo-H₁₂BsubPc motif displays two interactions that seem to stabilize the structure (Kietaibl, 1974; Fulford et al., 2012). The packing structure of Br-BsubPc (Fulford et al., 2012) is shown in Fig. 5(a) as an example. The first interaction is a concave–concave head-to-tail π-stacking interaction which forms ribbons in one dimension. The second interaction is a centrosymmetric pair of convex–convex π-stacked isoindoline units which links the ribbons of BsubPc molecules together. In contrast, the halo-F₁₂BubPc motif is characterized by columns of BsubPc molecules oriented approximately perpendicular to the BsubPc molecular plane (Rodríguez-Morgade et al., 2008; Fukuda et al., 2002; Morse, Maka et al., 2010). An example of this motif is shown by the crystal structure of Br-F₁₂BsubPc (Morse, Maka et al., 2010) in Fig. 5(b). These columns are associated through the halogen atom on B, which sits directly under the next BsubPc and consistently displays an intermolecular B to halogen distance that is shorter than the sum of the van der Waals radii. These motifs are also consistent with peripherally fused or hybrid BsubPcs. For example, fluorinated BsubPc dimers joined peripherally through one isoindole unit in both the cis and trans forms crystallize according to the F₁₂BsubPc motif (Fukuda et al., 2002). The crystal structure of the cis form shows columns of BsubPcs as the F₁₂BsubPc motif would predict, with the other BsubPc of the dimer protruding from the stack and alternating in opposite directions with neighbouring molecules. These half-molecules that are not within the columns are π-stacked with other half-molecules not in their own columns through their concave faces, thereby linking the columns together. The trans form follows the F₁₂BsubPc motif more closely, with both BsubPc parts of the dimer in neighbouring columns facing opposite directions. An example of a hybrid halo-BsubPc is an asymmetric BsubPc with two fluorinated isoindoles and one peripherally hydrogenated π-extended isoindole (Stork et al., 1999). This structure shows examples of both motifs: the fluorinated sides stack into columns with the halogen in the bowl of the next BsubPc unit, while the naphthalene side of the molecule forms a convex–convex π-stacking interaction with its closest neighbours.

Since the size and polarity of the sulfonate unit are different from the halogens in the same position on the halo-BsubPcs, we would expect to see differences in the solid-state arrangements. However, we can note important similarities. The structures of TsO-BsubPc, ClsO-BsubPc and (I) demonstrate convex–convex π-stacking as in the halo-H₁₂BsubPc motif. In contrast, the solid-state arrangement of (II) shows the most similarity to that of halo-F₁₂BsubPc. It contains oriented stacks linked together by S—O···π interactions, whereas the halo-F₁₂BsubPcs have oriented stacks connected by halogen···π interactions. A difference between them is that the nitrobenzene group is present between two neighbouring BsubPc ligands in the column, although the angle at which it is oriented to the BsubPc units, as well as its distance, precludes it from being involved in stabilizing π-stacking interactions. This additional molecular fragment in the column causes the increase in the B···B distance to 7.197 (7) Å for (II), compared, for example, with 5.471 (5) Å for Br-F₁₂BsubPc (Morse, Maka et al., 2010). The similarity between these structures is likely to result from the electron-withdrawing nature of the nitro group on the benzenesulfonate, which, coupled with the electron-deficient BsubPc ligand, prevents strong π-stacking interactions within the crystal that could outcompete even the weak S—O···π interactions that are present. The dichloromethane solvate of (III) shows concave-concave head-to-tail overlap as found in the halo-H₁₂BsubPc crystal structures. The new non-solvated structure of (III) shows even more similarity to that of the halo-BsubPcs. The concave–concave head-to-tail overlap that exists in the MsO-BsubPc structure at 3.793 (7) Å is the same Cg···N interaction that is seen in the crystal structures of Cl-BsubPc (Kietaibl, 1974) and Br-BsubPc (Fulford et al., 2012), at 3.701 (1) and 3.689 (7) Å, respectively.

As a final comment, one might expect that (I) and (II) would crystallize in a similar motif to ClsO-BsubPc and TsO-BsubPc, since those two compounds are also benzenesulfonate derivatives. However, there are more differences than similarities. Compound (I) does possess similar concave–concave π-stacking of the BsubPc ligands (see Fig. 2b), but the centrosymmetric interaction between the benzenesulfonate groups is based on C—H···O hydrogen bonds, and not on π-stacking as it is for ClsO-BsubPc and TsO-BsubPc (Fig. 1a). We propose that this is likely to be due to the dipole produced in the para-derivatives of benzenesulfonate, which does not occur in the nonsubstituted benzenesulfonate itself. The centrosymmetric C—H···O interactions in (I) are evidently weaker than the π-stacking produced by the substituted benzenesulfonates. The structure of (II) (Fig. 3b) is even more different, with no concave–concave π-stacking and no interactions between benzenesulfonate units. What is present, however, is an S—O···π interaction from the sulfonate group to the neighbouring BsubPc unit. Both of these observations are likely to result from the strongly electron-withdrawing nature of the nitro group on the benzenesulfonate, which would make π-stacking less favourable (Paton et al., 2011) and cause the sulfonate to be electron-deficient and therefore a better group to accept electrons in a weak hydrogen bond. The new unsolvated structure of (III) (Fig. 4b) does not correspond to any of the previously published sulfonate structures. The fact that it displays a head-to-tail concave–concave interaction between the π-system of one BsubPc and the imine N of another, which is similar to that of Cl-BsubPc and Br-BsubPc, is of special note since it has been shown that the electrochemical and optical properties of (III) and Cl-BsubPc are also quite similar (Paton et al., 2012). In solid-state applications where Cl-BsubPc is currently used, we therefore suggest that (III) would be an alternative to consider.

Related literature

For related literature, see: Claessens et al. (2002, 2003); Fukuda et al. (2002); Fulford et al. (2012); Gommans et al. (2009); Kietaibl (1974); Morse, Helander, Maka, Lu & Bender (2010); Morse, Maka, Lough & Bender (2010); Paton et al. (2011, 2012); Rodríguez-Morgade, Claessens, Medina, González-Rodríguez, Gutiérrez-Puebla, Monge, Alkorta, Elguero & Torres (2008); Stork et al. (1999); Zyskowski & Kennedy (2000).

S2. Experimental

The synthesis and characterization of the title compounds are described in detail in a previous publication (Paton et al., 2012). The crystallization conditions are as follows. Evaporation of the solvent from a solution in chloroform produced crystals of (I) overnight. For (II), evaporation of the solvent from a solution in benzene produced crystals suitable for diffraction over a period of a few days. The sublimation of (III) was performed in a custom-built trained sublimation apparatus, at a temperature of 558 K and 80 mTorr of pressure (1 Torr = 133.322 Pa).

S3. Refinement

All H atoms were included in calculated positions and refined as riding, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C), or C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for the methyl group in (III).

Computing details

For all compounds, data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The crystal structures of (a) ClsO-BsubPc (TsO-BsubPc is isostructural), (b) MsO-BsubPc (needle; disordered solvent not included), and (c) MsO-BsubPc.CH2Cl2 (rhomboid). All structures redrawn from Paton et al. (2012). The ring centroids and main interactions are displayed. H atoms have been omitted.
	Fig. 2. (a) The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. (b) The packing structure of (I), with the ring centroids indicated by large circles and the main interactions displayed as dashed lines. H atoms have been omitted.
	Fig. 3. (a) The molecular structure of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. (b) The packing structure of (II), with the ring centroids indicated by large circles and the main interactions displayed as dashed lines. H atoms have been omitted.
	Fig. 4. (a) The molecular structure of (III), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. (b) The packing structure of (III), with the ring centroids indicated by large circles and the main interactions displayed as dashed lines. H atoms have been omitted.
	Fig. 5. The crystal structures of (a) Br-BsubPc (redrawn from Fulford et al., 2012) and (b) Br-F12BsubPc (redrawn from Morse, Maka et al., 2010). The main interactions are indicated as dashed lines. In (a), the ring centroids are shown as large circles and H atoms have been omitted.

(I) (benzenesulfonato)(subphthalocyaninato)boron

Crystal data

C30H17BN6O3S	Z = 2
Mr = 552.37	F(000) = 568
Triclinic, P1	Dx = 1.521 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.5118 (9) Å	Cell parameters from 8754 reflections
b = 11.0929 (10) Å	θ = 2.5–27.5°
c = 11.2047 (10) Å	µ = 0.18 mm^−1
α = 72.749 (2)°	T = 150 K
β = 75.862 (2)°	Needle, purple
γ = 81.398 (2)°	0.20 × 0.10 × 0.08 mm
V = 1205.77 (18) Å^3

Data collection

Bruker APEX DUO CCD area-detector diffractometer	5579 independent reflections
Radiation source: fine-focus sealed tube	4211 reflections with I > 2σ(I)
Bruker Triumph monochromator	Rint = 0.035
ϕ and ω scans	θmax = 27.6°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→12
Tmin = 0.715, Tmax = 0.946	k = −14→8
20057 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0421P)^2 + 0.3932P] where P = (Fo^2 + 2Fc^2)/3
5579 reflections	(Δ/σ)max = 0.001
370 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.52 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
S1	0.04716 (4)	0.67755 (4)	0.75006 (4)	0.01701 (10)
O1	0.16416 (11)	0.75883 (10)	0.72392 (10)	0.0173 (2)
O2	−0.03168 (12)	0.74448 (11)	0.65995 (12)	0.0252 (3)
O3	−0.01156 (12)	0.64718 (11)	0.88320 (11)	0.0235 (3)
N1	0.36300 (13)	0.82684 (12)	0.74420 (12)	0.0163 (3)
N2	0.27949 (13)	0.99241 (12)	0.84392 (13)	0.0176 (3)
N3	0.19354 (13)	0.79054 (12)	0.92946 (13)	0.0156 (3)
N4	0.19052 (13)	0.58294 (12)	1.07274 (13)	0.0171 (3)
N5	0.31533 (13)	0.61910 (12)	0.86048 (13)	0.0158 (3)
N6	0.51408 (14)	0.65361 (13)	0.70417 (13)	0.0186 (3)
C1	0.48178 (16)	0.77845 (15)	0.68720 (15)	0.0172 (3)
C2	0.56333 (17)	0.88431 (15)	0.63535 (15)	0.0183 (3)
C3	0.69352 (17)	0.89383 (16)	0.56736 (16)	0.0219 (4)
H3A	0.7445	0.8232	0.5433	0.026*
C4	0.74579 (18)	1.00829 (17)	0.53622 (17)	0.0252 (4)
H4A	0.8328	1.0177	0.4865	0.030*
C5	0.67378 (18)	1.11135 (17)	0.57617 (17)	0.0253 (4)
H5A	0.7128	1.1892	0.5528	0.030*
C6	0.54749 (17)	1.10223 (15)	0.64866 (16)	0.0211 (4)
H6A	0.5006	1.1713	0.6786	0.025*
C7	0.49056 (16)	0.98882 (15)	0.67674 (15)	0.0178 (3)
C8	0.36527 (16)	0.94607 (14)	0.75451 (15)	0.0166 (3)
C9	0.20031 (16)	0.91166 (14)	0.93494 (16)	0.0169 (3)
C10	0.13896 (16)	0.91349 (15)	1.06516 (16)	0.0170 (3)
C11	0.11463 (17)	1.00941 (16)	1.12693 (16)	0.0209 (4)
H11A	0.1321	1.0942	1.0808	0.025*
C12	0.06438 (18)	0.97740 (16)	1.25712 (17)	0.0241 (4)
H12A	0.0459	1.0417	1.3006	0.029*
C13	0.04003 (17)	0.85256 (17)	1.32667 (17)	0.0234 (4)
H13A	0.0050	0.8340	1.4161	0.028*
C14	0.06597 (16)	0.75560 (16)	1.26765 (16)	0.0197 (3)
H14A	0.0512	0.6706	1.3153	0.024*
C15	0.11458 (16)	0.78681 (15)	1.13586 (16)	0.0173 (3)
C16	0.15877 (15)	0.70832 (15)	1.04828 (15)	0.0161 (3)
C17	0.27304 (16)	0.54069 (15)	0.97941 (15)	0.0169 (3)
C18	0.35451 (16)	0.42199 (15)	0.98084 (16)	0.0178 (3)
C19	0.34643 (17)	0.30302 (16)	1.06801 (17)	0.0221 (4)
H19A	0.2820	0.2887	1.1456	0.026*
C20	0.43599 (18)	0.20613 (16)	1.03727 (17)	0.0241 (4)
H20A	0.4301	0.1230	1.0932	0.029*
C21	0.53475 (18)	0.22747 (16)	0.92608 (18)	0.0253 (4)
H21A	0.5951	0.1589	0.9086	0.030*
C22	0.54616 (17)	0.34632 (16)	0.84116 (17)	0.0223 (4)
H22A	0.6153	0.3611	0.7672	0.027*
C23	0.45361 (16)	0.44387 (15)	0.86690 (16)	0.0183 (3)
C24	0.43261 (16)	0.57594 (15)	0.79563 (16)	0.0176 (3)
C25	0.12334 (16)	0.53933 (15)	0.70805 (16)	0.0182 (3)
C26	0.14201 (17)	0.42956 (16)	0.80298 (17)	0.0217 (4)
H26A	0.1094	0.4265	0.8906	0.026*
C27	0.20939 (19)	0.32401 (17)	0.7672 (2)	0.0308 (4)
H27A	0.2238	0.2478	0.8308	0.037*
C28	0.2556 (2)	0.32921 (19)	0.6397 (2)	0.0351 (5)
H28A	0.3028	0.2568	0.6162	0.042*
C29	0.2341 (2)	0.43833 (19)	0.5457 (2)	0.0343 (5)
H29A	0.2647	0.4403	0.4581	0.041*
C30	0.16772 (19)	0.54509 (17)	0.57946 (17)	0.0269 (4)
H30A	0.1529	0.6209	0.5156	0.032*
B1	0.25285 (18)	0.74749 (17)	0.81371 (18)	0.0161 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0168 (2)	0.01689 (19)	0.0187 (2)	−0.00052 (15)	−0.00433 (16)	−0.00670 (15)
O1	0.0185 (6)	0.0161 (5)	0.0174 (6)	−0.0033 (5)	−0.0043 (5)	−0.0035 (4)
O2	0.0258 (7)	0.0233 (6)	0.0314 (7)	0.0040 (5)	−0.0157 (6)	−0.0098 (5)
O3	0.0224 (6)	0.0289 (6)	0.0195 (6)	−0.0056 (5)	0.0017 (5)	−0.0106 (5)
N1	0.0171 (7)	0.0160 (6)	0.0152 (7)	−0.0008 (5)	−0.0026 (6)	−0.0045 (5)
N2	0.0184 (7)	0.0160 (6)	0.0176 (7)	0.0003 (5)	−0.0045 (6)	−0.0038 (5)
N3	0.0158 (7)	0.0142 (6)	0.0169 (7)	−0.0010 (5)	−0.0038 (6)	−0.0043 (5)
N4	0.0175 (7)	0.0171 (6)	0.0180 (7)	−0.0021 (5)	−0.0035 (6)	−0.0064 (5)
N5	0.0161 (7)	0.0165 (6)	0.0154 (7)	−0.0011 (5)	−0.0025 (6)	−0.0059 (5)
N6	0.0194 (7)	0.0194 (7)	0.0179 (7)	−0.0010 (6)	−0.0031 (6)	−0.0078 (5)
C1	0.0172 (8)	0.0216 (8)	0.0133 (8)	−0.0016 (7)	−0.0027 (7)	−0.0058 (6)
C2	0.0208 (9)	0.0205 (8)	0.0138 (8)	−0.0033 (7)	−0.0055 (7)	−0.0026 (6)
C3	0.0208 (9)	0.0271 (9)	0.0170 (9)	−0.0030 (7)	−0.0022 (7)	−0.0055 (7)
C4	0.0202 (9)	0.0317 (9)	0.0223 (10)	−0.0077 (8)	−0.0021 (7)	−0.0043 (7)
C5	0.0255 (9)	0.0239 (9)	0.0257 (10)	−0.0107 (7)	−0.0055 (8)	−0.0015 (7)
C6	0.0242 (9)	0.0192 (8)	0.0205 (9)	−0.0029 (7)	−0.0079 (7)	−0.0031 (7)
C7	0.0201 (8)	0.0191 (8)	0.0132 (8)	−0.0021 (7)	−0.0056 (7)	−0.0012 (6)
C8	0.0181 (8)	0.0147 (7)	0.0172 (8)	−0.0017 (6)	−0.0063 (7)	−0.0023 (6)
C9	0.0173 (8)	0.0153 (7)	0.0194 (9)	0.0016 (6)	−0.0065 (7)	−0.0059 (6)
C10	0.0137 (8)	0.0188 (8)	0.0185 (9)	0.0018 (6)	−0.0039 (7)	−0.0065 (6)
C11	0.0206 (9)	0.0195 (8)	0.0238 (9)	0.0009 (7)	−0.0054 (7)	−0.0082 (7)
C12	0.0251 (9)	0.0251 (9)	0.0261 (10)	0.0034 (7)	−0.0062 (8)	−0.0148 (7)
C13	0.0233 (9)	0.0299 (9)	0.0177 (9)	0.0010 (7)	−0.0033 (7)	−0.0101 (7)
C14	0.0181 (8)	0.0221 (8)	0.0188 (9)	−0.0013 (7)	−0.0038 (7)	−0.0056 (7)
C15	0.0136 (8)	0.0193 (8)	0.0202 (9)	−0.0008 (6)	−0.0038 (7)	−0.0073 (6)
C16	0.0133 (8)	0.0186 (7)	0.0163 (8)	−0.0024 (6)	−0.0029 (6)	−0.0044 (6)
C17	0.0174 (8)	0.0171 (7)	0.0171 (8)	−0.0036 (6)	−0.0051 (7)	−0.0040 (6)
C18	0.0186 (8)	0.0186 (8)	0.0199 (9)	0.0002 (7)	−0.0085 (7)	−0.0078 (6)
C19	0.0250 (9)	0.0209 (8)	0.0222 (9)	−0.0010 (7)	−0.0105 (7)	−0.0046 (7)
C20	0.0296 (10)	0.0173 (8)	0.0268 (10)	0.0030 (7)	−0.0157 (8)	−0.0025 (7)
C21	0.0253 (9)	0.0213 (8)	0.0336 (11)	0.0082 (7)	−0.0147 (8)	−0.0119 (7)
C22	0.0197 (9)	0.0229 (8)	0.0266 (10)	0.0014 (7)	−0.0069 (7)	−0.0099 (7)
C23	0.0185 (8)	0.0183 (8)	0.0212 (9)	−0.0012 (7)	−0.0077 (7)	−0.0074 (6)
C24	0.0178 (8)	0.0200 (8)	0.0180 (9)	0.0007 (7)	−0.0049 (7)	−0.0097 (6)
C25	0.0178 (8)	0.0174 (8)	0.0213 (9)	−0.0015 (6)	−0.0036 (7)	−0.0086 (6)
C26	0.0220 (9)	0.0209 (8)	0.0248 (10)	−0.0035 (7)	−0.0096 (7)	−0.0053 (7)
C27	0.0336 (11)	0.0202 (8)	0.0464 (13)	0.0032 (8)	−0.0239 (10)	−0.0110 (8)
C28	0.0285 (10)	0.0323 (10)	0.0559 (14)	0.0096 (9)	−0.0164 (10)	−0.0292 (10)
C29	0.0351 (11)	0.0385 (11)	0.0336 (11)	−0.0005 (9)	−0.0012 (9)	−0.0224 (9)
C30	0.0332 (11)	0.0253 (9)	0.0215 (10)	−0.0029 (8)	−0.0023 (8)	−0.0077 (7)
B1	0.0158 (9)	0.0169 (8)	0.0160 (9)	−0.0012 (7)	−0.0028 (7)	−0.0054 (7)

Geometric parameters (Å, º)

S1—O3	1.4263 (12)	C10—C15	1.420 (2)
S1—O2	1.4275 (12)	C11—C12	1.380 (2)
S1—O1	1.5525 (11)	C11—H11A	0.9500
S1—C25	1.7580 (16)	C12—C13	1.400 (2)
O1—B1	1.498 (2)	C12—H12A	0.9500
N1—C8	1.366 (2)	C13—C14	1.384 (2)
N1—C1	1.367 (2)	C13—H13A	0.9500
N1—B1	1.476 (2)	C14—C15	1.394 (2)
N2—C9	1.342 (2)	C14—H14A	0.9500
N2—C8	1.344 (2)	C15—C16	1.449 (2)
N3—C16	1.371 (2)	C17—C18	1.458 (2)
N3—C9	1.3761 (19)	C18—C19	1.390 (2)
N3—B1	1.477 (2)	C18—C23	1.420 (2)
N4—C17	1.338 (2)	C19—C20	1.385 (2)
N4—C16	1.342 (2)	C19—H19A	0.9500
N5—C17	1.367 (2)	C20—C21	1.397 (3)
N5—C24	1.367 (2)	C20—H20A	0.9500
N5—B1	1.476 (2)	C21—C22	1.380 (2)
N6—C24	1.339 (2)	C21—H21A	0.9500
N6—C1	1.343 (2)	C22—C23	1.391 (2)
C1—C2	1.451 (2)	C22—H22A	0.9500
C2—C3	1.397 (2)	C23—C24	1.459 (2)
C2—C7	1.423 (2)	C25—C26	1.384 (2)
C3—C4	1.374 (2)	C25—C30	1.387 (2)
C3—H3A	0.9500	C26—C27	1.387 (2)
C4—C5	1.400 (3)	C26—H26A	0.9500
C4—H4A	0.9500	C27—C28	1.379 (3)
C5—C6	1.377 (2)	C27—H27A	0.9500
C5—H5A	0.9500	C28—C29	1.380 (3)
C6—C7	1.392 (2)	C28—H28A	0.9500
C6—H6A	0.9500	C29—C30	1.386 (3)
C7—C8	1.449 (2)	C29—H29A	0.9500
C9—C10	1.449 (2)	C30—H30A	0.9500
C10—C11	1.395 (2)
O3—S1—O2	119.16 (8)	C13—C14—C15	117.74 (16)
O3—S1—O1	109.10 (7)	C13—C14—H14A	121.1
O2—S1—O1	105.92 (7)	C15—C14—H14A	121.1
O3—S1—C25	109.75 (8)	C14—C15—C10	121.02 (15)
O2—S1—C25	108.46 (8)	C14—C15—C16	131.29 (15)
O1—S1—C25	103.24 (7)	C10—C15—C16	107.50 (14)
B1—O1—S1	125.67 (10)	N4—C16—N3	123.03 (14)
C8—N1—C1	113.57 (13)	N4—C16—C15	129.70 (15)
C8—N1—B1	122.62 (14)	N3—C16—C15	105.69 (13)
C1—N1—B1	122.40 (13)	N4—C17—N5	122.12 (14)
C9—N2—C8	117.37 (13)	N4—C17—C18	131.91 (15)
C16—N3—C9	112.48 (13)	N5—C17—C18	104.97 (13)
C16—N3—B1	122.80 (13)	C19—C18—C23	121.11 (15)
C9—N3—B1	122.60 (13)	C19—C18—C17	131.60 (16)
C17—N4—C16	117.05 (14)	C23—C18—C17	107.28 (14)
C17—N5—C24	113.66 (13)	C20—C19—C18	117.38 (17)
C17—N5—B1	123.47 (13)	C20—C19—H19A	121.3
C24—N5—B1	122.17 (13)	C18—C19—H19A	121.3
C24—N6—C1	116.64 (14)	C19—C20—C21	121.72 (16)
N6—C1—N1	122.89 (14)	C19—C20—H20A	119.1
N6—C1—C2	130.56 (15)	C21—C20—H20A	119.1
N1—C1—C2	105.23 (13)	C22—C21—C20	121.20 (16)
C3—C2—C7	120.30 (15)	C22—C21—H21A	119.4
C3—C2—C1	132.03 (15)	C20—C21—H21A	119.4
C7—C2—C1	107.42 (14)	C21—C22—C23	118.14 (17)
C4—C3—C2	118.10 (16)	C21—C22—H22A	120.9
C4—C3—H3A	121.0	C23—C22—H22A	120.9
C2—C3—H3A	121.0	C22—C23—C18	120.35 (15)
C3—C4—C5	121.48 (16)	C22—C23—C24	132.26 (16)
C3—C4—H4A	119.3	C18—C23—C24	107.39 (14)
C5—C4—H4A	119.3	N6—C24—N5	122.52 (14)
C6—C5—C4	121.38 (16)	N6—C24—C23	131.30 (15)
C6—C5—H5A	119.3	N5—C24—C23	104.84 (14)
C4—C5—H5A	119.3	C26—C25—C30	121.73 (16)
C5—C6—C7	118.09 (16)	C26—C25—S1	119.68 (13)
C5—C6—H6A	121.0	C30—C25—S1	118.55 (13)
C7—C6—H6A	121.0	C25—C26—C27	118.47 (17)
C6—C7—C2	120.52 (15)	C25—C26—H26A	120.8
C6—C7—C8	132.05 (16)	C27—C26—H26A	120.8
C2—C7—C8	107.21 (14)	C28—C27—C26	120.29 (18)
N2—C8—N1	122.60 (14)	C28—C27—H27A	119.9
N2—C8—C7	130.20 (14)	C26—C27—H27A	119.9
N1—C8—C7	105.43 (14)	C27—C28—C29	120.78 (17)
N2—C9—N3	122.10 (15)	C27—C28—H28A	119.6
N2—C9—C10	130.06 (14)	C29—C28—H28A	119.6
N3—C9—C10	105.68 (13)	C28—C29—C30	119.82 (19)
C11—C10—C15	120.32 (15)	C28—C29—H29A	120.1
C11—C10—C9	132.19 (15)	C30—C29—H29A	120.1
C15—C10—C9	107.19 (13)	C29—C30—C25	118.89 (17)
C12—C11—C10	117.98 (15)	C29—C30—H30A	120.6
C12—C11—H11A	121.0	C25—C30—H30A	120.6
C10—C11—H11A	121.0	N5—B1—N1	105.22 (13)
C11—C12—C13	121.65 (16)	N5—B1—N3	105.30 (13)
C11—C12—H12A	119.2	N1—B1—N3	105.89 (13)
C13—C12—H12A	119.2	N5—B1—O1	115.26 (13)
C14—C13—C12	121.27 (16)	N1—B1—O1	108.04 (13)
C14—C13—H13A	119.4	N3—B1—O1	116.22 (14)
C12—C13—H13A	119.4
O3—S1—O1—B1	33.24 (14)	C16—N4—C17—C18	161.40 (16)
O2—S1—O1—B1	162.67 (12)	C24—N5—C17—N4	155.84 (15)
C25—S1—O1—B1	−83.42 (13)	B1—N5—C17—N4	−14.8 (2)
C24—N6—C1—N1	−10.1 (2)	C24—N5—C17—C18	−13.95 (17)
C24—N6—C1—C2	154.82 (16)	B1—N5—C17—C18	175.42 (14)
C8—N1—C1—N6	157.41 (15)	N4—C17—C18—C19	21.3 (3)
B1—N1—C1—N6	−9.3 (2)	N5—C17—C18—C19	−170.33 (17)
C8—N1—C1—C2	−10.73 (18)	N4—C17—C18—C23	−160.35 (17)
B1—N1—C1—C2	−177.47 (14)	N5—C17—C18—C23	8.01 (17)
N6—C1—C2—C3	13.0 (3)	C23—C18—C19—C20	−2.1 (2)
N1—C1—C2—C3	179.89 (17)	C17—C18—C19—C20	176.10 (16)
N6—C1—C2—C7	−161.01 (17)	C18—C19—C20—C21	2.9 (3)
N1—C1—C2—C7	5.86 (17)	C19—C20—C21—C22	−0.8 (3)
C7—C2—C3—C4	−3.4 (2)	C20—C21—C22—C23	−2.2 (3)
C1—C2—C3—C4	−176.83 (17)	C21—C22—C23—C18	3.0 (2)
C2—C3—C4—C5	3.0 (3)	C21—C22—C23—C24	−176.13 (17)
C3—C4—C5—C6	0.1 (3)	C19—C18—C23—C22	−0.9 (2)
C4—C5—C6—C7	−2.8 (3)	C17—C18—C23—C22	−179.44 (15)
C5—C6—C7—C2	2.3 (2)	C19—C18—C23—C24	178.44 (15)
C5—C6—C7—C8	176.19 (17)	C17—C18—C23—C24	−0.11 (17)
C3—C2—C7—C6	0.8 (2)	C1—N6—C24—N5	6.5 (2)
C1—C2—C7—C6	175.69 (14)	C1—N6—C24—C23	−158.18 (17)
C3—C2—C7—C8	−174.43 (15)	C17—N5—C24—N6	−154.32 (15)
C1—C2—C7—C8	0.43 (18)	B1—N5—C24—N6	16.4 (2)
C9—N2—C8—N1	8.3 (2)	C17—N5—C24—C23	13.86 (18)
C9—N2—C8—C7	−154.19 (17)	B1—N5—C24—C23	−175.37 (14)
C1—N1—C8—N2	−155.23 (15)	C22—C23—C24—N6	−21.9 (3)
B1—N1—C8—N2	11.5 (2)	C18—C23—C24—N6	158.89 (17)
C1—N1—C8—C7	11.02 (18)	C22—C23—C24—N5	171.39 (17)
B1—N1—C8—C7	177.72 (14)	C18—C23—C24—N5	−7.83 (17)
C6—C7—C8—N2	−16.3 (3)	O3—S1—C25—C26	−12.64 (16)
C2—C7—C8—N2	158.23 (16)	O2—S1—C25—C26	−144.37 (14)
C6—C7—C8—N1	178.93 (17)	O1—S1—C25—C26	103.57 (14)
C2—C7—C8—N1	−6.57 (17)	O3—S1—C25—C30	169.76 (13)
C8—N2—C9—N3	−8.3 (2)	O2—S1—C25—C30	38.04 (16)
C8—N2—C9—C10	152.54 (17)	O1—S1—C25—C30	−74.02 (15)
C16—N3—C9—N2	152.38 (15)	C30—C25—C26—C27	1.3 (3)
B1—N3—C9—N2	−11.5 (2)	S1—C25—C26—C27	−176.19 (13)
C16—N3—C9—C10	−12.50 (18)	C25—C26—C27—C28	−0.4 (3)
B1—N3—C9—C10	−176.36 (14)	C26—C27—C28—C29	−1.0 (3)
N2—C9—C10—C11	18.2 (3)	C27—C28—C29—C30	1.4 (3)
N3—C9—C10—C11	−178.59 (17)	C28—C29—C30—C25	−0.4 (3)
N2—C9—C10—C15	−155.33 (17)	C26—C25—C30—C29	−0.9 (3)
N3—C9—C10—C15	7.89 (17)	S1—C25—C30—C29	176.62 (15)
C15—C10—C11—C12	−1.2 (2)	C17—N5—B1—N1	138.94 (15)
C9—C10—C11—C12	−174.00 (17)	C24—N5—B1—N1	−30.9 (2)
C10—C11—C12—C13	1.0 (3)	C17—N5—B1—N3	27.3 (2)
C11—C12—C13—C14	0.3 (3)	C24—N5—B1—N3	−142.55 (14)
C12—C13—C14—C15	−1.4 (3)	C17—N5—B1—O1	−102.16 (17)
C13—C14—C15—C10	1.2 (2)	C24—N5—B1—O1	87.98 (18)
C13—C14—C15—C16	175.56 (17)	C8—N1—B1—N5	−138.06 (15)
C11—C10—C15—C14	0.1 (2)	C1—N1—B1—N5	27.5 (2)
C9—C10—C15—C14	174.52 (15)	C8—N1—B1—N3	−26.8 (2)
C11—C10—C15—C16	−175.49 (15)	C1—N1—B1—N3	138.69 (15)
C9—C10—C15—C16	−1.05 (18)	C8—N1—B1—O1	98.31 (17)
C17—N4—C16—N3	8.2 (2)	C1—N1—B1—O1	−96.15 (17)
C17—N4—C16—C15	−155.35 (16)	C16—N3—B1—N5	−24.2 (2)
C9—N3—C16—N4	−155.08 (15)	C9—N3—B1—N5	138.00 (15)
B1—N3—C16—N4	8.7 (2)	C16—N3—B1—N1	−135.36 (15)
C9—N3—C16—C15	11.84 (18)	C9—N3—B1—N1	26.8 (2)
B1—N3—C16—C15	175.67 (14)	C16—N3—B1—O1	104.69 (17)
C14—C15—C16—N4	−15.4 (3)	C9—N3—B1—O1	−93.10 (18)
C10—C15—C16—N4	159.51 (16)	S1—O1—B1—N5	53.60 (18)
C14—C15—C16—N3	178.84 (17)	S1—O1—B1—N1	170.93 (10)
C10—C15—C16—N3	−6.21 (17)	S1—O1—B1—N3	−70.29 (17)
C16—N4—C17—N5	−5.3 (2)

(II) (3-nitrobenzenesulfonato)(subphthalocyaninato)boron

Crystal data

C30H16BN7O5S	F(000) = 1224
Mr = 597.37	Dx = 1.552 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 5951 reflections
a = 13.8349 (7) Å	θ = 3.5–65.1°
b = 13.8988 (8) Å	µ = 1.64 mm^−1
c = 14.3887 (8) Å	T = 150 K
β = 112.466 (4)°	Cube, purple
V = 2556.8 (2) Å^3	0.09 × 0.09 × 0.09 mm
Z = 4

Data collection

Bruker Kappa APEX DUO CCD area-detector diffractometer	4159 independent reflections
Radiation source: Bruker ImuS	3342 reflections with I > 2σ(I)
Multi-layer optics monochromator	Rint = 0.042
ϕ and ω scans	θmax = 65.6°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→15
Tmin = 0.867, Tmax = 0.867	k = −16→16
13374 measured reflections	l = −16→13

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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.216	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.1371P)^2 + 2.6986P] where P = (Fo^2 + 2Fc^2)/3
4159 reflections	(Δ/σ)max = 0.001
397 parameters	Δρmax = 1.14 e Å^−3
0 restraints	Δρmin = −0.60 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
S1	0.77332 (7)	0.23044 (7)	0.64888 (7)	0.0306 (3)
O1	0.6980 (2)	0.25242 (17)	0.70014 (19)	0.0290 (6)
O2	0.7192 (2)	0.2467 (2)	0.5450 (2)	0.0377 (7)
O3	0.8192 (2)	0.1367 (2)	0.6813 (2)	0.0447 (7)
O4	1.2200 (3)	0.3828 (5)	0.8887 (4)	0.1102 (19)
O5	1.1647 (3)	0.2373 (4)	0.8834 (3)	0.0872 (15)
N1	0.6526 (2)	0.3209 (2)	0.8313 (2)	0.0262 (7)
N2	0.5089 (2)	0.2212 (2)	0.8194 (2)	0.0332 (7)
N3	0.6703 (2)	0.1522 (2)	0.8330 (2)	0.0282 (7)
N4	0.8367 (2)	0.0849 (2)	0.9283 (2)	0.0296 (7)
N5	0.8205 (2)	0.25115 (19)	0.8835 (2)	0.0228 (6)
N6	0.8012 (2)	0.4169 (2)	0.9177 (2)	0.0285 (7)
N7	1.1518 (3)	0.3221 (5)	0.8621 (3)	0.0670 (14)
C1	0.6973 (3)	0.4052 (3)	0.8737 (2)	0.0270 (8)
C2	0.6108 (3)	0.4630 (3)	0.8787 (3)	0.0315 (8)
C3	0.6039 (3)	0.5575 (3)	0.9067 (3)	0.0379 (9)
H3A	0.6629	0.5990	0.9268	0.045*
C4	0.5074 (3)	0.5894 (3)	0.9044 (3)	0.0396 (10)
H4A	0.4998	0.6542	0.9214	0.048*
C5	0.4220 (3)	0.5272 (3)	0.8775 (3)	0.0420 (10)
H5A	0.3577	0.5507	0.8777	0.050*
C6	0.4273 (3)	0.4346 (3)	0.8510 (3)	0.0371 (9)
H6A	0.3684	0.3932	0.8336	0.045*
C7	0.5218 (3)	0.4020 (3)	0.8500 (3)	0.0324 (9)
C8	0.5525 (3)	0.3085 (3)	0.8260 (2)	0.0294 (8)
C9	0.5712 (3)	0.1449 (3)	0.8305 (3)	0.0332 (9)
C10	0.5634 (3)	0.0473 (3)	0.8649 (3)	0.0356 (9)
C11	0.4791 (4)	−0.0035 (3)	0.8723 (3)	0.0426 (10)
H11A	0.4106	0.0230	0.8489	0.051*
C12	0.5007 (4)	−0.0948 (3)	0.9156 (3)	0.0434 (11)
H12A	0.4447	−0.1320	0.9193	0.052*
C13	0.6002 (4)	−0.1329 (3)	0.9533 (3)	0.0470 (11)
H13A	0.6116	−0.1946	0.9841	0.056*
C14	0.6824 (4)	−0.0830 (3)	0.9469 (3)	0.0426 (10)
H14A	0.7511	−0.1089	0.9739	0.051*
C15	0.6636 (3)	0.0067 (3)	0.9002 (3)	0.0343 (9)
C16	0.7341 (3)	0.0779 (3)	0.8847 (3)	0.0306 (8)
C17	0.8784 (3)	0.1728 (3)	0.9322 (3)	0.0268 (8)
C18	0.9759 (3)	0.2119 (3)	1.0016 (3)	0.0284 (8)
C19	1.0678 (3)	0.1686 (3)	1.0674 (3)	0.0353 (9)
H19A	1.0756	0.1006	1.0707	0.042*
C20	1.1475 (3)	0.2289 (3)	1.1281 (3)	0.0428 (10)
H20A	1.2117	0.2014	1.1717	0.051*
C21	1.1352 (3)	0.3285 (3)	1.1265 (3)	0.0400 (10)
H21A	1.1909	0.3671	1.1698	0.048*
C22	1.0451 (3)	0.3722 (3)	1.0643 (3)	0.0364 (9)
H22A	1.0374	0.4401	1.0647	0.044*
C23	0.9649 (3)	0.3143 (3)	1.0001 (3)	0.0292 (8)
C24	0.8606 (3)	0.3374 (2)	0.9283 (3)	0.0252 (8)
C25	0.8728 (3)	0.3169 (3)	0.6966 (3)	0.0353 (9)
C26	0.9705 (3)	0.2850 (3)	0.7593 (3)	0.0385 (10)
H26A	0.9847	0.2189	0.7758	0.046*
C27	1.0461 (4)	0.3550 (4)	0.7964 (3)	0.0500 (12)
C28	1.0275 (4)	0.4519 (4)	0.7725 (4)	0.0612 (15)
H28A	1.0816	0.4981	0.7996	0.073*
C29	0.9286 (5)	0.4795 (4)	0.7085 (4)	0.0626 (14)
H29A	0.9140	0.5453	0.6908	0.075*
C30	0.8506 (4)	0.4110 (3)	0.6700 (3)	0.0468 (11)
H30A	0.7824	0.4294	0.6256	0.056*
B1	0.7118 (3)	0.2429 (3)	0.8090 (3)	0.0256 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0313 (5)	0.0381 (5)	0.0237 (5)	−0.0016 (4)	0.0120 (4)	−0.0038 (4)
O1	0.0282 (13)	0.0399 (15)	0.0190 (13)	0.0007 (10)	0.0089 (10)	−0.0020 (10)
O2	0.0408 (16)	0.0511 (17)	0.0211 (15)	−0.0045 (12)	0.0115 (12)	−0.0046 (11)
O3	0.0471 (17)	0.0303 (15)	0.0602 (19)	0.0017 (12)	0.0245 (15)	−0.0004 (13)
O4	0.053 (2)	0.182 (6)	0.090 (3)	−0.056 (3)	0.020 (2)	−0.043 (3)
O5	0.039 (2)	0.145 (5)	0.062 (3)	0.001 (2)	0.0020 (19)	0.032 (3)
N1	0.0295 (16)	0.0291 (16)	0.0196 (15)	0.0034 (12)	0.0090 (12)	−0.0007 (12)
N2	0.0296 (17)	0.0470 (19)	0.0206 (16)	−0.0087 (14)	0.0067 (13)	−0.0045 (13)
N3	0.0289 (16)	0.0354 (17)	0.0215 (15)	−0.0076 (13)	0.0111 (13)	−0.0050 (12)
N4	0.0389 (18)	0.0243 (15)	0.0289 (17)	−0.0008 (13)	0.0166 (14)	−0.0040 (12)
N5	0.0267 (15)	0.0239 (15)	0.0180 (15)	0.0001 (11)	0.0089 (12)	−0.0005 (11)
N6	0.0412 (18)	0.0226 (15)	0.0240 (16)	−0.0009 (13)	0.0151 (13)	0.0025 (11)
N7	0.041 (2)	0.118 (4)	0.041 (2)	−0.028 (3)	0.0146 (19)	−0.010 (3)
C1	0.0299 (19)	0.0307 (18)	0.0179 (17)	0.0020 (15)	0.0063 (15)	0.0044 (14)
C2	0.040 (2)	0.037 (2)	0.0166 (17)	0.0105 (16)	0.0098 (15)	0.0042 (14)
C3	0.048 (2)	0.039 (2)	0.026 (2)	0.0080 (18)	0.0142 (18)	0.0016 (17)
C4	0.053 (3)	0.035 (2)	0.032 (2)	0.0188 (19)	0.0168 (19)	0.0050 (16)
C5	0.042 (2)	0.054 (3)	0.032 (2)	0.015 (2)	0.0157 (19)	0.0088 (18)
C6	0.033 (2)	0.051 (2)	0.027 (2)	0.0090 (18)	0.0107 (16)	0.0061 (17)
C7	0.032 (2)	0.045 (2)	0.0175 (18)	0.0059 (16)	0.0065 (15)	0.0017 (15)
C8	0.0303 (19)	0.043 (2)	0.0132 (16)	0.0084 (16)	0.0064 (14)	0.0009 (15)
C9	0.032 (2)	0.044 (2)	0.0212 (18)	−0.0016 (17)	0.0080 (15)	−0.0061 (16)
C10	0.047 (2)	0.037 (2)	0.0242 (19)	−0.0181 (18)	0.0156 (17)	−0.0107 (16)
C11	0.046 (2)	0.054 (3)	0.030 (2)	−0.016 (2)	0.0166 (19)	−0.0142 (19)
C12	0.063 (3)	0.038 (2)	0.035 (2)	−0.026 (2)	0.025 (2)	−0.0134 (18)
C13	0.065 (3)	0.036 (2)	0.047 (3)	−0.016 (2)	0.030 (2)	−0.0071 (19)
C14	0.061 (3)	0.034 (2)	0.039 (2)	−0.0077 (19)	0.026 (2)	−0.0049 (17)
C15	0.041 (2)	0.035 (2)	0.029 (2)	−0.0102 (17)	0.0157 (17)	−0.0076 (16)
C16	0.042 (2)	0.0273 (19)	0.0244 (19)	−0.0031 (16)	0.0153 (16)	−0.0041 (14)
C17	0.0325 (19)	0.0297 (18)	0.0207 (17)	0.0049 (15)	0.0129 (15)	0.0016 (14)
C18	0.0278 (19)	0.036 (2)	0.0223 (18)	0.0018 (15)	0.0103 (15)	0.0017 (15)
C19	0.037 (2)	0.044 (2)	0.026 (2)	0.0094 (17)	0.0129 (17)	0.0042 (16)
C20	0.030 (2)	0.071 (3)	0.024 (2)	0.006 (2)	0.0069 (17)	0.0059 (19)
C21	0.033 (2)	0.050 (3)	0.033 (2)	−0.0074 (18)	0.0071 (17)	−0.0008 (18)
C22	0.034 (2)	0.042 (2)	0.028 (2)	−0.0096 (17)	0.0064 (17)	−0.0026 (16)
C23	0.031 (2)	0.035 (2)	0.0214 (18)	−0.0035 (16)	0.0098 (15)	0.0017 (15)
C24	0.0296 (18)	0.0256 (17)	0.0190 (17)	−0.0038 (14)	0.0077 (14)	0.0018 (13)
C25	0.042 (2)	0.038 (2)	0.028 (2)	−0.0120 (18)	0.0157 (18)	−0.0048 (16)
C26	0.036 (2)	0.051 (2)	0.029 (2)	−0.0095 (19)	0.0131 (18)	−0.0022 (18)
C27	0.043 (2)	0.073 (3)	0.036 (2)	−0.024 (2)	0.017 (2)	−0.010 (2)
C28	0.070 (4)	0.062 (3)	0.062 (3)	−0.040 (3)	0.037 (3)	−0.027 (3)
C29	0.084 (4)	0.045 (3)	0.065 (3)	−0.022 (3)	0.036 (3)	−0.011 (2)
C30	0.058 (3)	0.041 (2)	0.043 (2)	0.001 (2)	0.021 (2)	−0.0010 (19)
B1	0.030 (2)	0.032 (2)	0.017 (2)	−0.0014 (16)	0.0110 (17)	−0.0019 (15)

Geometric parameters (Å, º)

S1—O2	1.411 (3)	C9—C10	1.463 (6)
S1—O3	1.446 (3)	C10—C15	1.400 (6)
S1—O1	1.520 (3)	C10—C11	1.401 (6)
S1—C25	1.757 (4)	C11—C12	1.395 (6)
O1—B1	1.510 (5)	C11—H11A	0.9500
O4—N7	1.213 (6)	C12—C13	1.378 (7)
O5—N7	1.214 (7)	C12—H12A	0.9500
N1—C1	1.356 (5)	C13—C14	1.365 (6)
N1—C8	1.368 (5)	C13—H13A	0.9500
N1—B1	1.466 (5)	C14—C15	1.392 (6)
N2—C9	1.337 (5)	C14—H14A	0.9500
N2—C8	1.344 (5)	C15—C16	1.465 (5)
N3—C9	1.361 (5)	C17—C18	1.444 (5)
N3—C16	1.377 (5)	C18—C19	1.398 (5)
N3—B1	1.480 (5)	C18—C23	1.431 (5)
N4—C16	1.318 (5)	C19—C20	1.395 (6)
N4—C17	1.344 (5)	C19—H19A	0.9500
N5—C17	1.374 (4)	C20—C21	1.395 (6)
N5—C24	1.374 (4)	C20—H20A	0.9500
N5—B1	1.481 (5)	C21—C22	1.368 (6)
N6—C1	1.341 (5)	C21—H21A	0.9500
N6—C24	1.350 (5)	C22—C23	1.396 (5)
N7—C27	1.478 (7)	C22—H22A	0.9500
C1—C2	1.465 (5)	C23—C24	1.453 (5)
C2—C3	1.388 (5)	C25—C30	1.365 (6)
C2—C7	1.420 (6)	C25—C26	1.380 (6)
C3—C4	1.395 (6)	C26—C27	1.378 (6)
C3—H3A	0.9500	C26—H26A	0.9500
C4—C5	1.394 (6)	C27—C28	1.389 (8)
C4—H4A	0.9500	C28—C29	1.380 (9)
C5—C6	1.352 (6)	C28—H28A	0.9500
C5—H5A	0.9500	C29—C30	1.386 (7)
C6—C7	1.388 (5)	C29—H29A	0.9500
C6—H6A	0.9500	C30—H30A	0.9500
C7—C8	1.449 (5)
O2—S1—O3	118.41 (18)	C14—C13—H13A	119.7
O2—S1—O1	107.30 (16)	C12—C13—H13A	119.7
O3—S1—O1	108.77 (16)	C13—C14—C15	118.8 (4)
O2—S1—C25	108.88 (18)	C13—C14—H14A	120.6
O3—S1—C25	107.97 (19)	C15—C14—H14A	120.6
O1—S1—C25	104.66 (17)	C14—C15—C10	120.8 (4)
B1—O1—S1	130.3 (2)	C14—C15—C16	131.8 (4)
C1—N1—C8	114.3 (3)	C10—C15—C16	107.3 (3)
C1—N1—B1	122.7 (3)	N4—C16—N3	123.6 (3)
C8—N1—B1	122.2 (3)	N4—C16—C15	129.5 (4)
C9—N2—C8	117.1 (3)	N3—C16—C15	105.2 (3)
C9—N3—C16	112.9 (3)	N4—C17—N5	122.8 (3)
C9—N3—B1	122.2 (3)	N4—C17—C18	130.1 (3)
C16—N3—B1	122.6 (3)	N5—C17—C18	105.2 (3)
C16—N4—C17	117.0 (3)	C19—C18—C23	120.2 (3)
C17—N5—C24	113.6 (3)	C19—C18—C17	132.3 (4)
C17—N5—B1	122.7 (3)	C23—C18—C17	107.3 (3)
C24—N5—B1	121.6 (3)	C20—C19—C18	117.5 (4)
C1—N6—C24	116.8 (3)	C20—C19—H19A	121.3
O4—N7—O5	125.0 (6)	C18—C19—H19A	121.3
O4—N7—C27	116.6 (6)	C21—C20—C19	121.6 (4)
O5—N7—C27	118.4 (4)	C21—C20—H20A	119.2
N6—C1—N1	122.6 (3)	C19—C20—H20A	119.2
N6—C1—C2	131.2 (3)	C22—C21—C20	121.8 (4)
N1—C1—C2	104.8 (3)	C22—C21—H21A	119.1
C3—C2—C7	120.0 (4)	C20—C21—H21A	119.1
C3—C2—C1	132.9 (4)	C21—C22—C23	118.2 (4)
C7—C2—C1	107.0 (3)	C21—C22—H22A	120.9
C2—C3—C4	117.7 (4)	C23—C22—H22A	120.9
C2—C3—H3A	121.1	C22—C23—C18	120.6 (3)
C4—C3—H3A	121.1	C22—C23—C24	131.7 (4)
C5—C4—C3	120.8 (4)	C18—C23—C24	107.6 (3)
C5—C4—H4A	119.6	N6—C24—N5	122.8 (3)
C3—C4—H4A	119.6	N6—C24—C23	131.1 (3)
C6—C5—C4	122.5 (4)	N5—C24—C23	104.7 (3)
C6—C5—H5A	118.8	C30—C25—C26	123.4 (4)
C4—C5—H5A	118.8	C30—C25—S1	119.1 (3)
C5—C6—C7	117.7 (4)	C26—C25—S1	117.4 (3)
C5—C6—H6A	121.1	C27—C26—C25	115.8 (4)
C7—C6—H6A	121.1	C27—C26—H26A	122.1
C6—C7—C2	121.2 (4)	C25—C26—H26A	122.1
C6—C7—C8	131.1 (4)	C26—C27—C28	123.2 (5)
C2—C7—C8	107.6 (3)	C26—C27—N7	116.7 (5)
N2—C8—N1	122.4 (3)	C28—C27—N7	120.1 (4)
N2—C8—C7	131.5 (3)	C29—C28—C27	118.5 (4)
N1—C8—C7	104.9 (3)	C29—C28—H28A	120.7
N2—C9—N3	122.8 (4)	C27—C28—H28A	120.7
N2—C9—C10	130.4 (4)	C28—C29—C30	119.8 (5)
N3—C9—C10	105.3 (3)	C28—C29—H29A	120.1
C15—C10—C11	120.5 (4)	C30—C29—H29A	120.1
C15—C10—C9	107.8 (3)	C25—C30—C29	119.3 (5)
C11—C10—C9	131.6 (4)	C25—C30—H30A	120.4
C12—C11—C10	116.7 (4)	C29—C30—H30A	120.4
C12—C11—H11A	121.6	N1—B1—N3	106.3 (3)
C10—C11—H11A	121.6	N1—B1—N5	106.4 (3)
C13—C12—C11	122.5 (4)	N3—B1—N5	105.9 (3)
C13—C12—H12A	118.8	N1—B1—O1	107.6 (3)
C11—C12—H12A	118.8	N3—B1—O1	114.2 (3)
C14—C13—C12	120.7 (4)	N5—B1—O1	115.8 (3)
O2—S1—O1—B1	176.6 (3)	C24—N5—C17—C18	−13.0 (4)
O3—S1—O1—B1	47.4 (3)	B1—N5—C17—C18	−176.7 (3)
C25—S1—O1—B1	−67.8 (3)	N4—C17—C18—C19	19.3 (7)
C24—N6—C1—N1	−7.2 (5)	N5—C17—C18—C19	−176.0 (4)
C24—N6—C1—C2	157.1 (4)	N4—C17—C18—C23	−156.8 (4)
C8—N1—C1—N6	155.6 (3)	N5—C17—C18—C23	7.9 (4)
B1—N1—C1—N6	−14.4 (5)	C23—C18—C19—C20	−1.8 (5)
C8—N1—C1—C2	−12.3 (4)	C17—C18—C19—C20	−177.4 (4)
B1—N1—C1—C2	177.7 (3)	C18—C19—C20—C21	2.4 (6)
N6—C1—C2—C3	19.3 (7)	C19—C20—C21—C22	−1.1 (6)
N1—C1—C2—C3	−174.3 (4)	C20—C21—C22—C23	−1.0 (6)
N6—C1—C2—C7	−158.8 (4)	C21—C22—C23—C18	1.6 (6)
N1—C1—C2—C7	7.6 (4)	C21—C22—C23—C24	178.0 (4)
C7—C2—C3—C4	−0.7 (5)	C19—C18—C23—C22	−0.2 (5)
C1—C2—C3—C4	−178.7 (4)	C17—C18—C23—C22	176.4 (3)
C2—C3—C4—C5	1.7 (6)	C19—C18—C23—C24	−177.4 (3)
C3—C4—C5—C6	−1.1 (6)	C17—C18—C23—C24	−0.8 (4)
C4—C5—C6—C7	−0.7 (6)	C1—N6—C24—N5	9.9 (5)
C5—C6—C7—C2	1.8 (5)	C1—N6—C24—C23	−154.3 (4)
C5—C6—C7—C8	179.7 (4)	C17—N5—C24—N6	−155.3 (3)
C3—C2—C7—C6	−1.1 (5)	B1—N5—C24—N6	8.6 (5)
C1—C2—C7—C6	177.3 (3)	C17—N5—C24—C23	12.4 (4)
C3—C2—C7—C8	−179.4 (3)	B1—N5—C24—C23	176.3 (3)
C1—C2—C7—C8	−1.0 (4)	C22—C23—C24—N6	−17.0 (7)
C9—N2—C8—N1	8.0 (5)	C18—C23—C24—N6	159.7 (3)
C9—N2—C8—C7	−157.2 (4)	C22—C23—C24—N5	176.6 (4)
C1—N1—C8—N2	−156.9 (3)	C18—C23—C24—N5	−6.6 (4)
B1—N1—C8—N2	13.2 (5)	O2—S1—C25—C30	45.5 (4)
C1—N1—C8—C7	11.7 (4)	O3—S1—C25—C30	175.2 (3)
B1—N1—C8—C7	−178.2 (3)	O1—S1—C25—C30	−69.0 (4)
C6—C7—C8—N2	−16.9 (6)	O2—S1—C25—C26	−134.2 (3)
C2—C7—C8—N2	161.2 (4)	O3—S1—C25—C26	−4.4 (4)
C6—C7—C8—N1	176.0 (4)	O1—S1—C25—C26	111.3 (3)
C2—C7—C8—N1	−6.0 (4)	C30—C25—C26—C27	1.3 (6)
C8—N2—C9—N3	−10.0 (5)	S1—C25—C26—C27	−179.1 (3)
C8—N2—C9—C10	153.9 (4)	C25—C26—C27—C28	−0.7 (6)
C16—N3—C9—N2	154.6 (3)	C25—C26—C27—N7	−178.8 (4)
B1—N3—C9—N2	−9.0 (5)	O4—N7—C27—C26	174.8 (4)
C16—N3—C9—C10	−12.8 (4)	O5—N7—C27—C26	−3.6 (7)
B1—N3—C9—C10	−176.3 (3)	O4—N7—C27—C28	−3.4 (7)
N2—C9—C10—C15	−157.3 (4)	O5—N7—C27—C28	178.3 (5)
N3—C9—C10—C15	8.6 (4)	C26—C27—C28—C29	0.0 (7)
N2—C9—C10—C11	18.5 (7)	N7—C27—C28—C29	178.0 (4)
N3—C9—C10—C11	−175.5 (4)	C27—C28—C29—C30	0.2 (8)
C15—C10—C11—C12	−0.1 (5)	C26—C25—C30—C29	−1.1 (7)
C9—C10—C11—C12	−175.6 (4)	S1—C25—C30—C29	179.2 (4)
C10—C11—C12—C13	2.4 (6)	C28—C29—C30—C25	0.3 (7)
C11—C12—C13—C14	−1.9 (6)	C1—N1—B1—N3	141.3 (3)
C12—C13—C14—C15	−1.0 (6)	C8—N1—B1—N3	−27.9 (4)
C13—C14—C15—C10	3.3 (6)	C1—N1—B1—N5	28.8 (4)
C13—C14—C15—C16	177.7 (4)	C8—N1—B1—N5	−140.5 (3)
C11—C10—C15—C14	−2.7 (6)	C1—N1—B1—O1	−95.9 (4)
C9—C10—C15—C14	173.7 (3)	C8—N1—B1—O1	94.9 (4)
C11—C10—C15—C16	−178.3 (3)	C9—N3—B1—N1	26.0 (5)
C9—C10—C15—C16	−1.9 (4)	C16—N3—B1—N1	−136.0 (3)
C17—N4—C16—N3	8.3 (5)	C9—N3—B1—N5	138.9 (3)
C17—N4—C16—C15	−154.3 (4)	C16—N3—B1—N5	−23.1 (4)
C9—N3—C16—N4	−154.6 (3)	C9—N3—B1—O1	−92.5 (4)
B1—N3—C16—N4	8.9 (5)	C16—N3—B1—O1	105.5 (4)
C9—N3—C16—C15	11.6 (4)	C17—N5—B1—N1	136.7 (3)
B1—N3—C16—C15	175.1 (3)	C24—N5—B1—N1	−25.7 (4)
C14—C15—C16—N4	−15.3 (7)	C17—N5—B1—N3	23.9 (4)
C10—C15—C16—N4	159.6 (4)	C24—N5—B1—N3	−138.5 (3)
C14—C15—C16—N3	179.6 (4)	C17—N5—B1—O1	−103.8 (4)
C10—C15—C16—N3	−5.4 (4)	C24—N5—B1—O1	93.8 (4)
C16—N4—C17—N5	−7.5 (5)	S1—O1—B1—N1	146.1 (3)
C16—N4—C17—C18	154.8 (4)	S1—O1—B1—N3	−96.2 (4)
C24—N5—C17—N4	153.1 (3)	S1—O1—B1—N5	27.3 (5)
B1—N5—C17—N4	−10.6 (5)

(III) (methanesulfonato)(subphthalocyaninato)boron

Crystal data

C25H15BN6O3S	F(000) = 1008
Mr = 490.30	Dx = 1.521 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 4770 reflections
a = 11.3713 (7) Å	θ = 4.6–66.3°
b = 11.6114 (7) Å	µ = 1.72 mm^−1
c = 16.2760 (11) Å	T = 147 K
β = 94.774 (4)°	Needle, purple
V = 2141.6 (2) Å^3	0.20 × 0.06 × 0.04 mm
Z = 4

Data collection

Bruker Kappa APEX DUO CCD area-detector diffractometer	3672 independent reflections
Radiation source: Bruker ImuS	3399 reflections with I > 2σ(I)
Multi-layer optics monochromator	Rint = 0.034
ϕ and ω scans	θmax = 66.3°, θmin = 4.6°
Absorption correction: multi-scan (TWINABS; Bruker, 2007)	h = −13→13
Tmin = 0.655, Tmax = 0.753	k = −13→13
23640 measured reflections	l = −19→19

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0339P)^2 + 2.5651P] where P = (Fo^2 + 2Fc^2)/3
3672 reflections	(Δ/σ)max = 0.001
325 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.49 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
S1	0.26680 (4)	0.49346 (4)	0.25798 (3)	0.01652 (15)
O1	0.18445 (13)	0.58102 (13)	0.29663 (9)	0.0206 (3)
O2	0.22321 (14)	0.46980 (14)	0.17479 (10)	0.0266 (4)
O3	0.28507 (15)	0.39803 (14)	0.31254 (11)	0.0321 (4)
N1	0.00254 (15)	0.65125 (15)	0.34437 (10)	0.0159 (4)
N2	−0.02642 (15)	0.82460 (15)	0.26745 (11)	0.0178 (4)
N3	0.01493 (15)	0.64919 (15)	0.19978 (10)	0.0159 (4)
N4	−0.05018 (15)	0.48029 (15)	0.12626 (11)	0.0169 (4)
N5	−0.00843 (15)	0.47548 (15)	0.27181 (10)	0.0154 (4)
N6	−0.07033 (15)	0.48428 (15)	0.40795 (11)	0.0175 (4)
C1	−0.04755 (18)	0.59762 (18)	0.40785 (12)	0.0159 (4)
C2	−0.09309 (18)	0.68946 (18)	0.45711 (12)	0.0171 (4)
C3	−0.15675 (19)	0.68749 (19)	0.52657 (13)	0.0204 (5)
H3A	−0.1712	0.6171	0.5537	0.025*
C4	−0.1983 (2)	0.7907 (2)	0.55492 (14)	0.0251 (5)
H4A	−0.2421	0.7911	0.6021	0.030*
C5	−0.1770 (2)	0.8950 (2)	0.51536 (14)	0.0279 (5)
H5A	−0.2046	0.9649	0.5373	0.033*
C6	−0.1166 (2)	0.8981 (2)	0.44503 (13)	0.0237 (5)
H6A	−0.1033	0.9689	0.4180	0.028*
C7	−0.07585 (18)	0.79453 (18)	0.41496 (13)	0.0176 (4)
C8	−0.02389 (18)	0.76595 (17)	0.33881 (13)	0.0166 (4)
C9	−0.01437 (18)	0.76344 (18)	0.19856 (13)	0.0172 (4)
C10	−0.05696 (19)	0.78898 (19)	0.11345 (13)	0.0186 (5)
C11	−0.0985 (2)	0.8894 (2)	0.07491 (14)	0.0241 (5)
H11A	−0.0928	0.9613	0.1029	0.029*
C12	−0.1486 (2)	0.8818 (2)	−0.00559 (15)	0.0280 (5)
H12A	−0.1767	0.9497	−0.0332	0.034*
C13	−0.1585 (2)	0.7764 (2)	−0.04675 (14)	0.0263 (5)
H13A	−0.1946	0.7738	−0.1015	0.032*
C14	−0.11704 (19)	0.6759 (2)	−0.00964 (13)	0.0212 (5)
H14A	−0.1240	0.6044	−0.0380	0.025*
C15	−0.06473 (18)	0.68238 (18)	0.07057 (13)	0.0171 (4)
C16	−0.02605 (18)	0.59288 (18)	0.12885 (13)	0.0166 (4)
C17	−0.04610 (18)	0.42409 (18)	0.19839 (13)	0.0165 (4)
C18	−0.10273 (18)	0.31780 (18)	0.22040 (13)	0.0173 (4)
C19	−0.15140 (19)	0.22745 (18)	0.17264 (14)	0.0202 (5)
H19A	−0.1500	0.2276	0.1144	0.024*
C20	−0.20181 (19)	0.13750 (19)	0.21295 (15)	0.0223 (5)
H20A	−0.2340	0.0741	0.1818	0.027*
C21	−0.20653 (19)	0.13771 (19)	0.29900 (15)	0.0228 (5)
H21A	−0.2414	0.0743	0.3247	0.027*
C22	−0.16145 (19)	0.22841 (18)	0.34705 (14)	0.0207 (5)
H22A	−0.1668	0.2293	0.4050	0.025*
C23	−0.10792 (18)	0.31842 (18)	0.30744 (13)	0.0171 (4)
C24	−0.05561 (18)	0.42585 (18)	0.33832 (13)	0.0163 (4)
C25	0.39701 (19)	0.5744 (2)	0.25912 (15)	0.0253 (5)
H25A	0.4585	0.5285	0.2359	0.038*
H25B	0.4230	0.5957	0.3160	0.038*
H25C	0.3823	0.6443	0.2261	0.038*
B1	0.0539 (2)	0.5873 (2)	0.27744 (14)	0.0160 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0152 (3)	0.0177 (3)	0.0171 (3)	0.00066 (19)	0.00366 (19)	−0.00011 (19)
O1	0.0156 (7)	0.0244 (8)	0.0216 (8)	0.0015 (6)	−0.0005 (6)	−0.0078 (6)
O2	0.0241 (8)	0.0364 (9)	0.0198 (8)	−0.0035 (7)	0.0036 (6)	−0.0095 (7)
O3	0.0320 (9)	0.0292 (9)	0.0367 (10)	0.0077 (7)	0.0120 (8)	0.0162 (8)
N1	0.0153 (9)	0.0161 (9)	0.0161 (9)	0.0006 (7)	−0.0001 (7)	−0.0016 (7)
N2	0.0198 (9)	0.0159 (9)	0.0178 (9)	−0.0026 (7)	0.0028 (7)	−0.0016 (7)
N3	0.0159 (9)	0.0160 (9)	0.0159 (9)	−0.0005 (7)	0.0029 (7)	−0.0026 (7)
N4	0.0160 (9)	0.0180 (9)	0.0169 (9)	0.0020 (7)	0.0026 (7)	−0.0023 (7)
N5	0.0149 (8)	0.0158 (9)	0.0152 (9)	0.0021 (7)	−0.0006 (7)	−0.0011 (7)
N6	0.0183 (9)	0.0172 (9)	0.0165 (9)	0.0035 (7)	−0.0018 (7)	0.0003 (7)
C1	0.0146 (10)	0.0191 (11)	0.0136 (10)	0.0020 (8)	−0.0015 (8)	0.0009 (8)
C2	0.0165 (10)	0.0201 (11)	0.0141 (10)	0.0022 (8)	−0.0026 (8)	−0.0012 (8)
C3	0.0212 (11)	0.0243 (11)	0.0154 (10)	0.0015 (9)	−0.0011 (8)	0.0007 (9)
C4	0.0281 (13)	0.0303 (13)	0.0171 (11)	0.0062 (10)	0.0036 (9)	−0.0020 (9)
C5	0.0366 (14)	0.0242 (12)	0.0228 (12)	0.0097 (10)	0.0024 (10)	−0.0063 (10)
C6	0.0321 (13)	0.0194 (11)	0.0194 (11)	0.0033 (9)	0.0009 (9)	−0.0018 (9)
C7	0.0174 (10)	0.0200 (11)	0.0151 (10)	0.0016 (8)	−0.0012 (8)	−0.0023 (8)
C8	0.0156 (10)	0.0150 (10)	0.0188 (11)	−0.0015 (8)	−0.0001 (8)	−0.0025 (8)
C9	0.0162 (10)	0.0163 (10)	0.0192 (11)	−0.0029 (8)	0.0023 (8)	−0.0006 (8)
C10	0.0186 (11)	0.0210 (11)	0.0167 (11)	−0.0022 (9)	0.0052 (8)	0.0015 (8)
C11	0.0315 (13)	0.0193 (11)	0.0222 (12)	0.0008 (10)	0.0066 (10)	0.0022 (9)
C12	0.0358 (14)	0.0245 (12)	0.0236 (12)	0.0053 (10)	0.0022 (10)	0.0081 (10)
C13	0.0297 (13)	0.0329 (13)	0.0160 (11)	0.0033 (10)	0.0007 (9)	0.0036 (10)
C14	0.0217 (11)	0.0245 (11)	0.0180 (11)	−0.0007 (9)	0.0055 (9)	−0.0008 (9)
C15	0.0164 (10)	0.0194 (11)	0.0160 (10)	−0.0007 (8)	0.0043 (8)	0.0015 (8)
C16	0.0139 (10)	0.0199 (11)	0.0162 (10)	0.0007 (8)	0.0031 (8)	−0.0029 (8)
C17	0.0145 (10)	0.0176 (10)	0.0172 (10)	0.0035 (8)	0.0011 (8)	−0.0048 (8)
C18	0.0142 (10)	0.0163 (10)	0.0212 (11)	0.0043 (8)	−0.0007 (8)	−0.0005 (8)
C19	0.0171 (11)	0.0202 (11)	0.0227 (11)	0.0033 (9)	−0.0018 (9)	−0.0023 (9)
C20	0.0159 (10)	0.0178 (11)	0.0325 (13)	0.0004 (8)	−0.0019 (9)	−0.0030 (9)
C21	0.0162 (11)	0.0185 (11)	0.0337 (13)	0.0001 (9)	0.0022 (9)	0.0027 (9)
C22	0.0182 (11)	0.0202 (11)	0.0236 (12)	0.0038 (9)	0.0019 (9)	0.0015 (9)
C23	0.0136 (10)	0.0167 (10)	0.0205 (11)	0.0045 (8)	−0.0011 (8)	−0.0002 (8)
C24	0.0146 (10)	0.0175 (10)	0.0165 (10)	0.0035 (8)	−0.0006 (8)	0.0017 (8)
C25	0.0177 (11)	0.0289 (12)	0.0295 (12)	−0.0027 (9)	0.0038 (9)	−0.0032 (10)
B1	0.0151 (11)	0.0175 (12)	0.0154 (11)	0.0013 (9)	0.0016 (9)	−0.0024 (9)

Geometric parameters (Å, º)

S1—O3	1.4243 (16)	C6—H6A	0.9500
S1—O2	1.4292 (16)	C7—C8	1.455 (3)
S1—O1	1.5507 (15)	C9—C10	1.459 (3)
S1—C25	1.752 (2)	C10—C11	1.388 (3)
O1—B1	1.493 (3)	C10—C15	1.420 (3)
N1—C8	1.367 (3)	C11—C12	1.387 (3)
N1—C1	1.370 (3)	C11—H11A	0.9500
N1—B1	1.478 (3)	C12—C13	1.395 (3)
N2—C9	1.344 (3)	C12—H12A	0.9500
N2—C8	1.344 (3)	C13—C14	1.379 (3)
N3—C9	1.368 (3)	C13—H13A	0.9500
N3—C16	1.374 (3)	C14—C15	1.391 (3)
N3—B1	1.489 (3)	C14—H14A	0.9500
N4—C16	1.336 (3)	C15—C16	1.450 (3)
N4—C17	1.341 (3)	C17—C18	1.451 (3)
N5—C17	1.372 (3)	C18—C19	1.393 (3)
N5—C24	1.374 (3)	C18—C23	1.423 (3)
N5—B1	1.479 (3)	C19—C20	1.383 (3)
N6—C1	1.341 (3)	C19—H19A	0.9500
N6—C24	1.343 (3)	C20—C21	1.406 (3)
C1—C2	1.455 (3)	C20—H20A	0.9500
C2—C3	1.392 (3)	C21—C22	1.385 (3)
C2—C7	1.421 (3)	C21—H21A	0.9500
C3—C4	1.382 (3)	C22—C23	1.394 (3)
C3—H3A	0.9500	C22—H22A	0.9500
C4—C5	1.402 (3)	C23—C24	1.454 (3)
C4—H4A	0.9500	C25—H25A	0.9800
C5—C6	1.384 (3)	C25—H25B	0.9800
C5—H5A	0.9500	C25—H25C	0.9800
C6—C7	1.392 (3)
O3—S1—O2	117.53 (11)	C11—C12—C13	121.3 (2)
O3—S1—O1	108.59 (9)	C11—C12—H12A	119.3
O2—S1—O1	109.68 (9)	C13—C12—H12A	119.3
O3—S1—C25	109.35 (11)	C14—C13—C12	121.4 (2)
O2—S1—C25	109.83 (11)	C14—C13—H13A	119.3
O1—S1—C25	100.50 (10)	C12—C13—H13A	119.3
B1—O1—S1	124.81 (13)	C13—C14—C15	118.0 (2)
C8—N1—C1	112.95 (17)	C13—C14—H14A	121.0
C8—N1—B1	122.59 (18)	C15—C14—H14A	121.0
C1—N1—B1	122.83 (18)	C14—C15—C10	120.9 (2)
C9—N2—C8	117.17 (18)	C14—C15—C16	131.1 (2)
C9—N3—C16	112.60 (17)	C10—C15—C16	107.46 (18)
C9—N3—B1	122.36 (17)	N4—C16—N3	123.14 (19)
C16—N3—B1	122.68 (18)	N4—C16—C15	129.07 (19)
C16—N4—C17	117.18 (18)	N3—C16—C15	105.77 (18)
C17—N5—C24	112.93 (18)	N4—C17—N5	122.44 (19)
C17—N5—B1	123.31 (18)	N4—C17—C18	130.29 (19)
C24—N5—B1	122.42 (18)	N5—C17—C18	105.53 (18)
C1—N6—C24	117.19 (18)	C19—C18—C23	120.8 (2)
N6—C1—N1	122.63 (19)	C19—C18—C17	131.8 (2)
N6—C1—C2	129.85 (19)	C23—C18—C17	107.31 (18)
N1—C1—C2	105.77 (17)	C20—C19—C18	117.7 (2)
C3—C2—C7	120.53 (19)	C20—C19—H19A	121.1
C3—C2—C1	131.9 (2)	C18—C19—H19A	121.1
C7—C2—C1	107.06 (18)	C19—C20—C21	121.5 (2)
C4—C3—C2	118.2 (2)	C19—C20—H20A	119.2
C4—C3—H3A	120.9	C21—C20—H20A	119.2
C2—C3—H3A	120.9	C22—C21—C20	121.4 (2)
C3—C4—C5	121.3 (2)	C22—C21—H21A	119.3
C3—C4—H4A	119.4	C20—C21—H21A	119.3
C5—C4—H4A	119.4	C21—C22—C23	117.7 (2)
C6—C5—C4	121.3 (2)	C21—C22—H22A	121.2
C6—C5—H5A	119.4	C23—C22—H22A	121.2
C4—C5—H5A	119.4	C22—C23—C18	120.83 (19)
C5—C6—C7	118.1 (2)	C22—C23—C24	131.7 (2)
C5—C6—H6A	120.9	C18—C23—C24	107.39 (18)
C7—C6—H6A	120.9	N6—C24—N5	122.48 (19)
C6—C7—C2	120.57 (19)	N6—C24—C23	130.47 (19)
C6—C7—C8	131.8 (2)	N5—C24—C23	105.24 (18)
C2—C7—C8	107.31 (18)	S1—C25—H25A	109.5
N2—C8—N1	122.66 (19)	S1—C25—H25B	109.5
N2—C8—C7	129.73 (19)	H25A—C25—H25B	109.5
N1—C8—C7	105.57 (18)	S1—C25—H25C	109.5
N2—C9—N3	122.83 (19)	H25A—C25—H25C	109.5
N2—C9—C10	129.5 (2)	H25B—C25—H25C	109.5
N3—C9—C10	105.79 (18)	N1—B1—N5	105.67 (17)
C11—C10—C15	120.3 (2)	N1—B1—N3	106.01 (17)
C11—C10—C9	132.3 (2)	N5—B1—N3	105.31 (17)
C15—C10—C9	106.95 (18)	N1—B1—O1	108.50 (17)
C12—C11—C10	118.1 (2)	N5—B1—O1	115.63 (18)
C12—C11—H11A	121.0	N3—B1—O1	114.93 (18)
C10—C11—H11A	121.0
O3—S1—O1—B1	−95.71 (18)	C9—N3—C16—C15	12.0 (2)
O2—S1—O1—B1	33.94 (19)	B1—N3—C16—C15	174.84 (18)
C25—S1—O1—B1	149.58 (17)	C14—C15—C16—N4	−13.8 (4)
C24—N6—C1—N1	−8.0 (3)	C10—C15—C16—N4	157.4 (2)
C24—N6—C1—C2	154.7 (2)	C14—C15—C16—N3	−177.7 (2)
C8—N1—C1—N6	155.29 (19)	C10—C15—C16—N3	−6.5 (2)
B1—N1—C1—N6	−10.5 (3)	C16—N4—C17—N5	−5.9 (3)
C8—N1—C1—C2	−11.0 (2)	C16—N4—C17—C18	156.8 (2)
B1—N1—C1—C2	−176.72 (18)	C24—N5—C17—N4	153.84 (19)
N6—C1—C2—C3	12.0 (4)	B1—N5—C17—N4	−13.2 (3)
N1—C1—C2—C3	176.8 (2)	C24—N5—C17—C18	−12.6 (2)
N6—C1—C2—C7	−159.9 (2)	B1—N5—C17—C18	−179.62 (18)
N1—C1—C2—C7	5.0 (2)	N4—C17—C18—C19	19.2 (4)
C7—C2—C3—C4	−2.5 (3)	N5—C17—C18—C19	−175.8 (2)
C1—C2—C3—C4	−173.4 (2)	N4—C17—C18—C23	−158.1 (2)
C2—C3—C4—C5	−0.2 (3)	N5—C17—C18—C23	6.8 (2)
C3—C4—C5—C6	1.9 (4)	C23—C18—C19—C20	−1.7 (3)
C4—C5—C6—C7	−0.8 (4)	C17—C18—C19—C20	−178.7 (2)
C5—C6—C7—C2	−1.9 (3)	C18—C19—C20—C21	1.4 (3)
C5—C6—C7—C8	171.1 (2)	C19—C20—C21—C22	0.4 (3)
C3—C2—C7—C6	3.6 (3)	C20—C21—C22—C23	−1.8 (3)
C1—C2—C7—C6	176.57 (19)	C21—C22—C23—C18	1.5 (3)
C3—C2—C7—C8	−170.93 (19)	C21—C22—C23—C24	178.1 (2)
C1—C2—C7—C8	2.0 (2)	C19—C18—C23—C22	0.2 (3)
C9—N2—C8—N1	7.1 (3)	C17—C18—C23—C22	177.95 (18)
C9—N2—C8—C7	−154.2 (2)	C19—C18—C23—C24	−177.06 (19)
C1—N1—C8—N2	−152.99 (19)	C17—C18—C23—C24	0.6 (2)
B1—N1—C8—N2	12.8 (3)	C1—N6—C24—N5	6.3 (3)
C1—N1—C8—C7	12.2 (2)	C1—N6—C24—C23	−156.1 (2)
B1—N1—C8—C7	178.00 (18)	C17—N5—C24—N6	−153.21 (19)
C6—C7—C8—N2	−18.3 (4)	B1—N5—C24—N6	14.0 (3)
C2—C7—C8—N2	155.4 (2)	C17—N5—C24—C23	12.9 (2)
C6—C7—C8—N1	178.0 (2)	B1—N5—C24—C23	−179.88 (18)
C2—C7—C8—N1	−8.3 (2)	C22—C23—C24—N6	−20.1 (4)
C8—N2—C9—N3	−8.6 (3)	C18—C23—C24—N6	156.8 (2)
C8—N2—C9—C10	153.4 (2)	C22—C23—C24—N5	175.2 (2)
C16—N3—C9—N2	153.33 (19)	C18—C23—C24—N5	−7.9 (2)
B1—N3—C9—N2	−9.6 (3)	C8—N1—B1—N5	−138.21 (19)
C16—N3—C9—C10	−12.3 (2)	C1—N1—B1—N5	26.2 (3)
B1—N3—C9—C10	−175.25 (18)	C8—N1—B1—N3	−26.8 (3)
N2—C9—C10—C11	15.7 (4)	C1—N1—B1—N3	137.65 (19)
N3—C9—C10—C11	−179.9 (2)	C8—N1—B1—O1	97.2 (2)
N2—C9—C10—C15	−156.8 (2)	C1—N1—B1—O1	−98.4 (2)
N3—C9—C10—C15	7.5 (2)	C17—N5—B1—N1	138.03 (19)
C15—C10—C11—C12	0.8 (3)	C24—N5—B1—N1	−27.8 (3)
C9—C10—C11—C12	−171.0 (2)	C17—N5—B1—N3	26.1 (3)
C10—C11—C12—C13	0.7 (4)	C24—N5—B1—N3	−139.75 (18)
C11—C12—C13—C14	−1.2 (4)	C17—N5—B1—O1	−102.0 (2)
C12—C13—C14—C15	0.0 (3)	C24—N5—B1—O1	92.2 (2)
C13—C14—C15—C10	1.5 (3)	C9—N3—B1—N1	25.2 (3)
C13—C14—C15—C16	171.7 (2)	C16—N3—B1—N1	−136.03 (19)
C11—C10—C15—C14	−1.9 (3)	C9—N3—B1—N5	136.91 (19)
C9—C10—C15—C14	171.71 (19)	C16—N3—B1—N5	−24.3 (3)
C11—C10—C15—C16	−174.2 (2)	C9—N3—B1—O1	−94.6 (2)
C9—C10—C15—C16	−0.6 (2)	C16—N3—B1—O1	104.1 (2)
C17—N4—C16—N3	7.6 (3)	S1—O1—B1—N1	160.97 (14)
C17—N4—C16—C15	−153.9 (2)	S1—O1—B1—N5	42.5 (2)
C9—N3—C16—N4	−153.15 (19)	S1—O1—B1—N3	−80.6 (2)
B1—N3—C16—N4	9.7 (3)