2-[N-(2,3-Dimethyl­phen­yl)­carbam­oyl]benzene­sulfonamide and the 3,4- and 2,6-dimethyl­phenyl analogues

The structures of 2-[(2,3-dimethyl­phen­yl)carbamo­yl]benzene­sulfonamide, 2-[(3,4-dimethyl­phen­yl)carbamo­yl]benzene­sulfon­amide and 2-[(2,6-dimethyl­phen­yl)carbamo­yl]benzene­sulfon­amide, all C₁₅H₁₆N₂O₃S, are stabilized by extensive intra- and inter­molecular hydrogen bonds. In all three structures, the sulfonamide and carbamoyl groups are involved in hydrogen bonding. In the 2,3-dimethyl and 2,6-dimethyl derivatives, dimeric units and chains of mol­ecules are formed parallel to the c axis. In the 3,4-dimethyl derivative, the hydrogen bonding creates tetra­meric units, resulting in macrocyclic R₄⁴(22) rings that form sheets in the ab plane. The three analogues are closely related to the fenamate class of nonsteroidal anti-inflammatory drugs.

S1. Comment

Saccharin derivatives have always been of interest because of their diverse applications (Marta et al., 2003; Culf et al., 1997). Their open-ring benzene sulfonamide derivatives have shown cyclooxygenase-2 (COX-2) inhibitory action and act as analgesic and anti-inflammatory agents (Eatedal et al., 2002). Various biologically important saccharin skeletons and their N-alkyl derivatives have been efficiently prepared (Xu et al., 2006) by chromium oxide-catalyzed oxidation of N-alkyl(o-methyl)arenesulfonamides in acetonitrile as well as by the already developed methodology utilizing irradiation from tungsten and mercury lamps (Masashi et al., 1999) for a similar type of conversion. In continuation of our research on benzene-1,2-benzothiazine-1,1-dioxide and saccharin derivatives (Siddiqui, Ahmad, Khan & Siddiqui, 2007; Siddiqui, Ahmad, Khan et al., 2008; Siddiqui, Ahmad, Siddiqui et al., 2007; Siddiqui, Ahmad, Tariq et al., 2008), we now report the syntheses and crystal structures of the title compounds, o-[(X-dimethylphenyl)carbamoyl]benzene sulfonamide [X = 2,3- for (I), 3,4- for (II) and 2,6- for (III)]. The three dimethylphenyl-substituted analogues are closely related to the fenamate class of non-steroidal anti-inflammatory drugs (NSAIDs) and are expected to exhibit very potent biological activities since sulfonamide and carbamoyl functions exist in the same nucleus simultaneously.

The molecular structure of (I) is presented in Fig. 1. The mean planes of the phenyl rings, C1–C6 and C8–C13, are inclined at 8.19 (8)° with respect to one another, while the carbamoyl group, O3/N2/C7, is inclined at 55.43 (13) and 48.73 (13)°, respectively, to these phenyl rings. Atoms S1 and C7 lie 0.062 (3) and 0.066 (4) Å from the mean plane of the C1–C6 phenyl ring, on opposite sides, indicating a significant strain on this portion of the molecule. The structure contains two distinct patterns of hydrogen bonds, involving intermolecular N—H···O interactions (Fig. 2). The sulfonamide groups are hydrogen bonded via atoms N1 and O1, forming dimers about inversion centers at (0, 1/2, 0) and (0, 0, 1/2) along the b and c axes. The eight-membered rings thus formed may be described in graph-set notation as R₂²(8) (Bernstein et al., 1994). The carbamoyl groups are also involved in hydrogen bonds, involving atoms O3 and N2, resulting in chains of molecules running parallel to the c axis and affording stability to the structure. In addition, there is a rather weak nonclassical intermolecular hydrogen bond (C4—H4···O1ⁱⁱⁱ; details of the hydrogen-bonding geometry are provided in Table 1). The structure is further stabilized by three additional intramolecular interactions, N1—H1N···O3, C2—H2···O1 and C14—H14D···N2, resulting in seven-, five- and five-membered rings, representing S(7), S(5) and S(5) motifs, respectively (Bernstein et al., 1994).

The molecular structure of (II) is presented in Fig. 3. The mean planes of the phenyl rings, C1–C6 and C8–C13, are inclined at 40.55 (8)° with respect to one another, while the carbamoyl group, O1/N2/C7, is inclined at 59.30 (13) and 26.05 (18)°, respectively, to these phenyl rings. A comparison of mean-plane angles shows that the conformations of (I) and (II) are significantly different from one another. Molecules of (II) related by translation symmetry along the a and b axes form a cluster of four molecules via N1—H1N···O1ⁱ and N2—H3N···O3ⁱⁱ hydrogen bonds (details of the hydogen-bonding geometry are provided in Table 2), resulting in a macrocyclic ring (Fig. 4) that may be described in graph-set notation as R₄⁴(22) (Bernstein et al., 1994). These hydrogen bonds result in the formation of sheets that are extended in the ab plane. The structure is further stabilized by three additional intramolecular interactions, N1—H2N···O3, C13—H13···O3 and C2—H2···O1, resulting in seven-, six- and five-membered rings, representing S(7), S(6) and S(5) motifs, respectively (Bernstein et al., 1994) (Fig. 3 and Table 2).

The asymmtric unit of (III) is composed of two independent molecules (hereafter called A and B) depicted in Figs. 5 and 6, respectively. In molecule A, the mean planes of the phenyl rings, C1a–C6a and C8a–C13a, are inclined at 6.53 (9)° with respect to each other, while the carbamoyl group, O3a/N2a/C7a, is inclined at 60.34 (16) and 57.20 (17)°, respectively, to these phenyl rings. The corresponding mean-planes angles in molecule B are 3.11 (10), 61.17 (16) and 59.10 (17)°, respectively. The conformations of both molecules of (III) are more closely related to the conformation of (I). The sulfonamide groups of the two molecules in (III) are hydrogen bonded to form dimeric units; the eight-membered rings thus formed represent R₂²(8) motifs (Bernstein et al., 1994). The carbamoyl groups of molecules A and B are hydrogen bonded to form chains of molecules running parallel to the a axis (Fig. 7). The two molecules contain an identical pair of intramolecular interactions, N1a/b—H···O3a/b and C2a/b—H2a/b···O1a/b, resulting in seven- and five-membered rings, representing S(7) and S(5) motifs, respectively (Bernstein et al., 1994). However, the intramolecular interactions involving hydrogen bonding to atom C15 show markedly different patterns in the two molecules; in molecule A, atom C15 is bonded to O3a, while in molecule B, it is bonded to N2b, resulting in S(7) and S(5) motifs, respectively.

The molecular dimensions in all the structures are in agreement with the corresponding dimensions reported for similar structures (Clark et al., 2003; Vyas et al., 2003; Singh et al., 2004; Bocelli et al., 1995; Sutton & Cody, 1989; Furuya et al., 1989; Siddiqui, Ahmad, Khan et al., 2008; and/or??? Siddiqui, Ahmad, Tariq et al., 2008), with S=O, S—N, S—C, N2—C7, N2—C8 and C=O distances lying in very close ranges of 1.430 (2)–1.438 (2), 1.598 (3)–1.614 (3), 1.773 (3)–1.781 (3), 1.331 (4)–1.338 (4), 1.429 (4)–1.440 (4) and 1.236 (3)–1.241 (3) Å, respectively. The bond angle C—N—C at N2 in (II) at 128.1 (3)° is significantly larger than the corresponding angles in (I), (IIIA) and (IIIB). The remaining angles lie within narrow ranges in all the three structures.

In all molecules, the conformation about the S—N bond is in agreement with the conformation of a handful of structures containing an o-C-substituted benzenesulfonamide fragment [Cambridge Structural Database (CSD), Version 5.29; Allen, 2002]. The N1 atoms in all these structures are tetrahedral, the sum of angles being in the range 334–340°. The H atoms bonded to atom N1, and atoms O1 and O2 bonded to S1, are staggered, as observed in chlorophenyl analogues of the title compounds (Siddiqui, Ahmad, Khan et al., 2008) and the compound with CSD refcode COYVER (Foresti et al., 1985). Several structures have been reported wherein the H and O atoms of the sulfonamide unit are eclipsed, e.g. CSD refcodes ENIROI (Vyas et al., 2003), GUFQED01 (Clark et al., 2003 or2005????) and ZZZULS01 (Tremayne et al., 2002). Fundamental work on the three-dimensional orientation of sulfonamides has been reported by several groups of investigators (e.g. Bordner et al., 1984, 1989; Beddoes et al., 1986; Street et al., 1987; Luger et al., 1996; Helliwell et al., 1997; Bhatt et al., 2005).

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1994); Bocelli et al. (1995); Clark et al. (2003); Culf et al. (1997); Eatedal et al. (2002); Furuya et al. (1989); Marta et al. (2003); Masashi et al. (1999); Siddiqui et al. (2007a, 2007b, 2008a, 2008b); Singh et al. (2004); Sutton & Cody (1989); Vyas et al. (2003); Xu et al. (2006).

S2. Experimental

Suspensions of saccharin (1.0 g, 5.46 mmol) and dimethylaniline (5 ml in the case of 2,3- and 2,6-dimethylaniline, and 0.5 g in the case of 3,4-dimethylaniline) in xylene (25 ml) were stirred at room temperature for 1.5 h and then heated at 373 K for 2–7 h. The reaction mixtures were subsequently cooled to room temperature, filtered and dried to obtain colorless solid products. The products were crystallized from MeOH:CH₃CN (1:3) solutions by slow evaporation at 313 K.

For (I): m.p. 463–465 K. IR (neat, ν_max, cm^-1): NH₂ 3415, 3325, CO 1650, SO₂ 1343, 1150; ¹H NMR (300 MHz, methanol-d₄): δ 2.30 (s, 3H, CH₃), 2.35 (s, 3H, CH₃), 7.12–7.34 (m, 3H, C₆H₃), 7.63–8.10 (m, 4H, C₆H₄); ¹³C NMR: δ 169.7, 142.2, 138.8, 137.3, 135.4, 134.3, 132.2, 131.7, 130.5, 129.5, 124.2, 120.5, 21.4, 20.8. LRMS (ES⁺): m/z: 304.09 [M⁺] (39.7%).

For (II): m.p. 443–444 K. IR (neat, ν_max, cm^-1): NH₂ 3425, 3365, CO 1705, SO₂ 1354, 1167; ¹H NMR (300 MHz, methanol-d₄): δ 2.30 (s, 3H, CH₃), 2.35 (s, 3H, CH₃), 7.12–7.32 (m, 2H, C₆H₃), 7.53–7.70 (m, 4H, C₆H₄), 8. 20 (m, 1H, C₆H₃); ¹³C NMR: δ 171.8, 144.2, 140.9, 139.2, 137.4, 136.3, 134.2, 133.7, 132.5, 131.6, 126.3, 122.5, 23.5, 22.9. LRMS (ES⁺): m/z: 304.09 [M⁺] (25.1%).

For (III): m.p. 496–497 K. IR (neat, ν_max, cm^-1): NH₂ 3423, 3345, CO 1715, SO₂ 1345, 1150; ¹H NMR (300 MHz, methanol-d₄): δ 2.30 (s, 3H, CH₃), 2.42 (s, 3H, CH₃), 7.26–7.52 (m, 3H, C₆H₃), 7.68–8.10 (m, 4H, C₆H₄); ¹³C NMR: δ 168.7, 141.2, 139.7, 139.2, 137.4, 136.3, 134.2, 133.7, 132.5, 130.4, 125.3, 121.1, 22.3, 21.1. LRMS (ES⁺): m/z: 304.09 [M⁺] (21.9%).

S3. Refinement

For the three structures, H atoms bonded to C atoms were included in the refinements at geometrically idealized positions with aromatic and methyl-type H atoms at C—H distances of 0.95 and 0.98 Å, respectively, and U_iso(H) values of 1.2 times U_eq of the atoms to which they were bonded; the H atoms bonded to atom C14 in (I) were equally disordered over six sites. H atoms bonded to N atoms were allowed to refine with U_iso(H) values of 1.2 times U_eq of the N atoms. The final difference maps were free of chemically significant features.

Computing details

For all compounds, data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. An ORTEP-3 (Farrugia, 1997) drawing of (I), with displacement ellipsoids plotted at the 50% probability level. Intramolecular interactions are shown as dashed lines.
	Fig. 2. Intermolecular interactions (dashed lines) in the unit cell of (I), showing eight-membered rings formed by sulfonamide groups and chains formed by carbamoyl groups running parallel to the c axis.
	Fig. 3. An ORTEP-3 (Farrugia, 1997) drawing of (II), with displacement ellipsoids plotted at the 50% probability level. Intramolecular interactions are shown as dashed lines. [Please provide]
	Fig. 4. Intermolecular interactions (dashed lines) in the unit cell of (II), showing macrocyclic rings formed by clusters of four molecules; these clusters are further extended into sheets in the ab plane.
	Fig. 5. An ORTEP-3 (Farrugia, 1997) drawing of molecule A of (III), with displacement ellipsoids plotted at the 50% probability level. Intramolecular interactions are shown as dashed lines.
	Fig. 6. An ORTEP-3 (Farrugia, 1997) drawing of molecule B of (III), with displacement ellipsoids plotted at the 50% probability level. Intramolecular interactions are shown as dashed lines.
	Fig. 7. Intermolecular interactions (dashed lines) in the unit cell of (III), showing eight-membered rings formed by sulfonamide groups and chains formed by carbamoyl groups running parallel to the a axis.

(I) 2-[(2,3-dimethylphenyl)carbamoyl]benzenesulfonamide

Crystal data

C15H16N2O3S	F(000) = 640
Mr = 304.36	Dx = 1.372 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9490 reflections
a = 12.842 (7) Å	θ = 3.0–25.1°
b = 15.153 (9) Å	µ = 0.23 mm^−1
c = 7.572 (4) Å	T = 173 K
β = 91.16 (4)°	Needle, colorless
V = 1473.2 (14) Å^3	0.40 × 0.04 × 0.02 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2583 independent reflections
Radiation source: fine-focus sealed tube	1926 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
ω and ϕ scans	θmax = 25.1°, θmin = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −15→15
Tmin = 0.913, Tmax = 0.995	k = −17→18
9490 measured reflections	l = −8→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0536P)^2 + 0.4285P] where P = (Fo^2 + 2Fc^2)/3
2583 reflections	(Δ/σ)max < 0.001
200 parameters	Δρmax = 0.26 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	Occ. (<1)
S1	0.85704 (4)	0.44450 (4)	0.13149 (8)	0.0377 (2)
O1	0.94617 (13)	0.48648 (12)	0.2130 (2)	0.0482 (5)
O2	0.75841 (12)	0.45083 (10)	0.2153 (2)	0.0413 (4)
O3	0.69083 (11)	0.35295 (10)	−0.1244 (2)	0.0368 (4)
N1	0.84482 (18)	0.48563 (14)	−0.0640 (3)	0.0414 (5)
H1N	0.795 (2)	0.4542 (17)	−0.127 (3)	0.050*
H2N	0.903 (2)	0.4880 (18)	−0.113 (3)	0.050*
N2	0.62325 (14)	0.25833 (13)	0.0763 (3)	0.0347 (5)
H3N	0.6390 (19)	0.2205 (17)	0.159 (3)	0.042*
C1	0.88627 (17)	0.33062 (15)	0.1115 (3)	0.0337 (5)
C2	0.98520 (18)	0.30161 (18)	0.1590 (3)	0.0421 (6)
H2	1.0369	0.3428	0.1963	0.050*
C3	1.00853 (19)	0.21287 (18)	0.1518 (3)	0.0455 (6)
H3	1.0763	0.1931	0.1855	0.055*
C4	0.9346 (2)	0.15268 (17)	0.0963 (3)	0.0436 (6)
H4	0.9517	0.0918	0.0897	0.052*
C5	0.83481 (18)	0.18134 (16)	0.0500 (3)	0.0383 (6)
H5	0.7837	0.1396	0.0128	0.046*
C6	0.80915 (17)	0.27031 (15)	0.0575 (3)	0.0330 (5)
C7	0.70203 (17)	0.29875 (15)	−0.0036 (3)	0.0326 (5)
C8	0.51544 (17)	0.27497 (15)	0.0345 (3)	0.0352 (5)
C9	0.44880 (18)	0.20341 (16)	0.0089 (3)	0.0384 (6)
C10	0.34323 (18)	0.22123 (19)	−0.0272 (3)	0.0470 (7)
C11	0.3098 (2)	0.3077 (2)	−0.0389 (4)	0.0551 (7)
H11	0.2384	0.3193	−0.0651	0.066*
C12	0.3772 (2)	0.3773 (2)	−0.0138 (4)	0.0559 (7)
H12	0.3524	0.4363	−0.0229	0.067*
C13	0.48080 (19)	0.36115 (17)	0.0246 (3)	0.0454 (6)
H13	0.5278	0.4087	0.0441	0.054*
C14	0.4895 (2)	0.11052 (18)	0.0191 (4)	0.0534 (7)
H14A	0.4320	0.0690	−0.0021	0.080*	0.50
H14B	0.5204	0.1000	0.1366	0.080*	0.50
H14C	0.5425	0.1020	−0.0706	0.080*	0.50
H14D	0.5646	0.1117	0.0447	0.080*	0.50
H14E	0.4763	0.0807	−0.0940	0.080*	0.50
H14F	0.4541	0.0786	0.1132	0.080*	0.50
C15	0.2666 (2)	0.1463 (2)	−0.0543 (4)	0.0646 (8)
H15A	0.1973	0.1705	−0.0819	0.078*
H15B	0.2637	0.1108	0.0537	0.078*
H15C	0.2891	0.1091	−0.1524	0.078*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0373 (3)	0.0341 (3)	0.0416 (4)	−0.0017 (3)	−0.0021 (2)	−0.0028 (2)
O1	0.0467 (10)	0.0465 (11)	0.0511 (11)	−0.0130 (8)	−0.0064 (8)	−0.0057 (8)
O2	0.0411 (9)	0.0363 (10)	0.0468 (10)	0.0048 (7)	0.0053 (7)	−0.0020 (7)
O3	0.0366 (9)	0.0364 (9)	0.0372 (9)	0.0001 (7)	−0.0042 (7)	0.0038 (7)
N1	0.0416 (12)	0.0373 (12)	0.0453 (13)	−0.0044 (10)	0.0001 (9)	0.0044 (9)
N2	0.0329 (11)	0.0325 (11)	0.0386 (11)	0.0001 (8)	−0.0045 (8)	0.0037 (8)
C1	0.0334 (12)	0.0367 (13)	0.0310 (12)	0.0018 (10)	0.0003 (9)	−0.0009 (9)
C2	0.0342 (13)	0.0528 (16)	0.0391 (14)	0.0040 (12)	−0.0021 (10)	−0.0004 (11)
C3	0.0389 (14)	0.0565 (17)	0.0411 (14)	0.0151 (12)	−0.0014 (10)	0.0044 (12)
C4	0.0528 (16)	0.0393 (14)	0.0387 (14)	0.0181 (13)	0.0043 (11)	0.0039 (11)
C5	0.0427 (14)	0.0356 (13)	0.0365 (13)	0.0037 (11)	0.0011 (10)	0.0012 (10)
C6	0.0349 (12)	0.0331 (13)	0.0310 (12)	0.0047 (10)	−0.0004 (9)	0.0009 (9)
C7	0.0366 (13)	0.0281 (12)	0.0330 (12)	−0.0005 (10)	−0.0038 (9)	−0.0057 (10)
C8	0.0308 (12)	0.0376 (14)	0.0373 (13)	0.0036 (10)	−0.0014 (9)	0.0026 (10)
C9	0.0366 (13)	0.0417 (14)	0.0368 (13)	−0.0011 (11)	−0.0017 (10)	0.0001 (10)
C10	0.0349 (14)	0.0681 (19)	0.0379 (14)	−0.0043 (12)	−0.0001 (10)	0.0001 (12)
C11	0.0333 (14)	0.077 (2)	0.0549 (17)	0.0126 (14)	0.0013 (11)	0.0120 (14)
C12	0.0451 (16)	0.0551 (18)	0.0676 (19)	0.0159 (14)	0.0072 (13)	0.0168 (14)
C13	0.0432 (15)	0.0373 (15)	0.0557 (16)	0.0057 (11)	0.0034 (12)	0.0066 (11)
C14	0.0512 (16)	0.0415 (16)	0.0674 (18)	−0.0076 (12)	−0.0033 (13)	−0.0049 (13)
C15	0.0440 (16)	0.092 (2)	0.0576 (18)	−0.0177 (16)	−0.0011 (13)	−0.0073 (16)

Geometric parameters (Å, º)

S1—O2	1.431 (2)	C8—C13	1.381 (3)
S1—O1	1.438 (2)	C8—C9	1.393 (3)
S1—N1	1.611 (2)	C9—C10	1.404 (3)
S1—C1	1.773 (3)	C9—C14	1.503 (4)
O3—C7	1.236 (3)	C10—C11	1.381 (4)
N1—H1N	0.92 (3)	C10—C15	1.514 (4)
N1—H2N	0.84 (3)	C11—C12	1.376 (4)
N2—C7	1.338 (3)	C11—H11	0.9500
N2—C8	1.436 (3)	C12—C13	1.378 (4)
N2—H3N	0.87 (3)	C12—H12	0.9500
C1—C2	1.385 (3)	C13—H13	0.9500
C1—C6	1.403 (3)	C14—H14A	0.9800
C2—C3	1.379 (4)	C14—H14B	0.9800
C2—H2	0.9500	C14—H14C	0.9800
C3—C4	1.376 (4)	C14—H14D	0.9800
C3—H3	0.9500	C14—H14E	0.9800
C4—C5	1.392 (3)	C14—H14F	0.9800
C4—H4	0.9500	C15—H15A	0.9800
C5—C6	1.389 (3)	C15—H15B	0.9800
C5—H5	0.9500	C15—H15C	0.9800
C6—C7	1.505 (3)
O2—S1—O1	118.95 (11)	C11—C10—C9	119.5 (2)
O2—S1—N1	108.12 (12)	C11—C10—C15	120.1 (2)
O1—S1—N1	106.57 (12)	C9—C10—C15	120.3 (3)
O2—S1—C1	107.08 (10)	C12—C11—C10	121.7 (2)
O1—S1—C1	107.41 (11)	C12—C11—H11	119.2
N1—S1—C1	108.36 (11)	C10—C11—H11	119.2
S1—N1—H1N	109 (2)	C11—C12—C13	119.7 (3)
S1—N1—H2N	111 (2)	C11—C12—H12	120.2
H1N—N1—H2N	114 (3)	C13—C12—H12	120.2
C7—N2—C8	123.7 (2)	C12—C13—C8	119.2 (2)
C7—N2—H3N	117 (2)	C12—C13—H13	120.4
C8—N2—H3N	119 (2)	C8—C13—H13	120.4
C2—C1—C6	120.5 (2)	C9—C14—H14A	109.5
C2—C1—S1	118.79 (18)	C9—C14—H14B	109.5
C6—C1—S1	120.64 (17)	H14A—C14—H14B	109.5
C3—C2—C1	119.9 (2)	C9—C14—H14C	109.5
C3—C2—H2	120.1	H14A—C14—H14C	109.5
C1—C2—H2	120.1	H14B—C14—H14C	109.5
C4—C3—C2	120.6 (2)	C9—C14—H14D	109.5
C4—C3—H3	119.7	H14A—C14—H14D	141.1
C2—C3—H3	119.7	H14B—C14—H14D	56.3
C3—C4—C5	119.8 (2)	H14C—C14—H14D	56.3
C3—C4—H4	120.1	C9—C14—H14E	109.5
C5—C4—H4	120.1	H14A—C14—H14E	56.3
C6—C5—C4	120.7 (2)	H14B—C14—H14E	141.1
C6—C5—H5	119.7	H14C—C14—H14E	56.3
C4—C5—H5	119.7	H14D—C14—H14E	109.5
C5—C6—C1	118.5 (2)	C9—C14—H14F	109.5
C5—C6—C7	118.8 (2)	H14A—C14—H14F	56.3
C1—C6—C7	122.6 (2)	H14B—C14—H14F	56.3
O3—C7—N2	124.2 (2)	H14C—C14—H14F	141.1
O3—C7—C6	120.6 (2)	H14D—C14—H14F	109.5
N2—C7—C6	115.1 (2)	H14E—C14—H14F	109.5
C13—C8—C9	122.2 (2)	C10—C15—H15A	109.5
C13—C8—N2	119.1 (2)	C10—C15—H15B	109.5
C9—C8—N2	118.7 (2)	H15A—C15—H15B	109.5
C8—C9—C10	117.7 (2)	C10—C15—H15C	109.5
C8—C9—C14	120.7 (2)	H15A—C15—H15C	109.5
C10—C9—C14	121.6 (2)	H15B—C15—H15C	109.5
O2—S1—C1—C2	−133.84 (18)	C1—C6—C7—O3	54.5 (3)
O1—S1—C1—C2	−5.0 (2)	C5—C6—C7—N2	55.6 (3)
N1—S1—C1—C2	109.7 (2)	C1—C6—C7—N2	−128.4 (2)
O2—S1—C1—C6	42.9 (2)	C7—N2—C8—C13	−48.6 (3)
O1—S1—C1—C6	171.7 (2)	C7—N2—C8—C9	132.8 (2)
N1—S1—C1—C6	−73.5 (2)	C13—C8—C9—C10	−0.2 (3)
C6—C1—C2—C3	0.5 (3)	N2—C8—C9—C10	178.3 (2)
S1—C1—C2—C3	177.2 (2)	C13—C8—C9—C14	179.5 (2)
C1—C2—C3—C4	0.6 (4)	N2—C8—C9—C14	−2.0 (3)
C2—C3—C4—C5	−1.2 (4)	C8—C9—C10—C11	1.1 (3)
C3—C4—C5—C6	0.6 (3)	C14—C9—C10—C11	−178.6 (2)
C4—C5—C6—C1	0.5 (3)	C8—C9—C10—C15	−179.4 (2)
C4—C5—C6—C7	176.6 (2)	C14—C9—C10—C15	0.9 (4)
C2—C1—C6—C5	−1.0 (3)	C9—C10—C11—C12	−0.9 (4)
S1—C1—C6—C5	−177.7 (2)	C15—C10—C11—C12	179.6 (3)
C2—C1—C6—C7	−177.0 (2)	C10—C11—C12—C13	−0.2 (4)
S1—C1—C6—C7	6.3 (3)	C11—C12—C13—C8	1.0 (4)
C8—N2—C7—O3	−1.8 (3)	C9—C8—C13—C12	−0.8 (4)
C8—N2—C7—C6	−178.8 (2)	N2—C8—C13—C12	−179.4 (2)
C5—C6—C7—O3	−121.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H3N···O3^i	0.87 (3)	2.08 (3)	2.941 (3)	170 (2)
N1—H2N···O1^ii	0.84 (3)	2.13 (3)	2.963 (3)	171 (3)
N1—H1N···O3	0.92 (3)	2.04 (3)	2.850 (3)	146 (2)
C2—H2···O1	0.95	2.47	2.877 (4)	105
C4—H4···O1^iii	0.95	2.53	3.268 (3)	134
C14—H14D···N2	0.98	2.36	2.851 (3)	110

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

(II) 2-[(3,4-dimethylphenyl)carbamoyl]benzenesulfonamide

Crystal data

C15H16N2O3S	F(000) = 640
Mr = 304.36	Dx = 1.445 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4440 reflections
a = 11.597 (9) Å	θ = 4.0–25.0°
b = 7.450 (3) Å	µ = 0.24 mm^−1
c = 16.324 (13) Å	T = 173 K
β = 97.29 (3)°	Prism, colorless
V = 1399.0 (17) Å^3	0.20 × 0.10 × 0.06 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2423 independent reflections
Radiation source: fine-focus sealed tube	1767 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
ω and ϕ scans	θmax = 25.0°, θmin = 4.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −13→13
Tmin = 0.953, Tmax = 0.986	k = −8→8
4440 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.096P)^2 + 0.014P] where P = (Fo^2 + 2Fc^2)/3
2423 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.41 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	0.31267 (6)	0.32180 (9)	0.24525 (4)	0.0291 (3)
O3	0.11651 (17)	0.0226 (2)	0.19202 (12)	0.0307 (5)
O1	0.41605 (18)	0.4207 (3)	0.27427 (12)	0.0377 (6)
O2	0.22327 (18)	0.4043 (3)	0.18927 (12)	0.0347 (5)
N1	0.3540 (3)	0.1450 (4)	0.19979 (17)	0.0337 (6)
H1N	0.419 (3)	0.105 (4)	0.222 (2)	0.040*
H2N	0.299 (3)	0.069 (4)	0.193 (2)	0.040*
N2	−0.0340 (2)	0.1951 (3)	0.22300 (15)	0.0278 (6)
H3N	−0.058 (3)	0.254 (4)	0.255 (2)	0.033*
C1	0.2466 (2)	0.2507 (4)	0.33248 (17)	0.0265 (7)
C2	0.3061 (3)	0.2794 (4)	0.41077 (18)	0.0313 (7)
H2	0.3803	0.3352	0.4170	0.038*
C3	0.2564 (3)	0.2261 (4)	0.47966 (19)	0.0345 (8)
H3	0.2976	0.2432	0.5332	0.041*
C4	0.1479 (3)	0.1486 (4)	0.47110 (19)	0.0330 (7)
H4	0.1146	0.1120	0.5187	0.040*
C5	0.0867 (3)	0.1237 (4)	0.39282 (18)	0.0287 (7)
H5	0.0110	0.0729	0.3873	0.034*
C6	0.1357 (2)	0.1726 (3)	0.32303 (18)	0.0252 (7)
C7	0.0722 (2)	0.1253 (4)	0.23908 (17)	0.0263 (7)
C8	−0.1107 (2)	0.1888 (3)	0.14731 (18)	0.0263 (7)
C9	−0.2264 (3)	0.2350 (3)	0.15047 (19)	0.0299 (7)
H9	−0.2524	0.2557	0.2026	0.036*
C10	−0.3048 (3)	0.2516 (4)	0.07911 (19)	0.0296 (7)
C11	−0.2658 (3)	0.2219 (4)	0.00208 (18)	0.0308 (7)
C12	−0.1515 (3)	0.1708 (3)	0.00051 (19)	0.0314 (7)
H12	−0.1256	0.1472	−0.0514	0.038*
C13	−0.0727 (3)	0.1524 (4)	0.07207 (18)	0.0303 (7)
H13	0.0052	0.1157	0.0692	0.036*
C14	−0.4282 (3)	0.3019 (4)	0.0860 (2)	0.0416 (8)
H14A	−0.4474	0.4136	0.0556	0.050*
H14B	−0.4378	0.3190	0.1443	0.050*
H14C	−0.4800	0.2059	0.0626	0.050*
C15	−0.3466 (3)	0.2435 (5)	−0.0776 (2)	0.0418 (8)
H15A	−0.3013	0.2406	−0.1244	0.050*
H15B	−0.3875	0.3585	−0.0771	0.050*
H15C	−0.4033	0.1453	−0.0830	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0291 (5)	0.0346 (4)	0.0236 (4)	−0.0028 (3)	0.0031 (3)	0.0020 (3)
O3	0.0306 (12)	0.0341 (10)	0.0267 (11)	0.0027 (9)	0.0010 (9)	−0.0028 (9)
O1	0.0335 (13)	0.0463 (12)	0.0336 (13)	−0.0154 (10)	0.0049 (10)	−0.0027 (9)
O2	0.0389 (13)	0.0400 (11)	0.0235 (11)	0.0027 (9)	−0.0020 (10)	0.0068 (9)
N1	0.0267 (15)	0.0446 (15)	0.0304 (15)	0.0005 (12)	0.0060 (12)	−0.0012 (12)
N2	0.0260 (15)	0.0316 (13)	0.0252 (14)	0.0011 (10)	0.0015 (11)	−0.0033 (10)
C1	0.0290 (17)	0.0259 (14)	0.0246 (17)	0.0040 (12)	0.0038 (13)	0.0030 (12)
C2	0.0297 (17)	0.0357 (16)	0.0274 (17)	0.0007 (13)	−0.0005 (13)	−0.0005 (13)
C3	0.040 (2)	0.0395 (17)	0.0230 (16)	0.0072 (14)	−0.0001 (14)	−0.0034 (13)
C4	0.042 (2)	0.0331 (15)	0.0250 (17)	0.0063 (13)	0.0087 (15)	0.0026 (12)
C5	0.0260 (16)	0.0290 (14)	0.0321 (18)	0.0030 (12)	0.0071 (13)	0.0013 (12)
C6	0.0253 (16)	0.0246 (14)	0.0252 (16)	0.0027 (11)	0.0010 (13)	0.0006 (11)
C7	0.0246 (16)	0.0244 (13)	0.0300 (17)	−0.0017 (12)	0.0043 (13)	0.0022 (12)
C8	0.0254 (16)	0.0228 (13)	0.0299 (17)	−0.0024 (11)	0.0006 (13)	0.0007 (11)
C9	0.0329 (18)	0.0279 (14)	0.0294 (17)	−0.0004 (12)	0.0065 (14)	0.0008 (13)
C10	0.0250 (17)	0.0284 (14)	0.0344 (18)	−0.0020 (12)	0.0001 (14)	0.0028 (13)
C11	0.0355 (19)	0.0283 (15)	0.0276 (17)	−0.0027 (12)	0.0000 (14)	0.0008 (12)
C12	0.0345 (18)	0.0310 (15)	0.0284 (17)	0.0030 (13)	0.0028 (14)	−0.0023 (12)
C13	0.0263 (17)	0.0323 (15)	0.0308 (17)	0.0028 (12)	−0.0017 (14)	−0.0016 (12)
C14	0.0294 (19)	0.0528 (19)	0.042 (2)	0.0042 (14)	0.0006 (15)	0.0030 (15)
C15	0.042 (2)	0.0452 (18)	0.0366 (19)	0.0036 (15)	−0.0029 (15)	−0.0010 (15)

Geometric parameters (Å, º)

S1—O2	1.431 (2)	C5—H5	0.9500
S1—O1	1.435 (2)	C6—C7	1.513 (4)
S1—N1	1.614 (3)	C8—C13	1.384 (4)
S1—C1	1.781 (3)	C8—C9	1.393 (4)
O3—C7	1.241 (3)	C9—C10	1.389 (4)
N1—H1N	0.85 (4)	C9—H9	0.9500
N1—H2N	0.85 (4)	C10—C11	1.407 (4)
N2—C7	1.331 (4)	C10—C14	1.497 (4)
N2—C8	1.429 (4)	C11—C12	1.382 (4)
N2—H3N	0.76 (3)	C11—C15	1.512 (5)
C1—C2	1.389 (4)	C12—C13	1.396 (4)
C1—C6	1.403 (4)	C12—H12	0.9500
C2—C3	1.385 (4)	C13—H13	0.9500
C2—H2	0.9500	C14—H14A	0.9800
C3—C4	1.376 (4)	C14—H14B	0.9800
C3—H3	0.9500	C14—H14C	0.9800
C4—C5	1.393 (4)	C15—H15A	0.9800
C4—H4	0.9500	C15—H15B	0.9800
C5—C6	1.385 (4)	C15—H15C	0.9800
O2—S1—O1	119.84 (13)	N2—C7—C6	114.8 (2)
O2—S1—N1	106.86 (15)	C13—C8—C9	119.9 (3)
O1—S1—N1	106.64 (15)	C13—C8—N2	122.7 (3)
O2—S1—C1	106.74 (14)	C9—C8—N2	117.2 (3)
O1—S1—C1	108.34 (14)	C10—C9—C8	121.4 (3)
N1—S1—C1	107.93 (13)	C10—C9—H9	119.3
S1—N1—H1N	113 (2)	C8—C9—H9	119.3
S1—N1—H2N	110 (2)	C9—C10—C11	119.0 (3)
H1N—N1—H2N	116 (3)	C9—C10—C14	119.3 (3)
C7—N2—C8	128.1 (3)	C11—C10—C14	121.7 (3)
C7—N2—H3N	120 (3)	C12—C11—C10	118.5 (3)
C8—N2—H3N	112 (3)	C12—C11—C15	120.3 (3)
C2—C1—C6	120.4 (3)	C10—C11—C15	121.2 (3)
C2—C1—S1	118.4 (2)	C11—C12—C13	122.6 (3)
C6—C1—S1	121.1 (2)	C11—C12—H12	118.7
C3—C2—C1	119.6 (3)	C13—C12—H12	118.7
C3—C2—H2	120.2	C8—C13—C12	118.4 (3)
C1—C2—H2	120.2	C8—C13—H13	120.8
C4—C3—C2	120.5 (3)	C12—C13—H13	120.8
C4—C3—H3	119.8	C10—C14—H14A	109.5
C2—C3—H3	119.8	C10—C14—H14B	109.5
C3—C4—C5	120.1 (3)	H14A—C14—H14B	109.5
C3—C4—H4	119.9	C10—C14—H14C	109.5
C5—C4—H4	119.9	H14A—C14—H14C	109.5
C6—C5—C4	120.4 (3)	H14B—C14—H14C	109.5
C6—C5—H5	119.8	C11—C15—H15A	109.5
C4—C5—H5	119.8	C11—C15—H15B	109.5
C5—C6—C1	119.0 (3)	H15A—C15—H15B	109.5
C5—C6—C7	118.7 (3)	C11—C15—H15C	109.5
C1—C6—C7	122.0 (2)	H15A—C15—H15C	109.5
O3—C7—N2	124.3 (3)	H15B—C15—H15C	109.5
O3—C7—C6	120.8 (2)
O2—S1—C1—C2	−137.3 (2)	C5—C6—C7—O3	−117.4 (3)
O1—S1—C1—C2	−7.0 (3)	C1—C6—C7—O3	57.2 (4)
N1—S1—C1—C2	108.1 (2)	C5—C6—C7—N2	59.6 (3)
O2—S1—C1—C6	40.7 (3)	C1—C6—C7—N2	−125.7 (3)
O1—S1—C1—C6	171.1 (2)	C7—N2—C8—C13	−19.2 (4)
N1—S1—C1—C6	−73.8 (3)	C7—N2—C8—C9	165.7 (3)
C6—C1—C2—C3	1.7 (4)	C13—C8—C9—C10	−2.2 (4)
S1—C1—C2—C3	179.7 (2)	N2—C8—C9—C10	173.0 (2)
C1—C2—C3—C4	−1.4 (4)	C8—C9—C10—C11	−0.4 (4)
C2—C3—C4—C5	−0.3 (4)	C8—C9—C10—C14	−179.9 (3)
C3—C4—C5—C6	1.6 (4)	C9—C10—C11—C12	2.4 (4)
C4—C5—C6—C1	−1.3 (4)	C14—C10—C11—C12	−178.1 (3)
C4—C5—C6—C7	173.5 (2)	C9—C10—C11—C15	−178.2 (3)
C2—C1—C6—C5	−0.3 (4)	C14—C10—C11—C15	1.3 (4)
S1—C1—C6—C5	−178.4 (2)	C10—C11—C12—C13	−1.9 (4)
C2—C1—C6—C7	−175.0 (2)	C15—C11—C12—C13	178.7 (3)
S1—C1—C6—C7	7.0 (4)	C9—C8—C13—C12	2.7 (4)
C8—N2—C7—O3	−9.3 (4)	N2—C8—C13—C12	−172.3 (2)
C8—N2—C7—C6	173.8 (2)	C11—C12—C13—C8	−0.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.85 (4)	2.35 (4)	3.131 (4)	153 (3)
N2—H3N···O3^ii	0.76 (3)	2.32 (3)	3.022 (3)	155 (3)
N1—H2N···O3	0.85 (4)	2.14 (4)	2.888 (4)	146 (3)
C2—H2···O1	0.95	2.50	2.902 (4)	106
C13—H13···O3	0.95	2.35	2.914 (4)	118

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

(III) 2-[(2,6-dimethylphenyl)carbamoyl]benzenesulfonamide

Crystal data

C15H16N2O3S	Z = 4
Mr = 304.36	F(000) = 640
Triclinic, P1	Dx = 1.405 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.968 (3) Å	Cell parameters from 9182 reflections
b = 8.509 (5) Å	θ = 2.6–25.0°
c = 21.510 (11) Å	µ = 0.24 mm^−1
α = 84.30 (2)°	T = 173 K
β = 82.46 (3)°	Prism, colorless
γ = 88.66 (3)°	0.12 × 0.07 × 0.06 mm
V = 1438.5 (12) Å^3

Data collection

Nonius KappaCCD diffractometer	5044 independent reflections
Radiation source: fine-focus sealed tube	3197 reflections with (I) > 2.0 σ(I)
Graphite monochromator	Rint = 0.062
ω and ϕ scans	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −9→9
Tmin = 0.972, Tmax = 0.986	k = −10→10
9182 measured reflections	l = −24→25

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.06P)^2] where P = (Fo^2 + 2Fc^2)/3
5044 reflections	(Δ/σ)max = 0.006
401 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.39 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
S1a	0.84210 (10)	−0.17712 (10)	0.67586 (4)	0.0302 (2)
O1a	0.8096 (3)	−0.2756 (3)	0.62844 (11)	0.0421 (6)
O2a	0.7201 (2)	−0.1656 (3)	0.73031 (10)	0.0349 (6)
O3a	1.0350 (2)	0.0410 (3)	0.76208 (10)	0.0275 (5)
N1a	1.0169 (3)	−0.2381 (3)	0.69916 (14)	0.0316 (7)
H1Na	1.087 (4)	−0.271 (4)	0.6658 (16)	0.038*
H2Na	1.060 (4)	−0.164 (4)	0.7200 (15)	0.038*
N2a	0.8060 (3)	0.1988 (3)	0.78462 (12)	0.0238 (6)
H3Na	0.728 (4)	0.258 (4)	0.7660 (14)	0.029*
C1a	0.8716 (4)	0.0189 (4)	0.64007 (14)	0.0259 (7)
C2a	0.8663 (4)	0.0484 (4)	0.57597 (15)	0.0318 (8)
H2a	0.8519	−0.0366	0.5517	0.038*
C3a	0.8819 (4)	0.2019 (4)	0.54667 (15)	0.0336 (8)
H3a	0.8791	0.2212	0.5026	0.040*
C4a	0.9017 (4)	0.3262 (4)	0.58194 (15)	0.0321 (8)
H4a	0.9133	0.4308	0.5620	0.039*
C5a	0.9044 (3)	0.2977 (4)	0.64662 (15)	0.0260 (7)
H5a	0.9159	0.3837	0.6707	0.031*
C6a	0.8905 (3)	0.1450 (4)	0.67662 (14)	0.0226 (7)
C7a	0.9141 (4)	0.1211 (4)	0.74519 (14)	0.0234 (7)
C8a	0.8284 (4)	0.2138 (4)	0.84909 (14)	0.0250 (7)
C9a	0.8431 (4)	0.3670 (4)	0.86593 (16)	0.0337 (8)
C10a	0.8700 (4)	0.3847 (5)	0.92737 (16)	0.0406 (9)
H10a	0.8825	0.4875	0.9397	0.049*
C11a	0.8788 (4)	0.2547 (5)	0.97083 (17)	0.0430 (9)
H11a	0.8976	0.2684	1.0127	0.052*
C12a	0.8603 (4)	0.1059 (4)	0.95346 (16)	0.0378 (9)
H12a	0.8655	0.0175	0.9838	0.045*
C13a	0.8340 (4)	0.0810 (4)	0.89243 (15)	0.0305 (8)
C14a	0.8327 (5)	0.5076 (4)	0.81857 (17)	0.0470 (10)
H14a	0.9175	0.4966	0.7819	0.070*
H14b	0.8544	0.6039	0.8376	0.070*
H14c	0.7195	0.5141	0.8053	0.070*
C15a	0.8117 (4)	−0.0861 (4)	0.87674 (16)	0.0386 (9)
H15a	0.9226	−0.1322	0.8630	0.058*
H15b	0.7405	−0.0848	0.8428	0.058*
H15c	0.7575	−0.1496	0.9142	0.058*
S1b	0.65579 (9)	0.53453 (10)	0.40494 (4)	0.0262 (2)
O1b	0.7086 (3)	0.5007 (3)	0.46629 (10)	0.0330 (6)
O2b	0.7605 (3)	0.4801 (3)	0.35173 (10)	0.0311 (5)
O3b	0.4598 (2)	0.6297 (3)	0.28083 (10)	0.0285 (5)
N1b	0.4736 (3)	0.4572 (3)	0.40832 (15)	0.0309 (7)
H1Nb	0.436 (4)	0.465 (4)	0.3749 (16)	0.037*
H2Nb	0.396 (4)	0.490 (4)	0.4424 (16)	0.037*
N2b	0.6867 (3)	0.7542 (3)	0.22309 (12)	0.0265 (6)
H3Nb	0.768 (4)	0.826 (4)	0.2240 (15)	0.032*
C1b	0.6366 (3)	0.7418 (4)	0.39049 (14)	0.0230 (7)
C2b	0.6516 (4)	0.8349 (4)	0.43874 (15)	0.0289 (8)
H2b	0.6732	0.7872	0.4788	0.035*
C3b	0.6352 (4)	0.9978 (4)	0.42859 (16)	0.0333 (8)
H3b	0.6447	1.0612	0.4619	0.040*
C4b	0.6050 (4)	1.0683 (4)	0.37044 (16)	0.0307 (8)
H4b	0.5921	1.1797	0.3638	0.037*
C5b	0.5937 (4)	0.9749 (4)	0.32151 (15)	0.0281 (8)
H5b	0.5746	1.0236	0.2813	0.034*
C6b	0.6098 (3)	0.8116 (4)	0.33064 (14)	0.0235 (7)
C7b	0.5813 (4)	0.7202 (4)	0.27624 (14)	0.0235 (7)
C8b	0.6604 (4)	0.7080 (4)	0.16261 (15)	0.0282 (8)
C9b	0.6375 (4)	0.8308 (4)	0.11589 (15)	0.0314 (8)
C10b	0.6104 (4)	0.7904 (5)	0.05707 (16)	0.0415 (9)
H10b	0.5941	0.8713	0.0246	0.050*
C11b	0.6070 (4)	0.6339 (5)	0.04513 (17)	0.0453 (10)
H11b	0.5879	0.6079	0.0047	0.054*
C12b	0.6310 (4)	0.5163 (5)	0.09157 (17)	0.0429 (10)
H12b	0.6285	0.4093	0.0827	0.051*
C13b	0.6587 (4)	0.5499 (4)	0.15112 (16)	0.0334 (8)
C14b	0.6456 (5)	1.0014 (4)	0.12832 (17)	0.0452 (10)
H14d	0.6249	1.0693	0.0905	0.068*
H14e	0.7579	1.0232	0.1392	0.068*
H14f	0.5592	1.0226	0.1634	0.068*
C15b	0.6875 (5)	0.4168 (4)	0.20061 (17)	0.0425 (9)
H15d	0.7460	0.3291	0.1803	0.064*
H15e	0.5782	0.3807	0.2232	0.064*
H15f	0.7569	0.4543	0.2304	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1a	0.0294 (4)	0.0248 (5)	0.0377 (5)	0.0002 (3)	−0.0091 (4)	−0.0036 (4)
O1a	0.0502 (15)	0.0289 (15)	0.0531 (16)	−0.0027 (11)	−0.0212 (12)	−0.0130 (12)
O2a	0.0282 (12)	0.0325 (15)	0.0407 (14)	0.0010 (10)	0.0015 (10)	0.0043 (11)
O3a	0.0247 (11)	0.0285 (13)	0.0299 (13)	0.0033 (9)	−0.0063 (9)	−0.0029 (10)
N1a	0.0280 (15)	0.0290 (18)	0.0394 (19)	0.0072 (12)	−0.0076 (13)	−0.0097 (14)
N2a	0.0244 (13)	0.0234 (16)	0.0238 (15)	0.0053 (11)	−0.0052 (11)	−0.0020 (12)
C1a	0.0254 (16)	0.028 (2)	0.0246 (19)	0.0021 (13)	−0.0046 (13)	−0.0027 (15)
C2a	0.0316 (18)	0.035 (2)	0.031 (2)	0.0031 (15)	−0.0088 (15)	−0.0096 (17)
C3a	0.0328 (18)	0.040 (2)	0.027 (2)	0.0037 (15)	−0.0046 (15)	0.0021 (17)
C4a	0.0297 (17)	0.030 (2)	0.035 (2)	0.0027 (14)	−0.0043 (15)	0.0033 (16)
C5a	0.0229 (16)	0.0233 (19)	0.031 (2)	0.0002 (13)	−0.0035 (13)	−0.0007 (15)
C6a	0.0189 (15)	0.0230 (19)	0.0255 (18)	0.0001 (13)	−0.0012 (12)	−0.0025 (14)
C7a	0.0251 (16)	0.0171 (17)	0.0285 (18)	−0.0049 (13)	−0.0048 (14)	−0.0011 (14)
C8a	0.0241 (16)	0.0252 (19)	0.0265 (18)	0.0025 (13)	−0.0047 (13)	−0.0052 (15)
C9a	0.0358 (18)	0.030 (2)	0.036 (2)	0.0022 (15)	−0.0034 (15)	−0.0059 (17)
C10a	0.048 (2)	0.039 (2)	0.037 (2)	−0.0017 (17)	−0.0051 (17)	−0.0165 (19)
C11a	0.050 (2)	0.051 (3)	0.029 (2)	0.0020 (18)	−0.0070 (17)	−0.0066 (19)
C12a	0.039 (2)	0.043 (2)	0.032 (2)	0.0018 (17)	−0.0099 (16)	−0.0001 (18)
C13a	0.0325 (17)	0.031 (2)	0.0274 (19)	−0.0011 (15)	−0.0038 (14)	−0.0013 (16)
C14a	0.071 (3)	0.023 (2)	0.049 (3)	−0.0044 (18)	−0.014 (2)	−0.0082 (19)
C15a	0.048 (2)	0.028 (2)	0.038 (2)	−0.0028 (16)	−0.0039 (17)	0.0021 (17)
S1b	0.0271 (4)	0.0231 (5)	0.0289 (5)	0.0027 (3)	−0.0056 (3)	−0.0025 (4)
O1b	0.0345 (12)	0.0375 (15)	0.0278 (13)	0.0024 (10)	−0.0113 (10)	0.0025 (11)
O2b	0.0340 (12)	0.0274 (14)	0.0318 (13)	0.0088 (10)	−0.0023 (10)	−0.0070 (11)
O3b	0.0261 (11)	0.0297 (14)	0.0311 (13)	−0.0018 (10)	−0.0065 (9)	−0.0048 (10)
N1b	0.0292 (15)	0.0275 (17)	0.0368 (18)	−0.0030 (12)	−0.0065 (13)	−0.0036 (14)
N2b	0.0271 (14)	0.0282 (17)	0.0256 (16)	−0.0028 (12)	−0.0061 (12)	−0.0055 (13)
C1b	0.0219 (15)	0.0226 (18)	0.0250 (18)	−0.0011 (12)	−0.0037 (13)	−0.0038 (14)
C2b	0.0304 (17)	0.033 (2)	0.0244 (18)	−0.0027 (15)	−0.0024 (14)	−0.0078 (16)
C3b	0.0323 (18)	0.032 (2)	0.037 (2)	−0.0022 (15)	−0.0001 (15)	−0.0144 (17)
C4b	0.0307 (17)	0.0185 (18)	0.043 (2)	0.0001 (14)	−0.0019 (15)	−0.0072 (16)
C5b	0.0250 (16)	0.028 (2)	0.0317 (19)	0.0031 (14)	−0.0046 (14)	−0.0047 (16)
C6b	0.0174 (15)	0.0261 (19)	0.0272 (18)	−0.0007 (13)	−0.0006 (13)	−0.0056 (15)
C7b	0.0229 (16)	0.0216 (18)	0.0271 (19)	0.0066 (13)	−0.0070 (13)	−0.0044 (14)
C8b	0.0262 (16)	0.034 (2)	0.0254 (19)	−0.0015 (14)	−0.0048 (13)	−0.0076 (16)
C9b	0.0302 (17)	0.036 (2)	0.0274 (19)	−0.0050 (15)	−0.0018 (14)	−0.0003 (16)
C10b	0.045 (2)	0.052 (3)	0.028 (2)	−0.0105 (18)	−0.0043 (16)	−0.0006 (18)
C11b	0.048 (2)	0.061 (3)	0.029 (2)	−0.0147 (19)	−0.0060 (17)	−0.011 (2)
C12b	0.050 (2)	0.043 (3)	0.038 (2)	−0.0082 (18)	−0.0048 (17)	−0.016 (2)
C13b	0.0337 (18)	0.035 (2)	0.033 (2)	−0.0001 (15)	−0.0046 (15)	−0.0087 (17)
C14b	0.061 (2)	0.037 (2)	0.037 (2)	−0.0027 (18)	−0.0084 (18)	0.0013 (18)
C15b	0.052 (2)	0.031 (2)	0.047 (2)	0.0061 (17)	−0.0114 (18)	−0.0137 (19)

Geometric parameters (Å, º)

S1a—O2a	1.430 (2)	S1b—O2b	1.434 (2)
S1a—O1a	1.435 (2)	S1b—O1b	1.437 (2)
S1a—N1a	1.599 (3)	S1b—N1b	1.598 (3)
S1a—C1a	1.774 (4)	S1b—C1b	1.767 (3)
O3a—C7a	1.239 (3)	O3b—C7b	1.239 (4)
N1a—H1Na	0.91 (3)	N1b—H1Nb	0.81 (3)
N1a—H2Na	0.91 (3)	N1b—H2Nb	0.95 (3)
N2a—C7a	1.338 (4)	N2b—C7b	1.338 (4)
N2a—C8a	1.440 (4)	N2b—C8b	1.438 (4)
N2a—H3Na	0.90 (3)	N2b—H3Nb	0.90 (3)
C1a—C2a	1.383 (4)	C1b—C2b	1.385 (4)
C1a—C6a	1.414 (4)	C1b—C6b	1.403 (4)
C2a—C3a	1.394 (5)	C2b—C3b	1.388 (5)
C2a—H2a	0.9500	C2b—H2b	0.9500
C3a—C4a	1.385 (4)	C3b—C4b	1.380 (5)
C3a—H3a	0.9500	C3b—H3b	0.9500
C4a—C5a	1.391 (4)	C4b—C5b	1.393 (4)
C4a—H4a	0.9500	C4b—H4b	0.9500
C5a—C6a	1.392 (4)	C5b—C6b	1.389 (4)
C5a—H5a	0.9500	C5b—H5b	0.9500
C6a—C7a	1.505 (4)	C6b—C7b	1.511 (4)
C8a—C13a	1.395 (5)	C8b—C13b	1.393 (5)
C8a—C9a	1.399 (4)	C8b—C9b	1.402 (5)
C9a—C10a	1.389 (4)	C9b—C10b	1.388 (5)
C9a—C14a	1.500 (5)	C9b—C14b	1.506 (5)
C10a—C11a	1.382 (5)	C10b—C11b	1.382 (5)
C10a—H10a	0.9500	C10b—H10b	0.9500
C11a—C12a	1.371 (5)	C11b—C12b	1.371 (5)
C11a—H11a	0.9500	C11b—H11b	0.9500
C12a—C13a	1.393 (4)	C12b—C13b	1.386 (5)
C12a—H12a	0.9500	C12b—H12b	0.9500
C13a—C15a	1.514 (5)	C13b—C15b	1.510 (5)
C14a—H14a	0.9800	C14b—H14d	0.9800
C14a—H14b	0.9800	C14b—H14e	0.9800
C14a—H14c	0.9800	C14b—H14f	0.9800
C15a—H15a	0.9800	C15b—H15d	0.9800
C15a—H15b	0.9800	C15b—H15e	0.9800
C15a—H15c	0.9800	C15b—H15f	0.9800
O2a—S1a—O1a	119.92 (15)	O2b—S1b—O1b	118.48 (13)
O2a—S1a—N1a	108.01 (15)	O2b—S1b—N1b	107.50 (15)
O1a—S1a—N1a	106.56 (15)	O1b—S1b—N1b	106.64 (16)
O2a—S1a—C1a	105.61 (14)	O2b—S1b—C1b	107.20 (14)
O1a—S1a—C1a	108.30 (15)	O1b—S1b—C1b	107.61 (14)
N1a—S1a—C1a	107.98 (15)	N1b—S1b—C1b	109.18 (14)
S1a—N1a—H1Na	109 (2)	S1b—N1b—H1Nb	114 (3)
S1a—N1a—H2Na	110 (2)	S1b—N1b—H2Nb	112 (2)
H1Na—N1a—H2Na	116 (3)	H1Nb—N1b—H2Nb	114 (3)
C7a—N2a—C8a	123.8 (3)	C7b—N2b—C8b	124.3 (3)
C7a—N2a—H3Na	115 (2)	C7b—N2b—H3Nb	117 (2)
C8a—N2a—H3Na	121 (2)	C8b—N2b—H3Nb	118 (2)
C2a—C1a—C6a	120.1 (3)	C2b—C1b—C6b	120.4 (3)
C2a—C1a—S1a	118.9 (2)	C2b—C1b—S1b	119.1 (3)
C6a—C1a—S1a	121.0 (2)	C6b—C1b—S1b	120.5 (2)
C1a—C2a—C3a	120.5 (3)	C1b—C2b—C3b	120.0 (3)
C1a—C2a—H2a	119.8	C1b—C2b—H2b	120.0
C3a—C2a—H2a	119.8	C3b—C2b—H2b	120.0
C4a—C3a—C2a	119.9 (3)	C4b—C3b—C2b	120.4 (3)
C4a—C3a—H3a	120.0	C4b—C3b—H3b	119.8
C2a—C3a—H3a	120.0	C2b—C3b—H3b	119.8
C3a—C4a—C5a	119.9 (3)	C3b—C4b—C5b	119.6 (3)
C3a—C4a—H4a	120.0	C3b—C4b—H4b	120.2
C5a—C4a—H4a	120.0	C5b—C4b—H4b	120.2
C4a—C5a—C6a	121.0 (3)	C6b—C5b—C4b	121.0 (3)
C4a—C5a—H5a	119.5	C6b—C5b—H5b	119.5
C6a—C5a—H5a	119.5	C4b—C5b—H5b	119.5
C5a—C6a—C1a	118.6 (3)	C5b—C6b—C1b	118.6 (3)
C5a—C6a—C7a	118.0 (3)	C5b—C6b—C7b	116.8 (3)
C1a—C6a—C7a	123.1 (3)	C1b—C6b—C7b	124.3 (3)
O3a—C7a—N2a	123.3 (3)	O3b—C7b—N2b	123.9 (3)
O3a—C7a—C6a	120.1 (3)	O3b—C7b—C6b	120.6 (3)
N2a—C7a—C6a	116.4 (3)	N2b—C7b—C6b	115.3 (3)
C13a—C8a—C9a	122.0 (3)	C13b—C8b—C9b	122.0 (3)
C13a—C8a—N2a	121.1 (3)	C13b—C8b—N2b	121.7 (3)
C9a—C8a—N2a	116.9 (3)	C9b—C8b—N2b	116.3 (3)
C10a—C9a—C8a	118.0 (3)	C10b—C9b—C8b	117.9 (3)
C10a—C9a—C14a	121.2 (3)	C10b—C9b—C14b	120.7 (3)
C8a—C9a—C14a	120.8 (3)	C8b—C9b—C14b	121.4 (3)
C11a—C10a—C9a	120.9 (3)	C11b—C10b—C9b	120.8 (4)
C11a—C10a—H10a	119.5	C11b—C10b—H10b	119.6
C9a—C10a—H10a	119.5	C9b—C10b—H10b	119.6
C12a—C11a—C10a	119.9 (3)	C12b—C11b—C10b	120.0 (3)
C12a—C11a—H11a	120.1	C12b—C11b—H11b	120.0
C10a—C11a—H11a	120.1	C10b—C11b—H11b	120.0
C11a—C12a—C13a	121.7 (4)	C11b—C12b—C13b	121.6 (4)
C11a—C12a—H12a	119.1	C11b—C12b—H12b	119.2
C13a—C12a—H12a	119.1	C13b—C12b—H12b	119.2
C12a—C13a—C8a	117.4 (3)	C12b—C13b—C8b	117.7 (3)
C12a—C13a—C15a	119.0 (3)	C12b—C13b—C15b	119.9 (3)
C8a—C13a—C15a	123.6 (3)	C8b—C13b—C15b	122.4 (3)
C9a—C14a—H14a	109.5	C9b—C14b—H14d	109.5
C9a—C14a—H14b	109.5	C9b—C14b—H14e	109.5
H14a—C14a—H14b	109.5	H14d—C14b—H14e	109.5
C9a—C14a—H14c	109.5	C9b—C14b—H14f	109.5
H14a—C14a—H14c	109.5	H14d—C14b—H14f	109.5
H14b—C14a—H14c	109.5	H14e—C14b—H14f	109.5
C13a—C15a—H15a	109.5	C13b—C15b—H15d	109.5
C13a—C15a—H15b	109.5	C13b—C15b—H15e	109.5
H15a—C15a—H15b	109.5	H15d—C15b—H15e	109.5
C13a—C15a—H15c	109.5	C13b—C15b—H15f	109.5
H15a—C15a—H15c	109.5	H15d—C15b—H15f	109.5
H15b—C15a—H15c	109.5	H15e—C15b—H15f	109.5
O2a—S1a—C1a—C2a	−131.9 (2)	O2b—S1b—C1b—C2b	−136.2 (2)
O1a—S1a—C1a—C2a	−2.2 (3)	O1b—S1b—C1b—C2b	−7.7 (3)
N1a—S1a—C1a—C2a	112.8 (3)	N1b—S1b—C1b—C2b	107.6 (3)
O2a—S1a—C1a—C6a	44.5 (3)	O2b—S1b—C1b—C6b	42.5 (3)
O1a—S1a—C1a—C6a	174.2 (2)	O1b—S1b—C1b—C6b	171.0 (2)
N1a—S1a—C1a—C6a	−70.8 (3)	N1b—S1b—C1b—C6b	−73.6 (3)
C6a—C1a—C2a—C3a	0.9 (4)	C6b—C1b—C2b—C3b	2.0 (4)
S1a—C1a—C2a—C3a	177.4 (2)	S1b—C1b—C2b—C3b	−179.3 (2)
C1a—C2a—C3a—C4a	−0.5 (5)	C1b—C2b—C3b—C4b	−0.5 (5)
C2a—C3a—C4a—C5a	−0.5 (5)	C2b—C3b—C4b—C5b	−1.0 (5)
C3a—C4a—C5a—C6a	1.1 (4)	C3b—C4b—C5b—C6b	0.9 (4)
C4a—C5a—C6a—C1a	−0.7 (4)	C4b—C5b—C6b—C1b	0.5 (4)
C4a—C5a—C6a—C7a	173.3 (3)	C4b—C5b—C6b—C7b	175.1 (3)
C2a—C1a—C6a—C5a	−0.3 (4)	C2b—C1b—C6b—C5b	−1.9 (4)
S1a—C1a—C6a—C5a	−176.7 (2)	S1b—C1b—C6b—C5b	179.3 (2)
C2a—C1a—C6a—C7a	−173.9 (3)	C2b—C1b—C6b—C7b	−176.2 (3)
S1a—C1a—C6a—C7a	9.7 (4)	S1b—C1b—C6b—C7b	5.1 (4)
C8a—N2a—C7a—O3a	7.6 (5)	C8b—N2b—C7b—O3b	8.8 (5)
C8a—N2a—C7a—C6a	−167.9 (3)	C8b—N2b—C7b—C6b	−166.0 (3)
C5a—C6a—C7a—O3a	−115.4 (3)	C5b—C6b—C7b—O3b	−114.4 (3)
C1a—C6a—C7a—O3a	58.3 (4)	C1b—C6b—C7b—O3b	59.9 (4)
C5a—C6a—C7a—N2a	60.2 (4)	C5b—C6b—C7b—N2b	60.5 (3)
C1a—C6a—C7a—N2a	−126.1 (3)	C1b—C6b—C7b—N2b	−125.2 (3)
C7a—N2a—C8a—C13a	−61.1 (4)	C7b—N2b—C8b—C13b	−63.9 (4)
C7a—N2a—C8a—C9a	119.3 (3)	C7b—N2b—C8b—C9b	116.4 (3)
C13a—C8a—C9a—C10a	2.3 (5)	C13b—C8b—C9b—C10b	0.9 (5)
N2a—C8a—C9a—C10a	−178.1 (3)	N2b—C8b—C9b—C10b	−179.5 (3)
C13a—C8a—C9a—C14a	−178.6 (3)	C13b—C8b—C9b—C14b	−177.9 (3)
N2a—C8a—C9a—C14a	1.0 (4)	N2b—C8b—C9b—C14b	1.8 (4)
C8a—C9a—C10a—C11a	−1.2 (5)	C8b—C9b—C10b—C11b	−0.3 (5)
C14a—C9a—C10a—C11a	179.8 (3)	C14b—C9b—C10b—C11b	178.5 (3)
C9a—C10a—C11a—C12a	−0.2 (5)	C9b—C10b—C11b—C12b	−0.2 (5)
C10a—C11a—C12a—C13a	0.6 (5)	C10b—C11b—C12b—C13b	0.1 (5)
C11a—C12a—C13a—C8a	0.5 (5)	C11b—C12b—C13b—C8b	0.4 (5)
C11a—C12a—C13a—C15a	−179.0 (3)	C11b—C12b—C13b—C15b	−179.0 (3)
C9a—C8a—C13a—C12a	−2.0 (5)	C9b—C8b—C13b—C12b	−1.0 (5)
N2a—C8a—C13a—C12a	178.4 (3)	N2b—C8b—C13b—C12b	179.4 (3)
C9a—C8a—C13a—C15a	177.5 (3)	C9b—C8b—C13b—C15b	178.4 (3)
N2a—C8a—C13a—C15a	−2.1 (5)	N2b—C8b—C13b—C15b	−1.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1a—H1Na···O2b^i	0.91 (3)	2.17 (3)	2.891 (4)	135 (3)
N2a—H3Na···O3b^ii	0.90 (3)	2.08 (3)	2.971 (3)	174 (3)
N1b—H1Nb···O1a^iii	0.81 (3)	2.58 (3)	2.996 (3)	114 (3)
N1b—H2Nb···O1b^ii	0.95 (3)	2.04 (3)	2.941 (4)	157 (3)
N2b—H3Nb···O3a^iv	0.90 (3)	2.03 (3)	2.921 (4)	170 (3)
N1a—H2Na···O3a	0.91 (3)	2.04 (3)	2.863 (4)	151 (3)
N1b—H1Nb···O3b	0.81 (3)	2.33 (4)	2.993 (4)	139 (3)
C2a—H2a···O1a	0.95	2.49	2.896 (5)	106
C2b—H2b···O1b	0.95	2.48	2.885 (4)	105
C15a—H15a···O3a	0.98	2.57	2.971 (4)	105
C15b—H15f···N2b	0.98	2.59	2.958 (5)	102

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