Proton-transfer compounds with 4-amino-N-(4,6-dimethylpyrimidin-2-yl) benzenesulfonamide (sulfamethazine): The structures and hydrogen bonding in the salts with 5-nitrosalicylic acid and picric acid

Article abstract of DOI:10.1107/S0108270113009487

The structures of the anhydrous proton-transfer compounds of the sulfa drug sulfamethazine with 5-nitrosalicylic acid and picric acid, namely 2-(4-aminobenzenesulfonamido)-4,6-dimethylpyrimidinium 2-hydroxy-5- nitrobenzoate, C₁₂H₁₅N₄O₂S ⁺·C₇H₄NO₄ ^-, (I), and 2-(4-aminobenzenesulfonamido)-4,6-dimethylpyrimidinium 2,4,6- trinitrophenolate, C₁₂H₁₅N₄O₂S ⁺·C₆H₂N₃O₇ ^-, (II), respectively, have been determined. In the asymmetric unit of (I), there are two independent but conformationally similar cation-anion heterodimer pairs which are formed through duplex intermolecular N⁺ - H···O_carboxylate and N - H·· ·O_carboxylate hydrogen-bond pairs, giving a cyclic motif [graph set R₂ ²(8)]. These heterodimers form separate and different non-associated substructures through aniline N - H·· ·O hydrogen bonds, one one-dimensional, involving carboxylate O-atom acceptors, the other two-dimensional, involving both carboxylate and hydroxy O-atom acceptors. The overall two-dimensional structure is stabilized by π-π interactions between the pyrimidinium ring and the 5-nitrosalicylate ring in both heterodimers [minimum ring-centroid separation = 3.4580 (8) A]. For picrate (II), the cation-anion interaction involves a slightly asymmetric chelating N - H···O R₂ ¹(6) hydrogen-bonding association with the phenolate O atom, together with peripheral conjoint R 1 ²(6) interactions between the same N - H groups and O atoms of the ortho-related nitro groups. An inter-unit amine N - H···O_sulfone hydrogen bond gives one-dimensional chains which extend along a and inter-associate through π-π interactions between the pyrimidinium rings [centroid-centroid separation = 3.4752 (9) A]. The two structures reported here now bring to a total of four the crystallographically characterized examples of proton-transfer salts of sulfamethazine with strong organic acids.

Full text of DOI:10.1107/S0108270113009487

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Comment
The drug sulfamethazine [or sulfadimidine; systematic name:
4-amino-N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide]
(O’Neil, 2001) has been used as a model for cocrystal
formation (Caira, 2007; Ghosh et al., 2011), commonly forming
1:1 adducts with carboxylic acids, predominantly the benzoic
acid analogues. The structures of a significant number of these
have been reported, e.g. with benzoic acid (Arman et al.,
2010), salicylic acid (Patel et al., 1988), anthranilic and
4-aminobenzoic acids (Caira, 1991), 4-aminosalicylic and
acetylsalicylic acids (Caira, 1992), 2-nitrobenzoic acid (Smith
& Wermuth, 2013a), 4-nitrobenzoic acid (Smith & Wermuth,
2012), 2,4-dinitrobenzoic and indole-2-carboxylic acids (Lynch
et al., 2000), 4-chlorobenzoic acid (Lucaciu et al., 2008), and
4-hydroxybenzoic, 2,4-dihydroxybenzoic, 3,4-dichlorobenzoic,
1-hydroxy-2-naphthoic and 3-hydroxy-2-naphthoic acids
(Ghosh et al., 2011). Only two aliphatic examples are known,
viz. with fumaric and sorbic acids. The structures of the
cocrystals with the amides benzamide, 4-hydroxybenzamide
and picolinamide (Ghosh et al., 2011) are also known. The
structures of the adducts with trimethoprim, viz. a 1:1
methanol monosolvate (Bettinetti & Sardone, 1997) and a 2:1
monohydrate (Sardone et al., 1997), represent a small number
of solvated examples.
ISSN 0108-2701
Proton-transfer compounds with
4-amino-N-(4,6-dimethylpyrimi-
din-2-yl)benzenesulfonamide
(sulfamethazine): the structures
and hydrogen bonding in the salts
with 5-nitrosalicylic acid and picric
acid
Graham Smith* and Urs D. Wermuth
Science and Engineering Faculty, Queensland University of Technology, GPO
Box 2434, Brisbane, Queensland 4001, Australia
Correspondence e-mail: g.smith@qut.edu.au
Received 26 February 2013
Accepted 7 April 2013
The structures of the anhydrous proton-transfer compounds
of the sulfa drug sulfamethazine with 5-nitrosalicylic acid and
picric acid, namely 2-(4-aminobenzenesulfonamido)-4,6-di-
methylpyrimidinium 2-hydroxy-5-nitrobenzoate, C12H15N4-
O2S+ꢀC7H4NO4ꢁ, (I), and 2-(4-aminobenzenesulfonamido)-
4,6-dimethylpyrimidinium 2,4,6-trinitrophenolate, C12H15N4-
O2S+ꢀC6H2N3O7ꢁ, (II), respectively, have been determined. In
the asymmetric unit of (I), there are two independent but
conformationally similar cation–anion heterodimer pairs
which are formed through duplex intermolecular N+—
Hꢀ ꢀ ꢀOcarboxylate and N—Hꢀ ꢀ ꢀOcarboxylate hydrogen-bond pairs,
giving a cyclic motif [graph set R22(8)]. These heterodimers
form separate and different non-associated substructures
through aniline N—Hꢀ ꢀ ꢀO hydrogen bonds, one one-dimen-
sional, involving carboxylate O-atom acceptors, the other two-
dimensional, involving both carboxylate and hydroxy O-atom
acceptors. The overall two-dimensional structure is stabilized
by ꢀ–ꢀ interactions between the pyrimidinium ring and the
5-nitrosalicylate ring in both heterodimers [minimum ring-
In the previously mentioned cocrystals of sulfamethazine,
heterodimers are usually formed through a cyclic hydrogen-
bonding motif [graph set R22(8); Etter et al., 1990], involving
amide N—Hꢀ ꢀ ꢀOcarboxy and carboxylic acid O—Hꢀ ꢀ ꢀNpyrimidine
pairs. Other structures not involving carboxylic acids are the
1:1 complex with saccharin (Lu et al., 2008), where a proto-
nated sulfamethazine cation is present, and the 2:1 complex
with theophylline (Lu et al., 2011), in which two tautomeric
forms of sulfamethazine are found, viz. the amidine and the
imidine forms, similar to those found in the benzamide
cocrystal (Ghosh et al., 2011). The structures of the parent
compound sulfamethazine (Tiwari et al., 1984) and its
methanol monosolvate (Rambaud et al., 1985) are also known.
However, no examples of proton-transfer salts of sulfa-
methazine with strong ‘conventional’ organic acids were
present in the crystallographic literature before that of the
˚
centroid separation = 3.4580 (8) A]. For picrate (II), the
cation–anion interaction involves a slightly asymmetric
chelating N—Hꢀ ꢀ ꢀO R21(6) hydrogen-bonding association with
the phenolate O atom, together with peripheral conjoint R12(6)
interactions between the same N—H groups and O atoms of
the ortho-related nitro groups. An inter-unit amine N—
Hꢀ ꢀ ꢀOsulfone hydrogen bond gives one-dimensional chains
which extend along a and inter-associate through ꢀ–ꢀ
interactions between the pyrimidinium rings [centroid–
˚
centroid separation = 3.4752 (9) A]. The two structures
reported here now bring to a total of four the crystal-
lographically characterized examples of proton-transfer salts
of sulfamethazine with strong organic acids.
538 # 2013 International Union of Crystallography
doi:10.1107/S0108270113009487
Acta Cryst. (2013). C69, 538–543

organic compounds
Figure 1
The molecular conformation and atom-numbering scheme for the two independent hydrogen-bonded heteromolecular pairs (A–D and B–C) in the
asymmetric unit of (I), with inter-species hydrogen bonds shown as dashed lines. Displacement ellipsoids are drawn at the 40% probability level.
˚
˚
structure of the anhydrous picrate salt with 3,5-dinitrosalicylic
acid (DNSA) (Smith & Wermuth, 2013b). In this salt, a
hydrogen-bonded heterodimer analogous to those in the non-
proton-transfer cocrystals is present, the subtle variation being
that, with proton transfer, one N+—Hꢀ ꢀ ꢀOcarboxy and one N—
Hꢀ ꢀ ꢀOcarboxy interaction are involved in the R22(8) motif. The
phenolate group is only involved in the intramolecular cyclic
carboxylic acid O—Hꢀ ꢀ ꢀO hydrogen bond, similar to that
found in the majority of the proton-transfer salts of DNSA
(Smith et al., 2007). We therefore carried out the reaction of
sulfamethazine with other strong organic acids under similar
conditions to those used in the DNSA preparation (1:1 stoi-
chiomety in 50% ethanol–water). Suitable crystalline products
were obtained with 5-nitrosalicylic acid (5-NSA) and picric
acid, namely the title salts 2-(4-aminobenzenesulfonamido)-
4,6-dimethylpyrimidinium 2-hydroxy-5-nitrobenzoate, (I)
(Fig. 1), and 2-(4-aminobenzenesulfonamido)-4,6-dimethyl-
pyrimidinium 2,4,6-trinitrophenolate, (II) (Fig. 2), and the
structures are reported herein. Although not as effective as
picric acid for producing crystalline proton-transfer salts with
amines, 5-NSA (pKa ’ 2.2) has proved relatively useful in this
respect, particularly with the aromatic amines (Smith et al.,
1996, 2005, 2006; Kumar et al., 2003).
2.724 (4) A and Nꢀ ꢀ ꢀO = 2.719 (4)–2.840 (4) A]. The corre-
sponding values in the DNSA proton-transfer salt (Smith &
˚
Wermuth, 2013b) are 2.617 (4) and 2.729 (4) A.
In (I), the cyclic motifs result in near-coplanarity of the
pyrimidinium and 5-NSA ring systems, with inter-ring dihedral
angles of 3.74 (7) and 7.84 (7)ꢁ for dimers A–D and B–C,
respectively. The heterodimers form separate and different
non-associated substructures through aniline N—Hꢀ ꢀ ꢀO
hydrogen bonds (Table 1), the first system being one-dimen-
sional (A–D), involving carboxylate O-atom acceptors
(O11D) and extending parallel to [010] (Fig. 3a). The second
system (B–C) is two-dimensional, involving both carboxylate
and hydroxy O-atom acceptors (O12B and O2C, respectively),
and extends parallel to the (011) plane (Fig. 3b). The
composite structure of (I) is two-dimensional (Fig. 3c), lying in
the (101) plane. Unlike the structure of the sulfamethazine salt
with 3,5-dinitrosalicylic acid, no intermolecular aniline N—
Hꢀ ꢀ ꢀOsulfone hydrogen-bonding interactions are present.
However, ꢀ–ꢀ interactions are present between the pyrimi-
In the 5-NSA salt of sulfamethazine, (I), the asymmetric
unit (Fig. 1) contains two independent cation–anion pairs
(cations labelled A and B, and anions labelled C and D,
respectively), which interact through N—Hꢀ ꢀ ꢀOcarboxylate
hydrogen-bonding pairs (Table 1), giving cyclic R22(8) hetero-
dimers (A–D and B–C). These differ from the heterodimer
adduct only in the presence in (I) of the transferred H atom on
the pyrimidine N atom of the sulfamethazine cation. Asym-
metry is found in the N+—Hꢀ ꢀ ꢀO [N+ꢀ ꢀ ꢀO = 2.5847 (17) (A)
˚
and 2.6162 (18) A (B)] and N—Hꢀ ꢀ ꢀO distances [Nꢀ ꢀ ꢀO =
˚
2.7810 (18) (A) and 2.7221 (18) A (B)] within the cyclic
Figure 2
association. This asymmetry is comparable with that found in
the cocrystal examples [O—Hꢀ ꢀ ꢀN and N—Hꢀ ꢀ ꢀO ranges for
eight examples (Lynch et al., 2000) are Oꢀ ꢀ ꢀN = 2.526 (4)–
The molecular conformation and atom-numbering scheme for (II), with
inter-species hydrogen bonds shown as dashed lines. Displacement
ellipsoids are drawn at the 40% probability level.
C12H15N4O2S+ꢀC7H4NO5 and C12H15N4O2S+ꢀC6H2N3O7
539
ꢃ
ꢃ
ꢂ
Acta Cryst. (2013). C69, 538–543
Smith and Wermuth

organic compounds
1
dine rings of both cations and both anions [Aꢀ ꢀ ꢀC(x ꢃ , ꢃy + 12,
2
z ꢃ ) and Bꢀ ꢀ ꢀD(x + 12, ꢃy + 23, z + 12); ring-centroid separations
1
2
˚
(Cgꢀ ꢀ ꢀCg) = 3.4580 (8) and 3.6815 (9) A, respectively].
For picrate salt (II) (Fig. 2), the pyrimidine ring of the
sulfamethazine molecule (A) is protonated at N1A and this
group, together with the adjacent amide N2A—H group, gives
a slighly asymmetric chelating hydrogen-bonding association
with the picrate anion through a cyclic R12(6) motif. Conjoint
lateral R21(6) cyclic associations are also formed between the
N1A—H donor group and the O-atom acceptors of adjacent
ortho-related picrate nitro groups (Table 2). A single inter-
molecular amine N41A—Hꢀ ꢀ ꢀOsulfone hydrogen-bonding
interaction between the cation–anion units gives one-dimen-
sional chains which extend along the [100] direction (Fig. 4).
Also present in the structure are ꢀ–ꢀ interactions between the
pyrimidine rings of centosymmetrically related sulfamethazine
ii
˚
cations [Cgꢀ ꢀ ꢀ Cg = 3.4752 (9) A; symmetry code: (ii) ꢃx + 2,
ꢃy + 1, ꢃz + 1] (Fig. 5). As found in the two structures
reported here and in many of the sulfamethazine adduct
structures, the 4-amino substituent is often only weakly or
partially involved in hydrogen-bonding associations in the
crystal structures. The planes of the nitro groups of the picrate
anion are variously rotated out of the plane of the benzene
ring [torsion angles C1—C2—N2—O22, C3—C4—N4—O42
and C5—C6—N6—O62 of ꢃ137.67 (15), 170.19 (15) and
146.91 (16)ꢁ, respectively].
In the sulfamethazine cations, the conformation differs
significantly between carboxylate (I) and picrate (II). For (I),
the dihedral angles between the planes of the pyrimidinium
and benzene rings of the sulfamethazine cations are 70.60 (7)
(A) and 84.78 (7)ꢁ (B), compared with 78.77 (8) and 82.33 (9)ꢁ
for those in the two independent heterodimers in the 4-
nitrobenzoic acid adduct (Smith & Wermuth, 2012). The value
for the equivalent pyrimidinium–benzene dihedral angle in
the cation of (II) [58.18 (7)ꢁ] is similar to that in the picrate
salt with DNSA [59.70 (17)ꢁ], but is significantly smaller than
commonly found in the other adduct structures and in (I), and
probably in the case of (II) is attributable to the markedly
different hydrogen-bonding pattern present in that structure.
In (I), the two interacting pyrimidine–5-NSA dimers are
essentially planar, with inter-ring dihedral angles of 3.74 (7)
and 7.84 (7)ꢁ, compared with a value of 12.2 (2)ꢁ in the
structure of the DNSA salt (Smith & Wermuth, 2013b).
The two structures presented here now give a small total of
four crystallographically characterized examples of proton-
transfer salts of sulfamethazine with strong organic acids.
Experimental
The title salts, (I) and (II), were prepared by the reaction of 4-amino-
N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide (sulfamethazine;
1 mmol, 280 mg) with, respectively, 5-nitrosalicylic acid (1 mmol,
180 mg) or picric acid (1 mmol, 230 mg) in 50% ethanol–water
(50 ml) under reflux for 10 min. Partial evaporation of the solvent
gave colourless plates of (I) (m.p. 478–479 K) or yellow blocks of (II)
(m.p. 469–471 K), from which specimens were cleaved for the X-ray
analyses.
Figure 3
(a) The one-dimensional hydrogen-bonded chain structure formed by the
A–D heterodimer units in (I), extending down b. Hydrogen-bonding
associations are shown as dashed lines and non-associative H atoms have
been omitted. (b) The two-dimensional hydrogen-bonded structure
formed by the B–C heterodimer units in (I). (c) The composite two-
dimensional hydrogen-bonded structure of (I), viewed down a. Symmetry
codes are as in Table 1.
C12H15N4O2S+ꢀC7H4NO5 and C12H15N4O2S+ꢀC6H2N3O7
Acta Cryst. (2013). C69, 538–543
ꢃ
ꢃ
ꢂ
540 Smith and Wermuth

organic compounds
Figure 4
A perspective view of the two-dimensional chain structure of (II), which extends along a, showing the hydrogen-bonding associations as dashed lines.
[Symmetry code: (i) x + 1, y, z.]
Figure 5
A view of (II) down the a axis of the unit cell, showing the ꢀ–ꢀ interactions of the centrosymmetrically related pyrimidinium rings of the sulfamethazine
cations as dotted lines. Hydrogen bonds are shown as dashed lines.
C12H15N4O2S+ꢀC7H4NO5 and C12H15N4O2S+ꢀC6H2N3O7
541
ꢃ
ꢃ
ꢂ
Acta Cryst. (2013). C69, 538–543
Smith and Wermuth

organic compounds
Table 1
Hydrogen-bond geometry (A, ) for (I).
Table 2
Hydrogen-bond geometry (A, ) for (II).
ꢁ
ꢁ
˚
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1A—H1Aꢀ ꢀ ꢀO12D
N1B—H1Bꢀ ꢀ ꢀO12C
N2A—H2Aꢀ ꢀ ꢀO11D
N2B—H2Bꢀ ꢀ ꢀO11C
N41A—H41Aꢀ ꢀ ꢀO11Di
N41B—H41Bꢀ ꢀ ꢀO2Cii
N41B—H42Bꢀ ꢀ ꢀO12Biii
O2C—H2Cꢀ ꢀ ꢀO12C
O2D—H2Dꢀ ꢀ ꢀO12D
0.939 (18)
0.91 (2)
0.85 (2)
0.889 (19)
0.82 (3)
0.89 (2)
0.83 (2)
0.89 (3)
0.90 (2)
1.647 (18)
1.71 (2)
1.94 (2)
1.836 (19)
2.57 (2)
2.49 (2)
2.45 (2)
1.70 (3)
1.70 (2)
2.5847 (17)
2.6162 (18)
2.7810 (18)
2.7221 (18)
3.217 (2)
3.269 (2)
3.106 (2)
2.5223 (17)
2.5215 (17)
176 (2)
176.4 (18)
177 (2)
174.3 (18)
138 (2)
147 (2)
136.6 (18)
152 (2)
151 (2)
N1A—H1Aꢀ ꢀ ꢀO1
N1A—H1Aꢀ ꢀ ꢀO21
N2A—H2Aꢀ ꢀ ꢀO1
N2A—H2Aꢀ ꢀ ꢀO62
N41A—H41Aꢀ ꢀ ꢀO12Ai
0.91 (2)
0.91 (2)
0.85 (2)
0.85 (2)
0.90 (2)
1.70 (2)
2.46 (2)
2.07 (2)
2.59 (2)
2.16 (2)
2.5545 (19)
2.974 (2)
2.7661 (19)
3.319 (2)
3.035 (2)
154 (2)
116.2 (18)
139.2 (17)
145.0 (15)
163 (2)
Symmetry code: (i) x þ 1; y; z.
1
2
1
2
3
2
1
2
1
1
3
1
Symmetry codes: (i) ꢃx þ ; y ꢃ ; ꢃz þ ; (ii) x ꢃ ; ꢃy þ ; z ꢃ ; (iii) ꢃx þ ; y þ ,
2
2
2
2
H atoms potentially involved in hydrogen-bonding interactions
were located by difference methods, and their positional and isotropic
displacement parameters were refined. In (I), the N1A—H1A
3
ꢃz þ .
2
˚
distance was restrained to 0.88 (2) A. All other H atoms were
˚
included at calculated positions (aromatic C—H = 0.95 A or methyl
Compound (I)
˚
C—H = 0.98 A) and treated as riding, with Uiso(H) = 1.2Ueq(C) for
Crystal data
C12H15N4O2S+ꢀC7H4NO5
ꢃ
3
˚
V = 4104.52 (10) A
Z = 8
Mo Kꢂ radiation
ꢃ = 0.21 mmꢃ1
T = 200 K
aromatic or 1.5Ueq(C) for methyl H atoms. For (I), in the absence of
any indication of twinning [‘no twin law detected’, TwinRotMat
(PLATON, Spek, 2009)], the pseudo-orthorhombic P21/n unit cell
was accepted. For (II), the H atoms of one of the methyl groups
(C42A) were rotationally disordered over six half-occupancy sites
and were treated accordingly in the refinement.
Mr = 461.46
Monoclinic, P21=n
˚
˚
a = 13.1611 (2) A
b = 14.0977 (2) A
˚
c = 22.1219 (3) A
0.35 ꢄ 0.35 ꢄ 0.15 mm
ꢁ = 90.094 (2)ꢁ
For both compounds, data collection: CrysAlis PRO (Oxford
Diffraction, 2010); cell refinement: CrysAlis PRO; data reduction:
CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare
et al., 1993); program(s) used to refine structure: SHELXL97 (Shel-
drick, 2008) within WinGX (Farrugia, 2012); molecular graphics:
PLATON (Spek, 2009); software used to prepare material for
publication: PLATON (Spek, 2009).
Data collection
Oxford Gemini-S Ultra CCD area-
detector diffractometer
Absorption correction: multi-scan
(CrysAlis PRO; Oxford
Diffraction, 2010)
30179 measured reflections
8057 independent reflections
5991 reflections with I > 2ꢄ(I)
Rint = 0.025
Tmin = 0.960, Tmax = 0.980
Refinement
The authors acknowledge financial support from the
Australian Reseach Council and the Science and Engineering
Faculty, Queensland University of Technology.
R[F2 > 2ꢄ(F2)] = 0.035
wR(F2) = 0.090
S = 0.95
8057 reflections
621 parameters
1 restraint
H atoms treated by a mixture of
independent and constrained
refinement
ꢃ3
˚
Áꢅmax = 0.28 e A
ꢃ3
˚
Áꢅmin = ꢃ0.30 e A
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: KY3031). Services for accessing these data are
described at the back of the journal.
Compound (II)
References
Crystal data
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Cryst. 26, 343–350.
C12H15N4O2S+ꢀC6H2N3O7
ꢃ
3
˚
V = 2127.74 (10) A
Z = 4
Mo Kꢂ radiation
ꢃ = 0.22 mmꢃ1
T = 200 K
Mr = 507.45
Monoclinic, P21=c
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a = 8.3131 (2) A
b = 19.2779 (5) A
˚
c = 13.4483 (4) A
˚
0.35 ꢄ 0.35 ꢄ 0.26 mm
ꢁ = 99.158 (3)ꢁ
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Oxford Gemini-S CCD area-
detector diffractometer
Absorption correction: multi-scan
(CrysAlis PRO; Oxford
Diffraction, 2010)
14211 measured reflections
4171 independent reflections
3318 reflections with I > 2ꢄ(I)
Rint = 0.024
Tmin = 0.970, Tmax = 0.981
Refinement
R[F2 > 2ꢄ(F2)] = 0.034
wR(F2) = 0.091
S = 1.04
4171 reflections
334 parameters
H atoms treated by a mixture of
independent and constrained
refinement
ꢃ3
˚
Áꢅmax = 0.27 e A
ꢃ3
˚
Áꢅmin = ꢃ0.42 e A
C12H15N4O2S+ꢀC7H4NO5 and C12H15N4O2S+ꢀC6H2N3O7
Acta Cryst. (2013). C69, 538–543
ꢃ
ꢃ
ꢂ
542 Smith and Wermuth

organic compounds
Rambaud, J., Maury, L., Pauvert, B., Audran, M., Lasserre, Y., Berge, G. &
Declercq, J.-P. (1985). Acta Cryst. C41, 133–134.
Smith, G. & Wermuth, U. D. (2013a). Acta Cryst. E69, o234.
Smith, G. & Wermuth, U. D. (2013b). Acta Cryst. E69, o472.
Sardone, N., Bettinetti, G. & Sorrenti, M. (1997). Acta Cryst. C53, 1295–1299.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2006). Aust. J. Chem.
59, 320–328.
Smith, G., Hortono, A. W., Wermuth, U. D., Healy, P. C., White, J. M. & Rae,
A. D. (2005). Aust. J. Chem. 58, 47–52.
Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2007). Aust. J. Chem.
60, 264–277.
Smith, G., Lynch, D. E., Byriel, K. A. & Kennard, C. H. L. (1996). Acta Cryst.
C52, 231–235.
Smith, G. & Wermuth, U. D. (2012). Acta Cryst. E68, o1649–o1650.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Tiwari, R. K., Haridas, M. & Singh, T. P. (1984). Acta Cryst. C40, 655–
657.
C12H15N4O2S+ꢀC7H4NO5 and C12H15N4O2S+ꢀC6H2N3O7
543
ꢃ
ꢃ
ꢂ
Acta Cryst. (2013). C69, 538–543
Smith and Wermuth

supplementary materials
supplementary materials
Acta Cryst. (2013). C69, 538-543 [doi:10.1107/S0108270113009487]
Proton-transfer compounds with 4-amino-N-(4,6-dimethylpyrimidin-2-
yl)benzenesulfonamide (sulfamethazine): the structures and hydrogen bonding
in the salts with 5-nitrosalicylic acid and picric acid
Graham Smith and Urs D. Wermuth
(I) 2-(4-Aminobenzenesulfonamido)-4,6-dimethylpyrimidinium 2-hydroxy-5-nitrobenzoate
Crystal data
C12H15N4O2S+·C7H4NO5−
Mr = 461.46
F(000) = 1920
Dx = 1.493 Mg m−3
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 13.1611 (2) Å
b = 14.0977 (2) Å
c = 22.1219 (3) Å
β = 90.094 (2)°
Melting point = 478–479 K
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 13808 reflections
θ = 3.2–28.7°
µ = 0.21 mm−1
T = 200 K
Plate, colourless
0.35 × 0.35 × 0.15 mm
V = 4104.52 (10) Å3
Z = 8
Data collection
Oxford Gemini-S Ultra CCD area-detector
diffractometer
Radiation source: Enhance (Mo) X-ray source
Graphite monochromator
30179 measured reflections
8057 independent reflections
5991 reflections with I > 2σ(I)
Rint = 0.025
ω scans
θmax = 26.0°, θmin = 3.3°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
h = −16→16
k = −17→17
l = −27→27
T
min = 0.960, Tmax = 0.980
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.035
wR(F2) = 0.090
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 0.95
8057 reflections
621 parameters
1 restraint
Primary atom site location: structure-invariant
direct methods
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0571P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.007
Δρmax = 0.28 e Å−3
Δρmin = −0.30 e Å−3
Acta Cryst. (2013). C69, 538-543
sup-1

supplementary materials
Special details
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are
estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the
estimation of distances, angles and torsion angles
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
S1A
0.07153 (3)
−0.02458 (8)
0.08020 (9)
0.12334 (9)
0.10773 (10)
0.10208 (9)
0.37418 (14)
0.11060 (11)
0.10701 (11)
0.11914 (11)
0.12785 (10)
0.16171 (12)
0.25203 (13)
0.32363 (13)
0.30519 (13)
0.09958 (15)
0.21385 (13)
0.14306 (12)
0.14456 (12)
0.92340 (3)
1.01786 (8)
0.91201 (9)
0.87859 (9)
0.90467 (10)
0.91195 (10)
0.58517 (14)
0.89904 (11)
0.90126 (11)
0.88147 (12)
0.86996 (11)
0.82365 (11)
0.72877 (12)
0.65008 (12)
0.66316 (12)
0.91208 (14)
0.75855 (12)
0.83785 (12)
0.84715 (13)
0.67064 (3)
0.62533 (8)
0.77122 (8)
0.56980 (9)
0.65526 (10)
0.49098 (9)
0.48612 (14)
0.56942 (10)
0.40782 (10)
0.40380 (11)
0.48715 (10)
0.61476 (11)
0.66125 (11)
0.61707 (12)
0.52674 (11)
0.32077 (12)
0.48115 (11)
0.52406 (11)
0.49267 (11)
0.25241 (3)
0.29519 (8)
0.15187 (8)
0.35527 (10)
0.26742 (10)
0.43170 (9)
0.44107 (13)
0.35379 (10)
0.51537 (11)
0.52088 (11)
0.43832 (11)
0.31070 (11)
0.26729 (11)
0.31123 (11)
0.39982 (11)
0.60161 (11)
0.44401 (11)
0.39970 (11)
0.43421 (12)
0.69347 (2)
0.70202 (5)
0.70003 (5)
0.53296 (6)
0.62149 (6)
0.62605 (6)
0.85115 (8)
0.59352 (7)
0.59619 (7)
0.53373 (7)
0.50191 (7)
0.73886 (7)
0.75263 (7)
0.78855 (7)
0.81264 (7)
0.63395 (8)
0.79852 (7)
0.76199 (7)
0.43539 (7)
0.79543 (2)
0.77910 (5)
0.78933 (5)
0.95621 (6)
0.86958 (6)
0.86353 (6)
0.66992 (9)
0.89624 (7)
0.89198 (7)
0.95369 (7)
0.98618 (7)
0.75987 (7)
0.75756 (7)
0.72858 (7)
0.70119 (7)
0.85326 (8)
0.70520 (7)
0.73375 (7)
1.05216 (8)
0.0288 (1)
0.0372 (4)
0.0387 (4)
0.0223 (4)
0.0268 (4)
0.0261 (4)
0.0476 (7)
0.0219 (4)
0.0269 (5)
0.0265 (5)
0.0231 (4)
0.0273 (5)
0.0301 (5)
0.0320 (5)
0.0315 (5)
0.0409 (6)
0.0331 (6)
0.0295 (5)
0.0293 (5)
0.0281 (1)
0.0375 (4)
0.0381 (4)
0.0241 (4)
0.0283 (4)
0.0266 (4)
0.0504 (7)
0.0233 (5)
0.0270 (5)
0.0286 (5)
0.0251 (5)
0.0245 (5)
0.0283 (5)
0.0299 (5)
0.0299 (5)
0.0369 (6)
0.0299 (5)
0.0272 (5)
0.0346 (6)
O11A
O12A
N1A
N2A
N3A
N41A
C2A
C4A
C5A
C6A
C11A
C21A
C31A
C41A
C42A
C51A
C61A
C62A
S1B
O11B
O12B
N1B
N2B
N3B
N41B
C2B
C4B
C5B
C6B
C11B
C21B
C31B
C41B
C42B
C51B
C61B
C62B
Acta Cryst. (2013). C69, 538-543
sup-2

supplementary materials
O2C
0.86063 (10)
0.87460 (9)
0.86850 (10)
0.88240 (11)
0.88819 (14)
0.88198 (11)
0.87128 (11)
0.86472 (11)
0.86229 (12)
0.86768 (12)
0.87478 (11)
0.87714 (11)
0.87166 (11)
0.14667 (11)
0.11640 (9)
0.13518 (10)
0.12968 (12)
0.11007 (10)
0.12073 (10)
0.12832 (11)
0.13815 (12)
0.14014 (13)
0.13393 (12)
0.12471 (11)
0.12100 (11)
0.12604 (12)
0.1296 (15)
0.1125 (14)
0.12140
0.12638 (9)
0.10804 (8)
0.19851 (8)
−0.29921 (9)
−0.23713 (10)
−0.23014 (10)
0.03235 (11)
0.04133 (11)
−0.03944 (12)
−0.12790 (12)
−0.13593 (11)
−0.05767 (11)
0.11811 (11)
0.79122 (9)
0.81801 (8)
0.72445 (8)
1.22050 (9)
1.16310 (8)
1.15325 (10)
0.88941 (11)
0.87685 (11)
0.95564 (12)
1.04569 (12)
1.05756 (11)
0.98103 (10)
0.80620 (11)
0.6270 (12)
0.7051 (14)
0.34440
1.12344 (6)
0.93667 (5)
1.01921 (5)
1.05247 (7)
0.96357 (7)
1.01871 (8)
1.03253 (7)
1.09589 (7)
1.13268 (8)
1.10761 (8)
1.04502 (8)
1.00755 (7)
0.99236 (7)
0.36510 (6)
0.55065 (5)
0.47061 (5)
0.42635 (7)
0.51618 (6)
0.46110 (7)
0.45319 (7)
0.39024 (7)
0.35148 (8)
0.37452 (8)
0.43673 (7)
0.47596 (7)
0.49551 (7)
0.5115 (9)
0.6004 (9)
0.51340
0.0409 (4)
0.0349 (4)
0.0407 (4)
0.0568 (5)
0.0721 (7)
0.0408 (6)
0.0249 (5)
0.0273 (5)
0.0330 (5)
0.0321 (5)
0.0285 (5)
0.0271 (5)
0.0274 (5)
0.0483 (5)
0.0357 (4)
0.0425 (4)
0.0572 (5)
0.0442 (5)
0.0348 (5)
0.0246 (5)
0.0293 (5)
0.0358 (6)
0.0322 (5)
0.0261 (5)
0.0248 (5)
0.0272 (5)
0.066 (7)*
0.050 (6)*
0.0320*
O11C
O12C
O51C
O52C
N5C
C1C
C2C
C3C
C4C
C5C
C6C
C11C
O2D
O11D
O12D
O51D
O52D
N5D
C1D
C2D
C3D
C4D
C5D
C6D
C11D
H1A
H2A
H5A
H21A
H31A
H41A
H42A
H43A
H44A
H45A
H51A
H61A
H63A
H64A
H65A
H1B
0.26440
0.72320
0.73740
0.0360*
0.38610
0.64820
0.79700
0.0380*
0.3718 (17)
0.4348 (18)
0.10930
0.4292 (18)
0.5140 (15)
0.26470
0.8578 (11)
0.8518 (10)
0.60840
0.076 (9)*
0.066 (7)*
0.0610*
0.03240
0.31800
0.65290
0.0610*
0.15210
0.32230
0.66540
0.0610*
0.20060
0.41980
0.81440
0.0400*
0.08150
0.49220
0.75240
0.0350*
0.21500
0.51120
0.42740
0.0440*
0.09840
0.53990
0.41790
0.0440*
0.13120
0.43060
0.41710
0.0440*
0.8742 (14)
0.8939 (13)
0.87600
0.2998 (14)
0.2133 (13)
0.58080
0.9766 (9)
0.8892 (9)
0.97310
0.050 (6)*
0.041 (5)*
0.0340*
H2B
H5B
H21B
H31B
H41B
H42B
H43B
0.71870
0.20720
0.77610
0.0340*
0.58550
0.28120
0.72700
0.0360*
0.5276 (18)
0.5908 (15)
0.86600
0.4084 (16)
0.4978 (15)
0.59680
0.6715 (11)
0.6598 (9)
0.81850
0.076 (8)*
0.052 (6)*
0.0550*
Acta Cryst. (2013). C69, 538-543
sup-3

supplementary materials
H44B
H45B
H51B
H61B
H63B
H64B
H65B
H2C
0.98230
0.89500
0.76820
0.90250
0.85550
0.89390
0.77700
0.8596 (18)
0.85690
0.86660
0.88270
0.1502 (17)
0.14580
0.13590
0.11350
0.60640
0.65820
0.50510
0.42960
0.49740
0.38980
0.41270
0.1687 (18)
−0.03270
−0.18290
−0.06540
0.7500 (15)
0.94650
1.09920
0.99110
0.83890
0.87690
0.68800
0.73580
1.06990
1.07190
1.05810
1.0934 (12)
1.17530
1.13240
0.96500
0.3961 (11)
0.30910
0.34840
0.51820
0.0550*
0.0550*
0.0360*
0.0330*
0.0520*
0.0520*
0.0520*
0.088 (9)*
0.0400*
0.0380*
0.0320*
0.069 (7)*
0.0430*
0.0390*
0.0300*
H3C
H4C
H6C
H2D
H3D
H4D
H6D
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
S1A
0.0366 (2)
0.0326 (6)
0.0566 (8)
0.0231 (7)
0.0393 (8)
0.0305 (7)
0.0518 (11)
0.0210 (7)
0.0271 (8)
0.0279 (8)
0.0192 (7)
0.0359 (9)
0.0445 (10)
0.0370 (9)
0.0412 (10)
0.0611 (12)
0.0459 (10)
0.0353 (9)
0.0324 (9)
0.0368 (2)
0.0336 (6)
0.0594 (8)
0.0285 (7)
0.0444 (8)
0.0318 (7)
0.0495 (11)
0.0251 (8)
0.0270 (8)
0.0335 (9)
0.0228 (8)
0.0330 (9)
0.0253 (2)
0.0433 (7)
0.0255 (6)
0.0198 (7)
0.0188 (7)
0.0219 (7)
0.0364 (11)
0.0223 (8)
0.0218 (8)
0.0195 (8)
0.0243 (8)
0.0255 (9)
0.0230 (8)
0.0297 (9)
0.0273 (9)
0.0245 (9)
0.0230 (9)
0.0266 (9)
0.0300 (9)
0.0250 (2)
0.0452 (7)
0.0246 (6)
0.0221 (7)
0.0196 (7)
0.0234 (7)
0.0296 (10)
0.0232 (8)
0.0239 (9)
0.0245 (9)
0.0272 (9)
0.0236 (8)
0.0246 (2)
0.0057 (2)
0.0063 (5)
0.0101 (5)
0.0007 (5)
0.0012 (6)
−0.0005 (5)
−0.0002 (9)
0.0016 (6)
−0.0009 (6)
−0.0002 (6)
0.0014 (6)
0.0006 (7)
−0.0031 (7)
−0.0040 (7)
0.0047 (7)
−0.0028 (8)
−0.0024 (7)
−0.0050 (7)
0.0030 (7)
0.0059 (2)
0.0075 (5)
0.0115 (5)
0.0000 (5)
0.0023 (6)
0.0012 (5)
−0.0001 (8)
0.0013 (6)
0.0001 (6)
−0.0005 (7)
−0.0010 (6)
0.0008 (6)
0.0043 (2)
0.0071 (5)
0.0032 (6)
−0.0004 (5)
0.0028 (6)
0.0009 (6)
−0.0185 (9)
0.0000 (6)
−0.0002 (7)
−0.0006 (7)
−0.0023 (6)
0.0038 (7)
0.0033 (7)
−0.0007 (7)
−0.0015 (7)
0.0039 (9)
0.0004 (8)
0.0022 (7)
−0.0019 (7)
0.0015 (2)
0.0063 (5)
−0.0033 (6)
−0.0007 (5)
−0.0004 (6)
0.0000 (6)
−0.0258 (9)
−0.0016 (6)
−0.0010 (7)
0.0016 (7)
−0.0011 (6)
0.0013 (6)
−0.0012 (2)
0.0024 (6)
−0.0046 (5)
0.0017 (6)
0.0017 (6)
0.0015 (6)
0.0039 (8)
0.0016 (6)
0.0009 (7)
−0.0047 (7)
−0.0016 (7)
−0.0027 (7)
−0.0025 (7)
−0.0073 (7)
−0.0054 (7)
0.0050 (8)
0.0026 (7)
−0.0009 (7)
−0.0026 (7)
−0.0006 (2)
0.0026 (6)
−0.0038 (5)
0.0017 (6)
0.0021 (6)
0.0013 (6)
0.0056 (9)
0.0013 (6)
0.0023 (7)
−0.0040 (7)
−0.0016 (7)
−0.0018 (6)
O11A
O12A
N1A
N2A
N3A
N41A
C2A
0.0358 (7)
0.0340 (7)
0.0239 (7)
0.0222 (7)
0.0258 (7)
0.0544 (12)
0.0225 (8)
0.0318 (9)
0.0322 (9)
0.0257 (8)
0.0204 (8)
0.0227 (8)
0.0293 (9)
0.0259 (9)
0.0370 (10)
0.0304 (10)
0.0265 (9)
0.0255 (9)
0.0224 (2)
0.0338 (7)
0.0304 (7)
0.0218 (7)
0.0209 (7)
0.0247 (7)
0.0719 (13)
0.0215 (8)
0.0302 (9)
0.0278 (9)
0.0252 (9)
0.0168 (8)
C4A
C5A
C6A
C11A
C21A
C31A
C41A
C42A
C51A
C61A
C62A
S1B
O11B
O12B
N1B
N2B
N3B
N41B
C2B
C4B
C5B
C6B
C11B
Acta Cryst. (2013). C69, 538-543
sup-4

supplementary materials
C21B
C31B
C41B
C42B
C51B
C61B
C62B
O2C
0.0412 (10)
0.0322 (9)
0.0374 (9)
0.0520 (11)
0.0443 (10)
0.0325 (9)
0.0421 (10)
0.0644 (9)
0.0451 (7)
0.0668 (9)
0.0772 (10)
0.1214 (15)
0.0386 (9)
0.0192 (7)
0.0273 (8)
0.0374 (9)
0.0267 (9)
0.0203 (8)
0.0210 (8)
0.0239 (8)
0.0902 (11)
0.0570 (8)
0.0757 (9)
0.0918 (11)
0.0656 (9)
0.0378 (8)
0.0268 (8)
0.0374 (9)
0.0490 (11)
0.0377 (9)
0.0261 (8)
0.0260 (8)
0.0302 (9)
0.0213 (8)
0.0254 (9)
0.0250 (9)
0.0261 (9)
0.0217 (8)
0.0260 (9)
0.0339 (10)
0.0274 (7)
0.0326 (7)
0.0249 (7)
0.0245 (7)
0.0410 (9)
0.0293 (9)
0.0252 (8)
0.0243 (9)
0.0339 (10)
0.0280 (9)
0.0248 (9)
0.0312 (9)
0.0279 (9)
0.0265 (7)
0.0265 (6)
0.0197 (6)
0.0228 (7)
0.0297 (7)
0.0219 (8)
0.0224 (8)
0.0232 (9)
0.0353 (10)
0.0270 (9)
0.0211 (8)
0.0253 (8)
0.0237 (9)
0.0224 (8)
0.0322 (9)
0.0274 (9)
0.0327 (10)
0.0236 (9)
0.0232 (8)
0.0279 (9)
0.0310 (7)
0.0269 (7)
0.0304 (7)
0.0686 (10)
0.0538 (10)
0.0545 (11)
0.0303 (9)
0.0303 (9)
0.0277 (9)
0.0415 (10)
0.0404 (10)
0.0290 (9)
0.0303 (9)
0.0283 (7)
0.0235 (6)
0.0320 (7)
0.0570 (9)
0.0373 (8)
0.0448 (10)
0.0246 (8)
0.0272 (9)
0.0230 (9)
0.0318 (10)
0.0311 (9)
0.0232 (8)
0.0278 (9)
−0.0014 (7)
−0.0033 (7)
0.0033 (7)
0.0004 (8)
−0.0025 (7)
−0.0030 (7)
−0.0030 (8)
−0.0040 (6)
−0.0026 (5)
−0.0046 (6)
0.0024 (6)
0.0047 (8)
0.0021 (7)
−0.0020 (6)
−0.0034 (7)
−0.0038 (8)
−0.0022 (7)
0.0005 (6)
0.0002 (6)
−0.0033 (7)
−0.0028 (7)
0.0013 (5)
0.0045 (6)
−0.0029 (7)
0.0035 (6)
−0.0005 (6)
−0.0019 (6)
−0.0029 (7)
−0.0057 (8)
−0.0042 (7)
−0.0018 (6)
0.0000 (6)
0.0009 (7)
0.0038 (7)
−0.0001 (7)
−0.0054 (7)
0.0047 (8)
−0.0012 (7)
0.0018 (7)
0.0045 (8)
0.0002 (6)
−0.0013 (5)
−0.0010 (6)
−0.0139 (8)
0.0094 (10)
−0.0038 (7)
−0.0025 (6)
−0.0013 (7)
−0.0007 (7)
−0.0015 (7)
−0.0012 (7)
−0.0004 (6)
−0.0020 (7)
0.0147 (7)
0.0009 (5)
0.0147 (6)
0.0057 (8)
−0.0029 (6)
−0.0030 (7)
0.0023 (6)
0.0065 (7)
0.0060 (8)
0.0011 (7)
−0.0009 (7)
0.0013 (6)
0.0032 (7)
0.0004 (7)
−0.0048 (7)
−0.0043 (7)
0.0043 (8)
0.0027 (7)
−0.0001 (7)
−0.0037 (8)
0.0009 (6)
0.0059 (5)
0.0051 (5)
0.0057 (7)
−0.0133 (8)
−0.0036 (8)
0.0049 (7)
0.0002 (7)
0.0058 (8)
0.0101 (8)
0.0011 (7)
−0.0013 (7)
0.0051 (7)
−0.0059 (6)
0.0034 (5)
0.0019 (5)
0.0089 (7)
−0.0090 (6)
0.0012 (7)
0.0013 (7)
−0.0016 (7)
0.0024 (7)
0.0084 (7)
0.0011 (7)
−0.0008 (7)
0.0019 (7)
O11C
O12C
O51C
O52C
N5C
C1C
C2C
C3C
C4C
C5C
C6C
C11C
O2D
O11D
O12D
O51D
O52D
N5D
C1D
C2D
C3D
C4D
C5D
C6D
C11D
Geometric parameters (Å, º)
S1A—O11A
S1A—O12A
S1A—N2A
S1A—C11A
S1B—O11B
S1B—O12B
S1B—N2B
1.4299 (11)
C5A—H5A
0.9500
1.4299 (12)
1.6770 (14)
1.7417 (16)
1.4287 (11)
1.4316 (12)
1.6726 (14)
1.7362 (15)
1.346 (2)
C21A—H21A
C31A—H31A
C42A—H45A
C42A—H43A
C42A—H44A
C51A—H51A
C61A—H61A
C62A—H65A
C62A—H63A
C62A—H64A
C4B—C5B
0.9500
0.9500
0.9800
0.9800
0.9800
0.9500
0.9500
0.9800
0.9800
0.9800
1.392 (2)
1.494 (2)
1.376 (2)
S1B—C11B
O2C—C2C
O11C—C11C
O12C—C11C
O51C—N5C
O52C—N5C
O2C—H2C
1.2408 (19)
1.2804 (19)
1.227 (2)
1.227 (2)
C4B—C42B
C5B—C6B
0.89 (3)
Acta Cryst. (2013). C69, 538-543
sup-5

supplementary materials
O2D—C2D
O11D—C11D
O12D—C11D
O51D—N5D
O52D—N5D
O2D—H2D
N1A—C2A
N1A—C6A
N2A—C2A
N3A—C4A
N3A—C2A
N41A—C41A
N1A—H1A
N2A—H2A
N41A—H41A
N41A—H42A
N1B—C6B
1.334 (2)
1.2378 (19)
1.2831 (19)
1.226 (2)
1.235 (2)
0.90 (2)
C6B—C62B
C11B—C21B
C11B—C61B
C21B—C31B
C31B—C41B
C41B—C51B
C51B—C61B
C5B—H5B
C21B—H21B
C31B—H31B
C42B—H45B
C42B—H44B
C42B—H43B
C51B—H51B
C61B—H61B
C62B—H65B
C62B—H63B
C62B—H64B
C1C—C11C
C1C—C6C
1.492 (2)
1.392 (2)
1.394 (2)
1.366 (2)
1.399 (2)
1.404 (2)
1.370 (2)
0.9500
1.350 (2)
1.3539 (19)
1.360 (2)
1.3473 (19)
1.3242 (19)
1.370 (2)
0.939 (18)
0.85 (2)
0.9500
0.9500
0.9800
0.9800
0.9800
0.9500
0.82 (3)
0.9500
0.89 (2)
0.9800
1.350 (2)
1.354 (2)
1.355 (2)
1.3264 (19)
1.344 (2)
1.367 (2)
0.91 (2)
0.9800
N1B—C2B
0.9800
N2B—C2B
1.501 (2)
1.386 (2)
1.410 (2)
1.400 (2)
1.367 (2)
1.393 (3)
1.380 (2)
0.9500
N3B—C2B
N3B—C4B
C1C—C2C
N41B—C41B
N1B—H1B
N2B—H2B
N41B—H41B
N41B—H42B
N5C—C5C
C2C—C3C
C3C—C4C
0.889 (19)
0.89 (2)
C4C—C5C
C5C—C6C
0.83 (2)
C3C—H3C
C4C—H4C
C6C—H6C
C1D—C6D
C1D—C11D
C1D—C2D
C2D—C3D
C3D—C4D
C4D—C5D
C5D—C6D
C3D—H3D
C4D—H4D
C6D—H6D
1.453 (2)
1.454 (2)
1.392 (2)
1.488 (2)
1.375 (2)
1.490 (2)
1.391 (2)
1.399 (2)
1.380 (2)
1.402 (2)
1.398 (2)
1.373 (2)
0.9500
N5D—C5D
C4A—C5A
C4A—C42A
C5A—C6A
C6A—C62A
C11A—C21A
C11A—C61A
C21A—C31A
C31A—C41A
C41A—C51A
C51A—C61A
0.9500
1.390 (2)
1.501 (2)
1.410 (2)
1.404 (2)
1.371 (2)
1.392 (2)
1.386 (2)
0.9500
0.9500
0.9500
O11A—S1A—O12A
O11A—S1A—N2A
O11A—S1A—C11A
O12A—S1A—N2A
O12A—S1A—C11A
N2A—S1A—C11A
O11B—S1B—N2B
O11B—S1B—C11B
O12B—S1B—N2B
O12B—S1B—C11B
120.00 (7)
108.70 (7)
108.90 (7)
101.64 (7)
109.63 (7)
107.13 (7)
108.92 (7)
110.08 (7)
101.66 (7)
110.30 (7)
N1B—C2B—N2B
N1B—C2B—N3B
N3B—C4B—C42B
C5B—C4B—C42B
N3B—C4B—C5B
C4B—C5B—C6B
N1B—C6B—C5B
C5B—C6B—C62B
N1B—C6B—C62B
116.83 (13)
123.20 (14)
115.81 (14)
122.33 (14)
121.86 (14)
119.06 (14)
117.86 (14)
124.49 (14)
117.64 (14)
S1B—C11B—C21B
119.10 (12)
Acta Cryst. (2013). C69, 538-543
sup-6

supplementary materials
N2B—S1B—C11B
O11B—S1B—O12B
C2C—O2C—H2C
C2D—O2D—H2D
C2A—N1A—C6A
S1A—N2A—C2A
C2A—N3A—C4A
C6A—N1A—H1A
C2A—N1A—H1A
S1A—N2A—H2A
C2A—N2A—H2A
C41A—N41A—H41A
H41A—N41A—H42A
C41A—N41A—H42A
C2B—N1B—C6B
S1B—N2B—C2B
105.78 (7)
119.02 (7)
105.0 (17)
105.7 (14)
120.37 (13)
123.73 (11)
117.13 (13)
118.6 (12)
121.1 (12)
116.0 (13)
119.1 (14)
119.8 (16)
118 (2)
S1B—C11B—C61B
120.80 (12)
120.10 (14)
119.84 (14)
120.97 (15)
118.65 (14)
120.92 (15)
120.41 (15)
120.48 (14)
119.93 (14)
120.00
C21B—C11B—C61B
C11B—C21B—C31B
C21B—C31B—C41B
C31B—C41B—C51B
N41B—C41B—C51B
N41B—C41B—C31B
C41B—C51B—C61B
C11B—C61B—C51B
C4B—C5B—H5B
C6B—C5B—H5B
120.00
C31B—C21B—H21B
C11B—C21B—H21B
C21B—C31B—H31B
C41B—C31B—H31B
C4B—C42B—H43B
C4B—C42B—H44B
H43B—C42B—H44B
C4B—C42B—H45B
H44B—C42B—H45B
H43B—C42B—H45B
C61B—C51B—H51B
C41B—C51B—H51B
C11B—C61B—H61B
C51B—C61B—H61B
H63B—C62B—H65B
H64B—C62B—H65B
C6B—C62B—H64B
H63B—C62B—H64B
C6B—C62B—H65B
C6B—C62B—H63B
C2C—C1C—C11C
C6C—C1C—C11C
C2C—C1C—C6C
120.00
120.00
114.8 (14)
120.75 (14)
123.29 (11)
117.23 (13)
120.0 (13)
119.2 (13)
123.3 (13)
113.2 (13)
118.5 (14)
113.6 (15)
126 (2)
120.00
120.00
109.00
C2B—N3B—C4B
C6B—N1B—H1B
C2B—N1B—H1B
C2B—N2B—H2B
S1B—N2B—H2B
109.00
109.00
110.00
110.00
109.00
C41B—N41B—H42B
C41B—N41B—H41B
H41B—N41B—H42B
O51C—N5C—C5C
O52C—N5C—C5C
O51C—N5C—O52C
O51D—N5D—O52D
O51D—N5D—C5D
O52D—N5D—C5D
N2A—C2A—N3A
N1A—C2A—N2A
N1A—C2A—N3A
N3A—C4A—C5A
N3A—C4A—C42A
C5A—C4A—C42A
C4A—C5A—C6A
N1A—C6A—C62A
N1A—C6A—C5A
C5A—C6A—C62A
S1A—C11A—C61A
S1A—C11A—C21A
C21A—C11A—C61A
C11A—C21A—C31A
C21A—C31A—C41A
N41A—C41A—C51A
N41A—C41A—C31A
C31A—C41A—C51A
C41A—C51A—C61A
120.00
120.00
120.00
118.80 (16)
118.44 (15)
122.77 (15)
122.88 (14)
118.78 (15)
118.33 (13)
119.57 (14)
116.84 (13)
123.59 (13)
121.85 (14)
116.05 (14)
122.10 (14)
118.89 (14)
117.56 (13)
118.17 (14)
124.25 (14)
120.29 (12)
119.64 (12)
120.07 (14)
119.73 (15)
120.69 (16)
121.05 (15)
120.09 (16)
118.82 (15)
120.76 (14)
120.00
109.00
109.00
109.00
109.00
110.00
110.00
121.10 (14)
120.09 (14)
118.81 (14)
117.41 (14)
120.42 (15)
122.18 (14)
120.33 (16)
118.77 (16)
119.24 (15)
122.26 (15)
118.49 (15)
119.41 (15)
116.00 (13)
124.26 (14)
119.73 (14)
120.00
O2C—C2C—C3C
C1C—C2C—C3C
O2C—C2C—C1C
C2C—C3C—C4C
C3C—C4C—C5C
N5C—C5C—C6C
C4C—C5C—C6C
N5C—C5C—C4C
C1C—C6C—C5C
O12C—C11C—C1C
O11C—C11C—O12C
O11C—C11C—C1C
C2C—C3C—H3C
C4C—C3C—H3C
120.00
C5C—C4C—H4C
121.00
Acta Cryst. (2013). C69, 538-543
sup-7

supplementary materials
C11A—C61A—C51A
C6A—C5A—H5A
119.92 (15)
121.00
121.00
120.00
120.00
120.00
120.00
110.00
109.00
109.00
109.00
109.00
109.00
120.00
120.00
120.00
120.00
109.00
109.00
109.00
109.00
110.00
109.00
119.97 (14)
C3C—C4C—H4C
C1C—C6C—H6C
C5C—C6C—H6C
121.00
120.00
120.00
C4A—C5A—H5A
C31A—C21A—H21A
C11A—C21A—H21A
C41A—C31A—H31A
C21A—C31A—H31A
H43A—C42A—H45A
C4A—C42A—H44A
H44A—C42A—H45A
C4A—C42A—H43A
C4A—C42A—H45A
H43A—C42A—H44A
C61A—C51A—H51A
C41A—C51A—H51A
C51A—C61A—H61A
C11A—C61A—H61A
C6A—C62A—H63A
C6A—C62A—H64A
H63A—C62A—H64A
H64A—C62A—H65A
C6A—C62A—H65A
H63A—C62A—H65A
N2B—C2B—N3B
C2D—C1D—C11D
C6D—C1D—C11D
C2D—C1D—C6D
O2D—C2D—C1D
O2D—C2D—C3D
C1D—C2D—C3D
C2D—C3D—C4D
C3D—C4D—C5D
N5D—C5D—C6D
C4D—C5D—C6D
N5D—C5D—C4D
C1D—C6D—C5D
O11D—C11D—C1D
O12D—C11D—C1D
O11D—C11D—O12D
C2D—C3D—H3D
C4D—C3D—H3D
C3D—C4D—H4D
C5D—C4D—H4D
C1D—C6D—H6D
C5D—C6D—H6D
121.32 (14)
119.92 (14)
118.77 (14)
122.23 (14)
117.38 (14)
120.39 (15)
120.31 (16)
118.98 (16)
119.27 (14)
121.93 (15)
118.78 (14)
119.61 (14)
120.77 (14)
115.61 (13)
123.62 (14)
120.00
120.00
120.00
121.00
120.00
120.00
O11A—S1A—N2A—C2A
O12A—S1A—N2A—C2A
C11A—S1A—N2A—C2A
O11A—S1A—C11A—C21A
O11A—S1A—C11A—C61A
O12A—S1A—C11A—C21A
O12A—S1A—C11A—C61A
N2A—S1A—C11A—C21A
N2A—S1A—C11A—C61A
N2B—S1B—C11B—C21B
N2B—S1B—C11B—C61B
O11B—S1B—N2B—C2B
O12B—S1B—N2B—C2B
C11B—S1B—N2B—C2B
O11B—S1B—C11B—C21B
O11B—S1B—C11B—C61B
O12B—S1B—C11B—C21B
O12B—S1B—C11B—C61B
C2A—N1A—C6A—C5A
C2A—N1A—C6A—C62A
C6A—N1A—C2A—N3A
C6A—N1A—C2A—N2A
S1A—N2A—C2A—N3A
S1A—N2A—C2A—N1A
−51.52 (14)
−179.01 (12)
66.00 (14)
−160.97 (12)
18.27 (15)
−27.88 (15)
151.36 (13)
81.64 (14)
−99.12 (14)
−78.04 (14)
102.11 (14)
59.70 (14)
−173.83 (12)
−58.59 (14)
164.44 (12)
−15.41 (15)
31.14 (15)
−148.71 (13)
0.00 (19)
C11A—C21A—C31A—C41A
C21A—C31A—C41A—C51A
C21A—C31A—C41A—N41A
N41A—C41A—C51A—C61A
C31A—C41A—C51A—C61A
C41A—C51A—C61A—C11A
C42B—C4B—C5B—C6B
N3B—C4B—C5B—C6B
−1.7 (2)
1.4 (2)
−176.06 (16)
177.13 (16)
−0.3 (2)
−0.5 (2)
178.39 (15)
−1.7 (2)
C4B—C5B—C6B—C62B
C4B—C5B—C6B—N1B
−179.08 (15)
0.0 (2)
C21B—C11B—C61B—C51B
S1B—C11B—C21B—C31B
C61B—C11B—C21B—C31B
S1B—C11B—C61B—C51B
C11B—C21B—C31B—C41B
C21B—C31B—C41B—C51B
C21B—C31B—C41B—N41B
C31B—C41B—C51B—C61B
N41B—C41B—C51B—C61B
C41B—C51B—C61B—C11B
C6C—C1C—C2C—O2C
−0.7 (2)
−178.54 (12)
1.3 (2)
179.14 (12)
−0.2 (2)
−1.4 (2)
176.95 (16)
2.0 (2)
−176.33 (16)
−1.0 (2)
−178.53 (13)
0.2 (2)
178.79 (14)
−1.2 (2)
179.44 (13)
−12.4 (2)
C6C—C1C—C2C—C3C
C2C—C1C—C11C—O11C
C2C—C1C—C11C—O12C
−177.96 (14)
1.8 (2)
168.33 (11)
Acta Cryst. (2013). C69, 538-543
sup-8

supplementary materials
C2A—N3A—C4A—C5A
C4A—N3A—C2A—N1A
C4A—N3A—C2A—N2A
C2A—N3A—C4A—C42A
C6B—N1B—C2B—N3B
C2B—N1B—C6B—C5B
C6B—N1B—C2B—N2B
C2B—N1B—C6B—C62B
S1B—N2B—C2B—N1B
S1B—N2B—C2B—N3B
C2B—N3B—C4B—C5B
C2B—N3B—C4B—C42B
C4B—N3B—C2B—N2B
C4B—N3B—C2B—N1B
O51C—N5C—C5C—C6C
O51C—N5C—C5C—C4C
O52C—N5C—C5C—C4C
O52C—N5C—C5C—C6C
O51D—N5D—C5D—C6D
O52D—N5D—C5D—C6D
O51D—N5D—C5D—C4D
O52D—N5D—C5D—C4D
N3A—C4A—C5A—C6A
C42A—C4A—C5A—C6A
C4A—C5A—C6A—C62A
C4A—C5A—C6A—N1A
C21A—C11A—C61A—C51A
S1A—C11A—C61A—C51A
S1A—C11A—C21A—C31A
C61A—C11A—C21A—C31A
−0.9 (2)
C6C—C1C—C11C—O11C
1.9 (2)
0.3 (2)
C6C—C1C—C11C—O12C
C11C—C1C—C2C—O2C
C11C—C1C—C2C—C3C
C2C—C1C—C6C—C5C
C11C—C1C—C6C—C5C
O2C—C2C—C3C—C4C
C1C—C2C—C3C—C4C
C2C—C3C—C4C—C5C
C3C—C4C—C5C—C6C
C3C—C4C—C5C—N5C
N5C—C5C—C6C—C1C
C4C—C5C—C6C—C1C
C6D—C1D—C2D—O2D
C6D—C1D—C2D—C3D
C11D—C1D—C2D—O2D
C11D—C1D—C2D—C3D
C2D—C1D—C6D—C5D
C11D—C1D—C6D—C5D
C2D—C1D—C11D—O11D
C2D—C1D—C11D—O12D
C6D—C1D—C11D—O11D
C6D—C1D—C11D—O12D
O2D—C2D—C3D—C4D
C1D—C2D—C3D—C4D
C2D—C3D—C4D—C5D
C3D—C4D—C5D—N5D
C3D—C4D—C5D—C6D
N5D—C5D—C6D—C1D
C4D—C5D—C6D—C1D
−178.37 (14)
−1.4 (2)
−178.99 (13)
178.67 (14)
0.2 (2)
178.65 (14)
1.0 (2)
0.7 (2)
−178.79 (13)
−179.05 (14)
0.9 (2)
−178.90 (13)
179.89 (13)
176.82 (10)
−2.3 (2)
−0.5 (2)
0.4 (2)
2.5 (2)
179.12 (14)
−179.38 (13)
−0.7 (2)
−177.57 (14)
177.27 (13)
−1.8 (2)
179.26 (15)
−0.2 (2)
178.18 (15)
−0.6 (2)
−0.5 (2)
179.97 (16)
−1.3 (2)
−180.00 (15)
−0.8 (2)
176.04 (15)
−2.8 (2)
179.02 (14)
−179.30 (15)
1.1 (2)
−2.9 (2)
178.27 (14)
1.0 (2)
0.9 (2)
−178.73 (14)
−178.60 (15)
0.9 (2)
−178.48 (15)
177.87 (14)
−0.6 (2)
−0.6 (2)
0.3 (2)
178.47 (14)
−0.4 (2)
−178.96 (12)
−179.96 (13)
0.8 (2)
−177.77 (13)
1.1 (2)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1A—H1A···O12D
N1B—H1B···O12C
N2A—H2A···O11D
N2B—H2B···O11C
N41A—H41A···O11Di
N41B—H41B···O2Cii
N41B—H42B···O12Biii
O2C—H2C···O12C
O2D—H2D···O12D
C5A—H5A···O52Div
C5B—H5B···O51Cv
C5B—H5B···O52Cv
C42A—H43A···O52Div
0.939 (18)
0.91 (2)
0.85 (2)
0.889 (19)
0.82 (3)
0.89 (2)
0.83 (2)
0.89 (3)
0.90 (2)
0.95
1.647 (18)
1.71 (2)
1.94 (2)
1.836 (19)
2.57 (2)
2.49 (2)
2.45 (2)
1.70 (3)
1.70 (2)
2.56
2.5847 (17)
2.6162 (18)
2.7810 (18)
2.7221 (18)
3.217 (2)
176 (2)
176.4 (18)
177 (2)
174.3 (18)
138 (2)
147 (2)
136.6 (18)
152 (2)
151 (2)
150
3.269 (2)
3.106 (2)
2.5223 (17)
2.5215 (17)
3.4175 (19)
3.348 (2)
0.95
2.44
160
0.95
2.58
3.420 (2)
147
0.98
2.49
3.428 (2)
159
Acta Cryst. (2013). C69, 538-543
sup-9

supplementary materials
C42B—H45B···O52Cv
C61A—H61A···O11A
0.98
0.95
2.42
2.59
3.350 (2)
158
102
2.9422 (19)
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+3/2, y+1/2, −z+3/2; (iv) x, y−1, z; (v) x, y+1, z.
(II) 2-(4-Aminobenzenesulfonamido)-4,6-dimethylpyrimidinium 2,4,6-trinitrophenolate
Crystal data
C12H15N4O2S+·C6H2N3O7−
Mr = 507.45
F(000) = 1048
Dx = 1.584 Mg m−3
Melting point = 469–471 K
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 7676 reflections
θ = 3.2–28.8°
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 8.3131 (2) Å
b = 19.2779 (5) Å
c = 13.4483 (4) Å
β = 99.158 (3)°
µ = 0.22 mm−1
T = 200 K
Block, yellow
0.35 × 0.35 × 0.26 mm
V = 2127.74 (10) Å3
Z = 4
Data collection
Oxford Gemini-S CCD area-detector
diffractometer
Radiation source: Enhance (Mo) X-ray source
Graphite monochromator
Detector resolution: 16.077 pixels mm-1
ω scans
14211 measured reflections
4171 independent reflections
3318 reflections with I > 2σ(I)
Rint = 0.024
θmax = 26.0°, θmin = 3.3°
h = −8→10
k = −23→23
l = −15→16
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
T
min = 0.970, Tmax = 0.981
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.034
wR(F2) = 0.091
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.04
4171 reflections
334 parameters
0 restraints
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0541P)2 + 0.1041P]
where P = (Fo2 + 2Fc2)/3
Primary atom site location: structure-invariant
direct methods
(Δ/σ)max = 0.005
Δρmax = 0.27 e Å−3
Δρmin = −0.42 e Å−3
Special details
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are
estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the
estimation of distances, angles and torsion angles
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Acta Cryst. (2013). C69, 538-543
sup-10

supplementary materials
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Occ. (<1)
S1A
O11A
O12A
N1A
N2A
N3A
N41A
C2A
C4A
C5A
C6A
C11A
C21A
C31A
C41A
C42A
C51A
C61A
C62A
O1
1.01736 (5)
1.01403 (16)
0.91002 (15)
0.81196 (16)
0.96357 (18)
0.95185 (16)
1.6891 (2)
0.90857 (19)
0.89632 (19)
0.79877 (19)
0.75510 (18)
1.2145 (2)
1.3454 (2)
1.5022 (2)
1.5335 (2)
0.9460 (2)
1.4001 (2)
1.2436 (2)
0.6501 (2)
0.81506 (14)
0.51094 (17)
0.35141 (16)
0.33961 (17)
0.56354 (17)
1.06573 (16)
1.06389 (16)
0.46886 (17)
0.48456 (19)
0.99501 (17)
0.7383 (2)
0.56423 (19)
0.4795 (2)
0.5685 (2)
0.7370 (2)
0.81761 (19)
1.706 (3)
0.72633 (2)
0.74900 (6)
0.75680 (6)
0.54828 (6)
0.64262 (7)
0.61463 (7)
0.73736 (9)
0.60189 (8)
0.57061 (8)
0.51355 (8)
0.50281 (8)
0.72872 (8)
0.72025 (8)
0.72321 (9)
0.73431 (8)
0.58500 (9)
0.74275 (8)
0.73988 (8)
0.44540 (9)
0.55856 (6)
0.58897 (8)
0.52229 (7)
0.59866 (9)
0.63473 (7)
0.58522 (8)
0.62078 (8)
0.56092 (7)
0.61225 (8)
0.59915 (8)
0.57497 (8)
0.57448 (8)
0.58495 (8)
0.60005 (8)
0.60378 (8)
0.59217 (8)
0.7434 (12)
0.5461 (10)
0.6323 (10)
0.48260
0.40874 (3)
0.30725 (10)
0.46966 (11)
0.42730 (11)
0.39275 (12)
0.56049 (10)
0.62678 (16)
0.46347 (13)
0.62539 (13)
0.59168 (13)
0.49024 (13)
0.47392 (13)
0.42106 (13)
0.47158 (14)
0.57572 (13)
0.73449 (13)
0.62754 (14)
0.57729 (13)
0.44236 (15)
0.23824 (9)
0.28921 (10)
0.18893 (11)
−0.16549 (11)
−0.20899 (10)
0.01325 (11)
0.16560 (11)
0.20714 (11)
−0.14630 (12)
0.08397 (12)
0.15227 (12)
0.12657 (12)
0.03122 (13)
−0.04467 (13)
−0.02677 (13)
0.06853 (13)
0.693 (2)
0.0286 (1)
0.0411 (4)
0.0381 (4)
0.0240 (4)
0.0289 (5)
0.0254 (4)
0.0419 (6)
0.0232 (5)
0.0247 (5)
0.0267 (5)
0.0244 (5)
0.0250 (5)
0.0300 (6)
0.0317 (6)
0.0275 (5)
0.0337 (6)
0.0299 (6)
0.0280 (5)
0.0326 (6)
0.0327 (4)
0.0483 (5)
0.0455 (5)
0.0573 (6)
0.0476 (5)
0.0492 (5)
0.0482 (5)
0.0301 (5)
0.0343 (5)
0.0333 (5)
0.0248 (5)
0.0236 (5)
0.0251 (5)
0.0256 (5)
0.0253 (5)
0.0259 (5)
0.061 (8)*
0.048 (6)*
0.037 (6)*
0.0320*
O21
O22
O41
O42
O61
O62
N2
N4
N6
C1
C2
C3
C4
C5
C6
H42A
H1A
H2A
H5A
H21A
H31A
H41A
H48A
H43A
H44A
H45A
H46A
0.784 (3)
0.3591 (17)
0.3307 (16)
0.63860
0.943 (2)
0.76320
1.32560
0.71250
0.35040
0.0360*
1.59070
0.71770
0.43540
0.0380*
1.771 (3)
0.7388 (10)
0.57810
0.5900 (16)
0.75290
0.039 (6)*
0.0510*
1.06370
0.500
0.500
0.500
0.500
0.500
0.88850
0.55330
0.77380
0.0510*
0.91840
0.63300
0.74880
0.0510*
0.85000
0.59820
0.76410
0.0510*
1.02530
0.62300
0.74320
0.0510*
Acta Cryst. (2013). C69, 538-543
sup-11

supplementary materials
H47A
H51A
H61A
H62A
H63A
H64A
H3
0.99530
1.41910
1.15470
0.61050
0.71360
0.55710
0.36400
0.79580
0.54330
0.75050
0.74550
0.41780
0.41570
0.46490
0.58190
0.61430
0.76820
0.69820
0.61310
0.49470
0.40390
0.39700
0.01800
−0.08000
0.0510*
0.0360*
0.0340*
0.0490*
0.0490*
0.0490*
0.0300*
0.0300*
0.500
H5
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
S1A
O11A
O12A
N1A
N2A
N3A
N41A
C2A
C4A
C5A
C6A
C11A
C21A
C31A
C41A
C42A
C51A
C61A
C62A
O1
0.0292 (2)
0.0486 (8)
0.0287 (7)
0.0241 (7)
0.0349 (8)
0.0256 (7)
0.0290 (9)
0.0207 (8)
0.0212 (8)
0.0256 (9)
0.0194 (8)
0.0264 (9)
0.0348 (10)
0.0284 (9)
0.0274 (9)
0.0379 (10)
0.0354 (10)
0.0297 (9)
0.0301 (9)
0.0325 (7)
0.0460 (8)
0.0446 (8)
0.0370 (9)
0.0496 (8)
0.0303 (7)
0.0344 (8)
0.0314 (8)
0.0355 (9)
0.0261 (8)
0.0303 (9)
0.0262 (9)
0.0227 (8)
0.0317 (10)
0.0301 (9)
0.0239 (9)
0.0220 (2)
0.0353 (7)
0.0291 (7)
0.0244 (7)
0.0273 (8)
0.0250 (7)
0.0555 (11)
0.0210 (8)
0.0267 (8)
0.0267 (9)
0.0221 (8)
0.0203 (8)
0.0327 (9)
0.0350 (10)
0.0221 (8)
0.0370 (10)
0.0295 (9)
0.0255 (9)
0.0283 (9)
0.0420 (7)
0.0731 (10)
0.0470 (8)
0.0912 (12)
0.0635 (9)
0.0740 (10)
0.0657 (9)
0.0318 (8)
0.0371 (8)
0.0386 (8)
0.0217 (8)
0.0225 (8)
0.0225 (8)
0.0227 (8)
0.0234 (8)
0.0248 (8)
0.0337 (3)
0.0360 (8)
0.0572 (9)
0.0228 (8)
0.0241 (9)
0.0253 (8)
0.0403 (11)
0.0280 (9)
0.0265 (9)
0.0292 (10)
0.0323 (10)
0.0286 (10)
0.0236 (10)
0.0347 (11)
0.0330 (10)
0.0266 (10)
0.0250 (10)
0.0309 (10)
0.0390 (11)
0.0225 (7)
0.0279 (8)
0.0493 (9)
0.0393 (9)
0.0298 (8)
0.0462 (9)
0.0420 (9)
0.0288 (9)
0.0288 (9)
0.0353 (9)
0.0224 (9)
0.0232 (9)
0.0298 (10)
0.0220 (9)
0.0240 (9)
0.0291 (10)
−0.0017 (2)
−0.0070 (6)
0.0035 (5)
−0.0015 (5)
−0.0086 (6)
−0.0006 (6)
−0.0033 (7)
0.0009 (6)
0.0051 (6)
0.0008 (6)
0.0012 (6)
−0.0028 (6)
−0.0052 (7)
−0.0029 (7)
−0.0024 (6)
−0.0003 (8)
0.0003 (7)
0.0010 (7)
−0.0059 (7)
−0.0006 (5)
0.0014 (7)
−0.0146 (6)
−0.0111 (8)
0.0009 (7)
0.0036 (6)
−0.0154 (6)
0.0044 (6)
0.0012 (7)
−0.0043 (6)
−0.0014 (6)
−0.0015 (6)
−0.0015 (6)
−0.0001 (7)
−0.0030 (6)
−0.0034 (6)
0.0023 (2)
0.0062 (2)
0.0162 (6)
0.0007 (6)
0.0012 (6)
0.0022 (6)
−0.0002 (6)
0.0042 (8)
0.0006 (6)
0.0011 (7)
0.0049 (7)
0.0031 (7)
0.0032 (7)
0.0015 (7)
0.0017 (8)
0.0032 (7)
−0.0009 (8)
−0.0021 (7)
−0.0023 (7)
−0.0008 (8)
0.0029 (5)
−0.0108 (7)
0.0014 (6)
0.0123 (8)
0.0190 (7)
0.0032 (7)
−0.0027 (7)
0.0029 (6)
0.0043 (7)
0.0052 (7)
−0.0030 (6)
−0.0004 (6)
−0.0005 (7)
0.0003 (7)
0.0010 (7)
−0.0011 (7)
−0.0037 (6)
0.0089 (6)
0.0016 (6)
0.0034 (7)
0.0036 (6)
0.0029 (8)
0.0045 (7)
0.0050 (7)
0.0089 (7)
0.0061 (7)
0.0054 (7)
0.0084 (7)
0.0138 (8)
0.0045 (7)
0.0064 (8)
0.0051 (8)
0.0114 (8)
0.0041 (8)
0.0009 (5)
0.0127 (6)
0.0213 (7)
−0.0076 (7)
0.0071 (7)
0.0153 (7)
−0.0012 (6)
0.0097 (7)
0.0008 (7)
0.0050 (7)
0.0042 (7)
0.0075 (7)
0.0030 (7)
0.0027 (7)
0.0090 (7)
0.0046 (7)
O21
O22
O41
O42
O61
O62
N2
N4
N6
C1
C2
C3
C4
C5
C6
Acta Cryst. (2013). C69, 538-543
sup-12

supplementary materials
Geometric parameters (Å, º)
S1A—O11A
S1A—O12A
S1A—N2A
S1A—C11A
O1—C1
1.4292 (14)
1.4301 (14)
1.6792 (14)
1.7318 (17)
1.269 (2)
1.229 (2)
1.221 (2)
1.220 (2)
1.227 (2)
1.225 (2)
1.228 (2)
1.351 (2)
1.355 (2)
1.367 (2)
1.350 (2)
1.320 (2)
1.366 (2)
0.91 (2)
C11A—C61A
C11A—C21A
C21A—C31A
C31A—C41A
C41A—C51A
C51A—C61A
C5A—H5A
C21A—H21A
C31A—H31A
C42A—H44A
C42A—H48A
C42A—H43A
C42A—H47A
C42A—H45A
C42A—H46A
C51A—H51A
C61A—H61A
C62A—H62A
C62A—H63A
C62A—H64A
C1—C2
1.389 (2)
1.401 (2)
1.372 (2)
1.400 (3)
1.410 (2)
1.368 (2)
0.9500
O21—N2
O22—N2
O41—N4
0.9500
O42—N4
0.9500
O61—N6
0.9800
O62—N6
0.9800
N1A—C2A
N1A—C6A
N2A—C2A
N3A—C4A
N3A—C2A
N41A—C41A
N1A—H1A
N2A—H2A
N41A—H42A
N41A—H41A
N2—C2
0.9800
0.9800
0.9800
0.9800
0.9500
0.9500
0.9800
0.85 (2)
0.9800
0.89 (3)
0.9800
0.90 (2)
1.433 (2)
1.432 (2)
1.376 (2)
1.384 (2)
1.385 (2)
1.367 (2)
0.9500
1.464 (2)
1.451 (2)
1.462 (2)
1.399 (2)
1.486 (2)
1.370 (2)
1.491 (2)
C1—C6
N4—C4
C2—C3
N6—C6
C3—C4
C4A—C5A
C4A—C42A
C5A—C6A
C6A—C62A
C4—C5
C5—C6
C3—H3
C5—H5
0.9500
O11A—S1A—O12A
O11A—S1A—N2A
O11A—S1A—C11A
O12A—S1A—N2A
O12A—S1A—C11A
N2A—S1A—C11A
C2A—N1A—C6A
S1A—N2A—C2A
C2A—N3A—C4A
C6A—N1A—H1A
C2A—N1A—H1A
C2A—N2A—H2A
S1A—N2A—H2A
H42A—N41A—H41A
C41A—N41A—H42A
C41A—N41A—H41A
O22—N2—C2
120.16 (8)
101.96 (8)
110.38 (8)
106.88 (7)
109.00 (8)
107.56 (8)
121.10 (15)
125.08 (13)
117.03 (14)
122.8 (14)
116.1 (14)
120.8 (13)
111.1 (13)
122 (2)
C4A—C5A—H5A
120.00
C11A—C21A—H21A
C31A—C21A—H21A
C41A—C31A—H31A
C21A—C31A—H31A
H43A—C42A—H44A
H45A—C42A—H46A
H45A—C42A—H47A
H46A—C42A—H47A
C4A—C42A—H47A
H48A—C42A—H43A
H48A—C42A—H44A
C4A—C42A—H43A
C4A—C42A—H44A
C4A—C42A—H45A
C4A—C42A—H46A
C4A—C42A—H48A
C41A—C51A—H51A
C61A—C51A—H51A
120.00
120.00
120.00
120.00
109.00
109.00
109.00
110.00
109.00
109.00
110.00
109.00
109.00
109.00
109.00
109.00
120.00
120.00
119.8 (16)
117.5 (14)
118.04 (14)
123.55 (15)
118.41 (14)
O21—N2—O22
O21—N2—C2
Acta Cryst. (2013). C69, 538-543
sup-13

supplementary materials
O42—N4—C4
118.33 (15)
123.30 (16)
118.36 (15)
123.76 (15)
118.33 (15)
117.87 (15)
120.80 (15)
115.75 (15)
123.44 (15)
116.81 (14)
121.51 (15)
121.67 (15)
119.31 (15)
116.68 (15)
117.43 (14)
125.89 (15)
119.28 (13)
120.71 (13)
120.01 (16)
119.83 (16)
120.84 (16)
118.47 (16)
121.33 (16)
120.20 (17)
120.80 (17)
120.06 (16)
120.00
C51A—C61A—H61A
120.00
O41—N4—O42
C11A—C61A—H61A
C6A—C62A—H63A
C6A—C62A—H64A
H62A—C62A—H64A
H63A—C62A—H64A
H62A—C62A—H63A
C6A—C62A—H62A
O1—C1—C2
120.00
O41—N4—C4
110.00
O61—N6—O62
109.00
O62—N6—C6
109.00
O61—N6—C6
109.00
N2A—C2A—N3A
N1A—C2A—N2A
N1A—C2A—N3A
N3A—C4A—C42A
C5A—C4A—C42A
N3A—C4A—C5A
C4A—C5A—C6A
N1A—C6A—C62A
N1A—C6A—C5A
C5A—C6A—C62A
S1A—C11A—C21A
S1A—C11A—C61A
C21A—C11A—C61A
C11A—C21A—C31A
C21A—C31A—C41A
C31A—C41A—C51A
N41A—C41A—C31A
N41A—C41A—C51A
C41A—C51A—C61A
C11A—C61A—C51A
C6A—C5A—H5A
109.00
109.00
124.07 (15)
123.16 (15)
112.68 (14)
117.87 (14)
117.30 (14)
124.83 (15)
117.63 (15)
119.69 (15)
118.47 (15)
121.84 (16)
119.07 (16)
119.34 (15)
116.80 (15)
123.86 (15)
121.00
O1—C1—C6
C2—C1—C6
N2—C2—C1
N2—C2—C3
C1—C2—C3
C2—C3—C4
N4—C4—C3
N4—C4—C5
C3—C4—C5
C4—C5—C6
N6—C6—C1
N6—C6—C5
C1—C6—C5
C2—C3—H3
C4—C3—H3
121.00
C4—C5—H5
120.00
C6—C5—H5
120.00
O11A—S1A—N2A—C2A
O12A—S1A—N2A—C2A
C11A—S1A—N2A—C2A
O11A—S1A—C11A—C21A
O11A—S1A—C11A—C61A
O12A—S1A—C11A—C21A
O12A—S1A—C11A—C61A
N2A—S1A—C11A—C21A
N2A—S1A—C11A—C61A
C6A—N1A—C2A—N2A
C6A—N1A—C2A—N3A
C2A—N1A—C6A—C5A
C2A—N1A—C6A—C62A
S1A—N2A—C2A—N1A
S1A—N2A—C2A—N3A
C4A—N3A—C2A—N1A
C4A—N3A—C2A—N2A
C2A—N3A—C4A—C5A
C2A—N3A—C4A—C42A
O21—N2—C2—C3
−162.41 (14)
−35.47 (17)
81.46 (16)
−28.19 (15)
150.90 (13)
−162.20 (12)
16.88 (15)
82.26 (14)
−98.65 (14)
177.49 (14)
−1.2 (2)
N3A—C4A—C5A—C6A
C42A—C4A—C5A—C6A
C4A—C5A—C6A—C62A
C4A—C5A—C6A—N1A
S1A—C11A—C21A—C31A
C61A—C11A—C21A—C31A
S1A—C11A—C61A—C51A
C21A—C11A—C61A—C51A
C11A—C21A—C31A—C41A
C21A—C31A—C41A—C51A
C21A—C31A—C41A—N41A
C31A—C41A—C51A—C61A
N41A—C41A—C51A—C61A
C41A—C51A—C61A—C11A
O1—C1—C2—N2
−1.5 (2)
179.47 (15)
−178.97 (15)
1.0 (2)
178.90 (13)
−0.2 (2)
−178.95 (12)
0.1 (2)
0.3 (2)
−0.3 (2)
−180.00 (16)
0.3 (2)
0.3 (2)
−179.73 (14)
154.00 (12)
−27.3 (2)
179.94 (16)
−0.2 (2)
6.3 (2)
0.7 (2)
O1—C1—C2—C3
−172.77 (15)
−177.07 (13)
3.8 (2)
−177.96 (15)
0.7 (2)
C6—C1—C2—N2
C6—C1—C2—C3
179.73 (14)
−138.41 (16)
−137.67 (15)
O1—C1—C6—N6
−7.2 (2)
O1—C1—C6—C5
173.80 (15)
176.16 (14)
O22—N2—C2—C1
C2—C1—C6—N6
Acta Cryst. (2013). C69, 538-543
sup-14

supplementary materials
O22—N2—C2—C3
O21—N2—C2—C1
O41—N4—C4—C3
O42—N4—C4—C3
O42—N4—C4—C5
O41—N4—C4—C5
O61—N6—C6—C5
O62—N6—C6—C1
O62—N6—C6—C5
O61—N6—C6—C1
41.5 (2)
C2—C1—C6—C5
N2—C2—C3—C4
C1—C2—C3—C4
C2—C3—C4—N4
C2—C3—C4—C5
N4—C4—C5—C6
C3—C4—C5—C6
C4—C5—C6—N6
C4—C5—C6—C1
−2.8 (2)
42.4 (2)
177.92 (14)
−3.0 (2)
−10.9 (2)
170.19 (15)
−10.0 (2)
168.93 (16)
−30.7 (2)
−32.2 (2)
146.91 (16)
150.26 (16)
−179.35 (14)
0.8 (2)
−179.78 (14)
0.0 (2)
−177.92 (14)
1.1 (2)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1A—H1A···O1
N1A—H1A···O21
N2A—H2A···O1
N2A—H2A···O62
N41A—H41A···O12Ai
0.91 (2)
0.91 (2)
0.85 (2)
0.85 (2)
0.90 (2)
1.70 (2)
2.46 (2)
2.07 (2)
2.59 (2)
2.16 (2)
2.5545 (19)
2.974 (2)
154 (2)
116.2 (18)
139.2 (17)
145.0 (15)
163 (2)
2.7661 (19)
3.319 (2)
3.035 (2)
Symmetry code: (i) x+1, y, z.
Acta Cryst. (2013). C69, 538-543
sup-15