Synthesis, crystal structure and studies on the interaction with albumin of a new silver(I) complex base on 2-(4-nitrobenzenesulfonamido)benzoic acid

Article abstract of DOI:10.1107/S2053229619008593

In the present work, the two-dimensional (2D) polymer poly[[μ4-2-(4-nitrobenzenesulfonamido)benzoato-κ4 O 1:O 1:O 1′:N 6]silver(I)] (AgL), [Ag(C13H9N2O6S)] n , was obtained from 2-(4-nitrobenzenesulfonamido)benzoic acid (HL), C13H10N2O6S. FT-IR, 1H and 13

Full text of DOI:10.1107/S2053229619008593

research papers
Synthesis, crystal structure and studies on the
interaction with albumin of a new silver(I) complex
based on 2-(4-nitrobenzenesulfonamido)benzoic
acid
ISSN 2053-2296
Lucius Flavius Ourives Bomfim Filho, Cleidivania Rocha, Bernardo Lages
Rodrigues,* Heloisa Beraldo and Leticia Regina Teixeira*
Received 10 April 2019
Accepted 17 June 2019
Chemistry Department, Universidade Federal de Minas Gerais, 31270-901 Belo Horizonte, Minas Gerais, Brazil.
*Correspondence e-mail: bernardo@qui.ufmg.br, lreginaufmg@gmail.com
Edited by B. D. Santarsiero, University of Illinois
at Chicago, USA
In the present work, the two-dimensional (2D) polymer poly[[ꢀ -2-(4-nitro-
4
Keywords: coordination polymer; crystal struc-
ture; silver complex; sulfonamide; Hirshfeld
surface; human serum albumin.
0
4
1
1
1
6
benzenesulfonamido)benzoato-ꢁ O :O :O :N ]silver(I)] (AgL), [Ag(C H -
13
9
N
(
O
S)]
, was obtained from 2-(4-nitrobenzenesulfonamido)benzoic acid
n
2
6
1
HL), C H N O S. FT–IR, H and C{ H} NMR spectroscopic analyses were
13
1
1
3
10
2
6
CCDC references: 1934725; 1934724
used to characterize both compounds. The crystal structures of HL and AgL
were determined by single-crystal X-ray diffraction. In the structure of HL,
O—Hꢀ ꢀ ꢀO hydrogen bonds between neighbouring molecules result in the
formation of dimers, while the silver(I) complex shows polymerization
Supporting information: this article has
supporting information at journals.iucr.org/c
ꢁ
associated with the O atoms of three distinct deprotonated ligands (L ). Thus,
the structure of the Ag complex can be considered as a coordination polymer
consisting of a one-dimensional linear chain, constructed by carboxylate
bridging groups, running parallel to the b axis. Neighbouring polymeric chains
are further bridged by Ag—C monohapto contacts, resulting in a 2D framework.
Fingerprint analysis of the Hirshfeld surfaces show that Oꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀO hydrogen
bonds are responsible for the most significant contacts in the crystal packing of
HL and AgL, followed by the Hꢀ ꢀ ꢀH and Oꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀO interactions. The
Agꢀ ꢀ ꢀAg, Agꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀAg and Agꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀAg interactions in the Hirshfeld
surface represent 12.1% of the total interactions in the crystal packing. Studies of
the interactions of the compounds with human serum albumin (HSA) indicated
that both HL and AgL interact with HSA.
1
. Introduction
The rational design and construction of metal–organic coor-
dination polymers has attracted considerable interest due to
their fascinating topologies and the promising applications of
these compounds as luminescence (Pan et al., 2018; Feng et al.,
2015) and magnetic probes (Chen et al., 2016), in the degra-
dation of organic pollutants (Wu et al., 2015) and as anti-
I
microbial agents (Roca et al., 2016). The Ag ion has a very
flexible coordination sphere, supporting variable coordination
numbers from two to six and numerous geometries, ranging
from linear all the way to octahedral (Yang et al., 2017). This
I
makes coordination to Ag an interesting strategy for
obtaining new metal–organic coordination polymers.
Silver(I) complexes and nanoparticles present a wide range
of applications. Silver compounds show antimicrobial, anti-
inflammatory and antiviral activities (Santos et al., 2018;
Guldiren & Aydin, 2017; Hussaini et al., 2019) and are
employed in ointments for burns (Hussain & Ferguson, 2006).
Carboxylic acids have been shown to be good building blocks
for the constructuion of diverse coordination polymers (Li et
al., 2006). 4-Aminobenzoic acid presents interesting poly-
#
2019 International Union of Crystallography
Acta Cryst. (2019). C75, 1011–1020
https://doi.org/10.1107/S2053229619008593 1011

research papers
morphism (Rosbottom et al., 2018) and numerous biological
activities (Prior et al., 2014; Igberase et al., 2019). In a previous
work, we reported the syntheses of 4-(2-nitrobenzene-
sulfonamido)benzoic acid and its tri-n-butyltin(IV) complex
eter (L1006m016, Agilent Technologies) also using a 1.0 cm
quartz cell.
2.1. Synthesis and crystallization
(
Bomfim Filho et al., 2019).
Studies on the interactions of small molecules and proteins
2
.1.1. Synthesis of 2-(4-nitrobenzenesulfonamido)benzoic
acid (HL). The synthesis followed a procedure described in the
literature (Deng & Mani, 2006). Stoichiometric amounts of
-nitrobenzenesulfonyl chloride and 2-aminobenzoic acid
may provide important information about the binding
mechanism, binding constants and interaction sites. Human
serum albumin (HSA) is the most abundant protein in human
blood plasma (ca 60%), being involved in the distribution,
metabolism and elimination of drugs (Ascenzi et al., 2014). It
has been shown that silver(I) complexes with a variety of
organic ligands bind to HSA (Yilmaz et al., 2017) and to
bovine serum albumin (BSA) (Tamayo et al., 2017), suggesting
that the complexes could be transported by albumins.
4
were suspended in distilled water (100 ml). Under vigorous
stirring, an aqueous solution of sodium carbonate was added
to adjust the pH to between 8.0 and 9.0. After the consump-
tion of the reagents and stabilization of the pH, concentrated
HCl solution was added to attain a pH of 2.0, which allowed
precipitation of HL. The solid was filtered off, washed with
water to remove excess HCl and dried in vacuo. Single crystals
suitable for X-ray analysis were obtained by slow evaporation
from an ethanol solution.
Analytical and spectroscopic data: yield (%) 81; m.p. 227–
ꢂ
2
29 C. Analysis calculated (%) for C H N O S: C 47.89, H
10
13
2
6
3
.07, N 8.53; found: C 48.45, H 3.13, N 8.69. FT–IR (selected
ꢁ
1
bands) (KBr pellet, cm ): ꢂ(N—H) 3100, ꢂ(C O) 1666,
ꢃ(N—H) 1582, ꢂ (NO ) 1530, ꢂ (SO )/ꢂ (NO ) 1348,
ꢂ(C—O) 1264, ꢂ (SO ) 1178, ꢂ(S—N) 926. H NMR (400 MHz,
as
2
as
2
s
2
1
s
2
3
DMSO-d , ppm): ꢃ 11.30 (s, 1H, NH), 8.36 (d, J = 8.8 Hz, 1H,
6
H
3
H9/H13), 8.06 (d, J = 8.7 Hz, 2H, H10/H12), 7.90 (d, J =
3
7
1
1
.2 Hz, 1H, H7), 7.65–7.44 (m, 2H, H4/H5), 7.18 (t, J = 7.1 Hz,
13
H, H6). C NMR (100 MHz, DMSO-d , ppm): ꢃ 169.4 (C1),
6
C
50.1 (C11), 144.1 (C8), 138.7 (C3), 134.5 (C5), 131.6 (C7), 128.5
(C10/C12), 124.7 (C9/C13), 124.1 (C6), 119.3 (C4), 117.9 (C2).
2.1.2. Synthesis of AgL. To an ethanol solution (40 ml)
containing HL (1.0 mmol) was added dropwise an aqueous
solution of NaOH to adjust the pH of the solution to 7.0. After
an hour of stirring, an aqueous solution of AgNO (1.0 mmol)
3
was added. The reaction mixture was stirred in the dark at
room temperature for a further 24 h. The resulting solid was
filtered off and washed with water, ethanol and diethyl ether,
and dried in vacuo. Single crystals suitable for X-ray analysis
were obtained by slow evaporation from the mother solution
stored in the dark at 298 K.
In the present work, we used 2-(4-nitrobenzenesulfon-
amido)benzoic acid (HL) (Fig. 1) to obtain a new silver(I)
complex (AgL) (see Scheme 1). The crystal structures of both
were determined by single-crystal X-ray diffraction. The
Hirshfeld surfaces were used to describe the intermolecular
interactions. In addition, the interaction of the compounds
with HSA was investigated by steady-state fluorescence
spectroscopy.
Analytical and spectroscopic data: yield (%) 63; m.p.
ꢂ
165.2 C (decomposition). Analysis calculated (%) for C H -
AgN O S: C 36.36, H 1.80, N 6.58; found: C 36.38, H 2.11, N
1
3
9
2
6
ꢁ
1
6
3
1
5
8
.53. FT–IR (selected bands) (KBr pellet, cm ): ꢂ(N—H)
106, ꢂ (COO) 1608, ꢂ (NO ) 1530, ꢂ (SO )/ꢂ (NO ) 1374/
2
. Experimental
as
as
2
as
2
s
2
348, ꢂ (COO) 1284, ꢂ (SO ) 1164, ꢂ(S—N) 942, ꢂ(Ag—O)
s
s
2
The reactants were purchased from Sigma–Aldrich and used
without further purification. Melting points were determined
using an MQAPF-302 apparatus and are reported without
correction. NMR spectra were recorded on a Bruker Avance
DRX-400 spectrometer in hexadeuterodimethyl sulfoxide
1
3
36. H NMR (400 MHz, DMSO-d , ppm): ꢃ 8.29 (d, J =
6
H
3
.7 Hz, 1H, H9/H13), 7.99 (d, J = 8.7 Hz, 2H, H10/H12), 7.88
3
d, J = 7.7 Hz, 1H, H7), 7.38 (d, J = 8.2 Hz, 1H, H4), 7.27 (t,
3
(
3
3
13
J = 7.7 Hz, 1H, H5), 6.88 (t, J = 7.5 Hz, 1H, H6). C NMR
100 MHz, DMSO-d , ppm): ꢃ 169.6 (C1), 149.3 (C11), 147.3
(
6
C
(DMSO-d ) with tetramethylsilane (TMS) as an internal
6
(
(
C8), 142.9 (C3), 132.1 (C5), 131.4 (C7), 127.9 (C10/C12), 124.4
C9/C13), 121.4 (C2), 120.9 (C4), 117.6 (C6).
standard. The IR spectra were recorded on a PerkinElmer
FT–IR GX spectrophotometer using KBr pellets. Electronic
spectra were recorded on a Shimadzu UV-2401PC UV–Vis
spectrophotometer using a 1.0 cm beam-path quartz cuvette.
Steady-state fluorescence measurements were performed on a
Varian–Agilent Cary Eclipse Fluorescence Spectrophotom-
2.2. Crystal structure determination
Crystal data, data collection and structure refinement
details are summarized in Table 1. The H atom of the sul-
ꢃ
1
012 Bomfim Filho et al.
Interaction with albumin of a new silver(I) complex
Acta Cryst. (2019). C75, 1011–1020

research papers
Table 1
Experimental details.
Experiments were carried out with Mo Kꢆ radiation using a Rigaku Xcalibur Atlas Gemini ultra diffractometer. Absorption was corrected for by multi-scan
methods (CrysAlis PRO; Rigaku OD, 2018). H-atom parameters were constrained.
HL
AgL
Crystal data
Chemical formula
13 10
C H
322.29
2
N O
6
S
[Ag(C13
429.15
9
H N
2 6
O S)]
M
r
Crystal system, space group
Temperature (K)
Triclinic, P1
301
6.9140 (3), 10.0641 (5), 10.1532 (5)
102.153 (4), 100.951 (4), 99.745 (4)
661.77 (6)
Monoclinic, P2
1
293
19.9216 (7), 5.2391 (2), 13.0860 (4)
90, 91.864 (3), 90
1365.08 (8)
/c
˚
a, b, c (A)
ꢆ, ꢇ, ꢈ ( )
ꢂ
˚
3
V (A )
Z
2
0.28
4
1.67
ꢁ
1
)
ꢀ
Crystal size (mm)
(mm
0.68 ꢄ 0.35 ꢄ 0.14
0.21 ꢄ 0.18 ꢄ 0.17
Data collection
T
min, Tmax
0.901, 1.000
13718, 4515, 3841
0.601, 1.000
22926, 3553, 2723
No. of measured, independent and observed
I > 2ꢉ(I)] reflections
[
R
int
0.043
0.761
0.046
0.693
˚
ꢁ1
)
(sin ꢊ/ꢋ)max (A
Refinement
2
2
2
R[F > 2ꢉ(F )], wR(F ), S
No. of reflections
No. of parameters
0.041, 0.116, 1.06
4515
200
0.33, ꢁ0.37
0.037, 0.082, 1.07
3553
208
0.82, ꢁ0.78
˚
ꢁ3
)
Áꢌmax, Áꢌmin (e A
Computer programs: CrysAlis PRO (Rigaku OD, 2018), SHELXS97 (Sheldrick, 2008), SHELXL2018 (Sheldrick, 2015) and Mercury (Macrae et al., 2008).
ꢁ
6
ꢁ1
fonamide group was located in a difference Fourier map and
˚
fixed to the parent atom, with N—H = 0.86 A and U (H) =
10 mol l . Protein concentration was determined by optical
density measurements at 280 nm using the molar absorption
iso
ꢁ1
ꢁ1
1.2U (N). The other H atoms were fixed geometrically
considering the hybridization of the parent atom, with
coefficient (") value at this wavelength (35 353 M cm ).
The interactions of HL and AgL with HSA were investi-
gated by monitoring the fluorescence quenching of the tryp-
tophan residue (Trp-214). The quenching plot was obtained by
the Stern–Volmer Equation (1):
eq
U (H) = 1.5U (O) and 1.2U (C).
iso
eq
eq
2.3. Hirshfeld surface analysis
Hirshfeld surfaces and the associated two-dimensional (2D)
fingerprint plots were generated for the crystal structures
using CrystalExplorer (Version 17.5; Spackman & Jayatilaka,
2009; Spackman & McKinnon, 2002; Turner et al., 2017). The
F=F ¼ 1 þ K ½Qꢅ ¼ 1 þ k ꢄ ½Qꢅ;
ð1Þ
where F and F are the fluorescence intensities of HSA in the
0
SV
q 0
0
presence and absence of the compounds, respectively, KSV is
the Stern–Volmer quenching constant, k is the bimolecular
q
3
D dnorm surfaces were mapped over a fixed colour scale of
0.600 (red) to +1.200 a.u. (blue). The 2D fingerprint plots
ꢁ8
quenching rate constant, ꢄ (ꢆ10 ) is the lifetime in the
0
ꢁ
absence of quencher and [Q] is the quencher concentration
(Lakowicz & Weber, 1973). The binding constant (K ), the
˚
were generated using the translated 0.4–3.0 A range, including
reciprocal contacts.
b
number of binding sites in compound–HSA (ꢅ) and the
change in free energy (ÁG) were calculated using Equations
2.4. Studies on the interactions of HL and AgL with HSA
(2) and (3):
Â
Ã
A stock solution of HSA was prepared by dissolving the
ꢁ
1
desired amount of HSA in an 8.3 mmol l Tris-HCl buffer at
ln ðF
0
=FÞ ꢁ 1 ¼ lnðK
b
Þ þ ꢅ ln½Qꢅ;
ð2Þ
ð3Þ
+
ꢁ1
pH 7.2 (Na = 83 mmol l ). The solutions were first prepared
using dimethyl sulfoxide (DMSO) as co-solvent, and then
diluted with a Tris-HCl buffer (pH 7.2). All fluorescence
spectra were measured after 5 min of incubation.
4
G ¼ ꢁRT lnðK Þ;
b
where K is the binding constant at the corresponding tem-
ꢁ
perature, R = 8.31 J mol
b
1
ꢁ1
K is the universal gas constant
The fluorescence emission spectra were measured at 298 K
using an excitation wavelength of 295 nm and an emission
wavelength in the 305–550 nm range, with excitation and
emission slits set at 10 nm. The HSA UV–Vis spectra were
measured at 298 K in the 200–300 nm range. The HSA
concentration was kept constant at 2.38 ꢄ 10 mol l , while
the HL and AgL concentrations ranged from 0 to 5.71 ꢄ
and T is the temperature in Kelvin. To eliminate any inner-
filter effect arising from UV–Vis absorption, the fluorescence
data were corrected according Equation (4):
½
ðAemþAexcÞ=2ꢅ;
F ¼ Fmeasured ꢄ 10
ð4Þ
where F is the corrected fluorescence intensity, Fmeasured is the
ꢁ6
ꢁ1
measured fluorescence intensity and Aexc and Aem are the
ꢃ
Acta Cryst. (2019). C75, 1011–1020
Bomfim Filho et al.
Interaction with albumin of a new silver(I) complex 1013

research papers
Table 2
Selected bonds lengths (A) and angles ( ).
complex was attributed to the ꢂ(AgO) mode, indicating that
˚
ꢂ
I
the ligand is attached to the Ag centre through a carboxylate
HL
AgL
O atom (Nakamoto, 2008).
1
The H NMR spectrum of HL shows a singlet at 11.30 ppm
O1—C1
O2—C1
S1—O3
S1—O4
S1—N1
S1—C8
O5—N2
O6—N2
N1—C3
N2—C11
C1—C2
1.3128 (15)
1.2368 (16)
1.4293 (10)
1.4271 (10)
1.6287 (11)
1.7733 (12)
1.2226 (16)
1.2232 (16)
1.4109 (16)
1.4742 (16)
1.4745 (17)
1.260 (3)
1.256 (3)
1.426 (2)
1.429 (2)
1.624 (2)
1.768 (3)
1.214 (4)
1.226 (4)
1.395 (4)
1.476 (4)
1.504 (4)
2.290 (2)
2.437 (2)
2.304 (2)
2.551 (3)
3.2926 (3)
120.67 (14)
103.59 (13)
109.82 (14)
108.40 (14)
107.19 (14)
106.35 (13)
130.8 (2)
111.09 (8)
124.83 (6)
99.39 (8)
104.70 (9)
128.72 (10)
88.52 (9)
attributed to the sulfonamide N—H group, which is absent in
the complex. The signals of the aromatic H atoms, mainly the
atoms of the aminobenzoic acid group, which are next to the
complexation binding site, observed at ꢃH 7.18–8.36 in HL,
undergo significant shifts to ꢃ 6.88–8.29 ppm in the complex.
H
13
1
The C{ H} NMR also shows shifts of the carbon signals in the
complex relative to their positions in the free ligand, in
particular, the upfield shift of the C6—H6 signals at ꢃ 7.18
H
i
Ag1—O1
Ag1—O1
Ag1—O2
Ag1—C6
and ꢃ 124.1 in the free ligand to ꢃ 6.88 and ꢃ 117.6 after
ii
C
H
C
complexation. This shift is explained by the monohapto
I
interaction of Ag with atom C6, as confirmed by the crystal
structure analysis.
i
Ag1—Ag1
O3—S1—O4
O3—S1—N1
O4—S1—N1
O3—S1—C8
O4—S1—C8
N1—S1—C8
C3—N1—S1
120.22 (6)
104.49 (6)
109.78 (6)
108.39 (6)
107.11 (6)
106.03 (6)
126.42 (8)
3.2. Structure description
HL crystallized in the triclinic space group P1, with one
molecule per asymmetric unit, while AgL crystallizes in the
i
O1 —Ag1—O2
monoclinic space group P2 /c, with the asymmetric unit
1
i
O1 —Ag1—O1
ii
I
formed by one Ag ion and one monoanionic L ligand
ꢁ
ii
O2—Ag1—O1
i
O1 —Ag1—C6
O2—Ag1—C6
(Fig. 1).
˚
HL presents characteristic C O [1.2368 (16) A] and C—O
ii
O1 —Ag1—C6
˚
1.3128 (15) A] bond lengths. For AgL, the carboxylate group
[
presents C—O bond lengths intermediate between single and
1
2
1
2
Symmetry codes: (i) ꢁx + 1, y + , ꢁz + ; (ii) x, y + 1, z.
˚
double bonds, with C1 O1 = 1.260 (3) A and C2 O2 =
measured absorbances at the excitation and emission wave-
lengths, respectively.
3
. Results and discussion
3.1. Spectroscopic analysis
The FT–IR spectrum of HL shows three common features
associated with the carboxylic acid group: a band attributed to
ꢁ
1
ꢂ(O—H) in the 3300–2500 cm range and two bands attrib-
ꢁ1
uted to ꢂ(C O) and ꢂ(C—O) at 1666 and 1264 cm ,
respectively. For AgL, the presence of two bands at 1608 and
ꢁ
1
284 cm was attributed to the asymmetric and symmetric
1
stretching vibration modes of the carboxylate group, respec-
ꢁ
1
tively. Áꢂ = ꢂ (COO) ꢁ ꢂ (COO) was found to be 324 cm ,
as
s
which is characteristic of anisobidentate coordination (Naka-
moto, 2008).
The sulfonamide group presents a narrow band related to
ꢁ
1
the ꢂ(N—H) stretching vibration in the 3106–3100 cm
range. In addition, an angular deformation vibration ꢃ(N—H)
ꢁ
1
at 1582 cm is observed in the HL spectrum, which is over-
lapped with the ꢂ (COO) vibration in the spectrum of the
as
complex. In addition, two bands in the 1374–1348 and 1178–
ꢁ
1
164 cm ranges were attributed to the S O asymmetric and
1
symmetric stretching vibration modes, respectively. The
ꢁ
1
Figure 1
ꢂ (NO ) mode was found at 1530 cm in both compounds.
as
2
View of the asymmetric units of (a) HL and (b) AgL, showing the atom-
numbering schemes used for the NMR characterization. Displacement
ellipsoids are drawn at the 50% probability level. Intramolecular
hydrogen bonds are represented by blue dashed lines.
The ꢂ (NO ) band overlapped with the ꢂ (SO ) vibration was
s
2
as
2
ꢁ
1
observed at 1348 cm in HL and at 1374 cm in AgL.
ꢁ1
ꢁ1
Moreover, an absorption at 467 cm in the spectrum of the
ꢃ
1
014 Bomfim Filho et al.
Interaction with albumin of a new silver(I) complex
Acta Cryst. (2019). C75, 1011–1020

research papers
˚
.256 (3) A (Table 2). The bond lengths of the sulfonamide
1
aromatic ring A. On the other hand, the nitro group is rotated
from the mean plane of aromatic ring B (atoms C8–C12), with
group (formed by the N1, S1, O3, O4 and C8 atoms) do not
change after complexation, similar to the bond lengths of the
NO group. In addition, both compounds show equivalent
ꢂ
ꢂ
a dihedral angle of 15.3 (2) in HL and 13.4 (1) in AgL.
The crystal structures of HL and AgL present two intra-
molecular hydrogen bonds each, viz. N1—H1Nꢀ ꢀ ꢀO2
2
S
O sulfonyl bond lengths, in good agreement with the
˚
˚
literature (Shakuntala et al., 2017). The sulfonamide group
presents a distorted tetrahedral arrangement around the S
atom (Table 2).
[N1ꢀ ꢀ ꢀO2 = 2.6559 (14) A for HL and 2.602 (3) A for AgL]
˚
and C4—H4ꢀ ꢀ ꢀO4 [C4ꢀ ꢀ ꢀO4 = 3.0729 (18) A for HL and
˚
3.062 (4) A for AgL]. These hydrogen bonds reduce the free
In HL, the carboxylic acid group is coplanar with aromatic
ꢂ
rotation at the C1—C2 and N1—S1 single bonds, generating
two S(6) rings (Fig. 1).
The characteristic dimer formation by the intermolecular
O1—H1ꢀ ꢀ ꢀO2 hydrogen bonds and the weak intermolecular
ring A (atoms C2–C7), with a dihedral angle of 1.1 (1)
between the planes, while in the complex, the carboxylate
ꢂ
i
group is rotated by 10.8 (2) from the mean plane through
Figure 2
Intermolecular hydrogen bonds in the crystal structure of HL.
ꢃ
Acta Cryst. (2019). C75, 1011–1020
Bomfim Filho et al. Interaction with albumin of a new silver(I) complex 1015

research papers
Table 3
Hydrogen-bond parameters (A, ) for HL and AgL.
˚
ꢂ
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
HL
N1—H1Nꢀ ꢀ ꢀO2
0.85
0.93
0.82
0.93
0.93
0.93
1.94
2.41
1.86
2.60
2.60
2.62
2.655 (1)
141
128
174
170
138
131
C4—H4ꢀ ꢀ ꢀO4
3.0729 (2)
2.6766 (14)
3.5150 (17)
3.3511 (18)
3.3042 (17)
i
O1—H1ꢀ ꢀ ꢀO2
ii
C5—H5ꢀ ꢀ ꢀO4
iii
C9—H9ꢀ ꢀ ꢀO6
iv
C12—H12ꢀ ꢀ ꢀO3
AgL
N1—H1Nꢀ ꢀ ꢀO2
0.85
0.93
0.93
0.93
0.93
0.93
1.85
2.41
2.65
2.56
2.49
2.70
2.602 (3)
3.062 (4)
3.457 (4)
3.2063 (1)
3.369 (4)
3.424 (4)
146
127
145
157
157
136
C4—H4ꢀ ꢀ ꢀO4
v
C5—H5ꢀ ꢀ ꢀO3
vi
C10—H10ꢀ ꢀ ꢀO4
C12—H12ꢀ ꢀ ꢀO6
C13—H13ꢀ ꢀ ꢀO5
vii
viii
Symmetry codes: (i) ꢁx + 1, ꢁy, ꢁz + 1; (ii) ꢁx + 1, ꢁy + 1, ꢁz + 1; (iii) x ꢁ 1, y, z; (iv)
Figure 4
3
2
1
2
1
2
1
2
x + 1, y, z; (v) x, y, z; (vi) x, ꢁy + , z + ; (vii) ꢁx, ꢁy, ꢁz; (viii) x, ꢁy + , z ꢁ .
A capped sticks perspective view of the 1D coordination polymers in
AgL along the c direction. The Ag atoms are shown in ball-and-stick
style. The intra- and intermolecular hydrogen bonds have been omitted
for clarity.
ii
C5—H5ꢀ ꢀ ꢀO4 hydrogen bonds between neighbouring HL
2
2
2
2
molecules form closed loops with graph-sets R (8) and R (14),
respectively (Fig. 2a and Table 3). These two intermolecular
hydrogen bonds form a one-dimensional (1D) layer in the
The carboxylate group acts as a bridging group where the O
I
atoms coordinate to two Ag ions in an anisobidentate mode
[
210] crystallographic direction. The propagation in the [101]
crystallographic direction is associated with a lone-pairꢀ ꢀ ꢀꢍ
lpꢀ ꢀ ꢀꢍ) O5ꢀ ꢀ ꢀN2 interaction (symmetry code: ꢁx + 1, ꢁy,
(Fig. 3). Thus, the structure of the complex can be considered
as a coordination polymer consisting of a 1D linear chain
constructed by carboxylate bridging groups, running parallel
to the b axis. Neighbouring polymeric chains are further
bridged by Ag—C bonds, resulting in a 2D framework (Fig. 4).
This shows the fundamental role exerted by the monohapto
aromatic coordination in the packing and stability of the
polymeric complex. The sulfonyl O atoms of AgL act as
acceptors in intermolecular hydrogen bonds from aromatic
(
ꢁ
˚
z + 2), with O5ꢀ ꢀ ꢀN2 = 2.9172 (12) A, and a ꢍ-stacking
C1ꢀ ꢀ ꢀC7 interaction (symmetry code: ꢁx, ꢁy, ꢁz + 1), with
˚
C1ꢀ ꢀ ꢀC7 = 3.3380 (19) A (Fig. 2b). The structure is also char-
iii
acterized by the presence of C9—H9ꢀ ꢀ ꢀO6 and C12—
iv
2
2
H12ꢀ ꢀ ꢀO3 hydrogen bonds, which form an R (10) ring
(
Fig. 2c).
i
In AgL, the Ag centre is coordinated to three O atoms (O1 ,
v
vi
ii
O1 and O2) of three distinct monoanionic ligands (L ), with
i
Ag—O1 varying from 2.290 (2) to 2.437 (2) A (Table 2 and
ꢁ
rings A (C5—H5ꢀ ꢀ ꢀO3 ) and B (C10—H10ꢀ ꢀ ꢀO4 ), forming
2
2
˚
an R (13) ring (Fig. 5). The phenyl–sulfonyl–phenyl unit
results in an infinite chain parallel to the [010] direction.
1
Fig. 3). The metal also shows a ꢅ aromatic interaction with the
vii
vii
Interchain C12—H12ꢀ ꢀ ꢀO6 and C13—H13ꢀ ꢀ ꢀO5 hydrogen
bonds extend the 2D polymer into a three-dimensional (3D)
framework (Table 3).
phenyl C6 atom of a neighbouring molecule, with Agꢀ ꢀ ꢀC6 =
˚
.551 (3) A. This suggests a strong monohapto aromatic
2
coordination to the Ag centre. Hence, the metal coordination
I
sphere can be considered to contain Ag atoms with fourfold
3.3. Hirshfeld surface
coordination. Moreover, analyzing the polymer structure, the
˚
Agꢀ ꢀ ꢀAg interaction, with Agꢀ ꢀ ꢀAg = 3.2926 (3) A, may be
On the Hirshfeld surfaces mapped over dnorm of HL
1
0
10
considered a d ꢀ ꢀ ꢀd noncovalent interaction (Sculfort &
Braunstein, 2011), resulting in an OOOCAgꢀ ꢀ ꢀAgOOOC
environment in the polymeric complex.
(Fig. 6a), the short interatomic Oꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀO interaction is
observed as intense red spots near the carboxylic acid group.
The light-red spots appearing near the phenyl H5, sulfonyl O4
Figure 3
(
[
a) A view in the ab plane of the propagation of AgL along the [010] crystallographic direction. (b) The distorted tetrahedral geometry of the complex
ii
O2—Ag1—O1 = 99.39 (8) ; symmetry code: (ii) x, y + 1, z].
ꢂ
ꢃ
1
016 Bomfim Filho et al.
Interaction with albumin of a new silver(I) complex
Acta Cryst. (2019). C75, 1011–1020

research papers
and nitro O6 atoms on the surface connect the molecules
through interatomic Oꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀO contacts (Fig. 6b). In
addition, a faint-red spot near the nitro group shows the
Oꢀ ꢀ ꢀN/Nꢀ ꢀ ꢀO interactions (green dashed) relative to the
lpꢀ ꢀ ꢀꢍ interaction in the crystal packing.
in Fig. 7a). The Hirshfeld surface for Ag1 shows the bonds
between the metal and the O atoms, as well as the monohapto
interaction of the phenyl C6 atom and Ag1 that can be easily
observed by the intense red spots (Fig. 7b). The red area in the
2D fingerprint plot of this surface (Fig. 7c) shows the high
Agꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀAg contribution to the structure stability being
The Hirshfeld surface for AgL shows light-red spots near
the phenyl H12 and nitro O6 atoms that connect the molecules
through interatomic Oꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀO contacts (blue dashed lines
I
associated with the three bonds between Ag and the O atoms
of the carboxylate groups.
Figure 5
(a) Intermolecular hydrogen bonds and (b) the 2D network in the AgL crystal structure. The Ag atoms are shown in ball-and-stick style.
ꢃ
Acta Cryst. (2019). C75, 1011–1020
Bomfim Filho et al.
Interaction with albumin of a new silver(I) complex 1017

research papers
fingerprint plot (Fig. 8b). In AgL, the Oꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀO contacts
I
˚
present d + d ꢆ2.4 A related to coordination to Ag through
e
i
the carboxylate site (Fig. 9b). Nevertheless, the percentage of
Oꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀO contacts is similar in HL and AgL, i.e. 36.3 and
3
1.6%, respectively. The second most predominant contribu-
tion to the total Hirshfeld surface in HL and AgL is the Hꢀ ꢀ ꢀH
interaction where the scattering points spread up at d ’ d <
e
i
˚
.2 A (van der Waals radius of the H atom) (Fig. 8c and 9c),
1
followed by the Oꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀO interaction, which present
similar pecentage in HL and AgL (Fig. 8d and 9d).
In addition, from Hirshfeld surface analysis, it is noticed
that the Agꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀAg region of the fingerprint plot for AgL
˚
results in a spike with d + d ꢆ2.2 A, which is directly
e
i
attributed to the Ag—O bonds in the polymer structure
(
4
Fig. 9e). The Agꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀAg interactions correspond to
.4%, suggesting the relevance of the monohapto interaction
in the crystal packing stability. Furthermore, the Agꢀ ꢀ ꢀAg
interaction represent 0.5% of the interactions in the polymeric
structure.
3.4. Human serum albumin (HSA) interaction analysis
Upon addition of increasing concentrations of the com-
pounds under study, a decrease of the fluorescence maximum
of HSA with a hypsochromic shift (ca 3 nm) is observed,
indicating an increase of the hydrophobic microenvironment
around the Trp-214 residue upon formation of the HSA–
compound complex (Fig. 10). The values of the Stern–Volmer
quenching constant (K ) and the bimolecular quenching rate
SV
constant (k ) are listed in Table 4. The calculated values for
q
Figure 6
the constants are higher than the quenching rate constant for
Hirshfeld surface for HL mapped over dnorm in the ꢁ0.600 to +1.200 a.u.
range, highlighting (a) short interatomic Oꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀO (blue dashed
lines) and (b) Nꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀN (green dashed lines) contacts.
10
ꢁ1 ꢁ1
diffusion-controlled processes (2.0 ꢄ 10 l mol s ) (Ware,
1962; Khan et al., 2012). Hence, the fluorescence quenching of
Trp-214 does not occur exclusively through a dynamic process,
but the static mechanism might also be involved.
The strong hydrogen bonds between the carboxylic acid
group of two neighbouring molecules of the free ligand are
The values of the binding constant (K ) for both com-
b
˚
observed as two spikes at d + d ꢆ 1.7 A for HL in the 2D
pounds suggest a moderate interaction with the biomolecule,
e
i
Figure 7
(
a) Hirshfeld surface for AgL mapped over dnorm highlighting short interatomic Oꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀO contacts (blue dashed lines). (b) Hirshfeld surface for Ag1
mapped over dnorm with Agꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀAg as a black dashed line. (c) The 2D fingerprint plot of the surface of Ag1, emphasizing the regions for interactions
Agꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀAg (1), Agꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀAg (2) and Agꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀAg (3).
ꢃ
1
018 Bomfim Filho et al.
Interaction with albumin of a new silver(I) complex
Acta Cryst. (2019). C75, 1011–1020

research papers
Figure 8
(
a) The full 2D fingerprint plots of HL and (b)/(c)/(d) those delineated into Oꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀO, Hꢀ ꢀ ꢀH and Oꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀO interactions, respectively, showing
the percentage contributions to the Hirshfeld surface.
Table 4
q b
Stern–Volmer quenching constant (KSV), bimolecular quenching rate constant (k ), binding constant (K ), number of binding sites per protein (ꢅ) and
free energy variation (ÁG) associated with the compound–HSA interaction in Tris-HCl Buffer (pH 7.2, ꢋexc = 295 nm).
a b
R is the correlation coefficient for the KSV values and R is the correlation coefficient for the K
b
values.
4
ꢁ1
12
ꢁ1 ꢁ1
a
4 ꢁ1
(10 M
b
R
ꢁ1
ÁG (kJ mol )
Compounds
K
SV (10 M
)
k
q
(10
M
s
)
R
K
b
)
ꢅ
HL
AgL
5.15
4.50
5.15
4.50
0.9987
0.9976
1.89
34.96
0.919
1.164
0.9973
0.9917
ꢁ24.39
ꢁ31.64
the AgL–HSA interaction being 20-times stronger compared
to HL–HSA. The correlation coefficients are larger than 0.99,
indicating that the interactions are compatible with the
binding model. The values of ꢅ were approximately equal to 1,
suggesting a single binding site in HSA for the compounds.
Moreover, the negative values of free energy changes suggest
thermodynamic stability and spontaneous binding to HSA.
(HL) was prepared and characterized by NMR and FT–IR
spectroscopies. The X-ray crystal structures of both com-
pounds were determined by single-crystal X-ray diffraction.
Structural analysis for HL shows a characteristic dimer
formation via intermolecular O—Hꢀ ꢀ ꢀO hydrogen bonding
between the carboxylic acid groups of neighbouring mol-
ecules. The AgL complex showed a polymeric structure with
the Ag atom presenting an OOOAgꢀ ꢀ ꢀAgOOO environment
and an Ag—C monohapto interaction. Hirshfeld surface
analysis and 2D fingerprint plots indicate that the Oꢀ ꢀ ꢀH/
Hꢀ ꢀ ꢀO interactions are more frequent in the crystal packing of
both HL and AgL, being essential to the stabilization of the
4
. Conclusions
In the present work, a polymeric AgL coordination frame-
work based on 2-(4-nitrophenylsulfonamido)benzoic acid
Figure 9
2
D fingerprint plots of AgL, showing (a) full and resolved into (b) Oꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀO, (c) Hꢀ ꢀ ꢀH, (d) Oꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀO, (e) Agꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀAg, (f) Agꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀAg
and (g) Agꢀ ꢀ ꢀAg interactions, showing the percentage contributions to the Hirshfeld surface.
ꢃ
Acta Cryst. (2019). C75, 1011–1020
Bomfim Filho et al.
Interaction with albumin of a new silver(I) complex 1019

research papers
crystal structure. Investigation of the interactions of HL and
AgL with HSA revealed that the compounds show a moderate
affinity for HSA, the AgL–HSA interaction being 20-times
stronger compared to the HL–HSA interaction. The strong
silver(I) complex interaction with the biomolecule suggests a
potential application for this kind of compound for biological
and the structure–activity studies.
Acknowledgements
The authors are grateful to Conselho Nacional de Desenvol-
vimento Cient ı´ fico e Tecnol o´ gico (CNPq) and Conselho de
Aperfei c¸ oamento de Pessoal de N ı´ vel Superior (CAPES)
Brazilian funding agencies for financial support.
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020 Bomfim Filho et al.
Interaction with albumin of a new silver(I) complex
Acta Cryst. (2019). C75, 1011–1020

supporting information
supporting information
Acta Cryst. (2019). C75, 1011-1020 [https://doi.org/10.1107/S2053229619008593]
Synthesis, crystal structure and studies on the interaction with albumin of a
new silver(I) complex based on 2-(4-nitrobenzenesulfonamido)benzoic acid
Lucius Flavius Ourives Bomfim Filho, Cleidivania Rocha, Bernardo Lages Rodrigues, Heloisa
Beraldo and Leticia Regina Teixeira
Computing details
For both structures, data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD,
2
2
2
018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXS97 (Sheldrick,
008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al.,
008); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015).
2-(4-Nitrobenzenesulfonamido)benzoic acid (HL)
Crystal data
C
13 10 2 6
H N O S
Z = 2
M
r
= 322.29
F(000) = 332
D = 1.617 Mg m
x
−3
Triclinic, P1
Hall symbol: -P 1
a = 6.9140 (3) Å
b = 10.0641 (5) Å
c = 10.1532 (5) Å
α = 102.153 (4)°
β = 100.951 (4)°
γ = 99.745 (4)°
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 5557 reflections
θ = 3.1–32.6°
µ = 0.28 mm
T = 301 K
−1
Prism, colourless
0.68 × 0.35 × 0.14 mm
3
V = 661.77 (6) Å
Data collection
Rigaku Xcalibur, Atlas, Gemini ultra
diffractometer
Graphite monochromator
Detector resolution: 10.4186 pixels mm
ω scans
13718 measured reflections
4515 independent reflections
3841 reflections with I > 2σ(I)
-1
R
int = 0.043
θ
max = 32.8°, θmin = 2.6°
Absorption correction: multi-scan
h = −10→10
k = −14→14
l = −15→14
(CrysAlis PRO; Rigaku OD, 2018)
T
min = 0.901, Tmax = 1.000
Refinement
2
Refinement on F
200 parameters
Least-squares matrix: full
0 restraints
2
2
R[F > 2σ(F )] = 0.041
Hydrogen site location: mixed
H-atom parameters constrained
2
wR(F ) = 0.116
2
2
2
S = 1.06
w = 1/[σ (F
o
) + (0.0534P) + 0.1382P]
2
2
4
515 reflections
where P = (F
o
+ 2F )/3
c
Acta Cryst. (2019). C75, 1011-1020
sup-1

supporting information
−3
(
Δ/σ)max < 0.001
Δρmin = −0.37 e Å
−3
Δρmax = 0.33 e Å
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Refinement. Single-crystal X-ray diffraction measurements were performed on an Agilent–Gemini diffractometer
equipped with a CCD area detector using MoK? (0.71073 Å) radiation. The CrysAlisPro software package (Rigaku,
2
015) was used for data collection and reduction (Oxford Diffraction Ltda, version 171.38.41). The structures were
2
solved by direct methods using SHELXS-97 and refined by full-matrix least squares on F using SHELXL-2018
(Sheldrick, 2015). All non-hydrogen atoms were refined using anisotropic displacement parameters.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
S1
0.12454 (4)
−0.33898 (16)
−0.443606
−0.32527 (14)
−0.01498 (16)
0.25416 (15)
0.58057 (18)
0.79937 (17)
−0.01504 (15)
−0.129422
0.64156 (17)
−0.25207 (18)
−0.06143 (17)
0.05425 (17)
0.2329 (2)
0.30801
0.47628 (3)
−0.03940 (10)
−0.066604
0.14767 (10)
0.51483 (10)
0.58008 (10)
0.11306 (11)
0.14961 (13)
0.36229 (11)
0.323849
0.16245 (12)
0.08679 (13)
0.14679 (12)
0.28066 (12)
0.33032 (15)
0.419659
0.24796 (17)
0.281618
0.11621 (16)
0.060917
0.06735 (14)
−0.020376
0.38494 (12)
0.30539 (16)
0.301506
0.74105 (3)
0.38167 (11)
0.404167
0.54881 (12)
0.82160 (11)
0.70247 (11)
1.12775 (11)
1.00541 (14)
0.60268 (11)
0.611424
1.03919 (12)
0.45781 (13)
0.42646 (12)
0.49812 (12)
0.46234 (14)
0.507179
0.36091 (16)
0.33951
0.29097 (15)
0.223264
0.32238 (14)
0.273293
0.83002 (12)
0.91162 (16)
0.919686
0.02885 (9)
0.0433 (2)
0.065*
0.0406 (2)
0.0403 (2)
0.0393 (2)
0.0458 (3)
0.0546 (3)
0.0308 (2)
0.037*
0.0358 (2)
0.0307 (2)
0.0276 (2)
0.0265 (2)
0.0361 (3)
0.043*
0.0418 (3)
0.05*
0.0414 (3)
0.05*
0.0364 (3)
0.044*
0.0280 (2)
0.0380 (3)
0.046*
O1
H1
O2
O3
O4
O5
O6
N1
H1N
N2
C1
C2
C3
C4
H4
C5
H5
C6
H6
C7
H7
C8
C9
H9
C10
H10
C11
C12
H12
C13
H13
0.2993 (2)
0.420223
0.1880 (2)
0.233994
0.0083 (2)
−0.068407
0.28090 (17)
0.2009 (2)
0.068394
0.3196 (2)
0.268501
0.51523 (19)
0.5970 (2)
0.72984
0.47850 (19)
0.53117
0.23221 (15)
0.178123
0.24128 (12)
0.32060 (15)
0.324516
0.98058 (15)
1.035203
0.96650 (13)
0.88735 (15)
0.880113
0.0373 (3)
0.045*
0.0300 (2)
0.0370 (3)
0.044*
0.39464 (15)
0.449933
0.81850 (14)
0.765428
0.0349 (3)
0.042*
Acta Cryst. (2019). C75, 1011-1020
sup-2

supporting information
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
S1
0.02764 (15)
0.0386 (5)
0.0288 (4)
0.0398 (5)
0.0375 (5)
0.0538 (6)
0.0403 (6)
0.0230 (4)
0.0355 (6)
0.0255 (5)
0.0251 (5)
0.0245 (5)
0.0309 (6)
0.0376 (7)
0.0457 (8)
0.0414 (7)
0.0261 (5)
0.0279 (6)
0.0345 (6)
0.0303 (6)
0.0266 (6)
0.0295 (6)
0.02435 (15)
0.0351 (5)
0.0346 (5)
0.0385 (5)
0.0283 (4)
0.0428 (6)
0.0572 (7)
0.0315 (5)
0.0292 (5)
0.0294 (6)
0.0295 (5)
0.0288 (5)
0.0377 (7)
0.0519 (8)
0.0464 (8)
0.0345 (6)
0.0274 (5)
0.0468 (8)
0.0420 (7)
0.0269 (5)
0.0461 (7)
0.0415 (7)
0.03087 (16)
0.0449 (6)
0.0517 (6)
0.0421 (5)
0.0465 (6)
0.0410 (6)
0.0746 (9)
0.0319 (5)
0.0378 (6)
0.0331 (6)
0.0266 (5)
0.0248 (5)
0.0360 (6)
0.0392 (7)
0.0355 (7)
0.0303 (6)
0.0277 (5)
0.0460 (8)
0.0413 (7)
0.0291 (5)
0.0417 (7)
0.0364 (6)
0.00152 (11)
−0.0104 (4)
−0.0038 (4)
0.0128 (4)
−0.0046 (4)
0.0088 (5)
0.0202 (5)
−0.0014 (4)
0.0047 (4)
−0.0002 (4)
0.0017 (4)
0.0022 (4)
−0.0037 (5)
0.0040 (6)
0.0098 (6)
0.0035 (5)
0.0018 (4)
0.0078 (5)
0.0059 (5)
0.0035 (4)
0.0067 (5)
0.0036 (5)
0.00438 (11)
0.0123 (4)
0.0147 (4)
0.0122 (4)
0.0031 (4)
0.0051 (5)
0.0156 (6)
0.0053 (4)
0.0019 (4)
0.0031 (4)
0.0043 (4)
0.0032 (4)
0.0097 (5)
0.0172 (6)
0.0192 (6)
0.0095 (5)
0.0051 (4)
0.0147 (5)
0.0139 (5)
0.0036 (4)
0.0114 (5)
0.0109 (5)
0.00453 (11)
−0.0017 (4)
0.0000 (4)
0.0032 (4)
0.0126 (4)
0.0176 (5)
0.0252 (6)
0.0022 (4)
0.0056 (4)
0.0071 (5)
0.0081 (4)
0.0087 (4)
0.0086 (5)
0.0160 (6)
0.0092 (6)
0.0041 (5)
0.0055 (4)
0.0207 (6)
0.0202 (6)
0.0042 (4)
0.0158 (6)
0.0159 (5)
O1
O2
O3
O4
O5
O6
N1
N2
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
Geometric parameters (Å, º)
S1—O4
S1—O3
S1—N1
S1—C8
O1—C1
O1—H1
O2—C1
O5—N2
O6—N2
N1—C3
N1—H1N
N2—C11
C1—C2
C2—C7
C2—C3
C3—C4
C4—C5
1.4271 (10)
C4—H4
C5—C6
C5—H5
C6—C7
C6—H6
C7—H7
C8—C13
C8—C9
C9—C10
C9—H9
C10—C11
C10—H10
C11—C12
C12—C13
C12—H12
C13—H13
0.93
1.380 (2)
0.93
1.378 (2)
0.93
0.93
1.3821 (17)
1.3919 (17)
1.3818 (19)
0.93
1.3771 (18)
0.93
1.3758 (18)
1.3869 (19)
0.93
1.4293 (10)
1.6287 (11)
1.7733 (12)
1.3128 (15)
0.82
1.2368 (16)
1.2226 (16)
1.2232 (16)
1.4109 (16)
0.8488
1.4742 (16)
1.4745 (17)
1.3988 (18)
1.4091 (16)
1.3950 (17)
1.381 (2)
0.93
O4—S1—O3
O4—S1—N1
120.22 (6)
109.78 (6)
C6—C5—H5
C4—C5—H5
119.7
119.7
Acta Cryst. (2019). C75, 1011-1020
sup-3

supporting information
O3—S1—N1
O4—S1—C8
O3—S1—C8
N1—S1—C8
C1—O1—H1
C3—N1—S1
C3—N1—H1N
S1—N1—H1N
O5—N2—O6
O5—N2—C11
O6—N2—C11
O2—C1—O1
O2—C1—C2
O1—C1—C2
C7—C2—C3
C7—C2—C1
C3—C2—C1
C4—C3—C2
C4—C3—N1
C2—C3—N1
C5—C4—C3
C5—C4—H4
C3—C4—H4
C6—C5—C4
104.49 (6)
107.12 (6)
108.39 (6)
106.03 (6)
109.5
126.42 (8)
113.2
114.7
124.50 (12)
117.92 (12)
117.58 (12)
121.85 (11)
123.80 (11)
114.34 (11)
118.68 (11)
118.77 (11)
122.55 (11)
119.19 (11)
121.53 (11)
119.27 (10)
120.56 (13)
119.7
C7—C6—C5
C7—C6—H6
C5—C6—H6
C6—C7—C2
C6—C7—H7
C2—C7—H7
119.39 (13)
120.3
120.3
121.45 (13)
119.3
119.3
121.35 (12)
119.98 (10)
118.67 (9)
119.56 (12)
120.2
120.2
118.42 (12)
120.8
C13—C8—C9
C13—C8—S1
C9—C8—S1
C10—C9—C8
C10—C9—H9
C8—C9—H9
C11—C10—C9
C11—C10—H10
C9—C10—H10
C12—C11—C10
C12—C11—N2
C10—C11—N2
C11—C12—C13
C11—C12—H12
C13—C12—H12
C8—C13—C12
C8—C13—H13
C12—C13—H13
120.8
122.67 (12)
118.86 (11)
118.47 (12)
119.04 (12)
120.5
120.5
118.95 (12)
120.5
119.7
120.67 (13)
120.5
O4—S1—N1—C3
O3—S1—N1—C3
C8—S1—N1—C3
O2—C1—C2—C7
O1—C1—C2—C7
O2—C1—C2—C3
O1—C1—C2—C3
C7—C2—C3—C4
C1—C2—C3—C4
C7—C2—C3—N1
C1—C2—C3—N1
S1—N1—C3—C4
S1—N1—C3—C2
C2—C3—C4—C5
N1—C3—C4—C5
C3—C4—C5—C6
C4—C5—C6—C7
C5—C6—C7—C2
C3—C2—C7—C6
C1—C2—C7—C6
57.75 (12)
−172.05 (10)
−57.63 (12)
179.10 (13)
−0.05 (17)
−0.3 (2)
O4—S1—C8—C13
O3—S1—C8—C13
N1—S1—C8—C13
O4—S1—C8—C9
O3—S1—C8—C9
N1—S1—C8—C9
C13—C8—C9—C10
S1—C8—C9—C10
C8—C9—C10—C11
C9—C10—C11—C12
C9—C10—C11—N2
O5—N2—C11—C12
O6—N2—C11—C12
O5—N2—C11—C10
O6—N2—C11—C10
C10—C11—C12—C13
N2—C11—C12—C13
C9—C8—C13—C12
S1—C8—C13—C12
C11—C12—C13—C8
−17.03 (12)
−148.14 (11)
100.16 (11)
162.39 (11)
31.28 (12)
−80.42 (12)
−1.3 (2)
179.30 (11)
0.3 (2)
0.3 (2)
−179.56 (12)
167.21 (13)
−13.63 (18)
−12.89 (18)
166.27 (13)
−0.1 (2)
179.83 (12)
1.6 (2)
−179.04 (11)
−0.9 (2)
−179.48 (11)
0.65 (18)
−179.91 (11)
179.55 (11)
−1.01 (17)
−32.39 (17)
148.74 (10)
−2.0 (2)
179.15 (12)
1.4 (2)
0.5 (2)
−1.8 (2)
1.3 (2)
−178.20 (13)
Acta Cryst. (2019). C75, 1011-1020
sup-4

supporting information
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
i
O1—H1···O2
C5—H5···O4
C9—H9···O6
0.82
0.93
0.93
1.86
2.6
2.6
2.6766 (14)
3.5150 (17)
3.3511 (18)
174
170
138
ii
iii
Symmetry codes: (i) −x−1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z.
(AgL)
Crystal data
[
M
Ag(C13
H
9
N
2 6
O S)]
F(000) = 848
D = 2.088 Mg m
x
−3
r
= 429.15
Monoclinic, P2
1
/c
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 8451 reflections
θ = 3.1–26.7°
µ = 1.67 mm
T = 293 K
Hall symbol: -P 2ybc
a = 19.9216 (7) Å
b = 5.2391 (2) Å
c = 13.0860 (4) Å
β = 91.864 (3)°
−1
Irregular, colourless
0.21 × 0.18 × 0.17 mm
3
V = 1365.08 (8) Å
Z = 4
Data collection
Rigaku Xcalibur, Atlas, Gemini ultra
diffractometer
Graphite monochromator
Detector resolution: 10.4186 pixels mm
ω scans
22926 measured reflections
3553 independent reflections
2723 reflections with I > 2σ(I)
-1
R
int = 0.046
θ
max = 29.5°, θmin = 3.1°
Absorption correction: multi-scan
h = −27→26
k = −7→7
(CrysAlis PRO; Rigaku OD, 2018)
T
min = 0.601, Tmax = 1.000
l = −18→16
Refinement
2
Refinement on F
Hydrogen site location: mixed
H-atom parameters constrained
Least-squares matrix: full
R[F > 2σ(F )] = 0.037
2
2
2
2
2
w = 1/[σ (F
o
) + (0.0311P) + 1.0461P]
2
2
2
wR(F ) = 0.082
where P = (F
o
+ 2F )/3
c
S = 1.07
(Δ/σ)max = 0.001
Δρmax = 0.82 e Å
Δρmin = −0.78 e Å
−
3
3
2
0
553 reflections
08 parameters
restraints
−
3
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Refinement. Single-crystal X-ray diffraction measurements were performed on an Agilent–Gemini diffractometer
equipped with a CCD area detector using MoK? (0.71073 Å) radiation. The CrysAlisPro software package (Rigaku,
2
015) was used for data collection and reduction (Oxford Diffraction Ltda, version 171.38.41). The structures were
2
solved by direct methods using SHELXS-97 and refined by full-matrix least squares on F using SHELXL-2018
Sheldrick, 2015). All non-hydrogen atoms were refined using anisotropic displacement parameters.
(
Acta Cryst. (2019). C75, 1011-1020
sup-5

supporting information
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
Ag1
S1
0.45005 (2)
0.23113 (4)
0.47283 (10)
0.41107 (11)
0.23823 (11)
0.21229 (12)
0.05200 (13)
−0.00680 (14)
0.30383 (12)
0.33012
0.04063 (14)
0.42645 (14)
0.38807 (13)
0.32950 (14)
0.29988 (17)
0.261568
0.32676 (17)
0.306998
0.38302 (17)
0.400465
0.41304 (15)
0.450893
0.17263 (14)
0.17305 (15)
0.202846
1.02405 (5)
0.89424 (14)
0.3610 (4)
0.7127 (4)
1.0962 (4)
0.9467 (4)
0.0407 (5)
0.0579 (5)
0.7539 (5)
0.786538
0.1248 (5)
0.5073 (5)
0.4301 (5)
0.5556 (5)
0.4801 (6)
0.563509
1.2170 (6)
1.262994
1.3464 (6)
1.482049
1.2716 (5)
1.358491
0.6715 (5)
0.6189 (6)
0.703349
0.4414 (6)
0.403094
0.3220 (6)
0.3743 (6)
0.291552
0.5524 (6)
0.591882
0.25327 (2)
0.01834 (6)
0.13073 (16)
0.14202 (16)
0.09090 (18)
−0.08584 (18)
0.2615 (2)
0.1205 (2)
0.02430 (19)
0.075391
0.1763 (2)
0.0991 (2)
0.0032 (2)
−0.0338 (2)
−0.1271 (2)
−0.152159
0.3173 (2)
0.254646
0.3546 (2)
0.318074
0.4467 (2)
0.471398
0.0643 (2)
0.1683 (2)
0.212837
0.2050 (2)
0.274379
0.04349 (10)
0.03421 (18)
0.0406 (5)
0.0445 (5)
0.0451 (6)
0.0482 (6)
0.0599 (7)
0.0663 (8)
0.0351 (6)
0.042*
0.0448 (7)
0.0315 (6)
0.0282 (6)
0.0299 (6)
0.0420 (8)
0.05*
0.0450 (8)
0.054*
0.0420 (8)
0.05*
0.0358 (7)
0.043*
0.0309 (6)
0.0376 (7)
0.045*
O1
O2
O3
O4
O5
O6
N1
H1N
N2
C1
C2
C3
C4
H4
C5
H5
C6
H6
C7
H7
C8
C9
H9
C10
H10
C11
C12
H12
C13
H13
0.12919 (16)
0.128829
0.08587 (14)
0.08370 (15)
0.053164
0.0385 (7)
0.046*
0.0347 (7)
0.0409 (7)
0.049*
0.1366 (2)
0.0338 (2)
−0.01005
−0.0029 (2)
−0.072238
0.12790 (16)
0.127533
0.0397 (7)
0.048*
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
Ag1
S1
0.04819 (17)
0.0330 (4)
0.04274 (16)
0.0303 (4)
0.03908 (16)
0.0392 (4)
−0.00480 (11)
0.0023 (3)
−0.0003 (9)
0.0017 (10)
0.0014 (9)
0.0014 (11)
−0.0083 (12)
−0.0333 (15)
0.0029 (10)
−0.00562 (11)
−0.0008 (3)
−0.0045 (9)
−0.0098 (10)
0.0011 (11)
−0.0049 (11)
0.0054 (14)
0.0068 (14)
−0.0049 (10)
−0.00134 (11)
0.0045 (3)
O1
O2
O3
O4
O5
O6
N1
0.0330 (11)
0.0459 (13)
0.0450 (13)
0.0484 (14)
0.0645 (18)
0.0653 (18)
0.0314 (13)
0.0440 (12)
0.0461 (13)
0.0298 (11)
0.0511 (14)
0.0561 (16)
0.0734 (18)
0.0384 (14)
0.0444 (13)
0.0406 (13)
0.0605 (15)
0.0449 (14)
0.0593 (18)
0.0604 (17)
0.0350 (14)
0.0083 (10)
−0.0123 (11)
−0.0065 (11)
0.0193 (11)
0.0165 (13)
−0.0132 (14)
−0.0071 (11)
Acta Cryst. (2019). C75, 1011-1020
sup-6

supporting information
N2
C1
C2
C3
C4
C5
C6
C7
C8
0.0419 (16)
0.0263 (14)
0.0276 (14)
0.0319 (15)
0.0436 (18)
0.057 (2)
0.0411 (15)
0.0366 (16)
0.0300 (14)
0.0309 (14)
0.050 (2)
0.0520 (18)
0.0317 (15)
0.0271 (14)
0.0272 (14)
0.0323 (16)
0.0287 (16)
0.0374 (18)
0.0378 (17)
0.0320 (15)
0.0334 (16)
0.0284 (16)
0.0380 (17)
0.0401 (18)
0.0299 (16)
−0.0050 (12)
−0.0057 (12)
−0.0056 (11)
−0.0068 (11)
−0.0041 (14)
0.0137 (16)
0.0081 (14)
0.0021 (12)
0.0046 (11)
−0.0044 (13)
−0.0035 (14)
0.0003 (12)
−0.0048 (14)
−0.0012 (14)
0.0104 (13)
0.0044 (11)
0.0050 (11)
0.0037 (11)
−0.0059 (13)
0.0040 (14)
0.0151 (15)
0.0104 (13)
−0.0012 (11)
−0.0010 (13)
0.0040 (13)
0.0049 (12)
−0.0063 (13)
−0.0040 (13)
−0.0079 (14)
0.0058 (13)
0.0025 (11)
0.0021 (11)
−0.0014 (14)
0.0086 (14)
0.0062 (14)
−0.0008 (13)
0.0001 (12)
−0.0055 (13)
−0.0014 (13)
−0.0034 (13)
−0.0047 (15)
0.0024 (14)
0.050 (2)
0.052 (2)
0.0372 (17)
0.0327 (15)
0.0302 (14)
0.0404 (17)
0.0437 (18)
0.0344 (16)
0.0449 (18)
0.0492 (18)
0.0376 (16)
0.0303 (15)
0.0390 (17)
0.0435 (18)
0.0320 (15)
0.0373 (17)
0.0397 (17)
C9
C10
C11
C12
C13
Geometric parameters (Å, º)
i
iv
Ag1—O1
2.290 (2)
2.304 (2)
2.437 (2)
2.551 (3)
C2—C7
1.391 (4)
Ag1—O2
Ag1—O1
C2—C3
C3—C4
C4—C5
1.411 (4)
1.396 (4)
1.381 (5)
0.93
1.385 (5)
0.93
1.385 (4)
0.93
0.93
1.380 (4)
1.389 (4)
1.373 (4)
0.93
1.373 (4)
0.93
1.372 (4)
1.381 (4)
0.93
ii
iv
Ag1—C6
i
Ag1—Ag1
Ag1—Ag1
3.2926 (3)
3.2926 (3)
1.426 (2)
1.426 (2)
1.429 (2)
1.624 (2)
1.768 (3)
1.260 (3)
1.256 (3)
0.000 (4)
1.214 (4)
1.226 (4)
1.394 (4)
0.8531
C4—H4
C5—C6
C5—H5
iii
S1—O3
S1—O3
S1—O4
S1—N1
S1—C8
O1—C1
O2—C1
O3—O3
O5—N2
O6—N2
N1—C3
N1—H1N
N2—C11
C1—C2
C6—C7
C6—H6
C7—H7
C8—C13
C8—C9
C9—C10
C9—H9
C10—C11
C10—H10
C11—C12
C12—C13
C12—H12
C13—H13
1.476 (4)
1.504 (4)
0.93
i
iv
O1 —Ag1—O2
111.09 (8)
124.83 (6)
99.39 (8)
104.70 (9)
128.73 (10)
88.52 (9)
85.46 (6)
137.59 (6)
44.04 (5)
79.27 (8)
C7 —C2—C3
118.5 (3)
117.9 (3)
123.6 (3)
122.4 (3)
118.3 (2)
119.3 (3)
120.8 (3)
119.6
i
ii
iv
O1 —Ag1—O1
C7 —C2—C1
ii
O2—Ag1—O1
C3—C2—C1
N1—C3—C4
N1—C3—C2
C4—C3—C2
i
O1 —Ag1—C6
O2—Ag1—C6
ii
O1 —Ag1—C6
i
i
iv
O1 —Ag1—Ag1
C5 —C4—C3
i
iv
O2—Ag1—Ag1
C5 —C4—H4
ii
i
O1 —Ag1—Ag1
C3—C4—H4
119.6
120.3 (3)
i
vi
C6—Ag1—Ag1
C4 —C5—C6
Acta Cryst. (2019). C75, 1011-1020
sup-7

supporting information
i
iii
vi
O1 —Ag1—Ag1
47.72 (5)
67.17 (5)
115.69 (5)
150.14 (7)
105.420 (14)
0.00 (18)
120.67 (14)
120.67 (14)
103.59 (13)
103.59 (13)
109.82 (14)
108.40 (14)
108.40 (14)
107.19 (14)
106.35 (13)
117.37 (19)
120.41 (18)
88.24 (7)
143.8 (2)
0 (10)
130.8 (2)
110.5
118.1
124.1 (3)
118.6 (3)
117.3 (3)
124.2 (3)
118.6 (3)
117.3 (3)
C4 —C5—H5
119.9
119.9
119.3 (3)
92.67 (19)
85.7 (2)
120.3
120.3
91.6
121.7 (3)
119.1
119.1
121.2 (3)
120.0 (2)
118.7 (2)
119.6 (3)
120.2
120.2
118.3 (3)
120.8
iii
O2—Ag1—Ag1
C6—C5—H5
C7—C6—C5
C7—C6—Ag1
C5—C6—Ag1
C7—C6—H6
C5—C6—H6
Ag1—C6—H6
ii
iii
O1 —Ag1—Ag1
iii
C6—Ag1—Ag1
i
iii
Ag1 —Ag1—Ag1
O3—S1—O3
O3—S1—O4
O3—S1—O4
O3—S1—N1
O3—S1—N1
O4—S1—N1
O3—S1—C8
O3—S1—C8
O4—S1—C8
N1—S1—C8
vi
C6—C7—C2
C6—C7—H7
vi
C2 —C7—H7
C13—C8—C9
C13—C8—S1
C9—C8—S1
C10—C9—C8
C10—C9—H9
C8—C9—H9
C9—C10—C11
C9—C10—H10
C11—C10—H10
C12—C11—C10
C12—C11—N2
C10—C11—N2
C11—C12—C13
C11—C12—H12
C13—C12—H12
C8—C13—C12
C8—C13—H13
C12—C13—H13
iii
C1—O1—Ag1
C1—O1—Ag1
Ag1 —O1—Ag1
v
iii
v
C1—O2—Ag1
O3—O3—S1
C3—N1—S1
C3—N1—H1N
S1—N1—H1N
O5—N2—O6
O5—N2—C11
O6—N2—C11
O2—C1—O1
O2—C1—C2
O1—C1—C2
120.8
123.1 (3)
118.9 (3)
117.9 (3)
118.5 (3)
120.8
120.8
119.3 (3)
120.4
120.4
vi
O4—S1—O3—O3
N1—S1—O3—O3
C8—S1—O3—O3
O3—S1—N1—C3
O3—S1—N1—C3
O4—S1—N1—C3
C8—S1—N1—C3
Ag1—O2—C1—O1
Ag1—O2—C1—C2
0.0 (6)
0.0 (6)
0.0 (6)
−174.6 (3)
−174.6 (3)
−44.4 (3)
71.3 (3)
C4 —C5—C6—Ag1
92.3 (3)
−0.2 (4)
vi
C5—C6—C7—C2
Ag1—C6—C7—C2
vi
−86.7 (3)
142.3 (2)
142.3 (2)
10.5 (3)
−106.9 (3)
−38.1 (3)
−38.1 (3)
−169.8 (2)
72.8 (3)
O3—S1—C8—C13
O3—S1—C8—C13
O4—S1—C8—C13
N1—S1—C8—C13
O3—S1—C8—C9
O3—S1—C8—C9
O4—S1—C8—C9
N1—S1—C8—C9
C13—C8—C9—C10
S1—C8—C9—C10
C8—C9—C10—C11
20.5 (5)
−158.7 (2)
−16.2 (4)
89.1 (3)
163.05 (17)
−91.7 (3)
168.7 (2)
−10.6 (4)
−9.4 (4)
171.3 (2)
15.8 (4)
iii
Ag1 —O1—C1—O2
v
Ag1 —O1—C1—O2
iii
Ag1 —O1—C1—C2
1.4 (5)
−178.3 (2)
−0.3 (5)
v
Ag1 —O1—C1—C2
iv
O2—C1—C2—C7
O1—C1—C2—C7
iv
C9—C10—C11—C12
C9—C10—C11—N2
O5—N2—C11—C12
O6—N2—C11—C12
−1.0 (5)
O2—C1—C2—C3
O1—C1—C2—C3
S1—N1—C3—C4
177.8 (3)
164.6 (3)
−16.0 (4)
Acta Cryst. (2019). C75, 1011-1020
sup-8

supporting information
S1—N1—C3—C2
C7 —C2—C3—N1
−165.0 (2)
178.6 (2)
−3.3 (4)
−2.2 (4)
175.9 (3)
179.9 (3)
0.7 (4)
O5—N2—C11—C10
O6—N2—C11—C10
−14.3 (4)
165.1 (3)
1.1 (5)
−177.7 (3)
−1.3 (5)
178.4 (2)
0.1 (5)
iv
C1—C2—C3—N1
C10—C11—C12—C13
N2—C11—C12—C13
C9—C8—C13—C12
S1—C8—C13—C12
C11—C12—C13—C8
iv
C7 —C2—C3—C4
C1—C2—C3—C4
N1—C3—C4—C5
iv
iv
C2—C3—C4—C5
vi
C4 —C5—C6—C7
1.7 (5)
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) −x+1, y−1/2, −z+1/2; (iv) x, −y+3/2, z−1/2; (v) x, y−1, z; (vi) x, −y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
C5—H5···O3
0.93
0.93
0.93
0.85
0.93
2.65
2.7
2.49
1.85
2.41
3.457 (4)
3.424 (4)
3.369 (4)
2.602 (3)
3.062 (4)
145
136
157
146
127
vii
C13—H13···O5
C12—H12···O6
N1—H1N···O2
C4—H4···O4
viii
Symmetry codes: (vii) x, −y+1/2, z−1/2; (viii) −x, −y, −z.
Acta Cryst. (2019). C75, 1011-1020
sup-9