Crystal structure of [2,13-bis­(acetamido)-5,16-dimethyl-2,6,13,17-tetra­aza­tri­cyclo­[16.4.0.07,12]docosane-κ4N]silver(II) dinitrate from synchrotron X-ray data

Moon, D.; Choi, J.-H.

doi:10.1107/S2056989018003560

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 74| Part 4| April 2018| Pages 461-464

https://doi.org/10.1107/S2056989018003560

Open

access

Crystal structure of [2,13-bis(acetamido)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.0^7,12]docosane-κ⁴N]silver(II) dinitrate from synchrotron X-ray data

Dohyun Moon ^a and Jong-Ha Choi ^b ^*

^aPohang Accelerator Laboratory, POSTECH, Pohang 37673, Republic of Korea, and ^bDepartment of Chemistry, Andong National University, Andong 36729, Republic of Korea
^*Correspondence e-mail: jhchoi@anu.ac.kr

Edited by J. Simpson, University of Otago, New Zealand (Received 26 February 2018; accepted 1 March 2018; online 6 March 2018)

The asymmetric unit of the title compound, [Ag(C₂₄H₄₆N₆O₂)](NO₃)₂ [C₂₄H₄₆N₆O₂ is (5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.0^7,12]docosane-2,13-diyl)diacetamide, L], consists of one independent half of the [Ag(C₂₄H₄₆N₆O₂)]²⁺ cation and one nitrate anion. The Ag atom, lying on an inversion centre, has a square-planar geometry and the complex adopts a stable trans-III conformation. Interestingly, the two O atoms of the pendant acetamide groups are not coordinated to the Ag^II ion. The longer distance of 2.227 (2) Å for Ag—N(tertiary) compared to 2.134 (2) Å for Ag—N(secondary) may be due to the effects of the attached acetamide group on the tertiary N atom. Two nitrate anions are very weakly bound to the Ag^II ion in the axial sites and are further connected to the ligand of the cation by N—H⋯O hydrogen bonds. The crystal packing is stabilized by hydrogen-bonding interactions among the N—H donor groups of the macrocycle and its actetamide substituents, and the O atoms of the nitrate anions and of an acetamide group as the acceptor atoms.

Keywords: crystal structure; macrocycle; synchrotron radiation; silver(II) complex; nitrate ion; trans-III conformation; hydrogen bonding.

CCDC reference: 1826672

1. Chemical context

Macrocycles with N-substituted groups on the polyaza macrocyclic ring and their transition metal complexes have attracted considerable attention because of their structural and chemical properties, which are different from those of the corresponding unsubstituted macrocyclic systems. Recently, it has been shown that the cyclam (1,4,8,11-tetraazacyclotetradecane) derivatives and their metal complexes exhibit anti-HIV activity (Ronconi & Sadler, 2007 ; De Clercq, 2010 ; Ross et al., 2012 ). These cyclam-based macrocyclic ligands have a moderately flexible structure, and can adopt both planar (trans) and folded (cis) configurations. There are five conformational trans isomers for the cyclam moiety, which differ in the chirality of the sec-NH centers (Choi, 2009 ). The trans-I, trans-II and trans-V configurations can fold to form cis-I, cis-II and cis-V isomers, respectively (Subhan et al., 2011 ). The conformation of the macrocyclic ligand and the orientations of the N–H bonds are very important factors for co-receptor recognition. Therefore, knowledge of the conformation and crystal packing of transition metal complexes containing the cyclam ligand has become important in the development of new highly effective anti-HIV drugs that specially target alternative events in the HIV replicative cycle (De Clercq, 2010). Partially N-substituted tetraazamacrocycles and their complexes have been much less widely studied. This may be due to the difficulty encountered in the attachment of only one or two pendant arms to the tetraaza macrocycle by several steps and in low yields. The presence of two methyl substituents on the macrocyclic ring carbon atoms next to the secondary amine groups facilitates syntheses, as N-substitution takes place only on the less sterically hindered nitrogen atoms.

The syntheses and crystal structures of transition metal complexes with the constrained cyclam ligand containing two acetamide groups on the nitrogen atoms have received much attention because of the effects of the functional groups on their chemical properties and coordination geometry (Choi et al., 2001a ,b ,c ; Choi & Lee, 2007 ). The nitrate ion can also coordinate to the transition metal ions in a monodentate, chelating bidentate or bridging bidentate fashion. The oxidation state of the metal, the nature of other ligands and steric factors influence the mode of coordination.

In this communication, we report the synthesis and structural characterization a new silver(II) complex, [Ag(C₂₄H₄₆N₆O₂)](NO₃)₂, (I) to confirm the conformation and bonding modes of the macrocyclic ligand and the nitrate anions.

2. Structural commentary

The structural analysis showed the space group to be P $[\overline1]$ with Z = 1. The asymmetric unit contains one independent half of the [Ag(C₂₄H₄₆N₆O₂)]²⁺ cation and one nitrate anion. The silver(II) cation is situated on a center of inversion in the small triclinic cell, which contains a single silver(II) complex. An ellipsoid plot of the title compound is shown in Fig. 1 along with the atomic numbering scheme. The two methyl groups on the six-membered chelate rings and the two –(CH₂)₄– parts of the cyclohexane backbones are anti with respect to the macrocyclic plane. Two pendant acetamide groups in the Ag^II complex molecule are also trans to each other, and thus the macrocyclic skeleton adopts the most stable trans-III (RRSS) conformation. The five-membered chelate rings adopt a gauche, and the six-membered rings are in chair conformations. The Ag^II cation is surrounded by a square-planar array of four nitrogen atoms from the secondary and tertiary amines in the macrocycle. Interestingly, the oxygen atoms of the acetamide substituents are not coordinated to the metal center. It is noteworthy that the Zn^II, Ni^II and Cu^II complexes of the same ligand have a tetragonally distorted octahedral environment with the four N atoms of the macrocyclic ligand in equatorial positions and the O atoms of the pendant acetamide groups in axial positions (Choi et al., 2001a,b,c; Choi & Lee, 2007). The Ag—N bond lengths of 2.134 (2) and 2.227 (2) Å from the donor atoms of the macrocycle can be compared to those determined in [Ag(cyclam)](ClO₄)₂ [2.158 (2)–2.192 (2) Å; Ito et al., 1981 ], [Ag(tmc)](ClO₄)₂ [2.194 (2)–2.196 (2) Å; tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; Po et al., 1991 ], [Ag(tet a)](NO₃)₂ [2.159 (3)–2.162 (3) Å; tet a = C-meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; Mertes, 1978 ] and [Ag(3,14-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.0^7,12]docosane)](NO₃)₂·4H₂O [2.140 (2)–2.150 (3) Å; Moon et al., 2010 ]. The longer Ag—N(tertiary) bond distance, compared to the length of the Ag—N(secondary) bond may be due to the steric and inductive effects of the pendant acetamide group on the tertiary N atom. The Ag—O distance of 3.109 (2) Å is longer than the corresponding distances in [Ag(cyclam)](ClO₄)₂ [2.788 (2) Å; Ito et al., 1981], [Ag(tmc)](ClO₄)₂ [2.889 (4) Å; Po et al., 1991], [Ag(tet a)](NO₃)₂ [2.807 (4) Å; Mertes, 1978] and [Ag(3,14-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.0^7,12]docosane)](NO₃)₂·4H₂O [2.923 (2) Å; Moon et al., 2010]. The longest N1—C4 bond distance is also probably due to the effect of the acetamide group and the cyclohexane ring. The nitrate anion has a slightly distorted trigonal-planar geometry because of the hydrogen bonding interactions and the very weak interaction with the silver(II) ion. Two nitrate ions are located above and below the coordination planes, and each are linked to the cation via N—H⋯O hydrogen bonds.

Figure 1
A perspective view (50% probability) of complex (I)

. The primed atoms are related by the symmetry operation (−x + 1, −y + 1, −z + 1). Hydrogen bonds are drawn as dashed lines.

3. Supramolecular features

Extensive hydrogen-bonding interactions occur in the crystal structure (Table 1). The nitrate ions are connected to the ligand of the cation via N—H⋯O hydrogen bonds. The nitrate anions have slightly distorted trigonal–planar geometries because of these interactions and the very weak interaction with the silver(II) cation. The supramolecular architecture involves hydrogen bonds between the N—H groups of both the macrocycle and its pendant acetamide substituents as donors, and the O atoms of the nitrate anions and the acetamides as acceptors. An array of these contacts generate a two-dimensional sheet of molecules stacked along the b-axis direction (Fig. 2). This hydrogen-bonded network helps to stabilize the crystal structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1N	1.00	2.59	3.214 (4)	121
N2—H2⋯O3N	1.00	1.93	2.925 (4)	172
N3—H3A⋯O1ⁱ	0.88	2.03	2.913 (4)	177
N3—H3B⋯O1Nⁱⁱ	0.88	2.06	2.930 (4)	168
N3—H3B⋯O2Nⁱⁱ	0.88	2.59	3.281 (4)	136
Symmetry codes: (i) -x, -y+1, -z; (ii) x-1, y, z.

Figure 2
The crystal packing in complex (I)

, viewed along the b-axis direction. Dashed lines represent N—H⋯O hydrogen-bonding interactions.

4. Database survey

A search of the Cambridge Structural Database (Version 5.38, May 2017 with three updates; Groom et al., 2016 ) gave four hits for the macrocycle (C₂₄H₄₆N₆O₂) unit. The crystal structures of [Cu(C₂₄H₄₆N₆O₂)]Cl₂·8H₂O (Choi et al., 2001a), [Zn(C₂₄H₄₆N₆O₂)]Cl₂·3H₂O (Choi et al., 2001b), [Ni(C₂₄H₄₆N₆O₂)](ClO₄)₂ (Choi et al., 2001c) and [Cu(C₂₄H₄₆N₆O₂)](ClO₄)₂ (Choi et al., 2001c) have been reported previously. In all of these structures, two O atoms of the acetamide substituents occupy the axial positions, giving rise to a tetragonally distorted octahedral geometry. This is quite unlike the square-planar geometry of the title compound as the two O atoms of the acetamide substituents are not bound to the silver(II) cation in this case. Until now, no structure of the complex ion [Ag(C₂₄H₄₆N₆O₂)]²⁺ with any anion has been reported.

5. Synthesis and crystallization

As a starting material, 3,14-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.0^7,12]docosane was prepared according to a published procedure (Kang et al., 1991 ). All other chemicals were purchased from commercial sources and used without further purification. The macrocyclic ligand 2,13-bis(acetamido)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.0^7,12]docosane (L) was prepared by a previously reported method (Maumela et al., 1995 ). AgNO₃ (0.34 g, 2 mmol) dissolved in water (10 mL) was mixed with a suspension of the ligand L (0.45 g, 1 mmol) in methanol (20 mL). The resulting mixture was heated at 313 K for 30 min and then filtered to remove metallic silver. The orange filtrate was left in an open beaker, protected from the light, at ambient temperature. After several days block-like dark-orange crystals of (I) suitable only for synchrotron X-ray analysis were formed.

In the synthesis of the title complex, two pertinent features are found. One is that the complex contains the silver in the unusually high oxidation state, Ag^II. This is stabilized by the macrocycle L. The complex is the product of the disproportionation of the Ag^I complex according to the following equation:

2Ag^I + L → Ag^IIL + Ag(s) ↓

It is generally understood that macrocyclic ligands possess a suitable cavity size and hard nitrogen donor atoms that can form stable Ag^II complexes in aqueous solution (Ali et al., 2004 ).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.98–1.00 Å and an N—H distance of 0.88–1.0 Å. All displacement parameters of H atoms U_iso(H) were set to 1.2 or 1.5U_eq of their respective parent atoms.

Table 2
Experimental details

Crystal data
Chemical formula	[Ag(C₂₄H₄₆N₆O₂)](NO₃)₂
M_r	682.56
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	173
a, b, c (Å)	8.3460 (17), 9.2874 (19), 10.171 (2)
α, β, γ (°)	104.32 (3), 90.28 (3), 109.60 (3)
V (Å³)	716.3 (3)
Z	1
Radiation type	Synchrotron, λ = 0.610 Å
μ (mm⁻¹)	0.51
Crystal size (mm)	0.02 × 0.02 × 0.01

Data collection
Diffractometer	ADSC Q210 CCD area detector
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.937, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7431, 3750, 3418
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.693

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.115, 1.05
No. of reflections	3750
No. of parameters	189
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.71, −2.17
Computer programs: PAL BL2D-SMDC Program (Shin et al., 2016 ), HKL3000sm (Otwinowski & Minor, 1997), SHELXT2014 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), DIAMOND 4 (Putz & Brandenburg, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1826672

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018003560/sj5548sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018003560/sj5548Isup2.hkl

checkCIF report

Computing details top

Data collection: PAL BL2D-SMDC Program (Shin et al., 2016); cell refinement: HKL3000sm (Otwinowski & Minor, 1997); data reduction: HKL3000sm (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND 4 (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

[(5,16-Dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.0^7,12]docosane-2,13-diyl)diacetamide-κ⁴N²,N⁶,N¹³,N¹⁷]silver(II) dinitrate top

Crystal data top

[Ag(C₂₄H₄₆N₆O₂)](NO₃)₂	Z = 1
M_r = 682.56	F(000) = 357
Triclinic, P1	D_x = 1.582 Mg m⁻³
a = 8.3460 (17) Å	Synchrotron radiation, λ = 0.610 Å
b = 9.2874 (19) Å	Cell parameters from 46429 reflections
c = 10.171 (2) Å	θ = 0.4–33.7°
α = 104.32 (3)°	µ = 0.51 mm⁻¹
β = 90.28 (3)°	T = 173 K
γ = 109.60 (3)°	Block, dark orange
V = 716.3 (3) Å³	0.02 × 0.02 × 0.01 mm

Data collection top

ADSC Q210 CCD area detector diffractometer	3418 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	R_int = 0.034
ω scan	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	h = −11→11
T_min = 0.937, T_max = 1.000	k = −12→12
7431 measured reflections	l = −14→14
3750 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0747P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.115	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.71 e Å⁻³
3750 reflections	Δρ_min = −2.17 e Å⁻³
189 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.065 (6)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ag1	0.500000	0.500000	0.500000	0.01559 (13)
O1	0.2273 (3)	0.5401 (3)	0.0700 (3)	0.0332 (6)
N1	0.3945 (3)	0.4502 (3)	0.2855 (2)	0.0138 (4)
N2	0.3842 (3)	0.2496 (3)	0.4657 (2)	0.0141 (4)
H2	0.480698	0.207953	0.460293	0.017*
N3	−0.0231 (4)	0.4445 (4)	0.1558 (3)	0.0287 (6)
H3A	−0.082643	0.448023	0.085766	0.034*
H3B	−0.075649	0.410273	0.222782	0.034*
C1	0.5320 (4)	0.5522 (4)	0.2206 (3)	0.0190 (6)
H1A	0.491733	0.531956	0.123804	0.023*
H1AB	0.633336	0.519689	0.222357	0.023*
C2	0.2334 (4)	0.4871 (4)	0.2920 (3)	0.0200 (6)
H2A	0.258145	0.591883	0.357970	0.024*
H2AB	0.149558	0.408176	0.330418	0.024*
C3	0.1459 (4)	0.4909 (4)	0.1604 (3)	0.0223 (6)
C4	0.3680 (4)	0.2774 (3)	0.2288 (3)	0.0167 (5)
H4	0.483624	0.268837	0.217142	0.020*
C5	0.2651 (4)	0.2038 (4)	0.0888 (3)	0.0218 (6)
H5A	0.148066	0.206799	0.096639	0.026*
H5B	0.319617	0.266303	0.024804	0.026*
C6	0.2561 (5)	0.0326 (4)	0.0329 (3)	0.0296 (7)
H6A	0.186557	−0.013650	−0.056301	0.035*
H6B	0.372603	0.030416	0.018612	0.035*
C7	0.1776 (5)	−0.0665 (4)	0.1307 (3)	0.0318 (8)
H7A	0.179869	−0.175056	0.095173	0.038*
H7B	0.056864	−0.074055	0.137454	0.038*
C8	0.2763 (5)	0.0082 (4)	0.2717 (3)	0.0249 (6)
H8A	0.393756	0.005616	0.265973	0.030*
H8B	0.220186	−0.054797	0.334862	0.030*
C9	0.2852 (4)	0.1794 (3)	0.3284 (3)	0.0148 (5)
H9	0.166364	0.180502	0.337656	0.018*
C10	0.2906 (4)	0.2024 (3)	0.5819 (3)	0.0182 (5)
H10	0.252172	0.084275	0.560973	0.022*
C11	0.4128 (4)	0.2696 (4)	0.7127 (3)	0.0207 (6)
H11A	0.357944	0.213455	0.780635	0.025*
H11B	0.517100	0.243381	0.692138	0.025*
C12	0.1312 (4)	0.2481 (4)	0.5968 (3)	0.0269 (7)
H12A	0.159371	0.357672	0.591454	0.040*
H12B	0.088753	0.238874	0.685098	0.040*
H12C	0.042823	0.177157	0.523376	0.040*
O1N	0.7629 (4)	0.3507 (3)	0.3690 (3)	0.0343 (6)
O2N	0.8673 (3)	0.1611 (3)	0.3122 (3)	0.0338 (6)
O3N	0.6869 (3)	0.1576 (3)	0.4643 (3)	0.0328 (6)
N1N	0.7737 (3)	0.2225 (3)	0.3815 (3)	0.0237 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.01841 (18)	0.01836 (19)	0.00929 (16)	0.00500 (12)	−0.00143 (10)	0.00443 (10)
O1	0.0323 (13)	0.0502 (16)	0.0254 (12)	0.0174 (12)	0.0029 (10)	0.0203 (11)
N1	0.0189 (11)	0.0161 (11)	0.0080 (9)	0.0073 (9)	−0.0004 (8)	0.0043 (8)
N2	0.0177 (11)	0.0149 (11)	0.0100 (10)	0.0054 (9)	0.0004 (8)	0.0042 (8)
N3	0.0271 (14)	0.0434 (18)	0.0213 (13)	0.0161 (13)	0.0001 (11)	0.0132 (12)
C1	0.0216 (14)	0.0232 (14)	0.0102 (11)	0.0044 (11)	0.0030 (10)	0.0058 (10)
C2	0.0248 (15)	0.0243 (15)	0.0128 (12)	0.0118 (12)	−0.0022 (10)	0.0038 (10)
C3	0.0306 (16)	0.0216 (15)	0.0172 (13)	0.0127 (13)	−0.0030 (11)	0.0045 (11)
C4	0.0200 (13)	0.0201 (14)	0.0084 (11)	0.0068 (11)	−0.0012 (9)	0.0013 (9)
C5	0.0291 (16)	0.0251 (15)	0.0103 (12)	0.0110 (13)	−0.0036 (10)	0.0007 (10)
C6	0.0408 (19)	0.0286 (17)	0.0162 (14)	0.0164 (15)	−0.0059 (13)	−0.0056 (12)
C7	0.044 (2)	0.0203 (16)	0.0237 (16)	0.0103 (15)	−0.0127 (14)	−0.0049 (12)
C8	0.0338 (17)	0.0178 (14)	0.0194 (14)	0.0074 (13)	−0.0060 (12)	0.0006 (11)
C9	0.0177 (13)	0.0165 (13)	0.0112 (11)	0.0079 (10)	−0.0011 (9)	0.0028 (9)
C10	0.0211 (14)	0.0175 (13)	0.0153 (12)	0.0036 (11)	0.0023 (10)	0.0073 (10)
C11	0.0275 (15)	0.0233 (15)	0.0136 (12)	0.0078 (12)	0.0017 (11)	0.0106 (11)
C12	0.0206 (15)	0.0370 (19)	0.0193 (14)	0.0072 (13)	0.0040 (11)	0.0046 (13)
O1N	0.0386 (15)	0.0353 (14)	0.0385 (14)	0.0187 (12)	0.0114 (11)	0.0183 (11)
O2N	0.0326 (14)	0.0448 (16)	0.0263 (12)	0.0211 (12)	0.0051 (10)	0.0027 (11)
O3N	0.0376 (14)	0.0359 (14)	0.0388 (14)	0.0232 (12)	0.0152 (11)	0.0195 (11)
N1N	0.0222 (13)	0.0297 (15)	0.0203 (12)	0.0137 (11)	−0.0037 (10)	0.0021 (10)

Geometric parameters (Å, º) top

Ag1—N2ⁱ	2.134 (2)	C5—H5A	0.9900
Ag1—N2	2.134 (2)	C5—H5B	0.9900
Ag1—N1	2.227 (2)	C6—C7	1.523 (5)
Ag1—N1ⁱ	2.227 (2)	C6—H6A	0.9900
O1—C3	1.234 (4)	C6—H6B	0.9900
N1—C2	1.493 (4)	C7—C8	1.527 (4)
N1—C1	1.496 (4)	C7—H7A	0.9900
N1—C4	1.504 (4)	C7—H7B	0.9900
N2—C9	1.494 (3)	C8—C9	1.527 (4)
N2—C10	1.495 (3)	C8—H8A	0.9900
N2—H2	1.0000	C8—H8B	0.9900
N3—C3	1.326 (4)	C9—H9	1.0000
N3—H3A	0.8800	C10—C12	1.524 (4)
N3—H3B	0.8800	C10—C11	1.532 (4)
C1—C11ⁱ	1.530 (4)	C10—H10	1.0000
C1—H1A	0.9900	C11—H11A	0.9900
C1—H1AB	0.9900	C11—H11B	0.9900
C2—C3	1.535 (4)	C12—H12A	0.9800
C2—H2A	0.9900	C12—H12B	0.9800
C2—H2AB	0.9900	C12—H12C	0.9800
C4—C5	1.531 (4)	O1N—N1N	1.261 (4)
C4—C9	1.540 (4)	O2N—N1N	1.240 (4)
C4—H4	1.0000	O3N—N1N	1.249 (4)
C5—C6	1.526 (5)

N2ⁱ—Ag1—N2	180.0	H5A—C5—H5B	108.1
N2ⁱ—Ag1—N1	96.57 (9)	C7—C6—C5	111.1 (3)
N2—Ag1—N1	83.43 (9)	C7—C6—H6A	109.4
N2ⁱ—Ag1—N1ⁱ	83.43 (9)	C5—C6—H6A	109.4
N2—Ag1—N1ⁱ	96.57 (9)	C7—C6—H6B	109.4
N1—Ag1—N1ⁱ	180.0 (2)	C5—C6—H6B	109.4
C2—N1—C1	114.7 (2)	H6A—C6—H6B	108.0
C2—N1—C4	114.1 (2)	C6—C7—C8	110.4 (3)
C1—N1—C4	111.6 (2)	C6—C7—H7A	109.6
C2—N1—Ag1	106.66 (16)	C8—C7—H7A	109.6
C1—N1—Ag1	105.59 (17)	C6—C7—H7B	109.6
C4—N1—Ag1	102.92 (15)	C8—C7—H7B	109.6
C9—N2—C10	115.8 (2)	H7A—C7—H7B	108.1
C9—N2—Ag1	109.76 (16)	C7—C8—C9	111.9 (3)
C10—N2—Ag1	113.18 (17)	C7—C8—H8A	109.2
C9—N2—H2	105.7	C9—C8—H8A	109.2
C10—N2—H2	105.7	C7—C8—H8B	109.2
Ag1—N2—H2	105.7	C9—C8—H8B	109.2
C3—N3—H3A	120.0	H8A—C8—H8B	107.9
C3—N3—H3B	120.0	N2—C9—C8	110.5 (2)
H3A—N3—H3B	120.0	N2—C9—C4	110.5 (2)
N1—C1—C11ⁱ	115.2 (2)	C8—C9—C4	109.6 (2)
N1—C1—H1A	108.5	N2—C9—H9	108.7
C11ⁱ—C1—H1A	108.5	C8—C9—H9	108.7
N1—C1—H1AB	108.5	C4—C9—H9	108.7
C11ⁱ—C1—H1AB	108.5	N2—C10—C12	111.9 (2)
H1A—C1—H1AB	107.5	N2—C10—C11	109.9 (2)
N1—C2—C3	119.0 (2)	C12—C10—C11	113.0 (2)
N1—C2—H2A	107.6	N2—C10—H10	107.3
C3—C2—H2A	107.6	C12—C10—H10	107.3
N1—C2—H2AB	107.6	C11—C10—H10	107.3
C3—C2—H2AB	107.6	C1ⁱ—C11—C10	117.6 (2)
H2A—C2—H2AB	107.0	C1ⁱ—C11—H11A	107.9
O1—C3—N3	123.2 (3)	C10—C11—H11A	107.9
O1—C3—C2	122.4 (3)	C1ⁱ—C11—H11B	107.9
N3—C3—C2	114.3 (3)	C10—C11—H11B	107.9
N1—C4—C5	113.8 (2)	H11A—C11—H11B	107.2
N1—C4—C9	111.8 (2)	C10—C12—H12A	109.5
C5—C4—C9	109.8 (2)	C10—C12—H12B	109.5
N1—C4—H4	107.0	H12A—C12—H12B	109.5
C5—C4—H4	107.0	C10—C12—H12C	109.5
C9—C4—H4	107.0	H12A—C12—H12C	109.5
C6—C5—C4	110.7 (3)	H12B—C12—H12C	109.5
C6—C5—H5A	109.5	O2N—N1N—O3N	120.6 (3)
C4—C5—H5A	109.5	O2N—N1N—O1N	120.7 (3)
C6—C5—H5B	109.5	O3N—N1N—O1N	118.6 (3)
C4—C5—H5B	109.5

C2—N1—C1—C11ⁱ	57.5 (3)	C6—C7—C8—C9	56.2 (4)
C4—N1—C1—C11ⁱ	−170.8 (2)	C10—N2—C9—C8	−78.2 (3)
Ag1—N1—C1—C11ⁱ	−59.7 (3)	Ag1—N2—C9—C8	152.1 (2)
C1—N1—C2—C3	53.5 (3)	C10—N2—C9—C4	160.3 (2)
C4—N1—C2—C3	−77.0 (3)	Ag1—N2—C9—C4	30.6 (3)
Ag1—N1—C2—C3	170.0 (2)	C7—C8—C9—N2	−179.4 (3)
N1—C2—C3—O1	−35.8 (4)	C7—C8—C9—C4	−57.4 (4)
N1—C2—C3—N3	147.4 (3)	N1—C4—C9—N2	−52.8 (3)
C2—N1—C4—C5	54.2 (3)	C5—C4—C9—N2	179.9 (2)
C1—N1—C4—C5	−77.8 (3)	N1—C4—C9—C8	−174.8 (2)
Ag1—N1—C4—C5	169.4 (2)	C5—C4—C9—C8	57.9 (3)
C2—N1—C4—C9	−70.9 (3)	C9—N2—C10—C12	−59.3 (3)
C1—N1—C4—C9	157.1 (2)	Ag1—N2—C10—C12	68.7 (3)
Ag1—N1—C4—C9	44.3 (2)	C9—N2—C10—C11	174.3 (2)
N1—C4—C5—C6	175.4 (3)	Ag1—N2—C10—C11	−57.7 (3)
C9—C4—C5—C6	−58.5 (3)	N2—C10—C11—C1ⁱ	73.2 (3)
C4—C5—C6—C7	57.5 (4)	C12—C10—C11—C1ⁱ	−52.5 (3)
C5—C6—C7—C8	−55.6 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1N	1.00	2.59	3.214 (4)	121
N2—H2···O3N	1.00	1.93	2.925 (4)	172
N3—H3A···O1ⁱⁱ	0.88	2.03	2.913 (4)	177
N3—H3B···O1Nⁱⁱⁱ	0.88	2.06	2.930 (4)	168
N3—H3B···O2Nⁱⁱⁱ	0.88	2.59	3.281 (4)	136

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

Funding information

This work was supported by a Research Grant of Andong National University. The X-ray crystallography experiment at PLS-II BL2D-SMC beamline was supported in part by MSIT and POSTECH.

References

Ali, M., Shames, A. I., Gangopadhyay, S., Saha, B. & Meyerstein, D. (2004). Transition Met. Chem. 29, 463–470. Web of Science CrossRef CAS Google Scholar
Choi, J.-H. (2009). Inorg. Chim. Acta, 362, 4231–4236. Web of Science CSD CrossRef CAS Google Scholar
Choi, K.-Y., Kim, Y.-S., Choo, G.-H., Kim, J.-G. & Suh, I.-H. (2001a). Acta Cryst. C57, 1014–1015. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Choi, K.-Y., Kim, H.-H. & Suh, I.-H. (2001b). J. Korean Chem. Soc. 45, 189–193. CAS Google Scholar
Choi, K.-Y. & Lee, H.-K. (2007). J. Chem. Crystallogr. 37, 669–673. Web of Science CSD CrossRef CAS Google Scholar
Choi, K.-Y., Lee, H.-H., Park, B. B., Kim, J. H., Kim, J., Kim, M.-W., Ryu, J.-W., Suh, M. & Suh, I.-H. (2001c). Polyhedron, 20, 2003–2009. Web of Science CSD CrossRef CAS Google Scholar
De Clercq, E. (2010). J. Med. Chem. 53, 1438–1450. Web of Science CrossRef PubMed CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ito, T., Ito, H. & Toriumi, K. (1981). Chem. Lett. 10, 1101–1104. CSD CrossRef Web of Science Google Scholar
Kang, S. G., Kweon, J. K. & Jung, S. K. (1991). Bull. Korean Chem. Soc. 12, 483–487. CAS Google Scholar
Maumela, H., Hancock, R. D., Carlton, L., Reibenspies, J. H. & Wainwright, K. P. (1995). J. Am. Chem. Soc. 117, 6698–6707. CSD CrossRef CAS Web of Science Google Scholar
Mertes, K. B. (1978). Inorg. Chem. 17, 49–52. CSD CrossRef CAS Web of Science Google Scholar
Moon, J. R., Lough, A. J., Yoon, Y. T., Kim, Y. I. & Kim, J. C. (2010). Inorg. Chim. Acta, 363, 2682–2685. Web of Science CSD CrossRef CAS Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Po, H. N., Brinkman, E. & Doedens, R. J. (1991). Acta Cryst. C47, 2310–2312. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Putz, H. & Brandenburg, K. (2014). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Ronconi, L. & Sadler, P. J. (2007). Coord. Chem. Rev. 251, 1633–1648. Web of Science CrossRef CAS Google Scholar
Ross, A., Choi, J.-H., Hunter, T. M., Pannecouque, C., Moggach, S. A., Parsons, S., De Clercq, E. & Sadler, P. J. (2012). Dalton Trans. 41, 6408–6418. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shin, J. W., Eom, K. & Moon, D. (2016). J. Synchrotron Rad. 23, 369–373. Web of Science CrossRef IUCr Journals Google Scholar
Subhan, M. A., Choi, J.-H. & Ng, S. W. (2011). Z. Anorg. Allg. Chem. 637, 2193–2197. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.