catena-Poly[3,3′-diethyl-1,1′-(propane-1,3-di­yl)di(1H-imidazol-3-ium) [silver(I)-di-μ-iodido-silver(I)-di-μ-iodido]]

Huo, J.-Z.; Zhao, Z.-X.; Shi, M.-C.; Li, H.-L.; Liu, Q.-X.

doi:10.1107/S1600536812020715

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page m787

doi:10.1107/S1600536812020715

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catena-Poly[3,3′-diethyl-1,1′-(propane-1,3-diyl)di(1H-imidazol-3-ium) [silver(I)-di-μ-iodido-silver(I)-di-μ-iodido]]

Jian-Zhong Huo,^a Zhi-Xiang Zhao,^a Men-Chao Shi,^a Hui-Long Li ^a ^* and Qing-Xiang Liu ^a

^aTianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University, Tianjin 300387, People's Republic of China
^*Correspondence e-mail: qxliu@eyou.com

(Received 28 March 2012; accepted 8 May 2012; online 23 May 2012)

The title compound, {(C₁₃H₂₂N₄)[Ag₂I₄]}_n, was prepared by reaction of 1,3-bis(N-ethylimidazolium-1-yl)propane iodide with silver (I) oxide. In the 3,3′-diethyl-1,1′-(propane-1,3-diyl)di(1H-imidazol-3-ium) cation, the dihedral angle between the imidazole rings is 49.3 (1)°. In the [Ag₂I₄]²⁻ anion, each Ag^I atom is bonded to three iodide anions, the two Ag^I atoms and two of the iodides forming Ag₂I₂ square-planar (r.m.s. deviation = 0.01 Å) units·The remaining two iodides, which are placed on opposite sides of the square, together with their centrosymmetric counterparts, link the square-planar Ag₂I₂ units into {[Ag₂I₄]²⁻}_n polymeric chains via Ag—I bonds.

Related literature

For background to the chemistry of imidazolium compounds, see: Wasserscheid & Keim (2000 ); Migowski & Dupont (2007 ). For some applications of imidazolium salts, see: Leclercq & Schmitzer (2009 ); Petkovic et al. (2011 ); Chen et al. (2006 ). For other polymeric chain structures formed via Ag—I bonds, see: Chen & Liu (2003 ).

Experimental

Crystal data

(C₁₃H₂₂N₄)[Ag₂I₄]
M_r = 957.69
Triclinic, $[P \overline 1]$
a = 9.1202 (18) Å
b = 11.543 (2) Å
c = 12.158 (2) Å
α = 74.677 (3)°
β = 70.566 (3)°
γ = 79.903 (3)°
V = 1158.7 (4) Å³
Z = 2
Mo Kα radiation
μ = 7.02 mm⁻¹
T = 296 K
0.25 × 0.24 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.932, T_max = 0.987
5868 measured reflections
4008 independent reflections
3692 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.075
S = 1.04
4008 reflections
211 parameters
H-atom parameters constrained
Δρ_max = 1.05 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812020715/lr2057sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020715/lr2057Isup2.hkl

checkCIF report

Comment top

The design and synthesis of functionalized imidazolium salts are driven by the need for understanding fundamental physical and chemical properties of low melting point salts and modifying them as specific materials (Wasserscheid & Keim, 2000; Migowski & Dupont, 2007). In recent years, the imidazolium salts have been widely studied in ionic liquids (Leclercq & Schmitzer, 2009; Petkovic et al., 2011) and catalytic chemistry (Chen et al., 2006). Herein, we report the preparation and crystal structure of a anionic complex with bis-imidazolium salt, [1,3-bis(N-ethylimidazolium-1-yl)propane][Ag₂I₄].

The title compound [1,3-dis(N-ethylimidazolium-1-yl)propane][Ag₂I₄] was prepared via the reaction of 1,3-dis(N-ethylimidazolium-1-yl)propane iodide with silver oxide (Fig. 1). In the cationic unit of title compound, the dihedral angle between two imidazole rings is 49.3 (1)° (Fig. 2). In the anionic unit [Ag₂I₄]^2-, two silver atoms and two iodine atoms formed a nearly coplanar [Ag₂I₂] moiety (the dihedral angle between I1—Ag1—I2 plane and I1—Ag2—I2 plane is 1.2 (5)°), and other two iodine atoms lie in two sides of the [Ag₂I₂] plane. Anionic complex [Ag₂I₄]^2- has been reported, and its formation is strongly influenced by the counteraction. Also, the anionic unit [Ag₂I₄]^2- can form one-dimensional polymeric chain [Ag₂I₄]_n^2n- via Ag—I bonds (Chen & Liu, 2003). In anion [Ag₂I₄]^2-, each silver atom is surrounded by four iodine atoms to afford a distorted tetrahedral geometry. The I1—Ag1—I2, Ag1—I1—Ag2 and I3—Ag1—I2 bond angles are 101.4 (1)°, 76.8 (2)° and 116.8 (7)°, respectively. The Ag1—I1, Ag1—I2 and Ag1—I3 bond distances are 2.912 (0) Å, 2.908 (9) Å and 2.861 (8) Å, respectively.

Related literature top

For background to the chemistry of imidazolium compounds, see: Wasserscheid & Keim (2000); Migowski & Dupont (2007). For some applications of imidazolium salts, see: Leclercq & Schmitzer (2009); Petkovic et al. (2011); Chen et al. (2006). For other polymeric chain structures formed via Ag—I bonds, see: Chen & Liu (2003).

Experimental top

A solution of 1-ethylimidazole (1.432 g, 14.9 mmol) and 1,3-diiodopropane (2.000 g, 6.8 mmol) in THF (100 ml) was stirred for three days under refluxing, and a precipitate was formed. The product was filtered and washed with THF, and the white powders of 1, 3-dis(N-ethylimidazolium-1-yl)propane iodide was obtained by recrystallization from methanol/diethyl ether. Yield: 2.838 g (86%). Mp: 100–102°C. A suspension of 1, 3-dis(N-ethylimidazolium-1-yl)propane iodide (0.200 g, 0.4 mmol) and silver(I) oxide (0.093 g, 0.4 mmol) in dichloromethane (30 ml) was refluxed for 12 h to give a brown solution. The resulting solution was filtered and concentrated to 8 ml, and then diethyl ether (5 ml) was added to precipitate a white powder [1,3-dis(N-ethylimidazolium-1-yl)propane][Ag₂I₄]. Yield: 0.216 g (55%). Mp: 178–180°C. Anal. Calcd for C₁₃H₂₂Ag₂I₄N₄: C 16.30, H 2.32, N 5.85%; found: C 16.45, H 2.63, N 5.91%. ¹H NMR (400 MHz, DMSO-d6): 1.59 (t, J = 7.2 Hz, 6H, CH₃), 1.76 (m, 2H, CH₂), 4.62 (q, J = 7.2 Hz, 4H, CH₂), 5.82 (t, J = 6.6 Hz, 4H, CH₂), 7.80 (s, 2H, imiH), 7.87 (s, 2H, imiH), 9.46 (s, 2H, 2-imiH) (imi = imidazole).

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Perspective view of the title compound with anisotropic displacement parameters depicting 30% probability. All hydrogen atoms were omitted for clarity.

catena-Poly[3,3'-diethyl-1,1'-(propane-1,3-diyl)di(1H- imidazol-3-ium) [silver(I)-di-µ-iodido-silver(I)-di-µ-iodido]] top

Crystal data top

(C₁₃H₂₂N₄)[Ag₂I₄]	Z = 2
M_r = 957.69	F(000) = 868
Triclinic, P1	D_x = 2.745 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1202 (18) Å	Cell parameters from 5325 reflections
b = 11.543 (2) Å	θ = 2.3–27.9°
c = 12.158 (2) Å	µ = 7.02 mm⁻¹
α = 74.677 (3)°	T = 296 K
β = 70.566 (3)°	Block, light yellow
γ = 79.903 (3)°	0.25 × 0.24 × 0.22 mm
V = 1158.7 (4) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	4008 independent reflections
Radiation source: fine-focus sealed tube	3692 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
phi and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
T_min = 0.932, T_max = 0.987	k = −13→13
5868 measured reflections	l = −14→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0283P)² + 2.6676P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4008 reflections	Δρ_max = 1.05 e Å⁻³
211 parameters	Δρ_min = −0.86 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00298 (17)

Crystal data top

(C₁₃H₂₂N₄)[Ag₂I₄]	γ = 79.903 (3)°
M_r = 957.69	V = 1158.7 (4) Å³
Triclinic, P1	Z = 2
a = 9.1202 (18) Å	Mo Kα radiation
b = 11.543 (2) Å	µ = 7.02 mm⁻¹
c = 12.158 (2) Å	T = 296 K
α = 74.677 (3)°	0.25 × 0.24 × 0.22 mm
β = 70.566 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4008 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3692 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.987	R_int = 0.025
5868 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.04	Δρ_max = 1.05 e Å⁻³
4008 reflections	Δρ_min = −0.86 e Å⁻³
211 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Ag1	0.49679 (5)	0.38435 (5)	0.12441 (5)	0.06103 (15)
Ag2	0.51160 (6)	0.13741 (5)	0.37420 (5)	0.06227 (15)
I1	0.60326 (4)	0.13113 (3)	0.12542 (3)	0.04516 (12)
I2	0.40256 (4)	0.38216 (3)	0.37820 (3)	0.05260 (12)
I3	0.75335 (4)	0.51943 (3)	−0.02697 (3)	0.04661 (12)
I4	0.71765 (4)	0.03787 (3)	0.51764 (3)	0.05221 (13)
N1	0.0416 (6)	0.6747 (4)	0.6691 (4)	0.0537 (11)
N2	−0.0555 (5)	0.7953 (4)	0.7900 (4)	0.0409 (9)
N3	0.0591 (6)	1.1532 (4)	0.7756 (4)	0.0520 (11)
N4	0.2501 (5)	1.2543 (4)	0.7546 (4)	0.0494 (11)
C1	0.0810 (13)	0.6785 (8)	0.4606 (7)	0.112 (3)
H1A	−0.0160	0.7252	0.4568	0.169*
H1B	0.1122	0.6284	0.4034	0.169*
H1C	0.1598	0.7318	0.4426	0.169*
C2	0.0617 (12)	0.6051 (7)	0.5769 (7)	0.091 (3)
H2A	0.1523	0.5465	0.5756	0.109*
H2B	−0.0290	0.5611	0.5993	0.109*
C3	−0.0752 (7)	0.7562 (5)	0.7026 (5)	0.0535 (14)
H3	−0.1577	0.7820	0.6704	0.064*
C4	0.0778 (6)	0.7339 (5)	0.8119 (6)	0.0527 (14)
H4	0.1185	0.7415	0.8701	0.063*
C5	0.1395 (7)	0.6616 (5)	0.7360 (6)	0.0570 (15)
H5	0.2323	0.6115	0.7297	0.068*
C6	−0.1652 (7)	0.8773 (6)	0.8592 (6)	0.0639 (17)
H6A	−0.2207	0.8311	0.9368	0.077*
H6B	−0.2414	0.9173	0.8182	0.077*
C7	−0.0831 (8)	0.9726 (6)	0.8771 (6)	0.0601 (15)
H7A	−0.1545	1.0129	0.9378	0.072*
H7B	0.0059	0.9340	0.9042	0.072*
C8	−0.0296 (8)	1.0630 (6)	0.7621 (6)	0.0629 (16)
H8A	−0.1194	1.1045	0.7374	0.076*
H8B	0.0367	1.0218	0.7004	0.076*
C9	−0.0017 (7)	1.2409 (5)	0.8407 (5)	0.0556 (14)
H9	−0.1052	1.2541	0.8859	0.067*
C10	0.1163 (7)	1.3039 (5)	0.8267 (5)	0.0576 (15)
H10	0.1090	1.3694	0.8598	0.069*
C11	0.2117 (7)	1.1627 (5)	0.7253 (5)	0.0525 (13)
H11	0.2805	1.1133	0.6774	0.063*
C12	0.4114 (8)	1.2921 (7)	0.7163 (6)	0.0737 (19)
H12A	0.4710	1.2680	0.6421	0.088*
H12B	0.4052	1.3794	0.7009	0.088*
C13	0.4953 (7)	1.2391 (7)	0.8069 (7)	0.0719 (19)
H13A	0.4354	1.2606	0.8814	0.108*
H13B	0.5956	1.2697	0.7797	0.108*
H13C	0.5089	1.1529	0.8181	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0493 (3)	0.0654 (3)	0.0668 (3)	−0.0107 (2)	−0.0207 (2)	−0.0044 (2)
Ag2	0.0636 (3)	0.0600 (3)	0.0629 (3)	−0.0068 (2)	−0.0189 (2)	−0.0128 (2)
I1	0.0412 (2)	0.0478 (2)	0.0471 (2)	−0.00823 (15)	−0.01187 (15)	−0.01073 (15)
I2	0.0532 (2)	0.0519 (2)	0.0513 (2)	−0.00460 (17)	−0.01208 (17)	−0.01417 (17)
I3	0.03871 (19)	0.0443 (2)	0.0542 (2)	−0.00964 (14)	−0.01653 (15)	0.00034 (16)
I4	0.0522 (2)	0.0540 (2)	0.0524 (2)	−0.01805 (17)	−0.01913 (17)	−0.00228 (17)
N1	0.059 (3)	0.051 (3)	0.051 (3)	−0.009 (2)	−0.016 (2)	−0.010 (2)
N2	0.033 (2)	0.043 (2)	0.048 (2)	−0.0121 (18)	−0.0158 (18)	−0.0016 (19)
N3	0.058 (3)	0.045 (2)	0.054 (3)	−0.011 (2)	−0.010 (2)	−0.017 (2)
N4	0.057 (3)	0.047 (2)	0.045 (3)	−0.014 (2)	−0.017 (2)	−0.004 (2)
C1	0.199 (11)	0.081 (6)	0.066 (5)	−0.043 (6)	−0.034 (6)	−0.019 (4)
C2	0.138 (8)	0.065 (4)	0.083 (5)	−0.014 (5)	−0.037 (5)	−0.027 (4)
C3	0.057 (3)	0.056 (3)	0.059 (3)	−0.012 (3)	−0.035 (3)	−0.004 (3)
C4	0.044 (3)	0.054 (3)	0.067 (4)	−0.011 (3)	−0.031 (3)	−0.002 (3)
C5	0.039 (3)	0.053 (3)	0.080 (4)	−0.008 (3)	−0.021 (3)	−0.010 (3)
C6	0.042 (3)	0.074 (4)	0.070 (4)	−0.021 (3)	0.003 (3)	−0.021 (3)
C7	0.063 (4)	0.064 (4)	0.054 (3)	−0.009 (3)	−0.011 (3)	−0.021 (3)
C8	0.075 (4)	0.060 (4)	0.063 (4)	−0.016 (3)	−0.027 (3)	−0.014 (3)
C9	0.051 (3)	0.057 (3)	0.059 (3)	−0.005 (3)	−0.009 (3)	−0.024 (3)
C10	0.071 (4)	0.052 (3)	0.055 (3)	−0.009 (3)	−0.018 (3)	−0.019 (3)
C11	0.058 (3)	0.044 (3)	0.053 (3)	−0.001 (3)	−0.014 (3)	−0.013 (3)
C12	0.073 (5)	0.084 (5)	0.064 (4)	−0.034 (4)	−0.019 (3)	−0.002 (4)
C13	0.050 (4)	0.093 (5)	0.074 (4)	−0.005 (3)	−0.023 (3)	−0.018 (4)

Geometric parameters (Å, º) top

Ag1—I3ⁱ	2.8383 (7)	C1—H1C	0.9600
Ag1—I3	2.8618 (7)	C2—H2A	0.9700
Ag1—I2	2.9089 (9)	C2—H2B	0.9700
Ag1—I1	2.9120 (8)	C3—H3	0.9300
Ag2—I2	2.8333 (8)	C4—C5	1.327 (9)
Ag2—I4	2.8735 (7)	C4—H4	0.9300
Ag2—I1	2.8749 (8)	C5—H5	0.9300
Ag2—I4ⁱⁱ	2.9054 (8)	C6—C7	1.529 (8)
I3—Ag1ⁱ	2.8383 (7)	C6—H6A	0.9700
I4—Ag2ⁱⁱ	2.9054 (7)	C6—H6B	0.9700
N1—C3	1.322 (8)	C7—C8	1.495 (9)
N1—C5	1.362 (7)	C7—H7A	0.9700
N1—C2	1.491 (8)	C7—H7B	0.9700
N2—C3	1.332 (7)	C8—H8A	0.9700
N2—C4	1.366 (7)	C8—H8B	0.9700
N2—C6	1.460 (7)	C9—C10	1.342 (8)
N3—C11	1.332 (7)	C9—H9	0.9300
N3—C9	1.376 (7)	C10—H10	0.9300
N3—C8	1.496 (7)	C11—H11	0.9300
N4—C11	1.333 (7)	C12—C13	1.488 (10)
N4—C10	1.376 (7)	C12—H12A	0.9700
N4—C12	1.495 (8)	C12—H12B	0.9700
C1—C2	1.415 (11)	C13—H13A	0.9600
C1—H1A	0.9600	C13—H13B	0.9600
C1—H1B	0.9600	C13—H13C	0.9600

I3ⁱ—Ag1—I3	105.33 (2)	C5—C4—H4	125.8
I3ⁱ—Ag1—I2	111.08 (2)	N2—C4—H4	125.8
I3—Ag1—I2	116.87 (2)	C4—C5—N1	107.1 (5)
I3ⁱ—Ag1—I1	115.75 (2)	C4—C5—H5	126.4
I3—Ag1—I1	106.74 (2)	N1—C5—H5	126.4
I2—Ag1—I1	101.418 (18)	N2—C6—C7	112.2 (5)
I2—Ag2—I4	112.83 (2)	N2—C6—H6A	109.2
I2—Ag2—I1	104.221 (19)	C7—C6—H6A	109.2
I4—Ag2—I1	121.64 (2)	N2—C6—H6B	109.2
I2—Ag2—I4ⁱⁱ	117.25 (2)	C7—C6—H6B	109.2
I4—Ag2—I4ⁱⁱ	98.81 (2)	H6A—C6—H6B	107.9
I1—Ag2—I4ⁱⁱ	102.35 (2)	C8—C7—C6	110.0 (5)
Ag2—I1—Ag1	76.825 (17)	C8—C7—H7A	109.7
Ag2—I2—Ag1	77.525 (17)	C6—C7—H7A	109.7
Ag1ⁱ—I3—Ag1	74.67 (2)	C8—C7—H7B	109.7
Ag2—I4—Ag2ⁱⁱ	81.19 (2)	C6—C7—H7B	109.7
C3—N1—C5	108.4 (5)	H7A—C7—H7B	108.2
C3—N1—C2	126.4 (6)	C7—C8—N3	111.0 (5)
C5—N1—C2	125.2 (6)	C7—C8—H8A	109.4
C3—N2—C4	107.0 (5)	N3—C8—H8A	109.4
C3—N2—C6	126.4 (5)	C7—C8—H8B	109.4
C4—N2—C6	126.1 (5)	N3—C8—H8B	109.4
C11—N3—C9	108.1 (5)	H8A—C8—H8B	108.0
C11—N3—C8	125.4 (5)	C10—C9—N3	107.2 (5)
C9—N3—C8	126.4 (5)	C10—C9—H9	126.4
C11—N4—C10	107.7 (5)	N3—C9—H9	126.4
C11—N4—C12	124.9 (5)	C9—C10—N4	107.9 (5)
C10—N4—C12	127.4 (5)	C9—C10—H10	126.1
C2—C1—H1A	109.5	N4—C10—H10	126.1
C2—C1—H1B	109.5	N3—C11—N4	109.1 (5)
H1A—C1—H1B	109.5	N3—C11—H11	125.4
C2—C1—H1C	109.5	N4—C11—H11	125.4
H1A—C1—H1C	109.5	C13—C12—N4	113.0 (6)
H1B—C1—H1C	109.5	C13—C12—H12A	109.0
C1—C2—N1	113.4 (6)	N4—C12—H12A	109.0
C1—C2—H2A	108.9	C13—C12—H12B	109.0
N1—C2—H2A	108.9	N4—C12—H12B	109.0
C1—C2—H2B	108.9	H12A—C12—H12B	107.8
N1—C2—H2B	108.9	C12—C13—H13A	109.5
H2A—C2—H2B	107.7	C12—C13—H13B	109.5
N1—C3—N2	109.0 (5)	H13A—C13—H13B	109.5
N1—C3—H3	125.5	C12—C13—H13C	109.5
N2—C3—H3	125.5	H13A—C13—H13C	109.5
C5—C4—N2	108.4 (5)	H13B—C13—H13C	109.5

I2—Ag2—I1—Ag1	0.813 (16)	C6—N2—C3—N1	−174.1 (5)
I4—Ag2—I1—Ag1	−127.96 (2)	C3—N2—C4—C5	1.8 (6)
I4ⁱⁱ—Ag2—I1—Ag1	123.43 (2)	C6—N2—C4—C5	175.1 (5)
I3ⁱ—Ag1—I1—Ag2	−121.10 (2)	N2—C4—C5—N1	−2.1 (7)
I3—Ag1—I1—Ag2	122.05 (2)	C3—N1—C5—C4	1.6 (7)
I2—Ag1—I1—Ag2	−0.783 (16)	C2—N1—C5—C4	−176.6 (6)
I4—Ag2—I2—Ag1	133.12 (2)	C3—N2—C6—C7	−137.1 (6)
I1—Ag2—I2—Ag1	−0.811 (16)	C4—N2—C6—C7	50.9 (8)
I4ⁱⁱ—Ag2—I2—Ag1	−113.07 (2)	N2—C6—C7—C8	72.4 (7)
I3ⁱ—Ag1—I2—Ag2	124.36 (2)	C6—C7—C8—N3	−176.8 (5)
I3—Ag1—I2—Ag2	−114.78 (3)	C11—N3—C8—C7	111.0 (7)
I1—Ag1—I2—Ag2	0.792 (16)	C9—N3—C8—C7	−69.5 (8)
I3ⁱ—Ag1—I3—Ag1ⁱ	0.0	C11—N3—C9—C10	1.0 (7)
I2—Ag1—I3—Ag1ⁱ	−123.85 (3)	C8—N3—C9—C10	−178.5 (6)
I1—Ag1—I3—Ag1ⁱ	123.56 (3)	N3—C9—C10—N4	−0.8 (7)
I2—Ag2—I4—Ag2ⁱⁱ	124.61 (3)	C11—N4—C10—C9	0.3 (7)
I1—Ag2—I4—Ag2ⁱⁱ	−110.47 (3)	C12—N4—C10—C9	−178.5 (6)
I4ⁱⁱ—Ag2—I4—Ag2ⁱⁱ	0.0	C9—N3—C11—N4	−0.8 (7)
C3—N1—C2—C1	63.8 (11)	C8—N3—C11—N4	178.7 (5)
C5—N1—C2—C1	−118.4 (9)	C10—N4—C11—N3	0.3 (6)
C5—N1—C3—N2	−0.4 (6)	C12—N4—C11—N3	179.2 (5)
C2—N1—C3—N2	177.7 (6)	C11—N4—C12—C13	−95.5 (8)
C4—N2—C3—N1	−0.8 (6)	C10—N4—C12—C13	83.2 (8)

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

Experimental details

Crystal data
Chemical formula	(C₁₃H₂₂N₄)[Ag₂I₄]
M_r	957.69
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.1202 (18), 11.543 (2), 12.158 (2)
α, β, γ (°)	74.677 (3), 70.566 (3), 79.903 (3)
V (Å³)	1158.7 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	7.02
Crystal size (mm)	0.25 × 0.24 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.932, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	5868, 4008, 3692
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.075, 1.04
No. of reflections	4008
No. of parameters	211
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.05, −0.86

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This project was supported by the National Science Foundation of China (project grant No. 21172172) and the Natural Science Foundation of Tianjin (11JCZDJC22000).

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