[μ-N,N′-Bis(2-amino­eth­yl)ethane-1,2-diamine-κ4N1,N1′:N2,N2′]bis­{[N,N′-bis­(2-amino­eth­yl)ethane-1,2-diamine-κ4N,N′,N′′,N′′′]cadmium} tetra­kis­(perchlorate)

Goudarziafshar, H.; Abbasityula, Y.; Eigner, V.; Dušek, M.

doi:10.1107/S1600536812033880

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages m1153-m1154

doi:10.1107/S1600536812033880

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[μ-N,N′-Bis(2-aminoethyl)ethane-1,2-diamine-κ⁴N¹,N^1′:N²,N^2′]bis{[N,N′-bis(2-aminoethyl)ethane-1,2-diamine-κ⁴N,N′,N′′,N′′′]cadmium} tetrakis(perchlorate)

Hamid Goudarziafshar,^a ^* Yunes Abbasityula,^a Václav Eigner ^b,^c and Michal Dušek ^c

^aFaculty of Science, Department of Chemistry, Ilam University, Ilam, Iran, ^bDepartment of Solid State Chemistry, Institute of Chemical Technology, Technická 5, 166 28 Prague, Czech Republic, and ^cInstitute of Physics AS CR, v.v.i., Na Slovance 2, 182 21 Prague 8, Czech Republic
^*Correspondence e-mail: hamid_gafshar@yahoo.com

(Received 21 July 2012; accepted 28 July 2012; online 4 August 2012)

The centrosymmetric dinuclear cadmium title complex, [Cd₂(C₆H₁₈N₄)₃](ClO₄)₄, was obtained by the reaction of N,N′-bis(2-aminoethyl)ethane-1,2-diamine (trien) with Cd(NO₃)₂·4H₂O and sodium perchlorate in methanol. The Cd^II cation is coordinated by four N atoms of a non-bridging trien ligand and by two N atoms of a bridging trien ligand in a slightly distorted octahedral coordination geometry. The bridging ligand shares another two N atoms with a neighboring symmetry-equivalent Cd^II cation. The structure displays C—H⋯O and N—H⋯O hydrogen bonding. The perchlorate anion is disordered over two sets of sites in a 0.854 (7): 0.146 (7) ratio.

Related literature

Polyamines are an important class of N-donor ligands, particularly for transition metals, see: Patel et al. (2007 ); Blackman (2005 ). For polynuclear complexes, see: Gustafsson et al. (2010 ); Ambrosi et al. (2009 ); You et al. (2011 ). For polynuclear complexes of cadmium, see: Evans & Lin (2002 ); For background to the use of the trien ligand in complexation, see: Cai et al. (2001a ,b ); Buckingham et al. (1974 , 1975 ); Chowdhury et al. (2007 ). Buckingham & Jones (1965 ); Shinohara et al. (1991 ); He (2009 ); Patel et al. (2008 ); Anderson et al. (1977 ); Shoukry et al. (1998 ); Hu et al. (2000 ). For dinuclear Cd complexes, see: Das et al. (2010 ); Nie et al. (2010 ); Wang et al. (2011 ); Sun et al. (2010 ). For details of the preparation, see: Harrowfield et al. (1996 ).

Experimental

Crystal data

[Cd₂(C₆H₁₈N₄)₃](ClO₄)₄
M_r = 1061.3
Monoclinic, P 2₁ /n
a = 8.8056 (2) Å
b = 15.0259 (3) Å
c = 14.7516 (3) Å
β = 95.4420 (17)°
V = 1943.02 (7) Å³
Z = 2
Mo Kα radiation
μ = 1.45 mm⁻¹
T = 120 K
0.70 × 0.51 × 0.33 mm

Data collection

Agilent Xcalibur Atlas Gemini ultra diffractometer
Absorption correction: analytical (CrysAlis PRO; Agilent, 2012 ) T_min = 0.509, T_max = 0.738
31295 measured reflections
4952 independent reflections
4373 reflections with I > 3σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.106
S = 2.02
4952 reflections
269 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.13 e Å⁻³
Δρ_min = −0.92 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N1	2.362 (2)
Cd1—N4	2.390 (3)
Cd1—N7	2.377 (3)
Cd1—N10	2.380 (3)
Cd1—N11	2.374 (3)
Cd1—N14	2.375 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H1c5⋯O4cⁱ	0.96	2.49	3.449 (3)	172
N1—H2n1⋯O3cⁱⁱ	0.80 (4)	2.46 (4)	3.149 (4)	145 (3)
N11—H1n11⋯O2cⁱⁱⁱ	0.82 (4)	2.40 (4)	3.140 (4)	149 (3)
N11—H2n11⋯O4aⁱⁱ	0.92 (4)	2.44 (4)	3.210 (5)	141 (3)
N4—H1n4⋯O4aⁱⁱ	0.98 (3)	2.36 (3)	3.271 (4)	154 (2)
N4—H1n4⋯O5aⁱⁱ	0.98 (3)	2.38 (3)	3.236 (4)	145 (2)
N4—H1n4⋯O5bⁱⁱ	0.98 (3)	2.22 (3)	3.113 (13)	151 (3)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z; (iii) -x, -y+1, -z.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ); program(s) used to refine structure: JANA2006 (Petříček et al., 2006 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812033880/ru2040sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812033880/ru2040Isup2.hkl

checkCIF report

Comment top

Polyamines are an important class of N donor ligands, particularly for the transition metals (Patel et al., 2007, 2008; Blackman, 2005). Considerable attention has been focused on the polynuclear complexes containing bridging ligands because of their interesting molecular topologies, as well as the fact that they may be designed with specific functionalities (Gustafsson et al. 2010;. Ambrosi et al. 2009; You et al. 2011). The investigation of polynuclear complexes of cadmium(II) is an important objective in view of their electronic and optoelectronic properties (Evans et al. 2002; Chowdhury et al. 2007).

The molecular structure of the title complex is shown in Fig. 1. The cadmium(II) centers are six-coordinate by four nitrogen atoms of the non-bridging tetradentate (trien) ligand and two nitrogen atoms of the bridging trien ligand, with a substantial departure from an ideal octahedral geometry [cisoid angles: 73.97 (8)–114.67 (9)°; transoid angles: 141.95 (1)–159.20 (6)°] (Table 1). The distance between the two cadmium(II) centers of the dinuclear complex is 7.735 Å, which is longer than the corresponding distance in dinickel(II) complex (7.497 Å) of the same ligand (Cai et al. 2001b) due to larger radius of cadmium. Cadmium atoms in the dinuclear complex are related by a 2 fold symmetry operation. Bond distance of Cd—N(trien) are in the range of 2.62 (3)- 2.90 (3) Å (Table 1). The structure exhibits disorder of one of the perchlorate anions in two positions with refined occupancy 0.854 (7) and 0.146 (7) for the major and minor componet,respectively. The disorder was described using the rigid body approach. In the title complex the C—H···O and N—H···O hydrogen bonds have been found between the amine nitrogen/carbon donors and perchlorate acceptors (Fig.2),(Table 2).

Related literature top

Polyamines are an important class of N-donor ligands, particularly for transition metals, see: Patel et al. (2007); Blackman (2005). For polynuclear complexes, see: Gustafsson et al. (2010); Ambrosi et al. (2009); You et al. (2011). For polynuclear complexes of cadmium(II), see: Evans & Lin (2002); For background to the use of the trien ligand in complexation, see: Cai et al. (2001a,b); Buckingham et al. (1974, 1975); Chowdhury et al. (2007). Buckingham & Jones (1965); Shinohara et al. (1991); He (2009); Patel et al. (2008); Anderson et al. (1977); Shoukry et al. (1998); Hu et al. (2000). For related structures, see: Cai et al. (2001a,b). For dinuclear Cd complexes, see: Das et al. (2010); Nie et al. (2010); Wang et al. (2011); Sun et al. (2010). For details of the preparation, see: Harrowfield et al. (1996).

Experimental top

N,N'-bis(2-aminoethyl)ethane-1,2-diamine (0.45 g, 3 mmol) was placed in one arm of a branched tube (Harrowfield et al., 1996) and a mixture of Cd(NO₃)₂.4H₂O (0.616 g, 2 mmol) and sodium perchlorate (0.488 g, 4 mmol) in the other. Methanol was then carefully added to fill both arms, the tube sealed and the ligand-containing arm immersed in a bath at 333 K, while the other was left at ambient temperature. After one week, colorless crystals were collected in the cooler arm. Then they were filtered off, washed with acetone and diethylether, and air dried. Yield: (53%).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petricek et al., 2006); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound with 50% probability displacement ellipsoids.
	Fig. 2. Unit-cell packing diagram of the title compound viewed along the crystallographic 〈 〉 a 〈 〉 axis. Hydrogen bonds are indicated by dashed lines; (orange = cadmium; green = chlorine; violet = nitrogen; grey = carbon; light-grey = hydrogen).

[µ-N,N'-Bis(2-aminoethyl)ethane-1,2-diamine- κ⁴N¹,N^1':N²,N^2']bis{[N,N'- bis(2-aminoethyl)ethane-1,2-diamine- κ⁴N,N',N'',N''']cadmium} tetrakis(perchlorate) top

Crystal data top

[Cd₂(C₆H₁₈N₄)₃](ClO₄)₄	F(000) = 1076
M_r = 1061.3	D_x = 1.814 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2yn	Cell parameters from 17686 reflections
a = 8.8056 (2) Å	θ = 2.9–29.3°
b = 15.0259 (3) Å	µ = 1.45 mm⁻¹
c = 14.7516 (3) Å	T = 120 K
β = 95.4420 (17)°	Prism, colourless
V = 1943.02 (7) Å³	0.70 × 0.51 × 0.33 mm
Z = 2

Data collection top

Agilent Xcalibur Atlas Gemini ultra diffractometer	4952 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4373 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 10.3784 pixels mm^-1	θ_max = 29.4°, θ_min = 2.9°
ω scans	h = −11→12
Absorption correction: analytical (CrysAlis PRO; Agilent, 2012)	k = −19→20
T_min = 0.509, T_max = 0.738	l = −20→19
31295 measured reflections

Refinement top

Refinement on F²	82 constraints
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.106	Weighting scheme based on measured s.u.'s w = 1/(σ²(I) + 0.0016I²)
S = 2.02	(Δ/σ)_max = 0.045
4952 reflections	Δρ_max = 1.13 e Å⁻³
269 parameters	Δρ_min = −0.92 e Å⁻³
0 restraints

Crystal data top

[Cd₂(C₆H₁₈N₄)₃](ClO₄)₄	V = 1943.02 (7) Å³
M_r = 1061.3	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.8056 (2) Å	µ = 1.45 mm⁻¹
b = 15.0259 (3) Å	T = 120 K
c = 14.7516 (3) Å	0.70 × 0.51 × 0.33 mm
β = 95.4420 (17)°

Data collection top

Agilent Xcalibur Atlas Gemini ultra diffractometer	4952 independent reflections
Absorption correction: analytical (CrysAlis PRO; Agilent, 2012)	4373 reflections with I > 3σ(I)
T_min = 0.509, T_max = 0.738	R_int = 0.022
31295 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 2.02	Δρ_max = 1.13 e Å⁻³
4952 reflections	Δρ_min = −0.92 e Å⁻³
269 parameters

Special details top

Experimental. Absorption correction: analytical: CrysAlisPro, Agilent Technologies, Version 1.171.35.19 Analytical numeric absorption correction based on crystal shape

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cd1	0.286722 (18)	0.787742 (11)	0.064763 (11)	0.01848 (7)
N1	0.5386 (3)	0.73266 (16)	0.08829 (18)	0.0272 (7)
C2	0.5399 (3)	0.63634 (18)	0.0671 (2)	0.0292 (8)
C3	0.4054 (3)	0.59042 (17)	0.10338 (19)	0.0283 (8)
N4	0.2615 (2)	0.62928 (15)	0.06265 (14)	0.0228 (6)
C5	0.1244 (3)	0.60375 (18)	0.10733 (18)	0.0300 (8)
C6	−0.0058 (3)	0.6674 (2)	0.08095 (19)	0.0319 (9)
N7	0.0352 (3)	0.76022 (18)	0.10385 (16)	0.0277 (7)
C8	0.0284 (3)	0.78350 (18)	0.1997 (2)	0.0330 (9)
C9	0.1157 (3)	0.8669 (2)	0.22447 (19)	0.0354 (9)
N10	0.2773 (3)	0.85403 (16)	0.21066 (15)	0.0286 (7)
N11	0.2454 (3)	0.77849 (15)	−0.09631 (18)	0.0296 (7)
C12	0.2788 (3)	0.86355 (17)	−0.14108 (17)	0.0274 (8)
C13	0.2345 (3)	0.94099 (17)	−0.08204 (17)	0.0231 (7)
N14	0.3148 (2)	0.93478 (13)	0.00986 (14)	0.0183 (6)
C15	0.4798 (3)	0.95387 (15)	0.01611 (16)	0.0200 (7)
H1c2	0.632977	0.610336	0.094187	0.035*
H2c2	0.535246	0.628241	0.002352	0.035*
H1c3	0.407828	0.528128	0.089118	0.034*
H2c3	0.411784	0.596978	0.168367	0.034*
H1c5	0.147832	0.604608	0.172219	0.036*
H2c5	0.094348	0.544411	0.089398	0.036*
H1c6	−0.035184	0.662706	0.016775	0.0383*
H2c6	−0.093123	0.650524	0.111322	0.0383*
H1c8	0.068971	0.735436	0.2374	0.0396*
H2c8	−0.076102	0.791229	0.211536	0.0396*
H1c9	0.106623	0.881033	0.287172	0.0424*
H2c9	0.074914	0.914972	0.18688	0.0424*
H1c12	0.221103	0.866719	−0.199579	0.0329*
H2c12	0.385736	0.866777	−0.14855	0.0329*
H1c13	0.260242	0.996164	−0.109623	0.0277*
H2c13	0.126385	0.940048	−0.07791	0.0277*
H1c15	0.530028	0.909867	−0.017582	0.024*
H2c15	0.523023	0.945412	0.077724	0.024*
H1n10	0.331 (4)	0.819 (2)	0.267 (2)	0.0344*
H2n10	0.340 (4)	0.909 (2)	0.227 (2)	0.0344*
H1n1	0.574 (4)	0.746 (2)	0.148 (2)	0.0326*
H1n7	−0.025 (5)	0.793 (2)	0.079 (3)	0.0332*
H1n14	0.278 (3)	0.964 (2)	0.037 (2)	0.0219*
H2n1	0.604 (4)	0.753 (3)	0.061 (2)	0.0326*
H1n11	0.153 (5)	0.768 (2)	−0.104 (3)	0.0355*
H2n11	0.285 (4)	0.736 (3)	−0.133 (3)	0.0355*
H1n4	0.241 (3)	0.610 (2)	−0.001 (2)	0.0274*
Cl1c	0.20589 (7)	0.15386 (4)	0.11243 (4)	0.03020 (19)
O2c	0.0975 (3)	0.18921 (16)	0.16787 (16)	0.0431 (7)
O3c	0.3065 (3)	0.22454 (16)	0.0906 (2)	0.0500 (9)
O4c	0.2906 (3)	0.08460 (15)	0.16043 (15)	0.0451 (8)
O5c	0.1347 (3)	0.11760 (15)	0.03083 (15)	0.0456 (7)
Cl1a	0.8393 (2)	0.42448 (12)	0.19271 (14)	0.0246 (3)	0.854 (7)
O2a	0.8867 (6)	0.5086 (2)	0.2242 (3)	0.0768 (18)	0.854 (7)
O3a	0.8423 (5)	0.3641 (3)	0.2674 (3)	0.0378 (8)	0.854 (7)
O4a	0.6891 (4)	0.4247 (3)	0.1474 (3)	0.0468 (11)	0.854 (7)
O5a	0.9442 (5)	0.3933 (3)	0.1297 (3)	0.0388 (9)	0.854 (7)
Cl1b	0.8447 (14)	0.4319 (9)	0.2081 (8)	0.0246 (3)	0.146 (7)
O2b	0.9407 (15)	0.4949 (9)	0.2534 (9)	0.0768 (18)	0.146 (7)
O3b	0.8281 (14)	0.3574 (9)	0.2662 (9)	0.0378 (8)	0.146 (7)
O4b	0.6967 (14)	0.4661 (9)	0.1803 (9)	0.0468 (11)	0.146 (7)
O5b	0.9136 (14)	0.4022 (9)	0.1280 (9)	0.0388 (9)	0.146 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01761 (13)	0.01696 (13)	0.02150 (13)	−0.00220 (5)	0.00519 (8)	0.00130 (5)
N1	0.0215 (11)	0.0231 (11)	0.0368 (13)	−0.0034 (9)	0.0021 (10)	−0.0032 (10)
C2	0.0242 (13)	0.0229 (12)	0.0407 (15)	0.0027 (10)	0.0053 (11)	−0.0014 (11)
C3	0.0302 (14)	0.0206 (12)	0.0338 (14)	−0.0002 (10)	0.0015 (11)	0.0043 (10)
N4	0.0252 (10)	0.0207 (11)	0.0227 (11)	−0.0071 (8)	0.0028 (8)	0.0030 (8)
C5	0.0324 (14)	0.0275 (13)	0.0306 (14)	−0.0112 (11)	0.0050 (11)	0.0044 (11)
C6	0.0200 (13)	0.0419 (17)	0.0339 (14)	−0.0112 (11)	0.0023 (10)	0.0042 (12)
N7	0.0187 (11)	0.0357 (13)	0.0289 (12)	0.0004 (9)	0.0041 (9)	0.0065 (10)
C8	0.0249 (14)	0.0429 (17)	0.0329 (15)	0.0045 (11)	0.0116 (12)	0.0036 (11)
C9	0.0357 (15)	0.0384 (16)	0.0336 (15)	0.0088 (12)	0.0118 (12)	−0.0014 (12)
N10	0.0310 (12)	0.0322 (12)	0.0231 (11)	0.0017 (10)	0.0047 (9)	−0.0011 (9)
N11	0.0434 (15)	0.0194 (11)	0.0265 (12)	−0.0092 (10)	0.0066 (11)	−0.0021 (9)
C12	0.0395 (15)	0.0222 (12)	0.0200 (11)	−0.0088 (11)	0.0001 (10)	0.0006 (10)
C13	0.0214 (11)	0.0208 (12)	0.0263 (12)	−0.0018 (9)	−0.0014 (9)	0.0026 (9)
N14	0.0182 (10)	0.0148 (9)	0.0224 (10)	−0.0017 (7)	0.0045 (8)	−0.0016 (7)
C15	0.0189 (11)	0.0173 (11)	0.0234 (12)	−0.0026 (9)	−0.0001 (9)	0.0023 (9)
Cl1c	0.0298 (3)	0.0308 (3)	0.0297 (3)	0.0041 (2)	0.0011 (3)	−0.0042 (2)
O2c	0.0390 (12)	0.0416 (11)	0.0498 (14)	0.0074 (10)	0.0101 (10)	−0.0168 (11)
O3c	0.0589 (17)	0.0402 (13)	0.0531 (14)	−0.0106 (10)	0.0159 (12)	−0.0020 (11)
O4c	0.0614 (15)	0.0400 (13)	0.0329 (11)	0.0157 (10)	0.0003 (10)	−0.0007 (9)
O5c	0.0517 (14)	0.0461 (13)	0.0361 (11)	0.0195 (10)	−0.0106 (10)	−0.0111 (10)
Cl1a	0.0346 (4)	0.0174 (5)	0.0224 (8)	−0.0034 (3)	0.0062 (4)	−0.0039 (4)
O2a	0.140 (4)	0.0407 (17)	0.060 (3)	−0.055 (2)	0.064 (3)	−0.0326 (18)
O3a	0.0459 (16)	0.0401 (14)	0.0267 (10)	−0.0048 (11)	0.0004 (10)	0.0130 (10)
O4a	0.0390 (14)	0.066 (2)	0.0348 (16)	0.0216 (14)	0.0008 (11)	0.0038 (15)
O5a	0.0396 (18)	0.0376 (16)	0.0420 (13)	−0.0078 (15)	0.0184 (13)	−0.0130 (11)
Cl1b	0.0310 (4)	0.0229 (5)	0.0196 (8)	−0.0082 (3)	0.0014 (4)	−0.0039 (4)
O2b	0.104 (4)	0.098 (2)	0.031 (3)	−0.084 (2)	0.023 (2)	−0.0276 (19)
O3b	0.0424 (15)	0.0356 (14)	0.0350 (11)	−0.0036 (11)	0.0020 (10)	0.0163 (10)
O4b	0.0542 (15)	0.049 (2)	0.0374 (17)	0.0258 (13)	0.0073 (12)	0.0057 (15)
O5b	0.0368 (18)	0.0497 (16)	0.0314 (14)	−0.0109 (14)	0.0112 (13)	−0.0133 (11)

Geometric parameters (Å, º) top

Cd1—N1	2.362 (2)	C9—H1c9	0.96
Cd1—N4	2.390 (3)	C9—H2c9	0.96
Cd1—N7	2.377 (3)	N11—C12	1.481 (4)
Cd1—N10	2.380 (3)	N11—H1n11	0.82 (4)
Cd1—N11	2.374 (3)	N11—H2n11	0.92 (4)
Cd1—N14	2.375 (2)	C12—C13	1.526 (4)
N1—C2	1.481 (4)	C12—H1c12	0.96
N1—H1n1	0.93 (3)	C12—H2c12	0.96
N1—H2n1	0.80 (4)	C13—N14	1.471 (3)
C2—C3	1.512 (4)	C13—H1c13	0.96
C2—H1c2	0.96	C13—H2c13	0.96
C2—H2c2	0.96	N14—C15	1.475 (3)
C3—N4	1.471 (3)	N14—H1n14	0.70 (3)
C3—H1c3	0.96	C15—C15ⁱ	1.519 (3)
C3—H2c3	0.96	C15—H1c15	0.96
N4—C5	1.480 (4)	C15—H2c15	0.96
C5—C6	1.515 (4)	Cl1c—O2c	1.418 (3)
C5—H1c5	0.96	Cl1c—O3c	1.439 (3)
C5—H2c5	0.96	Cl1c—O4c	1.428 (2)
C6—N7	1.472 (4)	Cl1c—O5c	1.413 (2)
C6—H1c6	0.96	Cl1a—O2a	1.397 (4)
C6—H2c6	0.96	Cl1a—O3a	1.425 (5)
N7—C8	1.463 (4)	Cl1a—O4a	1.424 (4)
N7—H1n7	0.78 (4)	Cl1a—O5a	1.449 (5)
C8—C9	1.497 (4)	Cl1b—O2b	1.397 (18)
C8—H1c8	0.96	Cl1b—O3b	1.425 (19)
C8—H2c8	0.96	Cl1b—O4b	1.424 (17)
C9—N10	1.469 (4)	Cl1b—O5b	1.449 (19)

N11—Cd1—N14	73.97 (8)	C8—C9—H2c9	109.47
N4—Cd1—N10	114.67 (9)	N10—C9—H1c9	109.47
N1—Cd1—N7	141.90 (9)	N10—C9—H2c9	109.47
N4—Cd1—N14	159.20 (6)	H1c9—C9—H2c9	109.17
Cd1—N1—C2	109.72 (16)	C12—N11—H1n11	110 (2)
Cd1—N1—H1n1	107 (2)	C12—N11—H2n11	103 (2)
Cd1—N1—H2n1	120 (3)	H1n11—N11—H2n11	102 (3)
C2—N1—H1n1	114 (2)	N11—C12—C13	109.4 (2)
C2—N1—H2n1	105 (3)	N11—C12—H1c12	109.47
H1n1—N1—H2n1	102 (3)	N11—C12—H2c12	109.47
N1—C2—C3	110.5 (2)	C13—C12—H1c12	109.47
N1—C2—H1c2	109.47	C13—C12—H2c12	109.47
N1—C2—H2c2	109.47	H1c12—C12—H2c12	109.59
C3—C2—H1c2	109.47	C12—C13—N14	110.6 (2)
C3—C2—H2c2	109.47	C12—C13—H1c13	109.47
H1c2—C2—H2c2	108.47	C12—C13—H2c13	109.47
C2—C3—N4	110.3 (2)	N14—C13—H1c13	109.47
C2—C3—H1c3	109.47	N14—C13—H2c13	109.47
C2—C3—H2c3	109.47	H1c13—C13—H2c13	108.36
N4—C3—H1c3	109.47	C13—N14—C15	115.44 (19)
N4—C3—H2c3	109.47	C13—N14—H1n14	106 (3)
H1c3—C3—H2c3	108.58	C15—N14—H1n14	111 (2)
C3—N4—C5	115.0 (2)	N14—C15—C15ⁱ	114.62 (18)
N4—C5—C6	110.6 (2)	N14—C15—H1c15	109.47
N4—C5—H1c5	109.47	N14—C15—H2c15	109.47
N4—C5—H2c5	109.47	C15ⁱ—C15—H1c15	109.47
C6—C5—H1c5	109.47	C15ⁱ—C15—H2c15	109.47
C6—C5—H2c5	109.47	H1c15—C15—H2c15	103.78
H1c5—C5—H2c5	108.35	O2c—Cl1c—O3c	108.37 (16)
C5—C6—N7	112.1 (2)	O2c—Cl1c—O4c	109.59 (14)
C5—C6—H1c6	109.47	O2c—Cl1c—O5c	111.57 (14)
C5—C6—H2c6	109.47	O3c—Cl1c—O4c	110.20 (15)
N7—C6—H1c6	109.47	O3c—Cl1c—O5c	109.05 (16)
N7—C6—H2c6	109.47	O4c—Cl1c—O5c	108.05 (13)
H1c6—C6—H2c6	106.74	O2a—Cl1a—O3a	109.7 (3)
C6—N7—C8	114.6 (2)	O2a—Cl1a—O4a	112.9 (3)
C6—N7—H1n7	110 (2)	O2a—Cl1a—O5a	108.5 (3)
C8—N7—H1n7	102 (3)	O3a—Cl1a—O4a	108.2 (3)
N7—C8—C9	111.7 (2)	O3a—Cl1a—O5a	108.9 (3)
N7—C8—H1c8	109.47	O4a—Cl1a—O5a	108.6 (3)
N7—C8—H2c8	109.47	O2b—Cl1b—O3b	109.7 (11)
C9—C8—H1c8	109.47	O2b—Cl1b—O4b	112.9 (11)
C9—C8—H2c8	109.47	O2b—Cl1b—O5b	108.5 (11)
H1c8—C8—H2c8	107.19	O3b—Cl1b—O4b	108.2 (11)
C8—C9—N10	109.8 (2)	O3b—Cl1b—O5b	108.9 (11)
C8—C9—H1c9	109.47	O4b—Cl1b—O5b	108.6 (11)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H1c5···O4cⁱⁱ	0.96	2.49	3.449 (3)	172
C8—H2c8···O3bⁱⁱ	0.96	2.48	3.412 (13)	163
N10—H1n10···O2cⁱⁱ	1.06 (3)	2.24 (4)	3.191 (3)	149 (3)
N10—H2n10···O2bⁱⁱⁱ	1.01 (3)	2.32 (3)	3.268 (13)	156 (3)
N1—H1n1···O3aⁱⁱⁱ	0.93 (3)	2.25 (3)	3.018 (5)	139 (3)
N1—H1n1···O3bⁱⁱⁱ	0.93 (3)	2.22 (4)	3.004 (13)	141 (3)
N7—H1n7···O5c^iv	0.78 (4)	2.25 (4)	2.999 (3)	159 (4)
N1—H2n1···O3c^v	0.80 (4)	2.46 (4)	3.149 (4)	145 (3)
N11—H1n11···O2c^iv	0.82 (4)	2.40 (4)	3.140 (4)	149 (3)
N11—H2n11···O4a^v	0.92 (4)	2.44 (4)	3.210 (5)	141 (3)
N4—H1n4···O4a^v	0.98 (3)	2.36 (3)	3.271 (4)	154 (2)
N4—H1n4···O5a^v	0.98 (3)	2.38 (3)	3.236 (4)	145 (2)
N4—H1n4···O5b^v	0.98 (3)	2.22 (3)	3.113 (13)	151 (3)

Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x, −y+1, −z; (v) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Cd₂(C₆H₁₈N₄)₃](ClO₄)₄
M_r	1061.3
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	8.8056 (2), 15.0259 (3), 14.7516 (3)
β (°)	95.4420 (17)
V (Å³)	1943.02 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.45
Crystal size (mm)	0.70 × 0.51 × 0.33

Data collection
Diffractometer	Agilent Xcalibur Atlas Gemini ultra diffractometer
Absorption correction	Analytical (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.509, 0.738
No. of measured, independent and observed [I > 3σ(I)] reflections	31295, 4952, 4373
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.691

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.106, 2.02
No. of reflections	4952
No. of parameters	269
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.13, −0.92

Computer programs: CrysAlis PRO (Agilent, 2012), SUPERFLIP (Palatinus & Chapuis, 2007), JANA2006 (Petricek et al., 2006), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Cd1—N1	2.362 (2)	Cd1—N10	2.380 (3)
Cd1—N4	2.390 (3)	Cd1—N11	2.374 (3)
Cd1—N7	2.377 (3)	Cd1—N14	2.375 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H1c5···O4cⁱ	0.96	2.49	3.449 (3)	172.30
N1—H2n1···O3cⁱⁱ	0.80 (4)	2.46 (4)	3.149 (4)	145 (3)
N11—H1n11···O2cⁱⁱⁱ	0.82 (4)	2.40 (4)	3.140 (4)	149 (3)
N11—H2n11···O4aⁱⁱ	0.92 (4)	2.44 (4)	3.210 (5)	141 (3)
N4—H1n4···O4aⁱⁱ	0.98 (3)	2.36 (3)	3.271 (4)	154 (2)
N4—H1n4···O5aⁱⁱ	0.98 (3)	2.38 (3)	3.236 (4)	145 (2)
N4—H1n4···O5bⁱⁱ	0.98 (3)	2.22 (3)	3.113 (13)	151 (3)

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

Acknowledgements

This work was supported by the University of Ilam, the Institutional research plan No. AVOZ10100521 of the Institute of Physics and the Praemium Academiae project of the Academy of Sciences (ASCR).

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