[μ-N,N'-Bis(2-amino-eth-yl)ethane-1,2-diamine-κ(4)N(1),N(1'):N(2),N(2')]bis-{[N,N'-bis-(2-amino-eth-yl)ethane-1,2-diamine-κ(4)N,N',N'',N''']cadmium} tetra-kis-(perchlorate).

The centrosymmetric dinuclear cadmium title complex, [Cd(2)(C(6)H(18)N(4))(3)](ClO(4))(4), was obtained by the reaction of N,N'-bis-(2-amino-eth-yl)ethane-1,2-diamine (trien) with Cd(NO(3))(2)·4H(2)O 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 octa-hedral 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 = 1061.3

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.106

S = 2.02

4952 reflections

269 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.13 e Å−3

Δρmin = −0.92 e Å−3

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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812033880/ru2040sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cd2(C6H18N4)3](ClO4)4	F(000) = 1076
Mr = 1061.3	Dx = 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

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

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	Δρmax = 1.13 e Å−3
269 parameters	Δρmin = −0.92 e Å−3
0 restraints

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

	x	y	z	Uiso*/Ueq	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)

	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)

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)

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···O5civ	0.78 (4)	2.25 (4)	2.999 (3)	159 (4)
N1—H2n1···O3cv	0.80 (4)	2.46 (4)	3.149 (4)	145 (3)
N11—H1n11···O2civ	0.82 (4)	2.40 (4)	3.140 (4)	149 (3)
N11—H2n11···O4av	0.92 (4)	2.44 (4)	3.210 (5)	141 (3)
N4—H1n4···O4av	0.98 (3)	2.36 (3)	3.271 (4)	154 (2)
N4—H1n4···O5av	0.98 (3)	2.38 (3)	3.236 (4)	145 (2)
N4—H1n4···O5bv	0.98 (3)	2.22 (3)	3.113 (13)	151 (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⋯O4c i	0.96	2.49	3.449 (3)	172
N1—H2n1⋯O3c ii	0.80 (4)	2.46 (4)	3.149 (4)	145 (3)
N11—H1n11⋯O2c iii	0.82 (4)	2.40 (4)	3.140 (4)	149 (3)
N11—H2n11⋯O4a ii	0.92 (4)	2.44 (4)	3.210 (5)	141 (3)
N4—H1n4⋯O4a ii	0.98 (3)	2.36 (3)	3.271 (4)	154 (2)
N4—H1n4⋯O5a ii	0.98 (3)	2.38 (3)	3.236 (4)	145 (2)
N4—H1n4⋯O5b ii	0.98 (3)	2.22 (3)	3.113 (13)	151 (3)

Symmetry codes: (i) ; (ii) ; (iii) .