The pseudosymmetric structure of bis-(pentane-1,5-diaminium) iodide tris-(triiodide).

The asymmetric unit of the title compound, [H(3)N(CH(2))(5)NH(3)](2)I[I(3)](3) or 2C(5)H(16)N(2) (2+)·3I(3) (-)·I(-), consists of two crystallographically independent pentane-1,5-diaminium dications and two triiodide anions in general positions besides two additional triiodide and two iodide anions located on twofold axes. The compound crystallizes in the centrosymmetric monoclinic space group P2/n. The structure refinement was handicapped by the pseudosymmetry (pseudo-centering) of the structure and by twinning. The crystal structure is composed of two alternate layers, which differ in their arrangement of the pentane-1,5-diaminium dications and the iodide/triiodide anions and which are connected via weak to medium-strong N-H⋯I hydrogen bonds, constructing a complex hydrogen-bonded network.

Related literature

For general background to polyiodides, see: Svensson & Kloo (2003 ▶). For materials constructed by α,ω-diaminiumalkanes, see: Feng et al. (2000 ▶); Wiebcke (2002 ▶); Frank & Reiss (1997 ▶); Johnson et al. (2000 ▶). For applications of polyiodides, see: O’Regan & Grätzel (1991 ▶); Gorlov & Kloo (2008 ▶); Yang et al. (2011 ▶). For Raman spectroscopy of polyiodides, see: Deplano et al. (1999 ▶). For polyiodide-containing compounds with other stick-shaped cationic templates, see: Tebbe & Bittner (1995 ▶); Svensson et al. (2008 ▶); Abate et al. (2010 ▶); Meyer et al. (2010 ▶); Müller et al. (2010 ▶); García et al. (2011 ▶); Reiss & van Megen (2012 ▶). For polyiodide-containing α,ω-diaminiumalkanes compounds, see: Reiss & Engel (2002 ▶, 2004 ▶). For background to hydrogen bonds, see: Steiner (2002 ▶). For graph sets, see: Etter et al. (1990 ▶). For elemental analysis of iodine, see: Egli (1969 ▶). For programmes used to handle the pseudosymmetry, see: Sheldrick (2008 ▶); Spek (2009 ▶).

Experimental

Crystal data

2C5H16N2 2+·3I3 −·I−

M = 1477.40

Monoclinic,

a = 11.24742 (18) Å

b = 24.4932 (3) Å

c = 11.49947 (16) Å

β = 99.5311 (14)°

V = 3124.21 (8) Å3

Z = 4

Mo Kα radiation

μ = 9.92 mm−1

T = 110 K

0.35 × 0.13 × 0.03 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer

Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009 ▶), using a multi-faceted crystal model (Clark & Reid, 1995 ▶)] T min = 0.184, T max = 0.746

42753 measured reflections

5507 independent reflections

5106 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.048

S = 1.78

5507 reflections

260 parameters

12 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.89 e Å−3

Δρmin = −0.85 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2011 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812014420/br2194sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014420/br2194Isup2.hkl

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

2C5H16N22+·3I3−·I−	F(000) = 2600
Mr = 1477.40	Dx = 3.141 Mg m−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 34080 reflections
a = 11.24742 (18) Å	θ = 2.9–32.9°
b = 24.4932 (3) Å	µ = 9.92 mm−1
c = 11.49947 (16) Å	T = 110 K
β = 99.5311 (14)°	Plate, dark-red
V = 3124.21 (8) Å3	0.35 × 0.13 × 0.03 mm
Z = 4

Oxford Diffraction Xcalibur Eos diffractometer	5507 independent reflections
Radiation source: fine-focus sealed tube	5106 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 16.2711 pixels mm-1	θmax = 25.0°, θmin = 2.9°
ω scan	h = −13→13
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009), using a multi-faceted crystal model (Clark & Reid, 1995)]	k = −29→29
Tmin = 0.184, Tmax = 0.746	l = −13→13
42753 measured reflections

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)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.048	w = 1/[σ2(Fo2) + (0.010P)2 + 2.P] where P = (Fo2 + 2Fc2)/3
S = 1.78	(Δ/σ)max = 0.002
5507 reflections	Δρmax = 0.89 e Å−3
260 parameters	Δρmin = −0.85 e Å−3
12 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: 0.000079 (7)

Experimental. Absorption correction: CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.44. Analytical numeric absorption correction using a multifaceted crystal model (Clark & Reid, 1995).

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.

	x	y	z	Uiso*/Ueq
I1	0.2500	−0.244327 (17)	0.2500	0.01394 (10)
I2	0.43884 (3)	−0.243981 (13)	0.46114 (2)	0.01481 (8)
I3	0.21847 (3)	0.122482 (12)	0.52226 (3)	0.01339 (8)
I4	0.21879 (3)	0.003697 (12)	0.52343 (2)	0.01055 (8)
I5	0.21699 (3)	−0.116102 (12)	0.52918 (3)	0.01481 (8)
I6	0.2500	0.239763 (18)	0.2500	0.01396 (10)
I7	0.2500	0.742057 (18)	0.7500	0.01391 (10)
I8	0.05106 (3)	0.741845 (13)	0.54698 (3)	0.01517 (8)
I9	0.51718 (3)	0.623905 (13)	0.71356 (3)	0.01481 (8)
I10	0.52267 (3)	0.505510 (12)	0.71916 (2)	0.01173 (8)
I11	0.53337 (3)	0.385420 (13)	0.72274 (3)	0.01511 (8)
I12	0.2500	0.253336 (18)	0.7500	0.01617 (10)
N1	0.5149 (4)	−0.15499 (17)	0.2316 (4)	0.0158 (9)
H11	0.496 (5)	−0.1876 (13)	0.259 (5)	0.037 (10)*
H12	0.487 (5)	−0.154 (2)	0.155 (2)	0.037 (10)*
H13	0.5955 (19)	−0.152 (2)	0.249 (5)	0.037 (10)*
N2	0.5001 (4)	0.15009 (17)	0.2556 (4)	0.0147 (9)
H21	0.574 (3)	0.158 (2)	0.295 (4)	0.024 (8)*
H22	0.453 (4)	0.1790 (15)	0.266 (4)	0.024 (8)*
H23	0.496 (5)	0.148 (2)	0.1766 (18)	0.024 (8)*
N3	0.2715 (4)	0.33075 (17)	0.4993 (4)	0.0160 (9)
H31	0.239 (5)	0.320 (2)	0.427 (3)	0.037 (10)*
H32	0.262 (5)	0.3018 (16)	0.545 (4)	0.037 (10)*
H33	0.3522 (19)	0.334 (2)	0.513 (5)	0.037 (10)*
N4	0.2500 (4)	0.63571 (17)	0.4891 (4)	0.0142 (9)
H41	0.326 (2)	0.640 (2)	0.525 (4)	0.024 (8)*
H42	0.211 (4)	0.6674 (13)	0.496 (4)	0.024 (8)*
H43	0.242 (5)	0.629 (2)	0.4116 (19)	0.024 (8)*
C1	0.4644 (4)	−0.10655 (19)	0.2854 (4)	0.0153 (10)
H1A	0.4858	−0.1084	0.3706	0.018*
H1B	0.3771	−0.1069	0.2655	0.018*
C2	0.5124 (4)	−0.05421 (19)	0.2416 (4)	0.0126 (10)
H2A	0.4923	−0.0528	0.1563	0.015*
H2B	0.5996	−0.0537	0.2627	0.015*
C3	0.4602 (4)	−0.00432 (18)	0.2939 (4)	0.0137 (10)
H3A	0.3731	−0.0049	0.2726	0.016*
H3B	0.4800	−0.0058	0.3792	0.016*
C4	0.5083 (4)	0.04858 (19)	0.2507 (4)	0.0112 (10)
H4A	0.5950	0.0501	0.2756	0.013*
H4B	0.4922	0.0493	0.1652	0.013*
C5	0.4506 (4)	0.09804 (19)	0.2983 (4)	0.0156 (10)
H5A	0.3641	0.0968	0.2727	0.019*
H5B	0.4661	0.0972	0.3838	0.019*
C6	0.1961 (4)	0.58547 (19)	0.5357 (4)	0.0163 (10)
H6A	0.1093	0.5856	0.5111	0.020*
H6B	0.2128	0.5854	0.6212	0.020*
C7	0.2497 (4)	0.53499 (19)	0.4888 (4)	0.0128 (10)
H7A	0.3367	0.5360	0.5113	0.015*
H7B	0.2312	0.5350	0.4034	0.015*
C8	0.2013 (4)	0.4825 (2)	0.5357 (4)	0.0146 (10)
H8A	0.2204	0.4822	0.6211	0.018*
H8B	0.1143	0.4815	0.5136	0.018*
C9	0.2558 (4)	0.43232 (19)	0.4869 (4)	0.0125 (10)
H9A	0.2336	0.4317	0.4017	0.015*
H9B	0.3430	0.4341	0.5059	0.015*
C10	0.2115 (4)	0.38037 (18)	0.5385 (4)	0.0162 (11)
H10A	0.2277	0.3825	0.6239	0.019*
H10B	0.1249	0.3773	0.5141	0.019*

	U11	U22	U33	U12	U13	U23
I1	0.0179 (2)	0.0086 (2)	0.0172 (2)	0.000	0.00819 (18)	0.000
I2	0.01940 (17)	0.01083 (17)	0.01497 (15)	0.00174 (12)	0.00510 (13)	0.00131 (12)
I3	0.01559 (16)	0.00995 (16)	0.01443 (15)	0.00031 (12)	0.00189 (13)	0.00010 (12)
I4	0.01090 (16)	0.01066 (16)	0.00983 (15)	0.00076 (11)	0.00097 (13)	−0.00075 (11)
I5	0.01700 (16)	0.00901 (16)	0.01688 (16)	0.00144 (12)	−0.00170 (13)	−0.00120 (12)
I6	0.0174 (2)	0.0088 (2)	0.0169 (2)	0.000	0.00622 (18)	0.000
I7	0.0179 (2)	0.0094 (2)	0.0164 (2)	0.000	0.00837 (18)	0.000
I8	0.01680 (16)	0.01138 (17)	0.01794 (16)	0.00001 (12)	0.00468 (13)	0.00029 (12)
I9	0.01788 (17)	0.01071 (17)	0.01540 (15)	0.00194 (12)	0.00146 (13)	−0.00085 (12)
I10	0.01125 (16)	0.01285 (17)	0.01060 (15)	0.00072 (11)	0.00034 (13)	−0.00022 (12)
I11	0.01647 (16)	0.01090 (17)	0.01654 (16)	0.00027 (12)	−0.00146 (13)	−0.00011 (12)
I12	0.0243 (2)	0.0087 (2)	0.0173 (2)	0.000	0.00892 (18)	0.000
N1	0.018 (2)	0.008 (2)	0.021 (2)	−0.0010 (18)	0.0036 (19)	0.0046 (18)
N2	0.019 (2)	0.007 (2)	0.017 (2)	0.0005 (17)	0.0021 (19)	−0.0019 (18)
N3	0.020 (2)	0.012 (2)	0.016 (2)	0.0002 (18)	0.0045 (19)	0.0004 (17)
N4	0.014 (2)	0.009 (2)	0.019 (2)	0.0044 (17)	0.0027 (18)	−0.0021 (18)
C1	0.020 (3)	0.010 (3)	0.017 (2)	−0.001 (2)	0.005 (2)	0.002 (2)
C2	0.012 (2)	0.013 (3)	0.012 (2)	−0.0026 (19)	0.002 (2)	0.0027 (19)
C3	0.014 (2)	0.014 (3)	0.013 (2)	−0.0008 (19)	0.004 (2)	0.0016 (19)
C4	0.011 (2)	0.010 (2)	0.012 (2)	0.0002 (19)	0.0018 (19)	−0.0010 (19)
C5	0.016 (2)	0.013 (3)	0.018 (2)	0.000 (2)	0.004 (2)	−0.001 (2)
C6	0.019 (3)	0.012 (3)	0.019 (2)	−0.002 (2)	0.005 (2)	−0.002 (2)
C7	0.014 (2)	0.012 (3)	0.012 (2)	−0.0004 (19)	0.000 (2)	0.0002 (19)
C8	0.016 (2)	0.013 (3)	0.015 (2)	0.000 (2)	0.003 (2)	−0.002 (2)
C9	0.013 (2)	0.014 (3)	0.010 (2)	−0.0008 (19)	0.0016 (19)	0.0027 (19)
C10	0.023 (3)	0.005 (2)	0.021 (2)	0.000 (2)	0.005 (2)	−0.002 (2)

I1—I2	2.9494 (3)	C1—H1B	0.9700
I1—I2i	2.9494 (3)	C2—C3	1.522 (6)
I3—I4	2.9095 (4)	C2—H2A	0.9700
I4—I5	2.9352 (4)	C2—H2B	0.9700
I7—I8ii	2.9542 (3)	C3—C4	1.519 (6)
I7—I8	2.9542 (3)	C3—H3A	0.9700
I9—I10	2.9010 (4)	C3—H3B	0.9700
I10—I11	2.9439 (4)	C4—C5	1.519 (6)
N1—C1	1.493 (6)	C4—H4A	0.9700
N1—H11	0.892 (19)	C4—H4B	0.9700
N1—H12	0.888 (19)	C5—H5A	0.9700
N1—H13	0.899 (19)	C5—H5B	0.9700
N2—C5	1.506 (6)	C6—C7	1.513 (7)
N2—H21	0.898 (19)	C6—H6A	0.9700
N2—H22	0.904 (19)	C6—H6B	0.9700
N2—H23	0.903 (19)	C7—C8	1.528 (7)
N3—C10	1.496 (6)	C7—H7A	0.9700
N3—H31	0.891 (19)	C7—H7B	0.9700
N3—H32	0.904 (19)	C8—C9	1.522 (7)
N3—H33	0.899 (19)	C8—H8A	0.9700
N4—C6	1.509 (6)	C8—H8B	0.9700
N4—H41	0.895 (19)	C9—C10	1.522 (6)
N4—H42	0.900 (19)	C9—H9A	0.9700
N4—H43	0.898 (19)	C9—H9B	0.9700
C1—C2	1.510 (6)	C10—H10A	0.9700
C1—H1A	0.9700	C10—H10B	0.9700
I2—I1—I2i	179.67 (2)	C2—C3—H3B	109.2
I3—I4—I5	178.805 (15)	H3A—C3—H3B	107.9
I8ii—I7—I8	179.80 (2)	C5—C4—C3	111.4 (4)
I9—I10—I11	178.713 (15)	C5—C4—H4A	109.3
C1—N1—H11	116 (4)	C3—C4—H4A	109.3
C1—N1—H12	107 (4)	C5—C4—H4B	109.3
H11—N1—H12	108 (5)	C3—C4—H4B	109.3
C1—N1—H13	107 (4)	H4A—C4—H4B	108.0
H11—N1—H13	106 (5)	N2—C5—C4	110.8 (4)
H12—N1—H13	114 (5)	N2—C5—H5A	109.5
C5—N2—H21	112 (3)	C4—C5—H5A	109.5
C5—N2—H22	111 (3)	N2—C5—H5B	109.5
H21—N2—H22	106 (5)	C4—C5—H5B	109.5
C5—N2—H23	109 (3)	H5A—C5—H5B	108.1
H21—N2—H23	114 (5)	N4—C6—C7	109.5 (4)
H22—N2—H23	104 (5)	N4—C6—H6A	109.8
C10—N3—H31	113 (4)	C7—C6—H6A	109.8
C10—N3—H32	111 (4)	N4—C6—H6B	109.8
H31—N3—H32	104 (5)	C7—C6—H6B	109.8
C10—N3—H33	112 (4)	H6A—C6—H6B	108.2
H31—N3—H33	116 (5)	C6—C7—C8	112.1 (4)
H32—N3—H33	101 (5)	C6—C7—H7A	109.2
C6—N4—H41	110 (3)	C8—C7—H7A	109.2
C6—N4—H42	116 (3)	C6—C7—H7B	109.2
H41—N4—H42	108 (5)	C8—C7—H7B	109.2
C6—N4—H43	103 (3)	H7A—C7—H7B	107.9
H41—N4—H43	114 (5)	C9—C8—C7	111.2 (4)
H42—N4—H43	106 (5)	C9—C8—H8A	109.4
N1—C1—C2	110.8 (4)	C7—C8—H8A	109.4
N1—C1—H1A	109.5	C9—C8—H8B	109.4
C2—C1—H1A	109.5	C7—C8—H8B	109.4
N1—C1—H1B	109.5	H8A—C8—H8B	108.0
C2—C1—H1B	109.5	C10—C9—C8	110.7 (4)
H1A—C1—H1B	108.1	C10—C9—H9A	109.5
C1—C2—C3	111.6 (4)	C8—C9—H9A	109.5
C1—C2—H2A	109.3	C10—C9—H9B	109.5
C3—C2—H2A	109.3	C8—C9—H9B	109.5
C1—C2—H2B	109.3	H9A—C9—H9B	108.1
C3—C2—H2B	109.3	N3—C10—C9	111.6 (4)
H2A—C2—H2B	108.0	N3—C10—H10A	109.3
C4—C3—C2	112.0 (4)	C9—C10—H10A	109.3
C4—C3—H3A	109.2	N3—C10—H10B	109.3
C2—C3—H3A	109.2	C9—C10—H10B	109.3
C4—C3—H3B	109.2	H10A—C10—H10B	108.0
N1—C1—C2—C3	179.0 (4)	N4—C6—C7—C8	178.4 (4)
C1—C2—C3—C4	179.8 (4)	C6—C7—C8—C9	179.6 (4)
C2—C3—C4—C5	177.0 (4)	C7—C8—C9—C10	177.4 (4)
C3—C4—C5—N2	179.5 (4)	C8—C9—C10—N3	−175.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···I2	0.89 (2)	2.87 (4)	3.632 (4)	144 (5)
N1—H12···I5i	0.89 (2)	3.00 (4)	3.757 (4)	145 (5)
N1—H13···I12iii	0.90 (2)	3.02 (5)	3.558 (4)	120 (4)
N2—H21···I5iii	0.90 (2)	3.02 (3)	3.786 (4)	145 (4)
N2—H22···I6	0.90 (2)	2.71 (3)	3.562 (4)	158 (4)
N3—H31···I6	0.89 (2)	2.85 (4)	3.607 (4)	144 (5)
N3—H32···I12	0.90 (2)	2.66 (3)	3.492 (4)	154 (5)
N4—H41···I9	0.90 (2)	2.82 (3)	3.634 (4)	153 (4)
N4—H42···I8	0.90 (2)	2.70 (2)	3.564 (4)	162 (4)
N4—H43···I11iv	0.90 (2)	2.94 (4)	3.621 (4)	134 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯I2	0.89 (2)	2.87 (4)	3.632 (4)	144 (5)
N1—H12⋯I5i	0.89 (2)	3.00 (4)	3.757 (4)	145 (5)
N1—H13⋯I12ii	0.90 (2)	3.02 (5)	3.558 (4)	120 (4)
N2—H21⋯I5ii	0.90 (2)	3.02 (3)	3.786 (4)	145 (4)
N2—H22⋯I6	0.90 (2)	2.71 (3)	3.562 (4)	158 (4)
N3—H31⋯I6	0.89 (2)	2.85 (4)	3.607 (4)	144 (5)
N3—H32⋯I12	0.90 (2)	2.66 (3)	3.492 (4)	154 (5)
N4—H41⋯I9	0.90 (2)	2.82 (3)	3.634 (4)	153 (4)
N4—H42⋯I8	0.90 (2)	2.70 (2)	3.564 (4)	162 (4)
N4—H43⋯I11iii	0.90 (2)	2.94 (4)	3.621 (4)	134 (4)

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