The diselanylbis(1,3-dimethyl-1H-imidazol-3-ium) dication stabilized by the polymeric catena-penta­chlorido­tricuprate(I) anion

In the title compound, catena-poly[diselanylbis(1,3-dimethyl-1H-imidazol-3-ium) [μ₃-chlorido-tetra-μ₂-chlorido-tri­cup­rate(I)]], {(C₁₀H₁₆N₄Se₂)[Cu₃Cl₅]}_n, the diselenide dication is stabilized by catena-[Cu₃Cl₅]²⁻ anions which associate through strong Cu—Cl bonds [average length = 2.3525 (13) Å] to form polymeric chains. The polymeric [Cu₃Cl₅]²⁻ anion contains crystallographically imposed twofold rotation symmetry, with distorted trigonal-planar and tetra­hedral geometries around the two symmetry-independent Cu atoms. Likewise, the Se—Se bond of the cation is centered on a twofold rotation axis.

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear (Rigaku/MSC, 2006); data reduction: CrystalClear (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXTL (Version 6.10; Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Version 6.10; Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Version 6.10; Sheldrick, 2008).

catena-poly[diselanylbis(1,3-dimethyl-1H-imidazol-3-ium) [µ₃-chlorido-tetra-µ₂-chlorido-tricuprate(I)]]

Crystal data

(C10H16N4Se2)[Cu3Cl5]	F(000) = 1376
Mr = 718.06	Dx = 2.383 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8327 reflections
a = 12.238 (2) Å	θ = 3.0–26.3°
b = 12.217 (2) Å	µ = 7.47 mm^−1
c = 14.123 (3) Å	T = 168 K
β = 108.61 (3)°	Prism, red
V = 2001.2 (7) Å^3	0.32 × 0.25 × 0.23 mm
Z = 4

Data collection

Rigaku AFC-8S diffractometer	2022 independent reflections
Radiation source: fine-focus sealed tube	1698 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 14.6306 pixels mm^-1	θmax = 26.3°, θmin = 3.0°
dtprofit.ref scans	h = −10→15
Absorption correction: multi-scan [REQAB (Jacobson, 1998) and CrystalClear (Rigaku/MSC, 2006)]	k = −15→15
Tmin = 0.199, Tmax = 0.279	l = −17→17
8327 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0525P)^2 + 17.9833P] where P = (Fo^2 + 2Fc^2)/3
2022 reflections	(Δ/σ)max < 0.001
112 parameters	Δρmax = 1.22 e Å^−3
0 restraints	Δρmin = −1.12 e Å^−3

Special details

Experimental. ¹H and ¹³C{¹H} NMR spectra were obtained on a Bruker AVANCE 500 NMR spectrometer. ¹H and ¹³C{¹H} NMR chemical shifts are reported in δ relative to trimethylsilane (TMS; δ 0). IR spectra were obtained using Nujol mulls on KBr salt plates using a Magna 550 IR spectrometer. Abbreviations used in the description of vibrational data are as follows: v, very strong; s, strong; m, medium; w, weak; b, broad. Electrospray ionization mass spectrometry (ESI–MS) was conducted using a QSTAR XL Hybrid MS/MS System from Applied Biosystems via direct injection of sample (0.05 ml/min flow rate) into a Turbo Ionspray ionization source. Samples were run under positive mode with an ionspray voltage of 5500, and in TOF scan mode. The melting point was determined using a Barnstead Electrothermal 9100 apparatus in glass capillary tube.

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 (Ų)

	x	y	z	Uiso*/Ueq
Se1	0.09498 (4)	0.50479 (4)	0.30948 (4)	0.02044 (17)
C1	0.1423 (4)	0.3795 (4)	0.2552 (4)	0.0229 (10)
C2	0.1735 (7)	0.4644 (6)	0.1053 (5)	0.0429 (16)
H2A	0.1389	0.5276	0.1243	0.064*
H2B	0.1309	0.4445	0.0378	0.064*
H2C	0.2517	0.4808	0.1098	0.064*
C3	0.1967 (6)	0.2673 (6)	0.1559 (5)	0.0397 (15)
H3A	0.2193	0.2413	0.1031	0.048*
C4	0.1825 (6)	0.2072 (6)	0.2300 (5)	0.0393 (15)
H4A	0.1929	0.1319	0.2379	0.047*
C5	0.1259 (7)	0.2423 (5)	0.3826 (5)	0.0412 (16)
H5A	0.1130	0.3058	0.4175	0.062*
H5B	0.1905	0.2020	0.4248	0.062*
H5C	0.0585	0.1967	0.3649	0.062*
N1	0.1720 (4)	0.3746 (4)	0.1711 (4)	0.0294 (10)
N2	0.1500 (4)	0.2762 (4)	0.2921 (4)	0.0289 (10)
Cu1	1.0000	0.21630 (12)	0.7500	0.0473 (3)
Cu2	0.99660 (7)	0.07647 (7)	0.58139 (6)	0.0400 (2)
Cl1	1.00610 (14)	0.26957 (10)	0.90297 (10)	0.0331 (3)
Cl3	0.84410 (11)	−0.00548 (11)	0.45362 (10)	0.0266 (3)
Cl2	1.0000	0.01325 (17)	0.7500	0.0364 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Se1	0.0223 (3)	0.0197 (3)	0.0192 (3)	−0.00136 (18)	0.0066 (2)	−0.00184 (18)
C1	0.016 (2)	0.027 (3)	0.024 (2)	−0.0002 (19)	0.0042 (19)	−0.005 (2)
C2	0.052 (4)	0.049 (4)	0.037 (3)	−0.016 (3)	0.027 (3)	−0.008 (3)
C3	0.035 (3)	0.044 (4)	0.040 (3)	0.005 (3)	0.013 (3)	−0.021 (3)
C4	0.039 (4)	0.032 (3)	0.042 (3)	0.015 (3)	0.005 (3)	−0.004 (3)
C5	0.057 (4)	0.031 (3)	0.026 (3)	0.000 (3)	0.001 (3)	0.005 (2)
N1	0.023 (2)	0.038 (3)	0.028 (2)	−0.003 (2)	0.0095 (19)	−0.011 (2)
N2	0.031 (2)	0.025 (2)	0.027 (2)	0.0067 (19)	0.003 (2)	−0.0046 (18)
Cu1	0.0458 (7)	0.0626 (8)	0.0308 (6)	0.000	0.0086 (5)	0.000
Cu2	0.0358 (5)	0.0387 (5)	0.0461 (5)	0.0001 (3)	0.0139 (4)	−0.0141 (3)
Cl1	0.0557 (9)	0.0172 (6)	0.0230 (6)	−0.0068 (6)	0.0077 (6)	0.0020 (5)
Cl3	0.0212 (6)	0.0356 (7)	0.0226 (6)	0.0000 (5)	0.0063 (5)	−0.0014 (5)
Cl2	0.0586 (14)	0.0302 (10)	0.0234 (9)	0.000	0.0174 (9)	0.000

Geometric parameters (Å, º)

Se1—C1	1.884 (5)	C5—H5B	0.9600
Se1—Se1^i	2.3946 (13)	C5—H5C	0.9600
C1—N1	1.349 (7)	Cu1—Cl1^ii	2.2346 (15)
C1—N2	1.357 (7)	Cu1—Cl1	2.2346 (15)
C2—N1	1.442 (9)	Cu1—Cl2	2.481 (3)
C2—H2A	0.9600	Cu1—Cu2	2.9201 (12)
C2—H2B	0.9600	Cu1—Cu2^ii	2.9201 (12)
C2—H2C	0.9600	Cu2—Cl3^iii	2.3264 (16)
C3—C4	1.335 (11)	Cu2—Cl3	2.3648 (17)
C3—N1	1.377 (8)	Cu2—Cl1^ii	2.3707 (16)
C3—H3A	0.9300	Cu2—Cl2	2.4910 (12)
C4—N2	1.364 (8)	Cu2—Cu2^iii	2.9843 (16)
C4—H4A	0.9300	Cl1—Cu2^ii	2.3708 (16)
C5—N2	1.460 (8)	Cl3—Cu2^iii	2.3264 (16)
C5—H5A	0.9600	Cl2—Cu2^ii	2.4910 (12)
C1—Se1—Se1^i	94.01 (15)	Cl1^ii—Cu1—Cl2	106.94 (5)
N1—C1—N2	106.9 (5)	Cl1—Cu1—Cl2	106.94 (5)
N1—C1—Se1	126.7 (4)	Cl1^ii—Cu1—Cu2	52.75 (4)
N2—C1—Se1	126.3 (4)	Cl1—Cu1—Cu2	161.11 (7)
N1—C2—H2A	109.5	Cl2—Cu1—Cu2	54.20 (3)
N1—C2—H2B	109.5	Cl1^ii—Cu1—Cu2^ii	161.11 (7)
H2A—C2—H2B	109.5	Cl1—Cu1—Cu2^ii	52.75 (4)
N1—C2—H2C	109.5	Cl2—Cu1—Cu2^ii	54.20 (3)
H2A—C2—H2C	109.5	Cu2—Cu1—Cu2^ii	108.39 (6)
H2B—C2—H2C	109.5	Cl3^iii—Cu2—Cl3	101.00 (5)
C4—C3—N1	108.1 (5)	Cl3^iii—Cu2—Cl1^ii	115.36 (6)
C4—C3—H3A	125.9	Cl3—Cu2—Cl1^ii	117.47 (6)
N1—C3—H3A	125.9	Cl3^iii—Cu2—Cl2	109.15 (6)
C3—C4—N2	107.5 (6)	Cl3—Cu2—Cl2	111.50 (6)
C3—C4—H4A	126.2	Cl1^ii—Cu2—Cl2	102.47 (6)
N2—C4—H4A	126.2	Cl3^iii—Cu2—Cu1	126.62 (5)
N2—C5—H5A	109.5	Cl3—Cu2—Cu1	132.25 (5)
N2—C5—H5B	109.5	Cl1^ii—Cu2—Cu1	48.61 (4)
H5A—C5—H5B	109.5	Cl2—Cu2—Cu1	53.87 (5)
N2—C5—H5C	109.5	Cl3^iii—Cu2—Cu2^iii	51.07 (4)
H5A—C5—H5C	109.5	Cl3—Cu2—Cu2^iii	49.93 (4)
H5B—C5—H5C	109.5	Cl1^ii—Cu2—Cu2^iii	134.38 (6)
C1—N1—C3	108.3 (5)	Cl2—Cu2—Cu2^iii	123.11 (7)
C1—N1—C2	126.6 (5)	Cu1—Cu2—Cu2^iii	176.25 (6)
C3—N1—C2	125.0 (5)	Cu1—Cl1—Cu2^ii	78.64 (6)
C1—N2—C4	109.1 (5)	Cu2^iii—Cl3—Cu2	79.00 (5)
C1—N2—C5	126.2 (5)	Cu1—Cl2—Cu2^ii	71.94 (5)
C4—N2—C5	124.7 (5)	Cu1—Cl2—Cu2	71.94 (5)
Cl1^ii—Cu1—Cl1	146.13 (10)	Cu2^ii—Cl2—Cu2	143.88 (10)

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