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The title compound, [Cu2I2(CH3CN)4], exhibits a centrosymmetric Cu2I2 core [Cu...Cu distance = 2.7482 (11) Å], the CuI atoms of which are further coordinated by four mol­ecules of aceto­nitrile. The CuI atom has an overall distorted tetra­hedral coordination environment evidenced by L—Cu—L angles (L = N or I) ranging from 100.47 (10) to 117.06 (2)°. The coordination geometries of the aceto­nitrile ligands deviate slightly from linearity as shown by Cu—N—C angles of 167.0 (2) and 172.7 (2)°. In the crystal, there are no significant hydrogen-bonding inter­actions present, so the crystal packing seems to be formed predominantly by van der Waals forces.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015018149/wm5208sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989015018149/wm5208Isup2.hkl
Contains datablock I

CCDC reference: 1427944

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.021
  • wR factor = 0.056
  • Data-to-parameter ratio = 22.3

checkCIF/PLATON results

No syntax errors found



Alert level G PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) I -- Cu .. 49.0 su PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) I -- Cu_a .. 36.5 su PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) . 1.25 Ratio
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 0 ALERT level C = Check. Ensure it is not caused by an omission or oversight 3 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Synthesis and crystallization top

The title compound occured as a byproduct from the synthesis of copper(I) iodide compounds (see: Related literature). CuI was dissolved in aceto­nitrile and treated with an excess of sulfur ligands (i.e. di­methyl sulfide). After stirring, the solution was stored in a refridgerator over night, followed by keeping it in a freezer (Knorr et al., 2015). In addition to the crystallized CuI compounds, the title compound could be isolated in traces.

Refinement top

Methyl hydrogen atoms were set geometrically and refined as a rotating group with Uiso(H) = 1.5Ueq(C).

Related literature top

The title molecule is the active species used for the synthesis of luminescent compounds with (CuI)n moieties, prepared by treatment with sulfur ligands. For more details of syntheses and properties of these compounds, see: Knorr et al. (2012, 2014, 2015). The N—Cu—N angle of 100.47 (10)° in the title compound is comparable with that found in the pyridine-coordinated CuI dimer (Dyason et al., 1984). For crystal structures of CuI dimers with additional diamine ligands, see: Haitko (2007); Garbauskas et al. (1986). The title compound represents, to the best of our knowledge, the first crystallographic characterization of CuI with acetonitrile as the only co-ligand, probably caused by the sensitive nature of the crystals. In the solid state, CuI appears as a polymer (Wyckoff & Posnjak, 1922).

Structure description top

The title molecule is the active species used for the synthesis of luminescent compounds with (CuI)n moieties, prepared by treatment with sulfur ligands. For more details of syntheses and properties of these compounds, see: Knorr et al. (2012, 2014, 2015). The N—Cu—N angle of 100.47 (10)° in the title compound is comparable with that found in the pyridine-coordinated CuI dimer (Dyason et al., 1984). For crystal structures of CuI dimers with additional diamine ligands, see: Haitko (2007); Garbauskas et al. (1986). The title compound represents, to the best of our knowledge, the first crystallographic characterization of CuI with acetonitrile as the only co-ligand, probably caused by the sensitive nature of the crystals. In the solid state, CuI appears as a polymer (Wyckoff & Posnjak, 1922).

Synthesis and crystallization top

The title compound occured as a byproduct from the synthesis of copper(I) iodide compounds (see: Related literature). CuI was dissolved in aceto­nitrile and treated with an excess of sulfur ligands (i.e. di­methyl sulfide). After stirring, the solution was stored in a refridgerator over night, followed by keeping it in a freezer (Knorr et al., 2015). In addition to the crystallized CuI compounds, the title compound could be isolated in traces.

Refinement details top

Methyl hydrogen atoms were set geometrically and refined as a rotating group with Uiso(H) = 1.5Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with anisotropic displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Part of the crystal packing of the title compound viewed along [001]. H atoms were omitted for clarity.
Di-µ-iodido-bis[bis(acetonitrile-κN)copper(I)] top
Crystal data top
[Cu2I2(C2H3N)4]F(000) = 504
Mr = 545.10Dx = 2.320 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.669 (3) ÅCell parameters from 5543 reflections
b = 14.367 (5) Åθ = 2.8–27.1°
c = 7.944 (3) ŵ = 6.66 mm1
β = 116.957 (5)°T = 173 K
V = 780.2 (5) Å3Block, colourless
Z = 20.4 × 0.3 × 0.2 mm
Data collection top
Bruker APEXII CCD
diffractometer
1628 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
phi and ω scansθmax = 27.0°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
h = 99
Tmin = 0.178, Tmax = 1k = 1818
18211 measured reflectionsl = 1010
1696 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.021 w = 1/[σ2(Fo2) + (0.0281P)2 + 0.2851P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.056(Δ/σ)max < 0.001
S = 1.16Δρmax = 0.77 e Å3
1696 reflectionsΔρmin = 0.70 e Å3
76 parametersExtinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0356 (10)
Crystal data top
[Cu2I2(C2H3N)4]V = 780.2 (5) Å3
Mr = 545.10Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.669 (3) ŵ = 6.66 mm1
b = 14.367 (5) ÅT = 173 K
c = 7.944 (3) Å0.4 × 0.3 × 0.2 mm
β = 116.957 (5)°
Data collection top
Bruker APEXII CCD
diffractometer
1696 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
1628 reflections with I > 2σ(I)
Tmin = 0.178, Tmax = 1Rint = 0.052
18211 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0210 restraints
wR(F2) = 0.056H-atom parameters constrained
S = 1.16Δρmax = 0.77 e Å3
1696 reflectionsΔρmin = 0.70 e Å3
76 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. 1. Fixed Uiso At 1.5 times of: All C(H,H,H) groups 2.a Idealized Me refined as rotating group: C2(H2A,H2B,H2C), C4(H4A,H4B,H4C)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2924 (4)0.35511 (17)0.2436 (4)0.0327 (5)
C20.3602 (5)0.3046 (2)0.1258 (5)0.0477 (7)
H2A0.31470.24000.11170.072*
H2B0.50350.30570.18510.072*
H2C0.30810.33410.00120.072*
C30.5869 (4)0.43439 (18)0.8689 (4)0.0327 (5)
C40.7870 (4)0.4169 (2)1.0081 (4)0.0440 (6)
H4A0.78810.37111.10000.066*
H4B0.84640.47501.07340.066*
H4C0.86170.39270.94510.066*
Cu0.17322 (5)0.46160 (2)0.52217 (4)0.03798 (12)
I0.09223 (2)0.36402 (2)0.57402 (3)0.03945 (11)
N10.2374 (3)0.39446 (16)0.3335 (3)0.0386 (5)
N20.4306 (3)0.44856 (16)0.7589 (3)0.0402 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0351 (13)0.0281 (12)0.0329 (13)0.0024 (9)0.0137 (11)0.0016 (9)
C20.0589 (18)0.0430 (15)0.0494 (17)0.0014 (13)0.0318 (15)0.0063 (13)
C30.0348 (13)0.0328 (12)0.0294 (11)0.0015 (10)0.0137 (10)0.0003 (10)
C40.0323 (13)0.0523 (17)0.0381 (14)0.0054 (12)0.0077 (11)0.0013 (12)
Cu0.03422 (19)0.0400 (2)0.03415 (19)0.00505 (13)0.01066 (14)0.00146 (13)
I0.03990 (14)0.03205 (13)0.04649 (15)0.00095 (6)0.01965 (10)0.00337 (6)
N10.0407 (12)0.0370 (12)0.0369 (12)0.0027 (10)0.0164 (10)0.0009 (10)
N20.0345 (12)0.0438 (13)0.0353 (11)0.0002 (10)0.0096 (10)0.0007 (10)
Geometric parameters (Å, º) top
C1—C21.454 (4)C4—H4B0.9800
C1—N11.132 (4)C4—H4C0.9800
C2—H2A0.9800Cu—Cui2.7482 (11)
C2—H2B0.9800Cu—Ii2.6108 (10)
C2—H2C0.9800Cu—I2.6532 (8)
C3—C41.450 (3)Cu—N12.022 (2)
C3—N21.137 (3)Cu—N22.025 (2)
C4—H4A0.9800I—Cui2.6108 (10)
N1—C1—C2179.2 (3)I—Cu—Cui57.78 (3)
C1—C2—H2A109.5Ii—Cu—Cui59.286 (14)
C1—C2—H2B109.5Ii—Cu—I117.06 (2)
C1—C2—H2C109.5N1—Cu—Cui129.99 (7)
H2A—C2—H2B109.5N1—Cu—I108.95 (7)
H2A—C2—H2C109.5N1—Cu—Ii110.27 (7)
H2B—C2—H2C109.5N1—Cu—N2100.47 (10)
N2—C3—C4179.4 (3)N2—Cu—Cui129.41 (8)
C3—C4—H4A109.5N2—Cu—I107.48 (8)
C3—C4—H4B109.5N2—Cu—Ii111.28 (7)
C3—C4—H4C109.5Cui—I—Cu62.94 (2)
H4A—C4—H4B109.5C1—N1—Cu172.7 (2)
H4A—C4—H4C109.5C3—N2—Cu167.0 (2)
H4B—C4—H4C109.5
Symmetry code: (i) x, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Cu2I2(C2H3N)4]
Mr545.10
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)7.669 (3), 14.367 (5), 7.944 (3)
β (°) 116.957 (5)
V3)780.2 (5)
Z2
Radiation typeMo Kα
µ (mm1)6.66
Crystal size (mm)0.4 × 0.3 × 0.2
Data collection
DiffractometerBruker APEXII CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.178, 1
No. of measured, independent and
observed [I > 2σ(I)] reflections
18211, 1696, 1628
Rint0.052
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.021, 0.056, 1.16
No. of reflections1696
No. of parameters76
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.77, 0.70

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXS2014 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

 

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