Crystal structure of di-μ-iodido-bis{[bis(piperidin-1-yl)methane-κ(2) N,N']copper(I)}.

The title compound, [Cu2I2(C11H22N2)2], crystallizes as a symmetric dimer with one quarter of the mol-ecule in the asymmetric unit. The copper(I) atom, the iodine atom and the central methyl-ene C atom of the di(piperidin-1-yl)methane ligand lie on a mirror plane and the complete molecule exhibits point group symmetry 2/m. To the best of our knowledge it is the first di-amine copper(I) complex containing a four-membered chelate ring. Compared to other di-amine copper(I) iodide dimers, the title compound has a short Cu⋯Cu distance of 2.5137 (11) Å, but a long Cu-N bond length of 2.213 (3) Å. The I-Cu-I angle [121.84 (2)°] is large, and the N-Cu-N angle = 66.61 (13)° is the smallest one found for copper(I) di-amine complexes. As a result of the four-membered ring, the ligands around the copper(I) atom have an extremely distorted tetra-hedral arrangement. In the crystal, there are no significant inter-molecular inter-actions present.

Related literature

To the best of our knowledge no related di­amine complexes with four-membered chelate rings are known. For di­amine complexes with five-membered chelate rings, see: Haitko (1984 ▸); Garbauskas et al. (1986 ▸). For a bi­pyridine complex containing a copper(I) iodide dimer, see: Huang et al. (2013 ▸). For the crystal structure of the μ,μ′-diiodido-bridged dimer, with four-coordinate copper(I), viz. [(py)2CuI2Cu(py)2] (py is pyridine), see: Dyason et al. (1984 ▸).

Experimental

Crystal data

[Cu2I2(C11H22N2)2]

M = 745.49

Orthorhombic,

a = 18.718 (4) Å

b = 8.4175 (15) Å

c = 17.074 (3) Å

V = 2690.1 (8) Å3

Z = 4

Mo Kα radiation

μ = 3.89 mm−1

T = 173 K

0.4 × 0.3 × 0.2 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Krause et al., 2015 ▸) T min = 0.256, T max = 0.459

38065 measured reflections

1704 independent reflections

1349 reflections with I > 2σ(I)

R int = 0.096

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.070

S = 1.07

1704 reflections

73 parameters

H-atom parameters constrained

Δρmax = 0.99 e Å−3

Δρmin = −0.44 e Å−3

Data collection: APEX2 (Bruker, 2003 ▸); cell refinement: SAINT (Bruker, 2003 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015b ▸); molecular graphics: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989015018757/su5211sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018757/su5211Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015018757/su5211fig1.tif

Mol­ecular structure of the title compound, with atom labelling. The displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

b . DOI: 10.1107/S2056989015018757/su5211fig2.tif

Crystal packing of the title compound viewed along b axis. H-atoms have been omitted for clarity.

CCDC reference: 1429684

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cu2I2(C11H22N2)2]	Dx = 1.841 Mg m−3
Mr = 745.49	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Cmce	Cell parameters from 38065 reflections
a = 18.718 (4) Å	θ = 2.2–28.2°
b = 8.4175 (15) Å	µ = 3.89 mm−1
c = 17.074 (3) Å	T = 173 K
V = 2690.1 (8) Å3	Block, colourless
Z = 4	0.4 × 0.3 × 0.2 mm
F(000) = 1472

Bruker APEXII CCD diffractometer	1349 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.096
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θmax = 28.2°, θmin = 2.2°
Tmin = 0.256, Tmax = 0.459	h = −24→24
38065 measured reflections	k = −11→11
1704 independent reflections	l = −22→22

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032	H-atom parameters constrained
wR(F2) = 0.070	w = 1/[σ2(Fo2) + (0.0354P)2 + 0.6685P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
1704 reflections	Δρmax = 0.99 e Å−3
73 parameters	Δρmin = −0.43 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
I1	0.5000	0.70816 (3)	0.58360 (2)	0.03716 (12)
Cu1	0.5000	0.40635 (6)	0.55733 (3)	0.03283 (16)
N1	0.56490 (13)	0.2603 (3)	0.63824 (16)	0.0259 (5)
C1	0.5000	0.1792 (5)	0.6679 (3)	0.0299 (10)
H1A	0.5000	0.0670	0.6505	0.036*
H1B	0.5000	0.1806	0.7259	0.036*
C2	0.60139 (18)	0.3498 (4)	0.70093 (19)	0.0333 (7)
H2A	0.6165	0.2756	0.7427	0.040*
H2B	0.5677	0.4274	0.7241	0.040*
C3	0.66608 (19)	0.4367 (4)	0.6694 (2)	0.0444 (9)
H3A	0.6504	0.5176	0.6310	0.053*
H3B	0.6905	0.4924	0.7129	0.053*
C4	0.7177 (2)	0.3238 (5)	0.6306 (3)	0.0497 (10)
H4A	0.7382	0.2510	0.6702	0.060*
H4B	0.7573	0.3844	0.6064	0.060*
C5	0.6785 (2)	0.2285 (5)	0.5680 (2)	0.0460 (9)
H5A	0.6628	0.3006	0.5255	0.055*
H5B	0.7114	0.1490	0.5451	0.055*
C6	0.61428 (18)	0.1448 (4)	0.60214 (19)	0.0333 (8)
H6A	0.5891	0.0858	0.5603	0.040*
H6B	0.6302	0.0674	0.6421	0.040*

	U11	U22	U33	U12	U13	U23
I1	0.0678 (3)	0.02108 (15)	0.02262 (17)	0.000	0.000	−0.00298 (11)
Cu1	0.0540 (4)	0.0219 (3)	0.0225 (3)	0.000	0.000	0.0030 (2)
N1	0.0293 (13)	0.0222 (11)	0.0262 (13)	0.0010 (10)	0.0021 (11)	−0.0001 (10)
C1	0.032 (3)	0.028 (2)	0.029 (3)	0.000	0.000	0.0092 (18)
C2	0.0359 (19)	0.0369 (17)	0.0271 (17)	0.0032 (14)	−0.0048 (14)	−0.0078 (14)
C3	0.040 (2)	0.041 (2)	0.052 (2)	−0.0066 (16)	−0.0035 (17)	−0.0046 (17)
C4	0.036 (2)	0.051 (2)	0.062 (3)	−0.0062 (17)	0.0047 (19)	0.0075 (19)
C5	0.043 (2)	0.047 (2)	0.048 (2)	0.0054 (18)	0.0177 (17)	0.0000 (18)
C6	0.040 (2)	0.0289 (16)	0.0314 (18)	0.0033 (14)	0.0023 (15)	−0.0046 (13)

Cu1—Cu1i	2.5137 (11)	C2—H2A	0.9900
I1—Cu1	2.5798 (8)	C2—H2B	0.9900
I1—Cu1i	2.5922 (7)	C3—C4	1.509 (5)
Cu1—N1	2.213 (3)	C3—H3A	0.9900
Cu1—N1ii	2.213 (3)	C3—H3B	0.9900
Cu1—I1i	2.5922 (7)	C4—C5	1.526 (6)
N1—C6	1.476 (4)	C4—H4A	0.9900
N1—C2	1.477 (4)	C4—H4B	0.9900
N1—C1	1.483 (3)	C5—C6	1.509 (5)
C1—N1ii	1.483 (3)	C5—H5A	0.9900
C1—H1A	0.9900	C5—H5B	0.9900
C1—H1B	0.9900	C6—H6A	0.9900
C2—C3	1.513 (5)	C6—H6B	0.9900
Cu1—I1—Cu1i	58.16 (2)	C3—C2—H2B	109.4
N1—Cu1—N1ii	66.61 (13)	H2A—C2—H2B	108.0
N1—Cu1—Cu1i	146.59 (7)	C4—C3—C2	111.4 (3)
N1ii—Cu1—Cu1i	146.59 (7)	C4—C3—H3A	109.4
N1—Cu1—I1	116.02 (7)	C2—C3—H3A	109.4
N1ii—Cu1—I1	116.01 (7)	C4—C3—H3B	109.4
Cu1i—Cu1—I1	61.17 (2)	C2—C3—H3B	109.4
N1—Cu1—I1i	111.90 (7)	H3A—C3—H3B	108.0
N1ii—Cu1—I1i	111.90 (7)	C3—C4—C5	109.3 (3)
Cu1i—Cu1—I1i	60.67 (3)	C3—C4—H4A	109.8
I1—Cu1—I1i	121.84 (2)	C5—C4—H4A	109.8
C6—N1—C2	110.4 (2)	C3—C4—H4B	109.8
C6—N1—C1	110.6 (3)	C5—C4—H4B	109.8
C2—N1—C1	111.5 (3)	H4A—C4—H4B	108.3
C6—N1—Cu1	116.7 (2)	C6—C5—C4	111.0 (3)
C2—N1—Cu1	115.02 (19)	C6—C5—H5A	109.4
C1—N1—Cu1	91.11 (18)	C4—C5—H5A	109.4
N1ii—C1—N1	110.0 (3)	C6—C5—H5B	109.4
N1ii—C1—H1A	109.7	C4—C5—H5B	109.4
N1—C1—H1A	109.7	H5A—C5—H5B	108.0
N1ii—C1—H1B	109.7	N1—C6—C5	110.6 (3)
N1—C1—H1B	109.7	N1—C6—H6A	109.5
H1A—C1—H1B	108.2	C5—C6—H6A	109.5
N1—C2—C3	111.0 (3)	N1—C6—H6B	109.5
N1—C2—H2A	109.4	C5—C6—H6B	109.5
C3—C2—H2A	109.4	H6A—C6—H6B	108.1
N1—C2—H2B	109.4
C6—N1—C1—N1ii	−128.9 (3)	C2—C3—C4—C5	54.5 (4)
C2—N1—C1—N1ii	107.7 (3)	C3—C4—C5—C6	−55.1 (4)
Cu1—N1—C1—N1ii	−9.8 (3)	C2—N1—C6—C5	−59.2 (4)
C6—N1—C2—C3	58.5 (3)	C1—N1—C6—C5	176.9 (3)
C1—N1—C2—C3	−178.0 (3)	Cu1—N1—C6—C5	74.6 (3)
Cu1—N1—C2—C3	−76.1 (3)	C4—C5—C6—N1	57.9 (4)
N1—C2—C3—C4	−56.9 (4)

Cu1Cu1i	2.5137(11)
I1Cu1	2.5798(8)
I1Cu1i	2.5922(7)
Cu1N1	2.213(3)

Cu1I1Cu1i	58.16(2)
N1Cu1N1ii	66.61(13)
N1Cu1I1	116.02(7)
N1Cu1I1i	111.90(7)
I1Cu1I1i	121.84(2)

Symmetry codes: (i) ; (ii) .