Di-μ-bromido-bis-{[N,N-dimethyl-N'-(thio-phen-2-yl-methyl-idene)ethane-1,2-diamine]-copper(I)]}.

In the crystal structure of the title compound, [Cu(2)Br(2)(C(9)H(14)N(2)S)(2)], the mol-ecule resides about a crystallographic inversion center. The coordination sphere around each copper ion has a distorted tetra-hedral geometry, with ligation by two bridging bromide ions, an amine N atom and an imine N atom. The thio-phene ring is disordered over two sites, with occupancies of 0.719 (3) and 0.281 (3). Weak C-H⋯π inter-actions feature in the crystal packing.

Related literature

For catalysts for polymerizations and organic transformations, see: Perrier et al. (2002 ▶), Cristau et al. (2005 ▶). For model complexes of copper proteins, see: Lee et al. (2010 ▶). For metal-mediated atom-transfer radical polymerizations, see: Matyjaszewski & Tsarevsky (2009 ▶). For related structures with a Cu2Br2 core, see Ball et al. (2001 ▶), Skelton et al. (1991 ▶), Churchill et al. (1984 ▶). For software for searching the Cambridge Structural Database, see: Bruno et al. (2002 ▶). For standard bond lengths, see Allen et al. (1987 ▶).

Experimental

Crystal data

[Cu2Br2(C9H14N2S)2]

M = 651.48

Monoclinic,

a = 10.2029 (3) Å

b = 15.4175 (3) Å

c = 8.04875 (19) Å

β = 108.628 (3)°

V = 1199.76 (5) Å3

Z = 2

Mo Kα radiation

μ = 5.29 mm−1

T = 173 K

0.15 × 0.07 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.406, T max = 1.000

13662 measured reflections

3928 independent reflections

3021 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.078

S = 1.05

3928 reflections

146 parameters

10 restraints

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.51 e Å−3

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

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812017989/fj2540sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017989/fj2540Isup2.hkl

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

[Cu2Br2(C9H14N2S)2]	F(000) = 648
Mr = 651.48	Dx = 1.803 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4548 reflections
a = 10.2029 (3) Å	θ = 3.1–32.2°
b = 15.4175 (3) Å	µ = 5.29 mm−1
c = 8.04875 (19) Å	T = 173 K
β = 108.628 (3)°	Rod, red
V = 1199.76 (5) Å3	0.15 × 0.07 × 0.05 mm
Z = 2

Oxford Diffraction Xcalibur Eos Gemini diffractometer	3928 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3021 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 16.1500 pixels mm-1	θmax = 32.2°, θmin = 3.1°
ω scans	h = −15→14
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −17→22
Tmin = 0.406, Tmax = 1.000	l = −11→11
13662 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)] = 0.036	H-atom parameters constrained
wR(F2) = 0.078	w = 1/[σ2(Fo2) + (0.0303P)2] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.002
3928 reflections	Δρmax = 0.50 e Å−3
146 parameters	Δρmin = −0.51 e Å−3
10 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: 0.0021 (6)

Experimental. 1H-NMR (CD3CN, 298 K): δ 8.57 (s, 1H, N=CH), 7.64 (m, 2H, thiophene H3, H5), 7.13 (t, J = 4.4 Hz, 1H, thiophene H4), 3.77 (t, J = 5.1 Hz, 2H, NCH2), 2.28 (t, J = 5.5 Hz, 2H, NCH2), 2.39 (s, 6H, NCH3) p.p.m.. 13C-NMR (CD3CN, 298 K): δ 158.11 (C=N), 141.40 (thiophene C2), 135.94 (thiophene C1 or C3), 132.90 (thiophene C1 or C3), 129.16 (thiophene C4), 61.17 (NCH2), 59.33 (NCH2), 47.69 (NCH3) p.p.m.. FTIR (cm-1): 3200 (w), 3073 (m), 2989 (versus), 2855 (versus), 2822 (versus), 2779 (versus), 1810 (w), 1611 (versus), 1452 (versus), 1430 (versus), 1262 (s), 1249 (s), 1046 (s), 1027 (s), 885 (s), 713 (versus). ESI-MS: m/z 427 ([(L)2Cu]+), m/z 245 ([(L)Cu]+).

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	Occ. (<1)
Br1	0.43830 (3)	0.598179 (15)	0.60809 (3)	0.03225 (9)
Cu1	0.48455 (3)	0.550941 (19)	0.33751 (4)	0.03010 (10)
N1	0.2808 (2)	0.54727 (13)	0.1227 (3)	0.0291 (4)
N2	0.5330 (2)	0.64590 (12)	0.1965 (3)	0.0272 (4)
S1A	0.8104 (2)	0.58936 (10)	0.4729 (3)	0.0405 (4)	0.719 (3)
C1A	0.7761 (7)	0.6723 (9)	0.3259 (10)	0.0267 (13)	0.719 (3)
C2A	0.8929 (7)	0.7219 (5)	0.3231 (9)	0.0410 (15)	0.719 (3)
H2AA	0.8950	0.7688	0.2511	0.049*	0.719 (3)
C3A	1.0107 (7)	0.6822 (3)	0.4607 (8)	0.0465 (13)	0.719 (3)
H3AA	1.0999	0.7042	0.4885	0.056*	0.719 (3)
C4A	0.9811 (5)	0.6116 (4)	0.5442 (7)	0.0396 (13)	0.719 (3)
H4AA	1.0466	0.5798	0.6295	0.048*	0.719 (3)
S1B	0.9238 (5)	0.7208 (4)	0.3547 (7)	0.0405 (4)	0.281 (3)
C1B	0.7753 (17)	0.670 (3)	0.357 (4)	0.0267 (13)	0.281 (3)
C2B	0.797 (2)	0.6021 (13)	0.484 (3)	0.0410 (15)	0.281 (3)
H2BA	0.7309	0.5676	0.5099	0.049*	0.281 (3)
C3B	0.9481 (16)	0.6001 (12)	0.563 (3)	0.0465 (13)	0.281 (3)
H3BA	0.9903	0.5596	0.6488	0.056*	0.281 (3)
C4B	1.0253 (17)	0.6584 (10)	0.5075 (19)	0.0396 (13)	0.281 (3)
H4BA	1.1212	0.6624	0.5501	0.048*	0.281 (3)
C5	0.6420 (3)	0.68954 (16)	0.2103 (3)	0.0308 (5)
H5A	0.6323	0.7374	0.1370	0.037*
C6	0.4062 (3)	0.67187 (17)	0.0565 (4)	0.0376 (6)
H6A	0.4305	0.7003	−0.0372	0.045*
H6B	0.3541	0.7126	0.1026	0.045*
C7	0.3187 (3)	0.59292 (18)	−0.0144 (3)	0.0373 (6)
H7A	0.2353	0.6106	−0.1061	0.045*
H7B	0.3695	0.5538	−0.0659	0.045*
C8	0.1727 (3)	0.59356 (19)	0.1696 (4)	0.0441 (7)
H8A	0.0927	0.5997	0.0675	0.066*
H8B	0.2060	0.6499	0.2143	0.066*
H8C	0.1484	0.5615	0.2577	0.066*
C9	0.2323 (3)	0.45972 (18)	0.0614 (4)	0.0440 (7)
H9A	0.1555	0.4636	−0.0449	0.066*
H9B	0.2036	0.4305	0.1494	0.066*
H9C	0.3059	0.4278	0.0398	0.066*

	U11	U22	U33	U12	U13	U23
Br1	0.04731 (18)	0.02362 (13)	0.02861 (14)	0.00286 (10)	0.01606 (11)	0.00094 (9)
Cu1	0.03302 (19)	0.02855 (17)	0.02764 (16)	−0.00042 (12)	0.00816 (13)	0.00348 (11)
N1	0.0276 (11)	0.0331 (11)	0.0266 (10)	−0.0016 (9)	0.0086 (8)	−0.0014 (8)
N2	0.0286 (11)	0.0240 (10)	0.0284 (10)	0.0017 (8)	0.0085 (8)	0.0006 (8)
S1A	0.0361 (7)	0.0372 (7)	0.0417 (7)	−0.0028 (5)	0.0033 (5)	0.0064 (6)
C1A	0.0332 (14)	0.0278 (14)	0.024 (4)	−0.0043 (10)	0.0161 (16)	−0.005 (3)
C2A	0.030 (3)	0.054 (3)	0.034 (3)	0.001 (2)	0.004 (2)	0.001 (2)
C3A	0.033 (3)	0.048 (3)	0.064 (4)	−0.010 (2)	0.023 (3)	−0.021 (2)
C4A	0.022 (2)	0.045 (3)	0.044 (2)	0.002 (2)	−0.0012 (19)	−0.010 (2)
S1B	0.0361 (7)	0.0372 (7)	0.0417 (7)	−0.0028 (5)	0.0033 (5)	0.0064 (6)
C1B	0.0332 (14)	0.0278 (14)	0.024 (4)	−0.0043 (10)	0.0161 (16)	−0.005 (3)
C2B	0.030 (3)	0.054 (3)	0.034 (3)	0.001 (2)	0.004 (2)	0.001 (2)
C3B	0.033 (3)	0.048 (3)	0.064 (4)	−0.010 (2)	0.023 (3)	−0.021 (2)
C4B	0.022 (2)	0.045 (3)	0.044 (2)	0.002 (2)	−0.0012 (19)	−0.010 (2)
C5	0.0361 (15)	0.0243 (12)	0.0340 (13)	−0.0020 (10)	0.0140 (11)	0.0022 (9)
C6	0.0387 (16)	0.0341 (14)	0.0357 (14)	−0.0003 (11)	0.0057 (11)	0.0111 (11)
C7	0.0346 (15)	0.0486 (16)	0.0265 (13)	−0.0048 (12)	0.0068 (11)	0.0045 (11)
C8	0.0316 (16)	0.0579 (18)	0.0443 (16)	0.0077 (13)	0.0140 (13)	0.0023 (13)
C9	0.0428 (17)	0.0437 (16)	0.0417 (16)	−0.0137 (13)	0.0084 (13)	−0.0083 (12)

Br1—Cu1i	2.4241 (4)	S1B—C1B	1.71 (2)
Br1—Cu1	2.4805 (4)	C1B—C2B	1.43 (2)
Cu1—N2	2.008 (2)	C1B—C5	1.521 (18)
Cu1—N1	2.240 (2)	C2B—C3B	1.473 (19)
Cu1—Br1i	2.4242 (4)	C2B—H2BA	0.9300
Cu1—Cu1i	2.9803 (6)	C3B—C4B	1.360 (14)
N1—C8	1.460 (3)	C3B—H3BA	0.9300
N1—C7	1.462 (3)	C4B—H4BA	0.9300
N1—C9	1.468 (3)	C5—H5A	0.9300
N2—C5	1.274 (3)	C6—C7	1.509 (4)
N2—C6	1.474 (3)	C6—H6A	0.9700
S1A—C4A	1.685 (5)	C6—H6B	0.9700
S1A—C1A	1.701 (9)	C7—H7A	0.9700
C1A—C5	1.413 (7)	C7—H7B	0.9700
C1A—C2A	1.422 (11)	C8—H8A	0.9600
C2A—C3A	1.482 (8)	C8—H8B	0.9600
C2A—H2AA	0.9300	C8—H8C	0.9600
C3A—C4A	1.364 (7)	C9—H9A	0.9600
C3A—H3AA	0.9300	C9—H9B	0.9600
C4A—H4AA	0.9300	C9—H9C	0.9600
S1B—C4B	1.641 (11)
Cu1i—Br1—Cu1	74.829 (13)	C1B—C2B—H2BA	128.6
N2—Cu1—N1	85.27 (8)	C3B—C2B—H2BA	128.6
N2—Cu1—Br1i	132.01 (6)	C4B—C3B—C2B	118.9 (18)
N1—Cu1—Br1i	106.45 (5)	C4B—C3B—H3BA	120.5
N2—Cu1—Br1	115.60 (6)	C2B—C3B—H3BA	120.5
N1—Cu1—Br1	107.16 (6)	C3B—C4B—S1B	109.8 (15)
Br1i—Cu1—Br1	105.171 (13)	C3B—C4B—H4BA	125.1
N2—Cu1—Cu1i	154.69 (6)	S1B—C4B—H4BA	125.1
N1—Cu1—Cu1i	118.42 (5)	N2—C5—C1A	126.4 (5)
Br1i—Cu1—Cu1i	53.447 (11)	N2—C5—C1B	120.1 (10)
Br1—Cu1—Cu1i	51.724 (11)	N2—C5—H5A	116.8
C8—N1—C7	111.3 (2)	C1A—C5—H5A	116.8
C8—N1—C9	109.6 (2)	C1B—C5—H5A	122.5
C7—N1—C9	109.3 (2)	N2—C6—C7	109.8 (2)
C8—N1—Cu1	112.30 (16)	N2—C6—H6A	109.7
C7—N1—Cu1	99.58 (15)	C7—C6—H6A	109.7
C9—N1—Cu1	114.39 (16)	N2—C6—H6B	109.7
C5—N2—C6	116.8 (2)	C7—C6—H6B	109.7
C5—N2—Cu1	134.54 (17)	H6A—C6—H6B	108.2
C6—N2—Cu1	108.42 (15)	N1—C7—C6	111.7 (2)
C4A—S1A—C1A	92.6 (3)	N1—C7—H7A	109.3
C5—C1A—C2A	121.9 (7)	C6—C7—H7A	109.3
C5—C1A—S1A	122.7 (6)	N1—C7—H7B	109.3
C2A—C1A—S1A	115.4 (5)	C6—C7—H7B	109.3
C1A—C2A—C3A	104.4 (6)	H7A—C7—H7B	107.9
C1A—C2A—H2AA	127.8	N1—C8—H8A	109.5
C3A—C2A—H2AA	127.8	N1—C8—H8B	109.5
C4A—C3A—C2A	116.4 (6)	H8A—C8—H8B	109.5
C4A—C3A—H3AA	121.8	N1—C8—H8C	109.5
C2A—C3A—H3AA	121.8	H8A—C8—H8C	109.5
C3A—C4A—S1A	111.2 (5)	H8B—C8—H8C	109.5
C3A—C4A—H4AA	124.4	N1—C9—H9A	109.5
S1A—C4A—H4AA	124.4	N1—C9—H9B	109.5
C4B—S1B—C1B	94.1 (10)	H9A—C9—H9B	109.5
C2B—C1B—C5	126 (2)	N1—C9—H9C	109.5
C2B—C1B—S1B	114.3 (12)	H9A—C9—H9C	109.5
C5—C1B—S1B	118.4 (15)	H9B—C9—H9C	109.5
C1B—C2B—C3B	102.8 (15)
Cu1i—Br1—Cu1—N2	−154.00 (7)	C2A—C3A—C4A—S1A	−2.6 (7)
Cu1i—Br1—Cu1—N1	113.00 (6)	C1A—S1A—C4A—C3A	1.5 (6)
Cu1i—Br1—Cu1—Br1i	0.0	C4B—S1B—C1B—C2B	2 (3)
N2—Cu1—N1—C8	−100.19 (18)	C4B—S1B—C1B—C5	−168 (2)
Br1i—Cu1—N1—C8	127.30 (16)	C5—C1B—C2B—C3B	167 (3)
Br1—Cu1—N1—C8	15.16 (18)	S1B—C1B—C2B—C3B	−2 (3)
Cu1i—Cu1—N1—C8	70.41 (18)	C1B—C2B—C3B—C4B	2 (3)
N2—Cu1—N1—C7	17.69 (15)	C2B—C3B—C4B—S1B	0 (2)
Br1i—Cu1—N1—C7	−114.82 (14)	C1B—S1B—C4B—C3B	−0.8 (19)
Br1—Cu1—N1—C7	133.04 (14)	C6—N2—C5—C1A	−175.2 (7)
Cu1i—Cu1—N1—C7	−171.71 (13)	Cu1—N2—C5—C1A	10.8 (7)
N2—Cu1—N1—C9	134.13 (18)	C6—N2—C5—C1B	176.8 (17)
Br1i—Cu1—N1—C9	1.62 (18)	Cu1—N2—C5—C1B	2.8 (18)
Br1—Cu1—N1—C9	−110.51 (17)	C2A—C1A—C5—N2	175.9 (7)
Cu1i—Cu1—N1—C9	−55.26 (19)	S1A—C1A—C5—N2	−2.0 (13)
N1—Cu1—N2—C5	−174.8 (2)	C2A—C1A—C5—C1B	−135 (14)
Br1i—Cu1—N2—C5	−66.8 (3)	S1A—C1A—C5—C1B	47 (12)
Br1—Cu1—N2—C5	78.5 (2)	C2B—C1B—C5—N2	4 (4)
Cu1i—Cu1—N2—C5	24.9 (3)	S1B—C1B—C5—N2	172.0 (16)
N1—Cu1—N2—C6	10.83 (16)	C2B—C1B—C5—C1A	−132 (16)
Br1i—Cu1—N2—C6	118.76 (15)	S1B—C1B—C5—C1A	37 (11)
Br1—Cu1—N2—C6	−95.95 (16)	C5—N2—C6—C7	146.5 (2)
Cu1i—Cu1—N2—C6	−149.55 (14)	Cu1—N2—C6—C7	−38.0 (3)
C4A—S1A—C1A—C5	177.9 (9)	C8—N1—C7—C6	75.1 (3)
C4A—S1A—C1A—C2A	−0.2 (9)	C9—N1—C7—C6	−163.7 (2)
C5—C1A—C2A—C3A	−179.2 (9)	Cu1—N1—C7—C6	−43.5 (2)
S1A—C1A—C2A—C3A	−1.1 (11)	N2—C6—C7—N1	58.7 (3)
C1A—C2A—C3A—C4A	2.3 (9)

D—H···A	D—H	H···A	D···A	D—H···A
C2A—H2AA···Cg3ii	0.93	2.87	3.721 (8)	153
C2A—H2AA···Cg4ii	0.93	2.70	3.573 (12)	157
C2B—H2BA···Cg1	0.93	2.55	3.45 (2)	162
C2B—H2BA···Cg1i	0.93	2.55	3.45 (2)	162

Table 1

Hydrogen-bond geometry (Å, °)

Cg1, Cg3 and Cg4 are the centroids of the Br1/Cu1/Br1A/Cu1A, S1A/C1A/C2A/C3A/C4A and S1B/C1B/C2B/C3B/C4B rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2A—H2AA⋯Cg3i	0.93	2.87	3.721 (8)	153
C2A—H2AA⋯Cg4i	0.93	2.70	3.573 (12)	157
C2B—H2BA⋯Cg1	0.93	2.55	3.45 (2)	162
C2B—H2BA⋯Cg1ii	0.93	2.55	3.45 (2)	162

Symmetry codes: (i) ; (ii) .