Di-μ-bromido-bis­{[N,N-dimethyl-N′-(thio­phen-2-yl­methyl­idene)ethane-1,2-diamine]­copper(I)]}

Goh, C.; Remillard, Z.D.; Martinez, A.P.; Keeley, A.C.; Jasinski, J.P.

doi:10.1107/S1600536812017989

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages m691-m692

doi:10.1107/S1600536812017989

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Di-μ-bromido-bis{[N,N-dimethyl-N′-(thiophen-2-ylmethylidene)ethane-1,2-diamine]copper(I)]}

Christopher Goh,^a Zachary D. Remillard,^a Andre P. Martinez,^a Amanda C. Keeley ^b and Jerry P. Jasinski ^b ^*

^aDepartment of Chemistry, Williams College, Williamstown, MA 01267, USA, and ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
^*Correspondence e-mail: jjasinski@keene.edu

(Received 3 April 2012; accepted 22 April 2012; online 28 April 2012)

In the crystal structure of the title compound, [Cu₂Br₂(C₉H₁₄N₂S)₂], the molecule resides about a crystallographic inversion center. The coordination sphere around each copper ion has a distorted tetrahedral geometry, with ligation by two bridging bromide ions, an amine N atom and an imine N atom. The thiophene ring is disordered over two sites, with occupancies of 0.719 (3) and 0.281 (3). Weak C—H⋯π interactions 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_r = 651.48
Monoclinic, P 2₁ /c
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 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) 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[F² > 2σ(F²)] = 0.036
wR(F²) = 0.078
S = 1.05
3928 reflections
146 parameters
10 restraints
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.51 e Å⁻³

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) $[x, -y+{\script{1\over 2}}, z-{\script{3\over 2}}]$ ; (ii) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812017989/fj2540sup1.cif

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

checkCIF report

Comment top

Copper complexes of ligands containing hetero-aromatic and amine donor moieties have found multiple applications in metal catalyzed processes. Examples include catalysts for polymerizations and organic transformations (Perrier et al., 2002; Cristau et al., 2005), and model complexes in the biomimetic study of copper proteins (Lee et al., 2010). Our group has been interested in the use of neutral tridentate hetero-aromatic-amine ligands in metal-mediated atom transfer radical polymerizations (ATRP) (Matyjaszewski & Tsarevsky, 2009).

Here we report the synthesis and structure of a doubly bromide bridged dinuclear copper(I) complex with the ligand N,N-dimethyl-N'-(thiophen-2-ylmethylene)ethane-1,2-diamine, [{(C₄H₃S)CHNCH₂CH₂N(CH₃)₂}CuBr]₂ (Fig. 1). A crystallographic inversion center generates the complete molecule from the asymmeric unit. The coordination sphere around each copper ion is arranged in a distorted tetrahedral geometry, with ligation by two bridging bromide ions, an amine nitrogen and an imine nitrogen. The thiophene ring is disordered (occupancy 0.719:0.281). The distances for the metal-amine bond (2.008 (2) Å) and the metal-imine bond (2.240 (2) Å) are within expected ranges (Allen et al., 1987). As a result of the chelate ring formation the N(am)—Cu—N(im) angle of 85.27 (8)° is significantly smaller than the tetrahedral angle leading to appreciable distortion of the tetrahedral geometry and a large N(im)—Cu—Br angle of 132.01 (6)°. The N1/C7/C6/N2 torsion angle is 58.7 (3)°. The thiophene ring and imine group are near planar, with the sulfur oriented towards the copper atoms. However, Cu—S distances of 3.20 (6) Å make interactions unlikely. The Cu₂Br₂ bridging unit forms a planar rhomboid arrangement, with an inversion center in the center. Related structures with a Cu₂Br₂ core are published (Ball et al., 2001; Skelton et al., 1991; Churchill, et al., 1984). Cu1 possesses one short (2.4241 (4) Å) and one long (2.4805 (4) Å) Cu–Br bond, and a Cu–Cu distance of 2.980 (0) Å, outside the sum of the van der Waals radii of copper. The arrangement of the bromide bridging unit is asymmetrical: the Cu–Br–Cu bridging angle is 74.829 (13)°, close to the mean value of 74.(9)° found in structural units of this kind in the Cambridge Structural Database (Bruno et al., 2002). Weak C—H···Cg π-ring intermolecular interactions contribute to molecular packing in the crystal (Table 1, Fig. 2).

Related literature top

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 top

The title compound was synthesized under a dinitrogen atmosphere by reacting a light green suspension of 233 mg of CuBr (1.6 mmol) in 8 mL of dry acetonitrile with 332 mg of the ligand N,N-dimethyl-N'-(thiophen-2-ylmethylene)ethane-1,2-diamine (L, 4.8 mmol) added dropwise with a pipet. Addition of ligand resulted in an immediate color change of the solution to red-orange and dissolution of CuBr. The reaction mixture was allowed to stir overnight and filtered. The filtrate was layered with diethyl ether and stored at -25 °C for 4 days. After this time, the product was isolated as orange crystals suitable for X-ray analysis. A second crop was obtained by further addition of diethyl ether and storage at -25°C for 4 days to yield a combined crop of 440 mg of crystalline product (84% yield).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound (I) showing the atom labeling scheme of the asymmetric unit and 30% probability displacement ellipsoids. A crystallographic inversion center generates the complete molecule. Only the major component (S1A/C1A/C2A/C3A/C4A) of the disordered thiophene ring (occupancy: 0.719) is displayed.
	Fig. 2. Packing diagram of the title compound viewed along the b axis. Only the major component (S1A/C1A/C2A/C3A/C4A) of the disordered thiophene ring (occupancy: 0.719) is displayed. The hydrogen atoms have been removed for clarity.

Di-µ-bromido-bis{[N,N-dimethyl-N'-(thiophen-2- ylmethylidene)ethane-1,2-diamine]copper(I)]} top

Crystal data top

[Cu₂Br₂(C₉H₁₄N₂S)₂]	F(000) = 648
M_r = 651.48	D_x = 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

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	3928 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3021 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 16.1500 pixels mm^-1	θ_max = 32.2°, θ_min = 3.1°
ω scans	h = −15→14
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −17→22
T_min = 0.406, T_max = 1.000	l = −11→11
13662 measured reflections

Refinement top

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(F_o²) + (0.0303P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.002
3928 reflections	Δρ_max = 0.50 e Å⁻³
146 parameters	Δρ_min = −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)

Crystal data top

[Cu₂Br₂(C₉H₁₄N₂S)₂]	V = 1199.76 (5) Å³
M_r = 651.48	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.2029 (3) Å	µ = 5.29 mm⁻¹
b = 15.4175 (3) Å	T = 173 K
c = 8.04875 (19) Å	0.15 × 0.07 × 0.05 mm
β = 108.628 (3)°

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	3928 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	3021 reflections with I > 2σ(I)
T_min = 0.406, T_max = 1.000	R_int = 0.046
13662 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	10 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.05	Δρ_max = 0.50 e Å⁻³
3928 reflections	Δρ_min = −0.51 e Å⁻³
146 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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···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

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

Experimental details

Crystal data
Chemical formula	[Cu₂Br₂(C₉H₁₄N₂S)₂]
M_r	651.48
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	10.2029 (3), 15.4175 (3), 8.04875 (19)
β (°)	108.628 (3)
V (Å³)	1199.76 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.29
Crystal size (mm)	0.15 × 0.07 × 0.05

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.406, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13662, 3928, 3021
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.750

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.078, 1.05
No. of reflections	3928
No. of parameters	146
No. of restraints	10
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.51

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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) x, −y+1/2, z−3/2; (ii) −x+1, −y+1, −z+1.

Acknowledgements

CG acknowledges financial support from the Research Corporation for Science Advancement through RCSA Award 10776 and from a Hellman Fellowship from Williams College. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
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Volume 68| Part 5| May 2012| Pages m691-m692

doi:10.1107/S1600536812017989

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Di-μ-bromido-bis­­{[N,N-di­methyl-N′-(thio­phen-2-yl­methyl­­idene)ethane-1,2-di­amine]­copper(I)]}

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Di-μ-bromido-bis{[N,N-dimethyl-N′-(thiophen-2-ylmethylidene)ethane-1,2-diamine]copper(I)]}