Crystal structure of bis-(μ2-tetra-bromo-phthalato-κ(2) O (1):O (2))bis[aqua(N,N,N',N'-tetra-methyl-ethane-1,2-di-amine-κ(2) N,N')copper(II)].

In the title complex, [Cu2(C8Br4O4)2(C6H16N2)2(H2O)2], the Cu(II) cation is chelated by a tetra-methyl-ethane-1,2-di-amine ligand and coordinated by a water mol-ecule as well as bridged by two tetra-bromo-phthalate anions in a distorted O3N2 trigonal-bipyramidal geometry. The two symmetry-related tetra-bromo-phthalate anions bridge the two Cu(II) cations, forming a centrosymmetric dinuclear complex in which the Cu⋯Cu separation is 5.054 (2) Å. Intra-molecular classic O-H⋯O hydrogen bonds and weak C-H⋯O hydrogen bonds occur in the dinuclear mol-ecule. In the crystal, the mol-ecules are linked by weak C-H⋯Br and C-H⋯O inter-actions into supra-molecular chains propagating along the b-axis direction.

Related literature

For the crystal structures of related copper(II) complexes with tetramethylethylen-1,2-diamine and carboxyl­ate ligands; see: Ene et al. (2009 ▸); Dorazco-González et al. (2013 ▸); Liang et al. (2004 ▸). For the synthesis of coordination compounds with one-dimensional polymeric structures, see: Hong & You (2004 ▸); Colacio et al. (2009 ▸); Rodpun et al. (2015 ▸); Yang et al. (2002 ▸). For their magnetic properties, see: Ene et al. (2009 ▸); Kozlevčar et al. (2004 ▸). For supra­molecular polymorphism, see: Dorazco-González et al. (2013 ▸); Stibrany et al. (2009 ▸); Aakeröy et al. (2003 ▸); Valdés-Martínez et al. (1993 ▸); Julve et al. (1984 ▸). For mol­ecular recognition and sensing; see: Dorazco-González & Yatsimirsky (2010 ▸); Mendy et al. (2010 ▸).

Experimental

Crystal data

[Cu2(C8Br4O4)2(C6H16N2)2(H2O)2]

M = 1354.97

Monoclinic,

a = 9.0961 (2) Å

b = 9.2281 (2) Å

c = 24.4026 (7) Å

β = 95.4910 (6)°

V = 2038.95 (9) Å3

Z = 2

Mo Kα radiation

μ = 8.94 mm−1

T = 100 K

0.25 × 0.15 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2012 ▸) T min = 0.442, T max = 0.745

17394 measured reflections

3739 independent reflections

3547 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.016

wR(F 2) = 0.039

S = 1.07

3739 reflections

245 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.80 e Å−3

Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker, 2012 ▸); cell refinement: SAINT (Bruker, 2012 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015015194/xu5866sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015015194/xu5866Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015015194/xu5866fig1.tif

The structure with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii.

Click here for additional data file.

. DOI: 10.1107/S2056989015015194/xu5866fig2.tif

View of inter­actions in the crystal.

CCDC reference: 1418832

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

[Cu2(C8Br4O4)2(C6H16N2)2(H2O)2]	F(000) = 1300
Mr = 1354.97	Dx = 2.207 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.0961 (2) Å	Cell parameters from 9880 reflections
b = 9.2281 (2) Å	θ = 2.4–25.7°
c = 24.4026 (7) Å	µ = 8.94 mm−1
β = 95.4910 (6)°	T = 100 K
V = 2038.95 (9) Å3	Prism, blue
Z = 2	0.25 × 0.15 × 0.08 mm

Bruker APEXII CCD diffractometer	3739 independent reflections
Radiation source: Incoatec ImuS	3547 reflections with I > 2σ(I)
Mirrors monochromator	Rint = 0.019
ω scans	θmax = 25.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −10→10
Tmin = 0.442, Tmax = 0.745	k = −11→11
17394 measured reflections	l = −29→29

Refinement on F2	2 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.016	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.039	w = 1/[σ2(Fo2) + (0.0162P)2 + 2.4857P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.002
3739 reflections	Δρmax = 0.80 e Å−3
245 parameters	Δρmin = −0.41 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	0.34950 (2)	0.30336 (3)	0.71377 (2)	0.01607 (6)
Br2	0.62992 (3)	0.47283 (3)	0.78249 (2)	0.02118 (6)
Br3	0.95418 (3)	0.47738 (3)	0.73268 (2)	0.01934 (6)
Br4	1.00627 (2)	0.27574 (3)	0.62483 (2)	0.01671 (6)
Cu1	0.32727 (3)	−0.12890 (3)	0.55897 (2)	0.01122 (6)
O1	0.45257 (16)	0.02014 (16)	0.59851 (6)	0.0143 (3)
O2	0.32220 (16)	0.22748 (16)	0.58559 (6)	0.0135 (3)
O3	0.65378 (16)	0.19336 (16)	0.52428 (6)	0.0132 (3)
O4	0.79787 (17)	0.02815 (16)	0.57131 (6)	0.0144 (3)
O5	0.17319 (17)	0.01324 (17)	0.53376 (6)	0.0133 (3)
H5A	0.205 (3)	0.091 (2)	0.5454 (10)	0.016*
H5B	0.179 (3)	0.014 (3)	0.5006 (7)	0.016*
N1	0.4780 (2)	−0.2831 (2)	0.58485 (7)	0.0153 (4)
N2	0.1667 (2)	−0.2787 (2)	0.57861 (8)	0.0180 (4)
C1	0.5567 (2)	0.2309 (2)	0.63834 (8)	0.0102 (4)
C2	0.5382 (2)	0.3046 (2)	0.68693 (8)	0.0108 (4)
C3	0.6563 (2)	0.3755 (2)	0.71631 (8)	0.0119 (4)
C4	0.7951 (2)	0.3723 (2)	0.69622 (8)	0.0123 (4)
C5	0.8155 (2)	0.2926 (2)	0.64905 (8)	0.0114 (4)
C6	0.6979 (2)	0.2221 (2)	0.62005 (8)	0.0101 (4)
C7	0.4303 (2)	0.1547 (2)	0.60456 (8)	0.0104 (4)
C8	0.7190 (2)	0.1388 (2)	0.56745 (8)	0.0112 (4)
C9	0.3941 (3)	−0.4200 (2)	0.57551 (10)	0.0206 (5)
H9A	0.4525	−0.5017	0.5925	0.025*
H9B	0.3757	−0.4388	0.5355	0.025*
C10	0.2483 (3)	−0.4091 (3)	0.60056 (11)	0.0267 (6)
H10A	0.1885	−0.4970	0.5915	0.032*
H10B	0.2665	−0.4022	0.6411	0.032*
C11	0.6075 (3)	−0.2849 (3)	0.55284 (11)	0.0221 (5)
H11A	0.5747	−0.2979	0.5137	0.033*
H11B	0.6728	−0.3651	0.5655	0.033*
H11C	0.6611	−0.1931	0.5581	0.033*
C12	0.5316 (3)	−0.2652 (3)	0.64386 (10)	0.0295 (6)
H12A	0.5925	−0.1776	0.6485	0.044*
H12B	0.5908	−0.3497	0.6564	0.044*
H12C	0.4470	−0.2564	0.6657	0.044*
C13	0.0750 (3)	−0.2171 (3)	0.61946 (10)	0.0270 (6)
H13A	0.0211	−0.1327	0.6036	0.040*
H13B	0.1384	−0.1874	0.6523	0.040*
H13C	0.0045	−0.2903	0.6297	0.040*
C14	0.0693 (3)	−0.3163 (3)	0.52836 (10)	0.0244 (5)
H14A	0.0251	−0.2277	0.5119	0.037*
H14B	−0.0091	−0.3815	0.5381	0.037*
H14C	0.1275	−0.3644	0.5019	0.037*

	U11	U22	U33	U12	U13	U23
Br1	0.01284 (11)	0.02352 (12)	0.01199 (11)	0.00231 (9)	0.00185 (8)	−0.00263 (9)
Br2	0.02459 (13)	0.02531 (13)	0.01399 (11)	−0.00390 (10)	0.00359 (9)	−0.01160 (9)
Br3	0.02013 (12)	0.02323 (13)	0.01411 (11)	−0.01075 (9)	−0.00115 (8)	−0.00597 (9)
Br4	0.01220 (11)	0.02355 (13)	0.01461 (11)	−0.00571 (9)	0.00253 (8)	−0.00292 (9)
Cu1	0.01308 (13)	0.00842 (13)	0.01167 (13)	−0.00056 (10)	−0.00133 (10)	−0.00121 (10)
O1	0.0144 (8)	0.0097 (8)	0.0178 (8)	−0.0008 (6)	−0.0039 (6)	−0.0018 (6)
O2	0.0123 (8)	0.0125 (8)	0.0151 (8)	0.0011 (6)	−0.0019 (6)	−0.0023 (6)
O3	0.0172 (8)	0.0142 (8)	0.0080 (7)	0.0012 (6)	0.0002 (6)	−0.0017 (6)
O4	0.0168 (8)	0.0129 (8)	0.0130 (7)	0.0032 (6)	−0.0005 (6)	−0.0012 (6)
O5	0.0160 (8)	0.0127 (8)	0.0109 (7)	−0.0013 (6)	−0.0006 (6)	−0.0043 (6)
N1	0.0210 (10)	0.0108 (9)	0.0136 (9)	−0.0004 (8)	−0.0011 (7)	0.0003 (7)
N2	0.0196 (10)	0.0167 (10)	0.0185 (10)	−0.0029 (8)	0.0052 (8)	0.0036 (8)
C1	0.0138 (10)	0.0060 (10)	0.0103 (10)	0.0006 (8)	−0.0015 (8)	0.0030 (8)
C2	0.0125 (10)	0.0084 (10)	0.0116 (10)	0.0017 (8)	0.0023 (8)	0.0020 (8)
C3	0.0190 (11)	0.0095 (10)	0.0070 (10)	0.0005 (9)	0.0003 (8)	−0.0012 (8)
C4	0.0160 (11)	0.0100 (10)	0.0100 (10)	−0.0037 (9)	−0.0040 (8)	0.0007 (8)
C5	0.0131 (10)	0.0115 (10)	0.0100 (10)	−0.0017 (8)	0.0032 (8)	0.0027 (8)
C6	0.0148 (11)	0.0084 (10)	0.0069 (10)	0.0001 (8)	−0.0003 (8)	0.0031 (8)
C7	0.0122 (10)	0.0117 (11)	0.0074 (9)	−0.0017 (8)	0.0022 (8)	−0.0004 (8)
C8	0.0104 (10)	0.0117 (11)	0.0116 (10)	−0.0047 (9)	0.0025 (8)	−0.0009 (8)
C9	0.0255 (13)	0.0097 (11)	0.0260 (13)	−0.0008 (10)	0.0003 (10)	0.0021 (9)
C10	0.0288 (14)	0.0165 (12)	0.0357 (15)	−0.0019 (11)	0.0077 (11)	0.0117 (11)
C11	0.0169 (12)	0.0180 (12)	0.0311 (14)	0.0039 (10)	0.0009 (10)	0.0069 (10)
C12	0.0426 (16)	0.0238 (14)	0.0194 (13)	0.0077 (12)	−0.0113 (11)	0.0013 (10)
C13	0.0276 (14)	0.0328 (15)	0.0228 (13)	0.0022 (12)	0.0140 (11)	0.0060 (11)
C14	0.0196 (12)	0.0228 (13)	0.0307 (14)	−0.0104 (10)	0.0010 (10)	−0.0042 (11)

Br1—C2	1.895 (2)	N1—C9	1.482 (3)
Br2—C3	1.883 (2)	N1—C12	1.485 (3)
Br3—C4	1.892 (2)	N2—C13	1.473 (3)
Br4—C5	1.893 (2)	N2—C14	1.484 (3)
Cu1—O5	1.9744 (16)	N2—C10	1.487 (3)
Cu1—O1	1.9776 (15)	C1—C2	1.391 (3)
Cu1—N1	2.0340 (19)	C1—C6	1.402 (3)
Cu1—N2	2.0995 (19)	C1—C7	1.521 (3)
Cu1—O3i	2.1396 (14)	C2—C3	1.396 (3)
O1—C7	1.269 (3)	C3—C4	1.398 (3)
O2—C7	1.243 (3)	C4—C5	1.393 (3)
O3—C8	1.263 (3)	C5—C6	1.387 (3)
O3—Cu1i	2.1396 (14)	C6—C8	1.524 (3)
O4—C8	1.246 (3)	C9—C10	1.516 (3)
N1—C11	1.475 (3)
O5—Cu1—O1	92.80 (6)	C2—C1—C7	122.73 (19)
O5—Cu1—N1	177.14 (7)	C6—C1—C7	117.98 (18)
O1—Cu1—N1	89.71 (7)	C1—C2—C3	121.13 (19)
O5—Cu1—N2	91.13 (7)	C1—C2—Br1	118.64 (16)
O1—Cu1—N2	136.68 (7)	C3—C2—Br1	120.21 (16)
N1—Cu1—N2	86.10 (8)	C2—C3—C4	119.12 (19)
O5—Cu1—O3i	90.46 (6)	C2—C3—Br2	120.61 (16)
O1—Cu1—O3i	124.17 (6)	C4—C3—Br2	120.27 (15)
N1—Cu1—O3i	89.26 (7)	C5—C4—C3	119.80 (19)
N2—Cu1—O3i	98.90 (7)	C5—C4—Br3	120.18 (16)
C7—O1—Cu1	130.25 (14)	C3—C4—Br3	120.02 (15)
C8—O3—Cu1i	127.37 (14)	C6—C5—C4	120.80 (19)
C11—N1—C9	109.53 (18)	C6—C5—Br4	119.17 (16)
C11—N1—C12	108.07 (19)	C4—C5—Br4	120.01 (16)
C9—N1—C12	111.12 (19)	C5—C6—C1	119.73 (19)
C11—N1—Cu1	113.14 (14)	C5—C6—C8	120.89 (19)
C9—N1—Cu1	103.09 (14)	C1—C6—C8	119.35 (18)
C12—N1—Cu1	111.86 (15)	O2—C7—O1	127.93 (19)
C13—N2—C14	108.52 (19)	O2—C7—C1	118.85 (18)
C13—N2—C10	111.32 (19)	O1—C7—C1	113.20 (18)
C14—N2—C10	110.3 (2)	O4—C8—O3	127.65 (19)
C13—N2—Cu1	110.61 (15)	O4—C8—C6	117.88 (18)
C14—N2—Cu1	109.81 (14)	O3—C8—C6	114.47 (18)
C10—N2—Cu1	106.31 (14)	N1—C9—C10	109.8 (2)
C2—C1—C6	119.26 (19)	N2—C10—C9	109.52 (19)
C6—C1—C2—C3	3.0 (3)	C2—C1—C6—C8	178.75 (18)
C7—C1—C2—C3	−178.78 (19)	C7—C1—C6—C8	0.5 (3)
C6—C1—C2—Br1	−175.50 (15)	Cu1—O1—C7—O2	−1.5 (3)
C7—C1—C2—Br1	2.7 (3)	Cu1—O1—C7—C1	−179.92 (13)
C1—C2—C3—C4	0.2 (3)	C2—C1—C7—O2	60.4 (3)
Br1—C2—C3—C4	178.71 (15)	C6—C1—C7—O2	−121.4 (2)
C1—C2—C3—Br2	−179.24 (15)	C2—C1—C7—O1	−121.0 (2)
Br1—C2—C3—Br2	−0.7 (2)	C6—C1—C7—O1	57.2 (2)
C2—C3—C4—C5	−3.3 (3)	Cu1i—O3—C8—O4	−6.9 (3)
Br2—C3—C4—C5	176.09 (16)	Cu1i—O3—C8—C6	172.16 (13)
C2—C3—C4—Br3	176.10 (15)	C5—C6—C8—O4	66.3 (3)
Br2—C3—C4—Br3	−4.5 (2)	C1—C6—C8—O4	−115.6 (2)
C3—C4—C5—C6	3.3 (3)	C5—C6—C8—O3	−112.8 (2)
Br3—C4—C5—C6	−176.16 (16)	C1—C6—C8—O3	65.3 (3)
C3—C4—C5—Br4	−175.18 (16)	C11—N1—C9—C10	−170.79 (19)
Br3—C4—C5—Br4	5.4 (2)	C12—N1—C9—C10	69.9 (2)
C4—C5—C6—C1	0.0 (3)	Cu1—N1—C9—C10	−50.1 (2)
Br4—C5—C6—C1	178.46 (15)	C13—N2—C10—C9	−148.7 (2)
C4—C5—C6—C8	178.09 (19)	C14—N2—C10—C9	90.8 (2)
Br4—C5—C6—C8	−3.4 (3)	Cu1—N2—C10—C9	−28.2 (2)
C2—C1—C6—C5	−3.1 (3)	N1—C9—C10—N2	54.4 (3)
C7—C1—C6—C5	178.62 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O2	0.81 (2)	1.87 (2)	2.649 (2)	161 (2)
O5—H5B···O4i	0.82 (2)	1.83 (2)	2.630 (2)	167 (3)
C10—H10A···Br4ii	0.99	2.84	3.729 (3)	150
C11—H11C···O4	0.98	2.40	3.376 (3)	179
C13—H13A···O4iii	0.98	2.58	3.506 (3)	158

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O5H5AO2	0.81(2)	1.87(2)	2.649(2)	161(2)
O5H5BO4i	0.82(2)	1.83(2)	2.630(2)	167(3)
C10H10ABr4ii	0.99	2.84	3.729(3)	150
C11H11CO4	0.98	2.40	3.376(3)	179
C13H13AO4iii	0.98	2.58	3.506(3)	158

Symmetry codes: (i) ; (ii) ; (iii) .