catena-Poly[copper(II)-{μ(3)-4,4'-dibromo-2,2'-[butane-1,4-diylbis(nitrilo-methanyl-yl-idene)]diphenolato-κN,O:N',O':O'}].

The asymmetric unit of the title coordination polymer, [Cu(C(18)H(16)Br(2)N(2)O(2))](n), consists of a Schiff base complex in which a crystallographic twofold rotation axis bis-ects the central C-C bonds of the n-butyl spacers of the designated Schiff base ligands, making symmetry-related dimer units, which are twisted around Cu(II) atoms in a bis-bidentate coordination mode. In the crystal, these dimeric units are connected through Cu-O bonds, forming one-dimensional coordination polymers, which propagate along [001]. The Cu(II) atom adopts a square-based pyramidal coordination geometry, being coordinated by two N and two O atoms of symmetry-related ligands and by a third O atom of a neighboring complex. Furthermore, inter-molecular π-π inter-actions [centroid-centroid distance = 3.786 (2) Å] and C-H⋯O inter-actions stabilize the crystal packing.

Related literature

For van der Waals radii, see: Bondi (1964 ▶). For background to coordination polymers, see: Kido & Okamoto (2002 ▶); Li et al. (2006 ▶); Eddaoudi et al. (2001 ▶); Dietzel et al. (2005 ▶). For background to bis-bidentate Schiff base complexes, see: Hannon et al. (1999 ▶); Lavalette et al. (2003 ▶). For the synthesis and structural variations of Schiff base complexes see: Granovski et al. (1993 ▶); Elmali et al. (2000 ▶). For the crystal structure of the chloro derivative, see: Kargar & Kia (2011 ▶).

Experimental

Crystal data

[Cu(C18H16Br2N2O2)]

M = 515.69

Monoclinic,

a = 24.0964 (9) Å

b = 10.5885 (3) Å

c = 15.3528 (5) Å

β = 117.354 (3)°

V = 3479.2 (2) Å3

Z = 8

Mo Kα radiation

μ = 5.86 mm−1

T = 100 K

0.41 × 0.32 × 0.17 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.197, T max = 0.439

36229 measured reflections

6017 independent reflections

4887 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.139

S = 1.19

6017 reflections

226 parameters

H-atom parameters constrained

Δρmax = 2.19 e Å−3

Δρmin = −0.73 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811009949/su2263sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009949/su2263Isup2.hkl

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

[Cu(C18H16Br2N2O2)]	F(000) = 2024
Mr = 515.69	Dx = 1.969 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9961 reflections
a = 24.0964 (9) Å	θ = 2.4–34.8°
b = 10.5885 (3) Å	µ = 5.86 mm−1
c = 15.3528 (5) Å	T = 100 K
β = 117.354 (3)°	Block, green
V = 3479.2 (2) Å3	0.41 × 0.32 × 0.17 mm
Z = 8

Bruker SMART APEXII CCD area-detector diffractometer	6017 independent reflections
Radiation source: fine-focus sealed tube	4887 reflections with I > 2σ(I)
graphite	Rint = 0.037
φ and ω scans	θmax = 32.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −35→35
Tmin = 0.197, Tmax = 0.439	k = −15→15
36229 measured reflections	l = −22→22

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H-atom parameters constrained
S = 1.19	w = 1/[σ2(Fo2) + (0.0486P)2 + 32.1161P] where P = (Fo2 + 2Fc2)/3
6017 reflections	(Δ/σ)max = 0.001
226 parameters	Δρmax = 2.19 e Å−3
0 restraints	Δρmin = −0.73 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.

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
Cu1	0.47745 (2)	−0.03938 (5)	0.38413 (4)	0.01976 (11)
Br1	0.819293 (19)	0.00198 (4)	0.58443 (3)	0.02766 (11)
Br2	0.134787 (18)	0.00911 (4)	0.11824 (3)	0.02394 (10)
O1	0.54761 (13)	0.0506 (3)	0.4822 (2)	0.0236 (6)
O2	0.40617 (13)	−0.1341 (3)	0.2998 (2)	0.0252 (6)
N1	0.53131 (15)	−0.1956 (3)	0.4080 (2)	0.0198 (6)
N2	0.43372 (16)	0.1252 (3)	0.3280 (3)	0.0217 (6)
C1	0.60593 (18)	0.0376 (4)	0.4980 (3)	0.0218 (7)
C2	0.64637 (19)	0.1423 (4)	0.5324 (3)	0.0249 (8)
H2A	0.6310	0.2195	0.5405	0.030*
C3	0.70866 (19)	0.1318 (4)	0.5542 (3)	0.0247 (8)
H3A	0.7347	0.2021	0.5755	0.030*
C4	0.73222 (18)	0.0156 (4)	0.5442 (3)	0.0213 (7)
C5	0.69348 (17)	−0.0878 (4)	0.5073 (3)	0.0209 (7)
H5A	0.7094	−0.1640	0.4987	0.025*
C6	0.62944 (17)	−0.0775 (4)	0.4828 (3)	0.0194 (7)
C7	0.59134 (18)	−0.1902 (4)	0.4466 (3)	0.0209 (7)
H7A	0.6123	−0.2657	0.4517	0.025*
C8	0.50307 (18)	−0.3230 (4)	0.3790 (3)	0.0214 (7)
H8A	0.4702	−0.3323	0.3984	0.026*
H8B	0.5347	−0.3863	0.4138	0.026*
C9	0.47575 (17)	−0.3465 (4)	0.2686 (3)	0.0208 (7)
H9A	0.4544	−0.4273	0.2533	0.025*
H9B	0.4449	−0.2817	0.2341	0.025*
C10	0.34829 (17)	−0.0968 (4)	0.2555 (3)	0.0204 (7)
C11	0.30077 (18)	−0.1890 (4)	0.2123 (3)	0.0223 (7)
H11A	0.3120	−0.2728	0.2115	0.027*
C12	0.23841 (18)	−0.1575 (4)	0.1715 (3)	0.0224 (7)
H12A	0.2080	−0.2199	0.1450	0.027*
C13	0.22092 (17)	−0.0308 (4)	0.1703 (3)	0.0194 (7)
C14	0.26555 (18)	0.0625 (4)	0.2037 (3)	0.0218 (7)
H14A	0.2534	0.1467	0.1980	0.026*
C15	0.32968 (18)	0.0317 (4)	0.2466 (3)	0.0209 (7)
C16	0.37388 (19)	0.1347 (4)	0.2777 (3)	0.0225 (7)
H16A	0.3576	0.2157	0.2597	0.027*
C17	0.47047 (19)	0.2436 (4)	0.3495 (3)	0.0229 (7)
H17A	0.4937	0.2543	0.4200	0.028*
H17B	0.4421	0.3145	0.3233	0.028*
C18	0.51627 (19)	0.2440 (4)	0.3057 (3)	0.0243 (8)
H18A	0.5427	0.3181	0.3289	0.029*
H18B	0.5429	0.1701	0.3289	0.029*

	U11	U22	U33	U12	U13	U23
Cu1	0.01465 (19)	0.0223 (2)	0.0209 (2)	0.00107 (16)	0.00695 (16)	−0.00268 (18)
Br1	0.01623 (17)	0.0374 (2)	0.0292 (2)	−0.00192 (15)	0.01023 (15)	−0.00306 (17)
Br2	0.01591 (17)	0.0263 (2)	0.0279 (2)	0.00093 (13)	0.00856 (15)	0.00019 (15)
O1	0.0168 (12)	0.0281 (15)	0.0256 (14)	−0.0010 (11)	0.0096 (11)	−0.0052 (12)
O2	0.0177 (12)	0.0233 (14)	0.0292 (15)	0.0028 (10)	0.0062 (11)	−0.0047 (12)
N1	0.0179 (14)	0.0220 (15)	0.0194 (14)	0.0005 (11)	0.0086 (12)	0.0001 (12)
N2	0.0222 (15)	0.0200 (15)	0.0246 (16)	−0.0012 (12)	0.0123 (13)	−0.0036 (13)
C1	0.0171 (15)	0.0266 (19)	0.0196 (16)	−0.0004 (14)	0.0066 (13)	−0.0041 (15)
C2	0.0224 (17)	0.0256 (19)	0.0271 (19)	−0.0002 (15)	0.0117 (16)	−0.0049 (16)
C3	0.0213 (17)	0.0268 (19)	0.0262 (19)	−0.0051 (14)	0.0111 (15)	−0.0053 (16)
C4	0.0159 (15)	0.031 (2)	0.0174 (16)	−0.0006 (14)	0.0083 (13)	−0.0012 (14)
C5	0.0178 (15)	0.0236 (18)	0.0198 (16)	0.0000 (13)	0.0075 (13)	−0.0022 (14)
C6	0.0174 (15)	0.0227 (17)	0.0169 (15)	0.0002 (13)	0.0068 (13)	−0.0002 (13)
C7	0.0199 (16)	0.0220 (17)	0.0196 (16)	0.0022 (13)	0.0080 (14)	−0.0004 (14)
C8	0.0186 (16)	0.0206 (17)	0.0245 (18)	−0.0019 (13)	0.0095 (14)	0.0003 (14)
C9	0.0165 (15)	0.0222 (17)	0.0234 (17)	−0.0019 (13)	0.0089 (14)	−0.0014 (14)
C10	0.0187 (16)	0.0234 (18)	0.0183 (16)	0.0015 (13)	0.0078 (13)	−0.0005 (14)
C11	0.0186 (16)	0.0224 (18)	0.0223 (18)	0.0013 (13)	0.0062 (14)	−0.0005 (14)
C12	0.0184 (16)	0.0235 (18)	0.0222 (17)	0.0007 (13)	0.0067 (14)	0.0004 (15)
C13	0.0141 (14)	0.0234 (17)	0.0177 (16)	0.0025 (12)	0.0047 (12)	0.0018 (13)
C14	0.0179 (16)	0.0194 (17)	0.0268 (18)	0.0008 (13)	0.0091 (14)	0.0011 (14)
C15	0.0196 (16)	0.0221 (17)	0.0188 (16)	0.0018 (13)	0.0070 (13)	−0.0004 (14)
C16	0.0219 (17)	0.0210 (17)	0.0254 (18)	0.0002 (14)	0.0115 (15)	−0.0023 (15)
C17	0.0221 (17)	0.0208 (18)	0.0286 (19)	−0.0033 (14)	0.0140 (15)	−0.0034 (15)
C18	0.0213 (17)	0.0277 (19)	0.0270 (19)	−0.0019 (14)	0.0138 (15)	−0.0010 (15)

Cu1—O2	1.894 (3)	C7—H7A	0.9300
Cu1—O1	1.922 (3)	C8—C9	1.530 (6)
Cu1—N2	2.014 (4)	C8—H8A	0.9700
Cu1—N1	2.029 (3)	C8—H8B	0.9700
Cu1—O1i	2.393 (3)	C9—C9ii	1.519 (7)
Br1—C4	1.901 (4)	C9—H9A	0.9700
Br2—C13	1.898 (4)	C9—H9B	0.9700
O1—C1	1.319 (5)	C10—C11	1.416 (5)
O1—Cu1i	2.393 (3)	C10—C15	1.420 (6)
O2—C10	1.301 (5)	C11—C12	1.377 (5)
N1—C7	1.288 (5)	C11—H11A	0.9300
N1—C8	1.484 (5)	C12—C13	1.404 (6)
N2—C16	1.289 (5)	C12—H12A	0.9300
N2—C17	1.481 (5)	C13—C14	1.374 (5)
C1—C6	1.408 (6)	C14—C15	1.412 (5)
C1—C2	1.409 (6)	C14—H14A	0.9300
C2—C3	1.384 (6)	C15—C16	1.444 (6)
C2—H2A	0.9300	C16—H16A	0.9300
C3—C4	1.393 (6)	C17—C18	1.534 (5)
C3—H3A	0.9300	C17—H17A	0.9700
C4—C5	1.380 (6)	C17—H17B	0.9700
C5—C6	1.414 (5)	C18—C18ii	1.519 (8)
C5—H5A	0.9300	C18—H18A	0.9700
C6—C7	1.451 (6)	C18—H18B	0.9700
O2—Cu1—O1	173.11 (14)	C9—C8—H8A	109.1
O2—Cu1—N2	91.94 (13)	N1—C8—H8B	109.1
O1—Cu1—N2	90.31 (14)	C9—C8—H8B	109.1
O2—Cu1—N1	89.76 (13)	H8A—C8—H8B	107.8
O1—Cu1—N1	90.18 (13)	C9ii—C9—C8	113.8 (4)
N2—Cu1—N1	161.46 (14)	C9ii—C9—H9A	108.8
O2—Cu1—O1i	93.04 (12)	C8—C9—H9A	108.8
O1—Cu1—O1i	80.22 (12)	C9ii—C9—H9B	108.8
N2—Cu1—O1i	96.98 (12)	C8—C9—H9B	108.8
N1—Cu1—O1i	101.37 (12)	H9A—C9—H9B	107.7
C1—O1—Cu1	124.9 (3)	O2—C10—C11	118.6 (4)
C1—O1—Cu1i	120.3 (3)	O2—C10—C15	123.8 (4)
Cu1—O1—Cu1i	99.78 (12)	C11—C10—C15	117.6 (3)
C10—O2—Cu1	127.9 (3)	C12—C11—C10	121.7 (4)
C7—N1—C8	116.2 (3)	C12—C11—H11A	119.2
C7—N1—Cu1	122.4 (3)	C10—C11—H11A	119.2
C8—N1—Cu1	121.3 (2)	C11—C12—C13	119.7 (4)
C16—N2—C17	117.2 (4)	C11—C12—H12A	120.2
C16—N2—Cu1	123.0 (3)	C13—C12—H12A	120.2
C17—N2—Cu1	119.7 (3)	C14—C13—C12	120.2 (3)
O1—C1—C6	122.4 (4)	C14—C13—Br2	120.9 (3)
O1—C1—C2	118.8 (4)	C12—C13—Br2	118.8 (3)
C6—C1—C2	118.8 (4)	C13—C14—C15	120.6 (4)
C3—C2—C1	121.0 (4)	C13—C14—H14A	119.7
C3—C2—H2A	119.5	C15—C14—H14A	119.7
C1—C2—H2A	119.5	C14—C15—C10	119.7 (4)
C2—C3—C4	119.7 (4)	C14—C15—C16	117.6 (4)
C2—C3—H3A	120.2	C10—C15—C16	122.7 (3)
C4—C3—H3A	120.2	N2—C16—C15	126.2 (4)
C5—C4—C3	120.9 (4)	N2—C16—H16A	116.9
C5—C4—Br1	120.7 (3)	C15—C16—H16A	116.9
C3—C4—Br1	118.4 (3)	N2—C17—C18	112.4 (3)
C4—C5—C6	119.9 (4)	N2—C17—H17A	109.1
C4—C5—H5A	120.1	C18—C17—H17A	109.1
C6—C5—H5A	120.1	N2—C17—H17B	109.1
C1—C6—C5	119.7 (4)	C18—C17—H17B	109.1
C1—C6—C7	122.9 (3)	H17A—C17—H17B	107.9
C5—C6—C7	117.4 (4)	C18ii—C18—C17	113.0 (4)
N1—C7—C6	126.3 (4)	C18ii—C18—H18A	109.0
N1—C7—H7A	116.8	C17—C18—H18A	109.0
C6—C7—H7A	116.8	C18ii—C18—H18B	109.0
N1—C8—C9	112.6 (3)	C17—C18—H18B	109.0
N1—C8—H8A	109.1	H18A—C18—H18B	107.8
N2—Cu1—O1—C1	−124.9 (3)	O1—C1—C6—C5	−175.7 (4)
N1—Cu1—O1—C1	36.6 (3)	C2—C1—C6—C5	3.5 (6)
O1i—Cu1—O1—C1	138.1 (4)	O1—C1—C6—C7	1.4 (6)
N2—Cu1—O1—Cu1i	97.03 (13)	C2—C1—C6—C7	−179.3 (4)
N1—Cu1—O1—Cu1i	−101.51 (13)	C4—C5—C6—C1	−1.3 (6)
O1i—Cu1—O1—Cu1i	0.0	C4—C5—C6—C7	−178.6 (4)
N2—Cu1—O2—C10	−21.9 (4)	C8—N1—C7—C6	−178.3 (4)
N1—Cu1—O2—C10	176.6 (4)	Cu1—N1—C7—C6	3.4 (6)
O1i—Cu1—O2—C10	75.2 (4)	C1—C6—C7—N1	13.1 (6)
O2—Cu1—N1—C7	164.8 (3)	C5—C6—C7—N1	−169.7 (4)
O1—Cu1—N1—C7	−22.1 (3)	C7—N1—C8—C9	−101.6 (4)
N2—Cu1—N1—C7	69.4 (6)	Cu1—N1—C8—C9	76.7 (4)
O1i—Cu1—N1—C7	−102.2 (3)	N1—C8—C9—C9ii	64.2 (3)
O2—Cu1—N1—C8	−13.5 (3)	Cu1—O2—C10—C11	−167.0 (3)
O1—Cu1—N1—C8	159.6 (3)	Cu1—O2—C10—C15	13.7 (6)
N2—Cu1—N1—C8	−108.9 (5)	O2—C10—C11—C12	174.4 (4)
O1i—Cu1—N1—C8	79.6 (3)	C15—C10—C11—C12	−6.3 (6)
O2—Cu1—N2—C16	17.4 (3)	C10—C11—C12—C13	1.5 (6)
O1—Cu1—N2—C16	−156.1 (3)	C11—C12—C13—C14	4.2 (6)
N1—Cu1—N2—C16	112.4 (5)	C11—C12—C13—Br2	−177.6 (3)
O1i—Cu1—N2—C16	−75.9 (3)	C12—C13—C14—C15	−4.9 (6)
O2—Cu1—N2—C17	−166.6 (3)	Br2—C13—C14—C15	177.0 (3)
O1—Cu1—N2—C17	19.9 (3)	C13—C14—C15—C10	−0.1 (6)
N1—Cu1—N2—C17	−71.6 (5)	C13—C14—C15—C16	178.4 (4)
O1i—Cu1—N2—C17	100.1 (3)	O2—C10—C15—C14	−175.2 (4)
Cu1—O1—C1—C6	−31.8 (6)	C11—C10—C15—C14	5.6 (6)
Cu1i—O1—C1—C6	98.5 (4)	O2—C10—C15—C16	6.4 (6)
Cu1—O1—C1—C2	148.9 (3)	C11—C10—C15—C16	−172.8 (4)
Cu1i—O1—C1—C2	−80.7 (4)	C17—N2—C16—C15	178.4 (4)
O1—C1—C2—C3	177.1 (4)	Cu1—N2—C16—C15	−5.6 (6)
C6—C1—C2—C3	−2.2 (6)	C14—C15—C16—N2	171.5 (4)
C1—C2—C3—C4	−1.4 (7)	C10—C15—C16—N2	−10.1 (7)
C2—C3—C4—C5	3.8 (6)	C16—N2—C17—C18	−118.7 (4)
C2—C3—C4—Br1	−175.2 (3)	Cu1—N2—C17—C18	65.1 (4)
C3—C4—C5—C6	−2.5 (6)	N2—C17—C18—C18ii	65.9 (3)
Br1—C4—C5—C6	176.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O2	0.97	2.28	2.973 (5)	128

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯O2	0.97	2.28	2.973 (5)	128