catena-Poly[bis­(μ4-adipato-1:2:1′:2′κ4O1:O1′:O4:O4′)bis­(N,N-dimethyl­formamide)-1κO,2κO-dicopper(II)]

Wu, G.-Y.; Ng, S.W.

doi:10.1107/S1600536810036093

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1258

doi:10.1107/S1600536810036093

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catena-Poly[bis(μ₄-adipato-1:2:1′:2′κ⁴O¹:O^1′:O⁴:O^4′)bis(N,N-dimethylformamide)-1κO,2κO-dicopper(II)]

Guo-Yun Wu ^a and Seik Weng Ng ^b ^*

^aHunan Medical Technical Secondary School, Changsha, Hunan 410014, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 6 September 2010; accepted 8 September 2010; online 15 September 2010)

In the title polymeric complex, [Cu₂(C₆H₈O₄)₂(C₃H₇NO)₂]_n, the carboxylate groups of the approximately U-shaped adipate dianion each bridge a pair of inversion-related, DMF-coordinated copper(II) atoms, generating a ribbon motif that runs along the b axis. The geometry of the copper(II) atom is distorted square-pyramidal; the apical site is occupied by the O atom of the DMF molecule whereas the four basal sites are occupied by carboxylate O atoms.

Related literature

For the crystal structure of diaquaadipatocopper(II), see: Bakalbassis et al. (2001 ); Zheng et al. (2001 ).

Experimental

Crystal data

[Cu₂(C₆H₈O₄)₂(C₃H₇NO)₂]
M_r = 561.52
Monoclinic, P 2₁ /n
a = 9.4764 (5) Å
b = 8.2618 (5) Å
c = 15.0990 (8) Å
β = 106.259 (1)°
V = 1134.85 (11) Å³
Z = 2
Mo Kα radiation
μ = 1.93 mm⁻¹
T = 173 K
0.45 × 0.40 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.477, T_max = 0.761
5917 measured reflections
2428 independent reflections
2153 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.072
S = 1.03
2428 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.9683 (14)
Cu1—O2ⁱ	1.9716 (14)
Cu1—O3ⁱⁱ	1.9695 (13)
Cu1—O4ⁱⁱⁱ	1.9584 (14)
Cu1—O5	2.1646 (15)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y+1, -z+1; (iii) x, y-1, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036093/xu5027sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810036093/xu5027Isup2.hkl

checkCIF report

Comment top

Copper adipate furnishes a number of adducts with oxygen- and nitrogen-donor ligands. The parent compound itself exists as dihydrate, with the copper atom in a square-planar environment (Bakalbassis et al., 2001; Zheng et al., 2001). The four-coordinate nature explains the ability of the compound to expand the coordination number of the metal atom. In the present study, the DMF solvent used in the synthesis functions as donor ligand. The DMF adduct is formally the dicopper diadipate bis-adduct (Scheme I). The carboxyl –CO₂ ends of the approximately U-shape adipate dianion of polymeric Cu₂(C₆H₈O₄)₂(C₃H₇NO)₂ each bridges a pair of inversion-related, DMF-coordinated copper atoms (Fig. 1) to generate a ribbon motif that runs along the b-axis of the monoclinic unit cell. The geometry of the copper atom is a square pyramid; the apical site is occupied by the O atom of the DMF molecule whereas the four basal sites are occupied by the O atoms of the carboxyl ends.

Related literature top

For the crystal structure of diaquaadipatocopper, see: Bakalbassis et al. (2001); Zheng et al. (2001).

Experimental top

(1H-Benzimidazol-2-yl)-methanol (0.074 g, 0.5 mmol) was dissolved in a methanol/DMF mixture (v/v 1:1, 20 ml) and to this was added copper nitrate trihydrate (0.241 g, 1 mmol) followed by adipic acid (0.073 g, 0.5 mmol). The mixture was filtered and then set aside. Blue crystals were isolated after two weeks.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of a portion of the ribbon structure of Cu₂(C₆H₈O₄)₂(C₃H₇NO)₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

catena-Poly[bis(µ₄-adipato- 1:2:1':2'κ⁴O¹:O^1':O⁴:O^4') bis(N,N-dimethylformamide)-1κO,2κO-dicopper(II)] top

Crystal data top

[Cu₂(C₆H₈O₄)₂(C₃H₇NO)₂]	F(000) = 580
M_r = 561.52	D_x = 1.643 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4192 reflections
a = 9.4764 (5) Å	θ = 2.3–27.0°
b = 8.2618 (5) Å	µ = 1.93 mm⁻¹
c = 15.0990 (8) Å	T = 173 K
β = 106.259 (1)°	Block, blue
V = 1134.85 (11) Å³	0.45 × 0.40 × 0.15 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	2428 independent reflections
Radiation source: fine-focus sealed tube	2153 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 27.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→12
T_min = 0.477, T_max = 0.761	k = −10→10
5917 measured reflections	l = −19→12

Refinement top

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0347P)² + 1.1165P] where P = (F_o² + 2F_c²)/3
2428 reflections	(Δ/σ)_max = 0.001
147 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

[Cu₂(C₆H₈O₄)₂(C₃H₇NO)₂]	V = 1134.85 (11) Å³
M_r = 561.52	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.4764 (5) Å	µ = 1.93 mm⁻¹
b = 8.2618 (5) Å	T = 173 K
c = 15.0990 (8) Å	0.45 × 0.40 × 0.15 mm
β = 106.259 (1)°

Data collection top

Bruker SMART APEX diffractometer	2428 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2153 reflections with I > 2σ(I)
T_min = 0.477, T_max = 0.761	R_int = 0.018
5917 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.03	Δρ_max = 0.41 e Å⁻³
2428 reflections	Δρ_min = −0.23 e Å⁻³
147 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.43225 (2)	−0.00484 (2)	0.564117 (15)	0.01597 (9)
O1	0.52755 (16)	0.20568 (17)	0.60153 (10)	0.0269 (3)
O2	0.64565 (17)	0.21315 (17)	0.49265 (10)	0.0266 (3)
O3	0.72585 (15)	0.89246 (17)	0.52815 (9)	0.0242 (3)
O4	0.60808 (16)	0.88250 (19)	0.63743 (10)	0.0282 (3)
O5	0.31493 (16)	−0.01217 (17)	0.66816 (10)	0.0240 (3)
N1	0.12143 (18)	0.0799 (2)	0.71426 (11)	0.0231 (3)
C1	0.6147 (2)	0.2692 (2)	0.56190 (13)	0.0192 (4)
C2	0.6893 (2)	0.4247 (2)	0.60485 (14)	0.0217 (4)
H2A	0.7516	0.3998	0.6678	0.026*
H2B	0.6124	0.5015	0.6110	0.026*
C3	0.7844 (2)	0.5086 (2)	0.55190 (14)	0.0221 (4)
H3A	0.7201	0.5715	0.5004	0.027*
H3B	0.8351	0.4253	0.5249	0.027*
C4	0.8997 (2)	0.6224 (2)	0.61229 (14)	0.0230 (4)
H4A	0.9740	0.5566	0.6569	0.028*
H4B	0.9504	0.6802	0.5726	0.028*
C5	0.8366 (2)	0.7468 (2)	0.66538 (13)	0.0218 (4)
H5A	0.7991	0.6896	0.7118	0.026*
H5B	0.9167	0.8196	0.6990	0.026*
C6	0.7139 (2)	0.8484 (2)	0.60538 (12)	0.0176 (4)
C7	0.1952 (2)	0.0576 (2)	0.65288 (14)	0.0238 (4)
H7	0.1530	0.0984	0.5924	0.029*
C8	0.1795 (3)	0.0257 (3)	0.80898 (15)	0.0324 (5)
H8A	0.2752	−0.0261	0.8166	0.049*
H8B	0.1114	−0.0523	0.8236	0.049*
H8C	0.1911	0.1187	0.8506	0.049*
C9	−0.0149 (2)	0.1724 (3)	0.69183 (16)	0.0311 (5)
H9A	−0.0436	0.1998	0.6261	0.047*
H9B	−0.0003	0.2720	0.7285	0.047*
H9C	−0.0925	0.1074	0.7058	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01828 (14)	0.01576 (14)	0.01519 (13)	0.00059 (8)	0.00683 (10)	−0.00014 (8)
O1	0.0302 (8)	0.0256 (7)	0.0286 (8)	−0.0089 (6)	0.0143 (6)	−0.0088 (6)
O2	0.0381 (8)	0.0200 (7)	0.0264 (7)	−0.0063 (6)	0.0169 (6)	−0.0056 (6)
O3	0.0232 (7)	0.0299 (7)	0.0204 (7)	0.0058 (6)	0.0075 (6)	0.0064 (6)
O4	0.0275 (8)	0.0383 (8)	0.0212 (7)	0.0110 (6)	0.0111 (6)	0.0085 (6)
O5	0.0225 (7)	0.0303 (8)	0.0215 (7)	0.0058 (6)	0.0100 (6)	0.0036 (5)
N1	0.0221 (8)	0.0269 (9)	0.0225 (8)	0.0027 (7)	0.0099 (7)	0.0002 (7)
C1	0.0186 (9)	0.0169 (8)	0.0206 (9)	0.0030 (7)	0.0032 (7)	0.0001 (7)
C2	0.0244 (10)	0.0186 (9)	0.0230 (9)	−0.0008 (8)	0.0082 (8)	−0.0039 (7)
C3	0.0262 (10)	0.0187 (9)	0.0227 (9)	−0.0004 (7)	0.0089 (8)	−0.0017 (7)
C4	0.0190 (9)	0.0205 (9)	0.0300 (10)	0.0017 (7)	0.0074 (8)	0.0024 (8)
C5	0.0215 (9)	0.0191 (9)	0.0214 (9)	−0.0002 (7)	0.0003 (8)	−0.0002 (7)
C6	0.0186 (9)	0.0144 (8)	0.0184 (9)	−0.0013 (7)	0.0030 (7)	−0.0015 (7)
C7	0.0282 (10)	0.0250 (10)	0.0213 (9)	0.0016 (8)	0.0122 (8)	0.0024 (8)
C8	0.0252 (11)	0.0518 (14)	0.0216 (10)	0.0005 (10)	0.0092 (9)	0.0013 (9)
C9	0.0284 (11)	0.0294 (11)	0.0387 (12)	0.0063 (9)	0.0150 (10)	−0.0017 (9)

Geometric parameters (Å, º) top

Cu1—O1	1.9683 (14)	C2—H2B	0.9900
Cu1—O2ⁱ	1.9716 (14)	C3—C4	1.533 (3)
Cu1—O3ⁱⁱ	1.9695 (13)	C3—H3A	0.9900
Cu1—O4ⁱⁱⁱ	1.9584 (14)	C3—H3B	0.9900
Cu1—O5	2.1646 (15)	C4—C5	1.525 (3)
Cu1—Cu1ⁱ	2.6069 (4)	C4—H4A	0.9900
O1—C1	1.262 (2)	C4—H4B	0.9900
O2—C1	1.251 (2)	C5—C6	1.512 (3)
O3—C6	1.256 (2)	C5—H5A	0.9900
O4—C6	1.262 (2)	C5—H5B	0.9900
O5—C7	1.235 (3)	C7—H7	0.9500
N1—C7	1.321 (3)	C8—H8A	0.9800
N1—C8	1.452 (3)	C8—H8B	0.9800
N1—C9	1.457 (3)	C8—H8C	0.9800
C1—C2	1.521 (3)	C9—H9A	0.9800
C2—C3	1.529 (3)	C9—H9B	0.9800
C2—H2A	0.9900	C9—H9C	0.9800

O4ⁱⁱⁱ—Cu1—O1	90.48 (7)	C4—C3—H3A	108.9
O4ⁱⁱⁱ—Cu1—O3ⁱⁱ	169.19 (6)	C2—C3—H3B	108.9
O1—Cu1—O3ⁱⁱ	89.05 (6)	C4—C3—H3B	108.9
O4ⁱⁱⁱ—Cu1—O2ⁱ	89.23 (7)	H3A—C3—H3B	107.8
O1—Cu1—O2ⁱ	169.11 (6)	C5—C4—C3	114.04 (16)
O3ⁱⁱ—Cu1—O2ⁱ	89.19 (6)	C5—C4—H4A	108.7
O4ⁱⁱⁱ—Cu1—O5	96.03 (6)	C3—C4—H4A	108.7
O1—Cu1—O5	95.97 (6)	C5—C4—H4B	108.7
O3ⁱⁱ—Cu1—O5	94.76 (6)	C3—C4—H4B	108.7
O2ⁱ—Cu1—O5	94.88 (6)	H4A—C4—H4B	107.6
O4ⁱⁱⁱ—Cu1—Cu1ⁱ	85.20 (4)	C6—C5—C4	114.07 (16)
O1—Cu1—Cu1ⁱ	84.51 (4)	C6—C5—H5A	108.7
O3ⁱⁱ—Cu1—Cu1ⁱ	84.00 (4)	C4—C5—H5A	108.7
O2ⁱ—Cu1—Cu1ⁱ	84.62 (4)	C6—C5—H5B	108.7
O5—Cu1—Cu1ⁱ	178.67 (4)	C4—C5—H5B	108.7
C1—O1—Cu1	122.68 (12)	H5A—C5—H5B	107.6
C1—O2—Cu1ⁱ	122.64 (13)	O3—C6—O4	125.38 (18)
C6—O3—Cu1ⁱⁱ	123.01 (13)	O3—C6—C5	117.60 (17)
C6—O4—Cu1^iv	122.10 (12)	O4—C6—C5	117.02 (16)
C7—O5—Cu1	118.87 (13)	O5—C7—N1	124.96 (19)
C7—N1—C8	121.24 (17)	O5—C7—H7	117.5
C7—N1—C9	121.29 (18)	N1—C7—H7	117.5
C8—N1—C9	117.24 (17)	N1—C8—H8A	109.5
O2—C1—O1	125.47 (18)	N1—C8—H8B	109.5
O2—C1—C2	118.63 (17)	H8A—C8—H8B	109.5
O1—C1—C2	115.89 (16)	N1—C8—H8C	109.5
C1—C2—C3	115.59 (16)	H8A—C8—H8C	109.5
C1—C2—H2A	108.4	H8B—C8—H8C	109.5
C3—C2—H2A	108.4	N1—C9—H9A	109.5
C1—C2—H2B	108.4	N1—C9—H9B	109.5
C3—C2—H2B	108.4	H9A—C9—H9B	109.5
H2A—C2—H2B	107.4	N1—C9—H9C	109.5
C2—C3—C4	113.16 (16)	H9A—C9—H9C	109.5
C2—C3—H3A	108.9	H9B—C9—H9C	109.5

O4ⁱⁱⁱ—Cu1—O1—C1	82.83 (16)	O1—C1—C2—C3	−175.00 (17)
O3ⁱⁱ—Cu1—O1—C1	−86.36 (16)	C1—C2—C3—C4	−158.25 (16)
O2ⁱ—Cu1—O1—C1	−5.6 (4)	C2—C3—C4—C5	−53.1 (2)
O5—Cu1—O1—C1	178.95 (15)	C3—C4—C5—C6	−54.7 (2)
Cu1ⁱ—Cu1—O1—C1	−2.30 (15)	Cu1ⁱⁱ—O3—C6—O4	−7.1 (3)
O4ⁱⁱⁱ—Cu1—O5—C7	175.47 (15)	Cu1ⁱⁱ—O3—C6—C5	173.25 (12)
O1—Cu1—O5—C7	84.35 (16)	Cu1^iv—O4—C6—O3	6.2 (3)
O3ⁱⁱ—Cu1—O5—C7	−5.19 (16)	Cu1^iv—O4—C6—C5	−174.09 (12)
O2ⁱ—Cu1—O5—C7	−94.78 (16)	C4—C5—C6—O3	−38.7 (2)
Cu1ⁱ—O2—C1—O1	−2.9 (3)	C4—C5—C6—O4	141.63 (18)
Cu1ⁱ—O2—C1—C2	175.51 (12)	Cu1—O5—C7—N1	−171.07 (16)
Cu1—O1—C1—O2	3.8 (3)	C8—N1—C7—O5	1.7 (3)
Cu1—O1—C1—C2	−174.68 (12)	C9—N1—C7—O5	176.2 (2)
O2—C1—C2—C3	6.4 (3)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₆H₈O₄)₂(C₃H₇NO)₂]
M_r	561.52
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	9.4764 (5), 8.2618 (5), 15.0990 (8)
β (°)	106.259 (1)
V (Å³)	1134.85 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.93
Crystal size (mm)	0.45 × 0.40 × 0.15

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.477, 0.761
No. of measured, independent and observed [I > 2σ(I)] reflections	5917, 2428, 2153
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.072, 1.03
No. of reflections	2428
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.23

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Cu1—O1	1.9683 (14)	Cu1—O4ⁱⁱⁱ	1.9584 (14)
Cu1—O2ⁱ	1.9716 (14)	Cu1—O5	2.1646 (15)
Cu1—O3ⁱⁱ	1.9695 (13)

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

Acknowledgements

We thank Hunan Medical Technical Secondary School and the University of Malaya for supporting this study.

References

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