catena-Poly[[[diaqua­copper(II)]-bis­[μ-1,1′-(butane-1,4-di­yl)diimidazole-κ2N3:N3′]] dinitrate]

Wang, X.-F.; Wang, J.-F.; Liu, X.-Y.

doi:10.1107/S1600536808027281

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page m1220

doi:10.1107/S1600536808027281

Open

access

catena-Poly[[[diaquacopper(II)]-bis[μ-1,1′-(butane-1,4-diyl)diimidazole-κ²N³:N^3′]] dinitrate]

Xiao-Feng Wang,^a Jin-Feng Wang ^a and Xiao-Yang Liu ^a ^*

^aState Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China
^*Correspondence e-mail: wangxf103@mail.jlu.edu.cn

(Received 22 July 2008; accepted 25 August 2008; online 30 August 2008)

In the title compound, {[Cu(C₁₀H₁₄N₄)₂(H₂O)₂](NO₃)₂}_n, the Cu^II ion lies on an inversion center and is six-coordinated in an octahedral environment by four N atoms from four different 1,1′-butane-1,4-diyldiimidazole ligands and two O atoms from the two water molecules. Bridging by the ligands results in a ribbon structure. Adjacent ribbons are linked to the nitrate anions via O—H⋯O hydrogen bonds, forming layers. One nitrate O atom is disordered equally over two positions.

Related literature

For background and the synthesis of 1,1′-butane-1,4-diyldiimidazole, see: Ma et al. (2003 ). For the crystal structure of a metal adduct, see: Che et al. (2006 ).

Experimental

Crystal data

[Cu(C₁₀H₁₄N₄)₂(H₂O)₂](NO₃)₂
M_r = 604.10
Monoclinic, C 2/c
a = 22.161 (11) Å
b = 10.334 (4) Å
c = 14.366 (7) Å
β = 126.375 (18)°
V = 2649 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 291 (2) K
0.48 × 0.36 × 0.25 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.673, T_max = 0.808
12704 measured reflections
3023 independent reflections
2753 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.113
S = 1.07
3023 reflections
188 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H11⋯O4ⁱ	0.85	1.96	2.801 (4)	170
O5—H12⋯O3ⁱⁱ	0.85	2.10	2.888 (8)	153
Symmetry codes: (i) $[-x+1, y+1, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808027281/ng2477sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027281/ng2477Isup2.hkl

checkCIF report

Comment top

The 1,1'-butane-1,4-diyldiimidazole can be used as a flexible ligand to construct coordination polymeric compounds (Ma et al., 2003; Che et al., 2006). In this paper, we report the new title compound, (I), synthesized by the reaction of 1,1'-butane-1,4-diyldiimidazole ligands and copper dinitrate in methanol.

The Cu^II atom is located on an inversion centre and is hexacoordinated by four N atoms of four different 1,1'-butane-1,4-diyldiimidazole ligands and two O atoms of two water molecules (Fig. 1). Adjacent Cu(II) ions are linked by pairs of 1,1'-butane-1,4- diyldiimidazole molecules, resulting in a ribbon motif (Fig. 2).

In the crystal structure, uncoordinated nitrate anions link these ribbons into a layer structure via O—H···O hydrogen bonds (Table 1,Figure 3).

Related literature top

For background and the synthesis of 1,1'-butane-1,4-diyldiimidazole, see: Ma et al. (2003). For the crystal structure of metal adduct, see: Che et al. (2006).

Experimental top

1,1'-Butane-1,4-diyldiimidazole was prepared from imidazole and 1,4-dibromobutane in DMSO (Ma et al., 2003). 1,1'-(1,4-Butanediyl)diimidazole (0.380 g, 2 mmol) and copper dinitrate (0.188 g, 2 mmol) were dissolved in hot methanol solution (15 ml) to give a clear solution was obtained. The resulting solution was allowed to stand in a desiccator at room temperature for several days. Blue crystals of (I) were obtained.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level for non-H atoms. Dashed lines indicate the hydrogen-bonding interactions [Symmetry code: (I) -x + 1, y, -z + 3/2; (II) -x + 1/2, -y + 3/2, -z - 1;(III) x + 1/2, -y + 3/2, z + 1/2].
	Fig. 2. A partial packing view, showing the ribbon chain structure.
	Fig. 3. A partial packing view, showing the two-dimensional network. Dashed lines indicate the hydrogen-bonding interactions and H atoms have been omitted.

catena-Poly[[[diaquacopper(II)]-bis[µ-1,1'-(butane-1,4- diyl)diimidazole-κ²N³:N^3']] dinitrate] top

Crystal data top

[Cu(C₁₀H₁₄N₄)₂(H₂O)₂](NO₃)₂	F(000) = 1260
M_r = 604.10	D_x = 1.515 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 11099 reflections
a = 22.161 (11) Å	θ = 3.3–27.5°
b = 10.334 (4) Å	µ = 0.89 mm⁻¹
c = 14.366 (7) Å	T = 291 K
β = 126.375 (18)°	Block, blue
V = 2649 (2) Å³	0.48 × 0.36 × 0.25 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	3023 independent reflections
Radiation source: fine-focus sealed tube	2753 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −28→28
T_min = 0.673, T_max = 0.808	k = −13→12
12704 measured reflections	l = −18→18

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0644P)² + 3.5066P] where P = (F_o² + 2F_c²)/3
3023 reflections	(Δ/σ)_max = 0.001
188 parameters	Δρ_max = 0.82 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[Cu(C₁₀H₁₄N₄)₂(H₂O)₂](NO₃)₂	V = 2649 (2) Å³
M_r = 604.10	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 22.161 (11) Å	µ = 0.89 mm⁻¹
b = 10.334 (4) Å	T = 291 K
c = 14.366 (7) Å	0.48 × 0.36 × 0.25 mm
β = 126.375 (18)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3023 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2753 reflections with I > 2σ(I)
T_min = 0.673, T_max = 0.808	R_int = 0.024
12704 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.07	Δρ_max = 0.82 e Å⁻³
3023 reflections	Δρ_min = −0.55 e Å⁻³
188 parameters

Special details top

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)
C1	0.43494 (12)	0.5667 (2)	0.87357 (19)	0.0360 (4)
H1	0.4387	0.4802	0.8600	0.043*
C2	0.40800 (13)	0.6108 (2)	0.9310 (2)	0.0395 (5)
H2	0.3901	0.5611	0.9638	0.047*
C3	0.44106 (11)	0.7749 (2)	0.87476 (18)	0.0321 (4)
H3	0.4495	0.8593	0.8627	0.038*
C4	0.38590 (14)	0.8327 (3)	0.9787 (2)	0.0460 (6)
H4A	0.4039	0.9190	0.9807	0.055*
H4B	0.4069	0.8078	1.0576	0.055*
C5	0.30100 (14)	0.8355 (3)	0.9086 (2)	0.0514 (7)
H5A	0.2872	0.8926	0.9467	0.062*
H5B	0.2836	0.7493	0.9084	0.062*
C6	0.26042 (14)	0.8803 (3)	0.7830 (2)	0.0473 (6)
H6A	0.2128	0.9186	0.7569	0.057*
H6B	0.2902	0.9470	0.7804	0.057*
C7	0.24623 (12)	0.7730 (2)	0.70083 (18)	0.0394 (5)
H7A	0.2938	0.7405	0.7214	0.047*
H7B	0.2205	0.7023	0.7082	0.047*
C8	0.22282 (12)	0.9038 (3)	0.5330 (2)	0.0427 (5)
H8	0.2696	0.9427	0.5699	0.051*
C9	0.16308 (12)	0.9201 (3)	0.42203 (19)	0.0402 (5)
H9	0.1619	0.9731	0.3687	0.048*
C10	0.12939 (11)	0.7874 (2)	0.49805 (18)	0.0325 (4)
H10	0.1010	0.7315	0.5086	0.039*
Cu1	0.5000	0.66433 (3)	0.7500	0.02769 (13)
N1	0.45588 (9)	0.67011 (16)	0.83845 (14)	0.0293 (4)
N2	0.41221 (9)	0.74259 (19)	0.93120 (14)	0.0328 (4)
N3	0.20075 (10)	0.81828 (18)	0.58036 (16)	0.0342 (4)
N4	0.10424 (9)	0.84658 (17)	0.39970 (15)	0.0317 (4)
N5	0.59796 (14)	0.1501 (2)	0.7259 (3)	0.0516 (6)
O1	0.5000	0.9027 (3)	0.7500	0.0740 (10)
H11	0.4628	0.9523	0.7254	0.111*
O2	0.5825 (2)	0.0978 (4)	0.6366 (3)	0.1229 (13)
O3	0.5894 (5)	0.2662 (7)	0.7011 (8)	0.089 (2)	0.50
O4	0.61485 (19)	0.0723 (3)	0.8025 (3)	0.0997 (10)
O5	0.5000	0.4120 (3)	0.7500	0.0640 (8)
H12	0.4690	0.3573	0.7433	0.082 (13)*
O3'	0.6140 (5)	0.2592 (7)	0.7753 (9)	0.099 (3)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0384 (11)	0.0388 (11)	0.0349 (10)	0.0060 (9)	0.0239 (9)	0.0065 (9)
C2	0.0400 (11)	0.0502 (13)	0.0353 (11)	0.0056 (10)	0.0263 (10)	0.0109 (10)
C3	0.0270 (9)	0.0405 (11)	0.0284 (9)	−0.0014 (8)	0.0162 (8)	−0.0031 (8)
C4	0.0390 (12)	0.0706 (17)	0.0274 (11)	0.0129 (11)	0.0191 (10)	−0.0063 (10)
C5	0.0388 (12)	0.089 (2)	0.0311 (12)	0.0203 (12)	0.0233 (11)	0.0022 (11)
C6	0.0419 (12)	0.0596 (14)	0.0324 (11)	0.0185 (11)	0.0178 (10)	0.0020 (11)
C7	0.0314 (10)	0.0485 (13)	0.0256 (10)	0.0068 (9)	0.0099 (9)	0.0054 (9)
C8	0.0284 (10)	0.0633 (15)	0.0339 (11)	−0.0104 (10)	0.0170 (9)	−0.0013 (10)
C9	0.0313 (10)	0.0588 (14)	0.0309 (10)	−0.0083 (10)	0.0187 (9)	0.0017 (10)
C10	0.0263 (9)	0.0397 (10)	0.0281 (10)	−0.0016 (8)	0.0144 (8)	0.0021 (8)
Cu1	0.02036 (18)	0.0421 (2)	0.02152 (19)	0.000	0.01289 (15)	0.000
N1	0.0239 (8)	0.0408 (9)	0.0241 (8)	0.0015 (6)	0.0147 (7)	−0.0004 (6)
N2	0.0254 (8)	0.0509 (10)	0.0216 (8)	0.0055 (7)	0.0135 (7)	−0.0009 (7)
N3	0.0252 (8)	0.0453 (10)	0.0258 (9)	0.0011 (7)	0.0116 (7)	0.0020 (7)
N4	0.0249 (8)	0.0436 (9)	0.0260 (8)	−0.0019 (7)	0.0147 (7)	0.0002 (7)
N5	0.0477 (12)	0.0460 (12)	0.0739 (17)	0.0010 (9)	0.0430 (13)	0.0065 (11)
O1	0.098 (2)	0.0383 (14)	0.134 (3)	0.000	0.095 (3)	0.000
O2	0.162 (3)	0.137 (3)	0.090 (2)	−0.032 (3)	0.086 (3)	−0.006 (2)
O3	0.112 (6)	0.045 (3)	0.150 (7)	0.023 (4)	0.098 (6)	0.024 (5)
O4	0.109 (2)	0.108 (2)	0.0686 (16)	−0.0290 (19)	0.0449 (16)	0.0012 (16)
O5	0.086 (2)	0.0417 (14)	0.097 (2)	0.000	0.072 (2)	0.000
O3'	0.085 (5)	0.043 (3)	0.158 (8)	0.002 (3)	0.066 (6)	0.001 (5)

Geometric parameters (Å, º) top

C1—C2	1.352 (3)	C8—C9	1.349 (3)
C1—N1	1.374 (3)	C8—N3	1.370 (3)
C1—H1	0.9300	C8—H8	0.9300
C2—N2	1.365 (3)	C9—N4	1.372 (3)
C2—H2	0.9300	C9—H9	0.9300
C3—N1	1.325 (3)	C10—N4	1.322 (3)
C3—N2	1.339 (3)	C10—N3	1.335 (3)
C3—H3	0.9300	C10—H10	0.9300
C4—N2	1.465 (3)	Cu1—N1	2.0120 (18)
C4—C5	1.519 (4)	Cu1—N1ⁱ	2.0120 (18)
C4—H4A	0.9700	Cu1—N4ⁱⁱ	2.020 (2)
C4—H4B	0.9700	Cu1—N4ⁱⁱⁱ	2.020 (2)
C5—C6	1.535 (3)	Cu1—O1	2.463 (3)
C5—H5A	0.9700	Cu1—O5	2.608 (3)
C5—H5B	0.9700	N4—Cu1ⁱⁱ	2.0203 (19)
C6—C7	1.510 (3)	N5—O4	1.228 (4)
C6—H6A	0.9700	N5—O3	1.234 (7)
C6—H6B	0.9700	N5—O2	1.239 (4)
C7—N3	1.470 (3)	O1—H11	0.8500
C7—H7A	0.9700	O5—H12	0.8500
C7—H7B	0.9700

C2—C1—N1	109.2 (2)	C8—C9—H9	125.1
C2—C1—H1	125.4	N4—C9—H9	125.1
N1—C1—H1	125.4	N4—C10—N3	111.30 (19)
C1—C2—N2	106.46 (19)	N4—C10—H10	124.3
C1—C2—H2	126.8	N3—C10—H10	124.3
N2—C2—H2	126.8	N1—Cu1—N1ⁱ	176.60 (10)
N1—C3—N2	110.72 (19)	N1—Cu1—N4ⁱⁱ	89.82 (8)
N1—C3—H3	124.6	N1ⁱ—Cu1—N4ⁱⁱ	90.37 (8)
N2—C3—H3	124.6	N1—Cu1—N4ⁱⁱⁱ	90.37 (8)
N2—C4—C5	112.4 (2)	N1ⁱ—Cu1—N4ⁱⁱⁱ	89.82 (8)
N2—C4—H4A	109.1	N4ⁱⁱ—Cu1—N4ⁱⁱⁱ	173.60 (10)
C5—C4—H4A	109.1	N1—Cu1—O1	88.30 (5)
N2—C4—H4B	109.1	N1ⁱ—Cu1—O1	88.30 (5)
C5—C4—H4B	109.1	N4ⁱⁱ—Cu1—O1	93.20 (5)
H4A—C4—H4B	107.8	N4ⁱⁱⁱ—Cu1—O1	93.20 (5)
C4—C5—C6	114.7 (2)	N1—Cu1—O5	91.70 (5)
C4—C5—H5A	108.6	N1ⁱ—Cu1—O5	91.70 (5)
C6—C5—H5A	108.6	N4ⁱⁱ—Cu1—O5	86.80 (5)
C4—C5—H5B	108.6	N4ⁱⁱⁱ—Cu1—O5	86.80 (5)
C6—C5—H5B	108.6	O1—Cu1—O5	180.000 (1)
H5A—C5—H5B	107.6	C3—N1—C1	105.91 (18)
C7—C6—C5	113.8 (2)	C3—N1—Cu1	126.85 (14)
C7—C6—H6A	108.8	C1—N1—Cu1	127.24 (14)
C5—C6—H6A	108.8	C3—N2—C2	107.66 (18)
C7—C6—H6B	108.8	C3—N2—C4	126.1 (2)
C5—C6—H6B	108.8	C2—N2—C4	126.2 (2)
H6A—C6—H6B	107.7	C10—N3—C8	107.36 (18)
N3—C7—C6	111.5 (2)	C10—N3—C7	126.27 (19)
N3—C7—H7A	109.3	C8—N3—C7	126.33 (19)
C6—C7—H7A	109.3	C10—N4—C9	105.44 (18)
N3—C7—H7B	109.3	C10—N4—Cu1ⁱⁱ	127.10 (15)
C6—C7—H7B	109.3	C9—N4—Cu1ⁱⁱ	127.43 (15)
H7A—C7—H7B	108.0	O4—N5—O3	144.0 (5)
C9—C8—N3	106.16 (19)	O4—N5—O2	113.1 (3)
C9—C8—H8	126.9	O3—N5—O2	103.0 (5)
N3—C8—H8	126.9	Cu1—O1—H11	127.1
C8—C9—N4	109.7 (2)	Cu1—O5—H12	131.6

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O4^iv	0.85	1.96	2.801 (4)	170
O5—H12···O3ⁱ	0.85	2.10	2.888 (8)	153

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₀H₁₄N₄)₂(H₂O)₂](NO₃)₂
M_r	604.10
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	291
a, b, c (Å)	22.161 (11), 10.334 (4), 14.366 (7)
β (°)	126.375 (18)
V (Å³)	2649 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.48 × 0.36 × 0.25

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.673, 0.808
No. of measured, independent and observed [I > 2σ(I)] reflections	12704, 3023, 2753
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.113, 1.07
No. of reflections	3023
No. of parameters	188
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.82, −0.55

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O4ⁱ	0.85	1.96	2.801 (4)	170.0
O5—H12···O3ⁱⁱ	0.85	2.10	2.888 (8)	153.2

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

Acknowledgements

The authors thank Jilin University for supporting this study.

References

Che, G.-B., Liu, H., Liu, C.-B. & Liu, B. (2006). Acta Cryst. E62, m286–m288. Web of Science CSD CrossRef IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Ma, J.-F., Yang, J., Zheng, G.-L. & Liu, J.-F. (2003). Inorg. Chem. 42, 7531–7534. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.