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Acta Cryst. (2007). E63, m2234    [ doi:10.1107/S1600536807036677 ]

Bis(2-aminopyridine-[kappa]N1)bis(N,N'-dimethylformamide-[kappa]O)(sulfato-[kappa]2O,O')copper(II)

G.-J. Li, Y. Xing and S.-Y. Song

Abstract top

In the title compound, [Cu(SO4)(C5H6N2)2(C3H7NO)2], the coordination geometry around the CuII atom is distorted octahedral, involving two O atoms from a bidentate sulfate anion, two N atoms from two 2-aminopyridine ligands and two O atoms from two N,N'-dimethylformamide molecules. The Cu and S atoms are located on a crystallographic twofold rotation axis. A one-dimensional chain structure is built via hydrogen bonds.

Comment top

The title compound was obtained as the product of an attempted synthesis of an open-framework compound of copper(II) using 2-aminopyridine as structure-directing agent.

As shown in Fig. 1, the coordination polyhedron around the CuII atom is a distorted octahedron, comprising two O atoms from a bidentate sulfate anion, two N atoms from two 2-aminopyridine molecules and two O atoms from two N,N'-dimethylformamide (DMF) molecules. The bond distances are similar to those in the literature (Hagrman et al., 1998). There is a weak Cu1—O3 interaction of 2.589 (2)Å (Table 1). The molecules are connected by intermolecular hydrogen-bonding interactions (Table 2), resulting in a one-dimentional supramolecular structure (Fig. 2).

Related literature top

The bond distances are similar to those reported in the literature (Hagrman et al., 1998).

Experimental top

Typically, CuSO4.5H2O (0.125 g, 0.5 mmol) was dispersed into DMF (10 ml) with stirring, then 2-aminopyridine (0.285 g, 0.3 mmol) was added to the above reaction mixture with stirring. The mixture with pH value of 5 was transferred into a 18 ml Teflon-lined stainless steel autoclave and heated at 353 K for 3 d. After cooling to room temperature, green block-shaped crystals of the title compound were obtained; they were filtered and washed thoroughly with deionized water and dried at room temperature.

Refinement top

All H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C,N), and Uiso(H) = 1.5Ueq(C) for CH3 groups.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) -x, y, 3/2 - z.]
[Figure 2] Fig. 2. One-dimensional structure built up via hydrogen-bonding interactions in the title compound.
Bis(2-aminopyridine-κN1)bis(N,N'-dimethylformamide-κO)(sulfato- κ2O,O')copper(II) top
Crystal data top
[Cu(SO4)(C5H6N2)2(C3H7NO)2]F(000) = 1028
Mr = 494.03Dx = 1.491 Mg m−3
Monoclinic, C2/cMelting point: not measured K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 11.528 (5) ÅCell parameters from 2666 reflections
b = 18.156 (5) Åθ = 2.1–28.3°
c = 10.828 (5) ŵ = 1.13 mm−1
β = 103.801 (5)°T = 293 K
V = 2200.9 (15) Å3Block, blue
Z = 40.19 × 0.15 × 0.12 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2666 independent reflections
Radiation source: fine-focus sealed tube2222 reflections with I > 2σ(I)
graphiteRint = 0.023
φ and ω scansθmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→10
Tmin = 0.814, Tmax = 0.877k = −23→24
6718 measured reflectionsl = −14→13
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0417P)2 + 0.588P]
where P = (Fo2 + 2Fc2)/3
2666 reflections(Δ/σ)max < 0.001
139 parametersΔρmax = 0.24 e Å−3
0 restraintsΔρmin = −0.28 e Å−3
Crystal data top
[Cu(SO4)(C5H6N2)2(C3H7NO)2]V = 2200.9 (15) Å3
Mr = 494.03Z = 4
Monoclinic, C2/cMo Kα radiation
a = 11.528 (5) ŵ = 1.13 mm−1
b = 18.156 (5) ÅT = 293 K
c = 10.828 (5) Å0.19 × 0.15 × 0.12 mm
β = 103.801 (5)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2666 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2222 reflections with I > 2σ(I)
Tmin = 0.814, Tmax = 0.877Rint = 0.023
6718 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.079Δρmax = 0.24 e Å−3
S = 1.05Δρmin = −0.28 e Å−3
2666 reflectionsAbsolute structure: ?
139 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.23305 (15)0.10448 (9)0.86610 (17)0.0350 (4)
C20.32604 (18)0.05410 (12)0.8644 (2)0.0531 (5)
H20.39570.05500.92890.064*
C30.3138 (2)0.00471 (13)0.7693 (3)0.0659 (7)
H30.3755−0.02780.76700.079*
C40.2086 (2)0.00265 (12)0.6749 (2)0.0636 (6)
H40.1983−0.03160.60930.076*
C50.12116 (19)0.05163 (10)0.68049 (18)0.0461 (4)
H50.05050.04990.61750.055*
C60.1553 (2)0.15450 (15)0.3507 (2)0.0672 (6)
H6A0.13030.14840.26300.101*
H6B0.12400.11690.39120.101*
H6C0.23830.15300.37500.101*
C70.1560 (2)0.29009 (15)0.3324 (2)0.0623 (6)
H7A0.13460.28740.24410.093*
H7B0.23870.29330.36000.093*
H7C0.12130.33160.35920.093*
C80.04146 (17)0.22969 (12)0.46322 (18)0.0437 (4)
H80.01970.27680.48300.052*
N10.13161 (12)0.10318 (7)0.77361 (13)0.0326 (3)
N20.24550 (13)0.15442 (9)0.95966 (16)0.0451 (4)
H2A0.18900.18520.96020.054*
H2B0.31000.15561.01910.054*
N30.11426 (14)0.22427 (10)0.38583 (15)0.0461 (4)
O10.10372 (10)0.26717 (6)0.76849 (12)0.0368 (3)
O20.01014 (11)0.36464 (7)0.86254 (12)0.0442 (3)
O30.00034 (14)0.17725 (8)0.51108 (14)0.0532 (4)
S10.00000.31992 (3)0.75000.02985 (13)
Cu10.00000.177216 (14)0.75000.03053 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0330 (8)0.0314 (8)0.0415 (9)0.0056 (7)0.0110 (7)0.0099 (7)
C20.0419 (10)0.0495 (12)0.0673 (14)0.0179 (9)0.0121 (10)0.0141 (10)
C30.0659 (15)0.0486 (12)0.0899 (18)0.0290 (11)0.0316 (13)0.0091 (12)
C40.0897 (17)0.0407 (11)0.0663 (15)0.0180 (12)0.0302 (14)−0.0085 (10)
C50.0590 (11)0.0357 (9)0.0436 (10)0.0062 (8)0.0124 (9)−0.0049 (8)
C60.0670 (15)0.0732 (16)0.0676 (16)0.0154 (13)0.0286 (13)−0.0051 (12)
C70.0502 (12)0.0835 (17)0.0540 (13)−0.0139 (12)0.0139 (10)0.0161 (12)
C80.0419 (10)0.0525 (11)0.0377 (10)0.0039 (9)0.0117 (8)0.0025 (8)
N10.0354 (7)0.0274 (7)0.0354 (7)0.0047 (5)0.0090 (6)0.0014 (5)
N20.0373 (8)0.0498 (9)0.0421 (8)0.0074 (7)−0.0023 (7)−0.0039 (7)
N30.0438 (9)0.0569 (10)0.0407 (9)0.0010 (8)0.0165 (7)0.0055 (7)
O10.0250 (5)0.0303 (6)0.0537 (8)0.0004 (4)0.0064 (5)−0.0001 (5)
O20.0506 (7)0.0354 (7)0.0422 (7)0.0043 (6)0.0022 (6)−0.0077 (5)
O30.0549 (8)0.0605 (9)0.0497 (8)−0.0010 (7)0.0234 (7)0.0091 (6)
S10.0272 (3)0.0246 (3)0.0349 (3)0.0000.0019 (2)0.000
Cu10.02611 (15)0.02407 (15)0.03997 (18)0.0000.00507 (12)0.000
Geometric parameters (Å, °) top
C1—N21.342 (2)C7—H7B0.9300
C1—N11.346 (2)C7—H7C0.9300
C1—C21.413 (2)C8—O31.232 (2)
C2—C31.347 (3)C8—N31.324 (2)
C2—H20.9300C8—H80.9300
C3—C41.388 (4)N1—Cu11.9972 (14)
C3—H30.9300N2—H2A0.8600
C4—C51.356 (3)N2—H2B0.8600
C4—H40.9300O1—S11.5076 (13)
C5—N11.360 (2)O1—Cu12.0056 (13)
C5—H50.9300O2—S11.4457 (13)
C6—N31.435 (3)O3—Cu12.589 (2)
C6—H6A0.9300S1—O2i1.4457 (13)
C6—H6B0.9300S1—O1i1.5076 (13)
C6—H6C0.9300Cu1—N1i1.9972 (14)
C7—N31.458 (3)Cu1—O1i2.0056 (13)
C7—H7A0.9300Cu1—O3i2.589 (2)
N2—C1—N1119.40 (15)O3i—Cu1—N193.10 (6)
N2—C1—C2120.18 (17)O3i—Cu1—N1i86.89 (6)
N1—C1—C2120.42 (17)O3—Cu1—O187.47 (6)
C3—C2—C1120.0 (2)O3i—Cu1—O192.47 (5)
C3—C2—H2120.0O3—Cu1—O1i92.47 (5)
C1—C2—H2120.0O3—Cu1—O3i179.99 (6)
C2—C3—C4119.6 (2)O3i—Cu1—O1i87.47 (6)
C2—C3—H3120.2N3—C8—H8117.5
C4—C3—H3120.2C1—N1—C5118.11 (15)
C5—C4—C3118.5 (2)C1—N1—Cu1125.59 (11)
C5—C4—H4120.7C5—N1—Cu1115.99 (12)
C3—C4—H4120.7C1—N2—H2A120.0
N1—C5—C4123.3 (2)C1—N2—H2B120.0
N1—C5—H5118.4H2A—N2—H2B120.0
C4—C5—H5118.4C8—N3—C6122.20 (19)
N3—C6—H6A109.5C8—N3—C7120.6 (2)
N3—C6—H6B109.5C6—N3—C7117.20 (19)
H6A—C6—H6B109.5S1—O1—Cu193.96 (6)
N3—C6—H6C109.5O2—S1—O2i111.66 (11)
H6A—C6—H6C109.5O2—S1—O1110.05 (7)
H6B—C6—H6C109.5O2i—S1—O1111.77 (7)
N3—C7—H7A109.5O2—S1—O1i111.77 (7)
N3—C7—H7B109.5O2i—S1—O1i110.05 (7)
H7A—C7—H7B109.5O1—S1—O1i101.11 (10)
N3—C7—H7C109.5N1i—Cu1—N195.40 (8)
H7A—C7—H7C109.5N1i—Cu1—O1167.79 (5)
H7B—C7—H7C109.5N1—Cu1—O196.81 (6)
O3—C8—N3125.1 (2)N1i—Cu1—O1i96.81 (6)
O3—C8—H8117.5N1—Cu1—O1i167.79 (5)
O3—Cu1—N186.89 (6)O1—Cu1—O1i70.97 (7)
O3—Cu1—N1i93.10 (6)
N2—C1—C2—C3−179.1 (2)C5—N1—Cu1—O1i−126.5 (2)
N1—C1—C2—C30.5 (3)C1—N1—Cu1—S147.13 (15)
C1—C2—C3—C4−1.4 (4)C5—N1—Cu1—S1−126.28 (12)
C2—C3—C4—C50.9 (4)S1—O1—Cu1—N1i0.2 (3)
C3—C4—C5—N10.5 (3)S1—O1—Cu1—N1−179.95 (6)
N2—C1—N1—C5−179.56 (16)S1—O1—Cu1—O1i0.0
C2—C1—N1—C50.9 (2)O2—S1—Cu1—N1i91.32 (8)
N2—C1—N1—Cu17.2 (2)O2i—S1—Cu1—N1i−88.68 (8)
C2—C1—N1—Cu1−172.40 (13)O1—S1—Cu1—N1i−179.94 (8)
C4—C5—N1—C1−1.4 (3)O1i—S1—Cu1—N1i0.06 (8)
C4—C5—N1—Cu1172.55 (17)O2—S1—Cu1—N1−88.68 (8)
O3—C8—N3—C6−1.1 (3)O2i—S1—Cu1—N191.32 (8)
O3—C8—N3—C7178.8 (2)O1—S1—Cu1—N10.06 (8)
Cu1—O1—S1—O2118.29 (7)O1i—S1—Cu1—N1−179.94 (8)
Cu1—O1—S1—O2i−117.04 (7)O2—S1—Cu1—O1−88.75 (9)
Cu1—O1—S1—O1i0.0O2i—S1—Cu1—O191.25 (9)
C1—N1—Cu1—N1i−132.87 (15)O1i—S1—Cu1—O1180.0
C5—N1—Cu1—N1i53.72 (12)O2—S1—Cu1—O1i91.25 (9)
C1—N1—Cu1—O147.16 (14)O2i—S1—Cu1—O1i−88.75 (9)
C5—N1—Cu1—O1−126.24 (13)O1—S1—Cu1—O1i180.0
C1—N1—Cu1—O1i47.0 (3)
Symmetry codes: (i) −x, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.862.553.087 (2)121
N2—H2A···O3i0.862.282.955 (2)135
N2—H2B···O2ii0.862.193.029 (2)164
Symmetry codes: (i) −x, y, −z+3/2; (ii) −x+1/2, −y+1/2, −z+2.
Table 1
Selected geometric parameters (Å, °) top
N1—Cu11.9972 (14)O3—Cu12.589 (2)
O1—Cu12.0056 (13)
O3—Cu1—N186.89 (6)N1i—Cu1—N195.40 (8)
O3—Cu1—N1i93.10 (6)N1i—Cu1—O1167.79 (5)
O3—Cu1—O187.47 (6)N1—Cu1—O196.81 (6)
O3—Cu1—O1i92.47 (5)O1—Cu1—O1i70.97 (7)
O3—Cu1—O3i179.99 (6)
Symmetry codes: (i) −x, y, −z+3/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.862.553.087 (2)121
N2—H2A···O3i0.862.282.955 (2)135
N2—H2B···O2ii0.862.193.029 (2)164
Symmetry codes: (i) −x, y, −z+3/2; (ii) −x+1/2, −y+1/2, −z+2.
Acknowledgements top

The authors thank the Analysis and Testing Foundation of Northeast Normal University for financial support.

references
References top

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Hagrman, D., Hammond, R. P., Haushalter, R. & Zubieta, J. (1998). Chem. Mater. 10, 2091–2100.

Sheldrick, G. M. (1990). SHELXTL-Plus. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.