metal-organic compounds
Dimethylammonium diaqua(pyridine-2,4-dicarboxylato-κ2N,O2)cuprate(II)
aCollege of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, People's Republic of China, bCollege of Information Technology and Engineering, Yanshan University, Qinhuangdao 066004, People's Republic of China, and cState Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, People's Republic of China
*Correspondence e-mail: JDWangYsu@gmail.com
The 2H8N)2[Cu(C7H3NO4)2(H2O)2], contains one-half of a mononuclear [Cu(C7H3NO4)2(H2O)2]2− anion, one dimethylammonium cation and one aqua ligand. The CuII atom, lying on an inversion center, is coordinated by two symmetry-related N atoms and two O atoms from one pyridine-2,4-dicarboxylate ligand and two symmetry-related aqua ligands and exhibits a distorted octahedral trans-[CuN2O4] coordination geometry. Multiple crystallographically independent O—H⋯O and N—H⋯O hydrogen bonds form a three-dimensional network in the crystal structure.
of the title compound, (CRelated literature
For the structural diversity and potential applications of coordination polymers constructed from metal ions and bridging ligands, see: Eddaoudi et al. (2001); Kitagawa et al. (2004). For general background to metal complexes of pyridine-2,4-dicarboxylates, see: Mahata & Natarajan (2005); Bai et al. (2008); Chen & Beatty (2008). For similar structures, see: Zou et al. (2008); Noro et al. (2005). For comparative bond lengths and angles, see: Chutia et al. (2009); Klein et al. (1982).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2007); cell 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.
Supporting information
https://doi.org/10.1107/S1600536810002497/bx2257sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810002497/bx2257Isup2.hkl
A solution of Cu(NO3)2.3H2O (0.024 g, 0.1 mmol) in H2O (3 ml) was added to a suspending solution of 2,4-pydc (0.017 g, 0.1 mmol) in H2O and DMF(1:1, 7 ml). The mixture was stirred for 30 minutes and sealed in a 15 ml Teflon-lined stainless steel autoclave and heated at 423 K for 3 d under autogenous pressure. When cooled to room temperature, green block crystals of the title compound were obtained (yield 0.045 g, 86% based on Cu).
H atoms of the pyridine ring were positioned geometrically and refined as riding atoms, with C—H = 0.93-0.96 Å and with Uiso(H) = 1.2Ueq(C) or 1.5 Ueq(C) for CH3 group. H atoms of water molecule were located in a difference Fourier map and refined as riding, with Uiso(H) = 1.2Ueq(O).
Coordination polymers constructed from metal ions and bridging ligands have been of great interest due to their structural diversity and many potential applications (Eddaoudi et al., 2001; Kitagawa et al., 2004). Pyridinedicarboxylates(pydc) have been extensively studied as excellent bridging ligands in the area of metal-organic frameworks (Mahata et al., 2005; Bai et al. 2008; Chen et al. 2008). Herein we report the
of the title compound [Cu(2,4-pydc)2(H2O)2][NH2(CH3)2]2, (2,4-pydc= pyridine-2,4-dicarboxylate) .The CuII atom, lying on an inversion center, is coordinated by two symmetry-related N atoms and two O atoms from one pyridine-2,4-dicarboxylate ligand and two symmetry-related aqua ligands and exhibits a distorted octahedral trans-[ CuN2O4] coordination geometry (Table 1 and Fig. 1). The bond lengths and angles are all in normal ranges (Chutia et al., 2009; Klein et al., 1982). Multiple crystallographically independent hydrogen bonds form a three-dimensional network in the Table 2.For the structural diversity and potential applications of coordination polymers constructed from metal ions and bridging ligands, see: Eddaoudi et al. (2001); Kitagawa et al. (2004). For general background to metal complexes of pyridine-2,4-dicarboxylates, see: Mahata & Natarajan (2005); Bai et al. (2008); Chen et al. (2008). For similar structures, see: Zou et al. (2008); Noro et al. (2005). For comparative bond lengths and angles, see: Chutia et al. (2009); Klein et al. (1982).
Data collection: SMART (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008).Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) -x, 1 - y, 2 - z.] |
(C2H8N)2[Cu(C7H3NO4)2(H2O)2] | F(000) = 542 |
Mr = 521.98 | Dx = 1.579 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3343 reflections |
a = 7.9854 (7) Å | θ = 2.6–26.0° |
b = 9.4648 (8) Å | µ = 1.06 mm−1 |
c = 14.9380 (12) Å | T = 293 K |
β = 103.540 (1)° | Block, green |
V = 1097.64 (16) Å3 | 0.31 × 0.16 × 0.16 mm |
Z = 2 |
Bruker SMART APEX CCD diffractometer | 2160 independent reflections |
Radiation source: sealed tube | 1992 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
φ and ω scans | θmax = 26.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.732, Tmax = 0.849 | k = −7→11 |
5508 measured reflections | l = −12→18 |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0456P)2 + 0.427P] where P = (Fo2 + 2Fc2)/3 |
2160 reflections | (Δ/σ)max = 0.001 |
159 parameters | Δρmax = 0.35 e Å−3 |
2 restraints | Δρmin = −0.26 e Å−3 |
(C2H8N)2[Cu(C7H3NO4)2(H2O)2] | V = 1097.64 (16) Å3 |
Mr = 521.98 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.9854 (7) Å | µ = 1.06 mm−1 |
b = 9.4648 (8) Å | T = 293 K |
c = 14.9380 (12) Å | 0.31 × 0.16 × 0.16 mm |
β = 103.540 (1)° |
Bruker SMART APEX CCD diffractometer | 2160 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1992 reflections with I > 2σ(I) |
Tmin = 0.732, Tmax = 0.849 | Rint = 0.016 |
5508 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 2 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.35 e Å−3 |
2160 reflections | Δρmin = −0.26 e Å−3 |
159 parameters |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.0000 | 0.5000 | 1.0000 | 0.02668 (12) | |
N1 | 0.15726 (18) | 0.55054 (15) | 0.92027 (9) | 0.0235 (3) | |
N2 | 0.7815 (2) | 0.47684 (16) | 0.59707 (11) | 0.0302 (3) | |
H2A | 0.6957 | 0.4670 | 0.6264 | 0.036* | |
H2B | 0.8078 | 0.3904 | 0.5793 | 0.036* | |
O1 | 0.15272 (15) | 0.33417 (12) | 1.02961 (8) | 0.0291 (3) | |
O2 | 0.38987 (16) | 0.24074 (13) | 0.99920 (9) | 0.0337 (3) | |
O3 | 0.57116 (18) | 0.46822 (17) | 0.72146 (10) | 0.0393 (3) | |
O4 | 0.4794 (2) | 0.68865 (19) | 0.68723 (12) | 0.0618 (5) | |
O1W | 0.18306 (19) | 0.62993 (16) | 1.12457 (10) | 0.0400 (3) | |
H1WA | 0.126 (3) | 0.687 (2) | 1.1473 (16) | 0.048* | |
H1WB | 0.250 (2) | 0.594 (2) | 1.1680 (12) | 0.048* | |
C1 | 0.2761 (2) | 0.33162 (18) | 0.98819 (11) | 0.0253 (3) | |
C2 | 0.2792 (2) | 0.45160 (18) | 0.92182 (11) | 0.0223 (3) | |
C3 | 0.3928 (2) | 0.45788 (18) | 0.86496 (11) | 0.0234 (3) | |
H3 | 0.4755 | 0.3880 | 0.8674 | 0.028* | |
C4 | 0.3812 (2) | 0.57093 (18) | 0.80377 (11) | 0.0249 (3) | |
C5 | 0.2608 (2) | 0.67552 (18) | 0.80637 (11) | 0.0277 (4) | |
H5 | 0.2545 | 0.7549 | 0.7690 | 0.033* | |
C6 | 0.1501 (2) | 0.66179 (18) | 0.86455 (11) | 0.0269 (4) | |
H6 | 0.0686 | 0.7319 | 0.8649 | 0.032* | |
C7 | 0.4887 (2) | 0.5772 (2) | 0.73205 (12) | 0.0337 (4) | |
C8 | 0.9339 (3) | 0.5361 (3) | 0.66186 (15) | 0.0414 (5) | |
H8A | 1.0242 | 0.5513 | 0.6303 | 0.062* | |
H8B | 0.9728 | 0.4712 | 0.7118 | 0.062* | |
H8C | 0.9037 | 0.6244 | 0.6856 | 0.062* | |
C9 | 0.7204 (3) | 0.5659 (2) | 0.51421 (13) | 0.0409 (5) | |
H9A | 0.6653 | 0.6490 | 0.5306 | 0.061* | |
H9B | 0.6396 | 0.5134 | 0.4686 | 0.061* | |
H9C | 0.8166 | 0.5931 | 0.4898 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.03408 (19) | 0.02407 (18) | 0.02744 (19) | 0.00826 (11) | 0.01843 (13) | 0.00608 (11) |
N1 | 0.0288 (7) | 0.0230 (7) | 0.0207 (6) | 0.0025 (6) | 0.0095 (5) | 0.0003 (6) |
N2 | 0.0352 (8) | 0.0289 (8) | 0.0295 (8) | −0.0024 (6) | 0.0136 (7) | −0.0061 (6) |
O1 | 0.0363 (7) | 0.0269 (6) | 0.0297 (6) | 0.0071 (5) | 0.0190 (5) | 0.0078 (5) |
O2 | 0.0357 (7) | 0.0289 (7) | 0.0411 (7) | 0.0097 (5) | 0.0183 (6) | 0.0119 (6) |
O3 | 0.0368 (7) | 0.0531 (8) | 0.0329 (7) | 0.0035 (6) | 0.0183 (6) | 0.0039 (6) |
O4 | 0.0617 (10) | 0.0642 (11) | 0.0720 (11) | 0.0089 (8) | 0.0411 (9) | 0.0378 (9) |
O1W | 0.0444 (8) | 0.0413 (8) | 0.0345 (7) | 0.0109 (6) | 0.0095 (6) | −0.0020 (6) |
C1 | 0.0304 (8) | 0.0230 (8) | 0.0242 (8) | 0.0016 (7) | 0.0097 (7) | 0.0016 (6) |
C2 | 0.0258 (8) | 0.0208 (8) | 0.0209 (7) | −0.0009 (6) | 0.0070 (6) | −0.0010 (6) |
C3 | 0.0236 (8) | 0.0235 (8) | 0.0240 (8) | 0.0001 (6) | 0.0074 (6) | −0.0001 (7) |
C4 | 0.0245 (8) | 0.0276 (9) | 0.0228 (8) | −0.0058 (6) | 0.0062 (6) | 0.0009 (7) |
C5 | 0.0333 (9) | 0.0245 (9) | 0.0250 (8) | −0.0027 (7) | 0.0063 (7) | 0.0059 (7) |
C6 | 0.0320 (8) | 0.0231 (8) | 0.0260 (8) | 0.0043 (7) | 0.0079 (7) | 0.0026 (7) |
C7 | 0.0277 (9) | 0.0459 (12) | 0.0287 (9) | −0.0047 (8) | 0.0090 (7) | 0.0085 (8) |
C8 | 0.0349 (10) | 0.0507 (12) | 0.0376 (11) | −0.0059 (9) | 0.0066 (8) | −0.0036 (10) |
C9 | 0.0472 (11) | 0.0445 (12) | 0.0319 (10) | 0.0041 (9) | 0.0110 (8) | 0.0005 (9) |
Cu1—O1 | 1.9733 (11) | O1W—H1WB | 0.815 (10) |
Cu1—O1i | 1.9733 (11) | C1—C2 | 1.512 (2) |
Cu1—N1i | 1.9810 (14) | C2—C3 | 1.381 (2) |
Cu1—N1 | 1.9810 (14) | C3—C4 | 1.396 (2) |
Cu1—O1Wi | 2.4162 (15) | C3—H3 | 0.9300 |
Cu1—O1W | 2.4162 (15) | C4—C5 | 1.387 (2) |
N1—C6 | 1.335 (2) | C4—C7 | 1.523 (2) |
N1—C2 | 1.347 (2) | C5—C6 | 1.383 (2) |
N2—C8 | 1.477 (3) | C5—H5 | 0.9300 |
N2—C9 | 1.483 (3) | C6—H6 | 0.9300 |
N2—H2A | 0.9000 | C8—H8A | 0.9600 |
N2—H2B | 0.9000 | C8—H8B | 0.9600 |
O1—C1 | 1.281 (2) | C8—H8C | 0.9600 |
O2—C1 | 1.234 (2) | C9—H9A | 0.9600 |
O3—C7 | 1.253 (2) | C9—H9B | 0.9600 |
O4—C7 | 1.242 (2) | C9—H9C | 0.9600 |
O1W—H1WA | 0.832 (10) | ||
O1—Cu1—O1i | 179.998 (1) | N1—C2—C3 | 122.38 (15) |
O1—Cu1—N1i | 96.81 (5) | N1—C2—C1 | 114.25 (14) |
O1i—Cu1—N1i | 83.18 (5) | C3—C2—C1 | 123.33 (15) |
O1—Cu1—N1 | 83.19 (5) | C2—C3—C4 | 118.89 (16) |
O1i—Cu1—N1 | 96.81 (5) | C2—C3—H3 | 120.6 |
N1i—Cu1—N1 | 180.00 (5) | C4—C3—H3 | 120.6 |
O1—Cu1—O1Wi | 89.92 (5) | C5—C4—C3 | 117.97 (15) |
O1i—Cu1—O1Wi | 90.08 (5) | C5—C4—C7 | 120.04 (15) |
N1i—Cu1—O1Wi | 89.18 (5) | C3—C4—C7 | 121.90 (16) |
N1—Cu1—O1Wi | 90.82 (5) | C6—C5—C4 | 119.98 (15) |
O1—Cu1—O1W | 90.08 (5) | C6—C5—H5 | 120.0 |
O1i—Cu1—O1W | 89.91 (5) | C4—C5—H5 | 120.0 |
N1i—Cu1—O1W | 90.82 (5) | N1—C6—C5 | 121.69 (15) |
N1—Cu1—O1W | 89.18 (5) | N1—C6—H6 | 119.2 |
O1Wi—Cu1—O1W | 180.00 (5) | C5—C6—H6 | 119.2 |
C6—N1—C2 | 118.96 (14) | O4—C7—O3 | 126.71 (18) |
C6—N1—Cu1 | 128.65 (12) | O4—C7—C4 | 116.09 (18) |
C2—N1—Cu1 | 112.29 (11) | O3—C7—C4 | 117.13 (16) |
C8—N2—C9 | 113.01 (16) | N2—C8—H8A | 109.5 |
C8—N2—H2A | 109.0 | N2—C8—H8B | 109.5 |
C9—N2—H2A | 109.0 | H8A—C8—H8B | 109.5 |
C8—N2—H2B | 109.0 | N2—C8—H8C | 109.5 |
C9—N2—H2B | 109.0 | H8A—C8—H8C | 109.5 |
H2A—N2—H2B | 107.8 | H8B—C8—H8C | 109.5 |
C1—O1—Cu1 | 114.32 (10) | N2—C9—H9A | 109.5 |
Cu1—O1W—H1WA | 110.7 (17) | N2—C9—H9B | 109.5 |
Cu1—O1W—H1WB | 124.4 (18) | H9A—C9—H9B | 109.5 |
H1WA—O1W—H1WB | 106 (2) | N2—C9—H9C | 109.5 |
O2—C1—O1 | 125.07 (15) | H9A—C9—H9C | 109.5 |
O2—C1—C2 | 119.13 (14) | H9B—C9—H9C | 109.5 |
O1—C1—C2 | 115.80 (14) |
Symmetry code: (i) −x, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4ii | 0.83 (2) | 1.85 (2) | 2.680 (2) | 174 |
O1W—H1Wb···O3iii | 0.81 (2) | 2.00 (2) | 2.809 (2) | 172 |
N2—H2A···O3 | 0.90 | 1.92 | 2.783 (2) | 161 |
N2—H2B···O2iv | 0.90 | 1.94 | 2.778 (2) | 154 |
Symmetry codes: (ii) x−1/2, −y+3/2, z+1/2; (iii) −x+1, −y+1, −z+2; (iv) x+1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | (C2H8N)2[Cu(C7H3NO4)2(H2O)2] |
Mr | 521.98 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.9854 (7), 9.4648 (8), 14.9380 (12) |
β (°) | 103.540 (1) |
V (Å3) | 1097.64 (16) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.06 |
Crystal size (mm) | 0.31 × 0.16 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.732, 0.849 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5508, 2160, 1992 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.079, 1.06 |
No. of reflections | 2160 |
No. of parameters | 159 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.35, −0.26 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4i | 0.83 (2) | 1.85 (2) | 2.680 (2) | 174 |
O1W—H1Wb···O3ii | 0.812 (18) | 2.002 (17) | 2.809 (2) | 172 |
N2—H2A···O3 | 0.90 | 1.92 | 2.783 (2) | 161 |
N2—H2B···O2iii | 0.90 | 1.94 | 2.778 (2) | 154 |
Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+2; (iii) x+1/2, −y+1/2, z−1/2. |
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Coordination polymers constructed from metal ions and bridging ligands have been of great interest due to their structural diversity and many potential applications (Eddaoudi et al., 2001; Kitagawa et al., 2004). Pyridinedicarboxylates(pydc) have been extensively studied as excellent bridging ligands in the area of metal-organic frameworks (Mahata et al., 2005; Bai et al. 2008; Chen et al. 2008). Herein we report the crystal structure of the title compound [Cu(2,4-pydc)2(H2O)2][NH2(CH3)2]2, (2,4-pydc= pyridine-2,4-dicarboxylate) .The CuII atom, lying on an inversion center, is coordinated by two symmetry-related N atoms and two O atoms from one pyridine-2,4-dicarboxylate ligand and two symmetry-related aqua ligands and exhibits a distorted octahedral trans-[ CuN2O4] coordination geometry (Table 1 and Fig. 1). The bond lengths and angles are all in normal ranges (Chutia et al., 2009; Klein et al., 1982). Multiple crystallographically independent hydrogen bonds form a three-dimensional network in the crystal structure, Table 2.