The title compound, [Cu(HCOO)(μ-HCOO)
2/2(2,2′-bpy)]·HCOOH (2,2′-bpy is 2,2′-bipyridine, C
10H
8N
2), consists of formic acid molecules and [Cu(2,2′-bpy)(HCOO)(μ-HCOO)
2/2]
n polymeric chains; the chains have square-pyramidal Cu atoms bridged by formate anions. The polymeric chains are further extended into three-dimensional networks
via interchain π–π interactions as well as C—H
O and O—H
O hydrogen bonds.
Supporting information
CCDC reference: 628006
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C)= 0.003 Å
- R factor = 0.030
- wR factor = 0.071
- Data-to-parameter ratio = 16.2
checkCIF/PLATON results
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Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: Crystal Structure (Rigaku/MSC,2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Poly-
catena-[(2,2'-bipyridine-N,
N')(formato)(µ-formato-O,
O')copper(II) formic acid solvate]
top
Crystal data top
[Cu(C10H8N2)(CHO2)2]·CH2O2 | F(000) = 724 |
Mr = 355.79 | Dx = 1.663 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 11352 reflections |
a = 9.6639 (19) Å | θ = 3.0–27.5° |
b = 15.692 (3) Å | µ = 1.57 mm−1 |
c = 10.083 (2) Å | T = 295 K |
β = 111.69 (3)° | Block, blue |
V = 1420.8 (6) Å3 | 0.44 × 0.31 × 0.22 mm |
Z = 4 | |
Data collection top
Rigaku R-AXIS RAPID IP diffractometer | 3244 independent reflections |
Radiation source: fine-focus sealed tube | 2755 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ω scans | θmax = 27.5°, θmin = 3.4° |
Absorption correction: multi-scan (ABSCOR; Higashi,1995) | h = −12→12 |
Tmin = 0.612, Tmax = 0.710 | k = −19→20 |
13687 measured reflections | l = −13→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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | Only H-atom displacement parameters refined |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0302P)2 + 1.0049P] where P = (Fo2 + 2Fc2)/3 |
3244 reflections | (Δ/σ)max = 0.001 |
200 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
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 | Uiso*/Ueq | |
Cu | 0.37524 (3) | 0.160908 (14) | 0.75733 (2) | 0.01294 (8) | |
N1 | 0.27871 (19) | 0.07120 (10) | 0.60987 (17) | 0.0158 (3) | |
N2 | 0.52056 (19) | 0.06652 (10) | 0.83814 (17) | 0.0148 (3) | |
C1 | 0.1556 (2) | 0.08109 (14) | 0.4943 (2) | 0.0220 (4) | |
H1 | 0.0952 | 0.1281 | 0.4890 | 0.026 (2)* | |
C2 | 0.1140 (3) | 0.02389 (15) | 0.3818 (2) | 0.0277 (5) | |
H2 | 0.0268 | 0.0319 | 0.3028 | 0.026 (2)* | |
C3 | 0.2050 (3) | −0.04532 (15) | 0.3896 (2) | 0.0269 (5) | |
H3 | 0.1809 | −0.0838 | 0.3143 | 0.026 (2)* | |
C4 | 0.3319 (2) | −0.05703 (13) | 0.5095 (2) | 0.0204 (4) | |
H4 | 0.3937 | −0.1036 | 0.5165 | 0.026 (2)* | |
C5 | 0.3658 (2) | 0.00228 (12) | 0.6197 (2) | 0.0146 (4) | |
C6 | 0.4986 (2) | −0.00283 (12) | 0.7524 (2) | 0.0155 (4) | |
C7 | 0.5949 (2) | −0.07162 (13) | 0.7898 (2) | 0.0206 (4) | |
H7 | 0.5782 | −0.1189 | 0.7303 | 0.026 (2)* | |
C8 | 0.7164 (3) | −0.06911 (14) | 0.9172 (2) | 0.0239 (5) | |
H8 | 0.7830 | −0.1145 | 0.9439 | 0.026 (2)* | |
C9 | 0.7376 (3) | 0.00160 (14) | 1.0042 (2) | 0.0246 (5) | |
H9 | 0.8179 | 0.0041 | 1.0908 | 0.026 (2)* | |
C10 | 0.6380 (2) | 0.06861 (13) | 0.9608 (2) | 0.0201 (4) | |
H10 | 0.6532 | 0.1165 | 1.0188 | 0.026 (2)* | |
O1 | 0.21318 (17) | 0.24305 (9) | 0.67693 (15) | 0.0188 (3) | |
O2 | 0.08930 (17) | 0.18554 (9) | 0.80244 (15) | 0.0208 (3) | |
C11 | 0.1040 (2) | 0.23887 (13) | 0.7177 (2) | 0.0181 (4) | |
H11 | 0.0287 | 0.2791 | 0.6812 | 0.026 (2)* | |
O3 | 0.48174 (16) | 0.23548 (9) | 0.91633 (14) | 0.0168 (3) | |
O4 | 0.49916 (16) | 0.29672 (9) | 1.12067 (14) | 0.0164 (3) | |
C12 | 0.4297 (2) | 0.25646 (12) | 1.0107 (2) | 0.0149 (4) | |
H12 | 0.3325 | 0.2404 | 0.9958 | 0.026 (2)* | |
O5 | 0.82585 (19) | 0.33536 (10) | 0.77809 (18) | 0.0289 (4) | |
O6 | 0.86199 (17) | 0.20494 (10) | 0.87720 (16) | 0.0243 (3) | |
C13 | 0.7892 (2) | 0.27710 (14) | 0.8358 (2) | 0.0232 (5) | |
H13 | 0.7014 | 0.2837 | 0.8525 | 0.026 (2)* | |
H6A | 0.9516 | 0.2025 | 0.8640 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.01386 (13) | 0.01350 (13) | 0.01163 (12) | 0.00051 (9) | 0.00491 (9) | −0.00048 (9) |
N1 | 0.0142 (8) | 0.0183 (8) | 0.0150 (8) | −0.0020 (6) | 0.0053 (7) | 0.0001 (7) |
N2 | 0.0164 (9) | 0.0147 (8) | 0.0137 (8) | −0.0011 (6) | 0.0061 (7) | 0.0020 (6) |
C1 | 0.0182 (11) | 0.0236 (11) | 0.0208 (10) | −0.0004 (8) | 0.0034 (9) | −0.0008 (9) |
C2 | 0.0206 (12) | 0.0349 (13) | 0.0203 (11) | −0.0049 (9) | −0.0011 (9) | −0.0032 (9) |
C3 | 0.0310 (13) | 0.0291 (12) | 0.0189 (10) | −0.0105 (10) | 0.0074 (9) | −0.0084 (9) |
C4 | 0.0255 (12) | 0.0170 (10) | 0.0211 (10) | −0.0028 (8) | 0.0115 (9) | −0.0031 (8) |
C5 | 0.0154 (10) | 0.0146 (9) | 0.0161 (9) | −0.0019 (7) | 0.0086 (8) | 0.0004 (7) |
C6 | 0.0187 (10) | 0.0148 (9) | 0.0146 (9) | −0.0016 (8) | 0.0081 (8) | 0.0012 (7) |
C7 | 0.0239 (11) | 0.0175 (10) | 0.0222 (10) | 0.0018 (8) | 0.0104 (9) | 0.0005 (8) |
C8 | 0.0240 (12) | 0.0198 (10) | 0.0276 (11) | 0.0040 (9) | 0.0091 (10) | 0.0081 (9) |
C9 | 0.0212 (12) | 0.0269 (11) | 0.0198 (10) | 0.0014 (9) | 0.0005 (9) | 0.0034 (9) |
C10 | 0.0218 (11) | 0.0205 (10) | 0.0150 (9) | −0.0011 (8) | 0.0032 (8) | −0.0002 (8) |
O1 | 0.0195 (8) | 0.0198 (7) | 0.0199 (7) | 0.0050 (6) | 0.0105 (6) | 0.0030 (6) |
O2 | 0.0183 (8) | 0.0245 (7) | 0.0205 (7) | 0.0009 (6) | 0.0084 (6) | 0.0034 (6) |
C11 | 0.0158 (11) | 0.0205 (10) | 0.0158 (9) | 0.0031 (8) | 0.0032 (8) | −0.0029 (8) |
O3 | 0.0191 (8) | 0.0194 (7) | 0.0143 (6) | −0.0017 (6) | 0.0087 (6) | −0.0037 (5) |
O4 | 0.0178 (8) | 0.0185 (7) | 0.0138 (7) | −0.0014 (6) | 0.0068 (6) | −0.0025 (5) |
C12 | 0.0160 (10) | 0.0133 (9) | 0.0158 (9) | 0.0010 (7) | 0.0064 (8) | 0.0022 (7) |
O5 | 0.0255 (9) | 0.0275 (8) | 0.0357 (9) | −0.0005 (7) | 0.0135 (7) | −0.0002 (7) |
O6 | 0.0199 (8) | 0.0289 (8) | 0.0277 (8) | −0.0011 (6) | 0.0132 (7) | 0.0005 (7) |
C13 | 0.0166 (11) | 0.0303 (12) | 0.0216 (10) | −0.0015 (9) | 0.0058 (9) | −0.0098 (9) |
Geometric parameters (Å, º) top
Cu—O1 | 1.958 (2) | C7—C8 | 1.384 (3) |
Cu—O3 | 1.944 (2) | C7—H7 | 0.9300 |
Cu—O4i | 2.235 (2) | C8—C9 | 1.382 (3) |
Cu—N1 | 2.009 (2) | C8—H8 | 0.9300 |
Cu—N2 | 1.996 (2) | C9—C10 | 1.383 (3) |
N1—C1 | 1.332 (3) | C9—H9 | 0.9300 |
N1—C5 | 1.351 (3) | C10—H10 | 0.9300 |
N2—C10 | 1.334 (3) | O1—C11 | 1.268 (3) |
N2—C6 | 1.357 (2) | O2—C11 | 1.241 (2) |
C1—C2 | 1.385 (3) | C11—H11 | 0.9300 |
C1—H1 | 0.9300 | O3—C12 | 1.273 (2) |
C2—C3 | 1.381 (3) | O4—C12 | 1.237 (2) |
C2—H2 | 0.9300 | O4—Cuii | 2.2349 (14) |
C3—C4 | 1.379 (3) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | O5—C13 | 1.205 (3) |
C4—C5 | 1.393 (3) | O6—C13 | 1.317 (3) |
C4—H4 | 0.9300 | O6—H6A | 0.9243 |
C5—C6 | 1.475 (3) | C13—H13 | 0.9300 |
C6—C7 | 1.383 (3) | | |
| | | |
O3—Cu—O1 | 92.51 (7) | C4—C5—C6 | 123.81 (18) |
O3—Cu—N2 | 91.83 (7) | N2—C6—C7 | 121.43 (19) |
O1—Cu—N2 | 172.77 (6) | N2—C6—C5 | 114.38 (17) |
O3—Cu—N1 | 172.51 (6) | C7—C6—C5 | 124.19 (18) |
O1—Cu—N1 | 94.20 (7) | C6—C7—C8 | 119.0 (2) |
N2—Cu—N1 | 81.17 (7) | C6—C7—H7 | 120.5 |
O3—Cu—O4i | 95.07 (6) | C8—C7—H7 | 120.5 |
O1—Cu—O4i | 94.46 (6) | C9—C8—C7 | 119.2 (2) |
N2—Cu—O4i | 90.91 (6) | C9—C8—H8 | 120.4 |
N1—Cu—O4i | 87.72 (6) | C7—C8—H8 | 120.4 |
C1—N1—C5 | 119.24 (17) | C8—C9—C10 | 119.1 (2) |
C1—N1—Cu | 125.89 (14) | C8—C9—H9 | 120.4 |
C5—N1—Cu | 113.59 (13) | C10—C9—H9 | 120.4 |
C10—N2—C6 | 119.29 (18) | N2—C10—C9 | 121.91 (19) |
C10—N2—Cu | 126.09 (14) | N2—C10—H10 | 119.0 |
C6—N2—Cu | 114.49 (13) | C9—C10—H10 | 119.0 |
N1—C1—C2 | 122.4 (2) | C11—O1—Cu | 117.76 (13) |
N1—C1—H1 | 118.8 | O2—C11—O1 | 125.37 (19) |
C2—C1—H1 | 118.8 | O2—C11—H11 | 117.3 |
C3—C2—C1 | 118.5 (2) | O1—C11—H11 | 117.3 |
C3—C2—H2 | 120.7 | C12—O3—Cu | 122.49 (13) |
C1—C2—H2 | 120.7 | C12—O4—Cuii | 117.92 (13) |
C4—C3—C2 | 119.7 (2) | O4—C12—O3 | 124.70 (19) |
C4—C3—H3 | 120.1 | O4—C12—H12 | 117.7 |
C2—C3—H3 | 120.1 | O3—C12—H12 | 117.7 |
C3—C4—C5 | 118.7 (2) | C13—O6—H6A | 114.2 |
C3—C4—H4 | 120.6 | O5—C13—O6 | 126.0 (2) |
C5—C4—H4 | 120.6 | O5—C13—H13 | 117.0 |
N1—C5—C4 | 121.33 (19) | O6—C13—H13 | 117.0 |
N1—C5—C6 | 114.83 (17) | | |
| | | |
N1—C5—C6—C7 | 173.89 (19) | C4—C5—C6—N2 | 172.28 (19) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O2iii | 0.920 | 1.680 | 2.591 (3) | 166 |
C1—H1···O1 | 0.93 | 2.56 | 3.066 (3) | 115 |
C4—H4···O4iv | 0.93 | 2.55 | 3.352 (3) | 145 |
C8—H8···O1iv | 0.93 | 2.55 | 3.245 (3) | 131 |
C10—H10···O3 | 0.93 | 2.46 | 2.973 (3) | 115 |
C12—H12···O2 | 0.93 | 2.58 | 3.371 (3) | 143 |
C12—H12···O1ii | 0.93 | 2.51 | 3.127 (3) | 123 |
C13—H13···O3 | 0.93 | 2.55 | 3.419 (3) | 156 |
Symmetry codes: (ii) x, −y+1/2, z+1/2; (iii) x+1, y, z; (iv) −x+1, y−1/2, −z+3/2. |