Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807060771/cv2355sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807060771/cv2355Isup2.hkl |
CCDC reference: 672739
CuCl2.2H2O (34 mg, 0.2 mmol), 2,2'-bipyridine (31 mg, 0.2 mmol) and cyanoacetic acid (51 mg, 0.6 mmol) were dissolved in ammonium hydroxide (20%, 10 ml). The solution was filtered and the filtrate was allowed to stand for about 30 days. Black crystals of (I) were isolated in about 20% yield with respect to Cu. The cyano groups and CuI ions in the product come from the in situ decomposition of cyanoacetic acid and the reduction of CuII ions, respectively.
H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).
[Cu2(CN)3(C10H8N2)] | F(000) = 716 |
Mr = 361.32 | Dx = 1.914 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 10053 reflections |
a = 8.3009 (17) Å | θ = 3.1–27.5° |
b = 13.972 (3) Å | µ = 3.39 mm−1 |
c = 10.814 (2) Å | T = 293 K |
β = 90.27 (3)° | Block, black |
V = 1254.2 (4) Å3 | 0.10 × 0.08 × 0.08 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2869 independent reflections |
Radiation source: fine-focus sealed tube | 2458 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ϕ and ω scan | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −10→10 |
Tmin = 0.948, Tmax = 1.000 | k = −17→18 |
12108 measured reflections | l = −13→14 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0283P)2 + 1.8789P] where P = (Fo2 + 2Fc2)/3 |
2869 reflections | (Δ/σ)max = 0.001 |
181 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.60 e Å−3 |
[Cu2(CN)3(C10H8N2)] | V = 1254.2 (4) Å3 |
Mr = 361.32 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.3009 (17) Å | µ = 3.39 mm−1 |
b = 13.972 (3) Å | T = 293 K |
c = 10.814 (2) Å | 0.10 × 0.08 × 0.08 mm |
β = 90.27 (3)° |
Bruker SMART CCD area-detector diffractometer | 2869 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 2458 reflections with I > 2σ(I) |
Tmin = 0.948, Tmax = 1.000 | Rint = 0.044 |
12108 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.50 e Å−3 |
2869 reflections | Δρmin = −0.60 e Å−3 |
181 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.07091 (5) | 0.42052 (3) | 0.51708 (3) | 0.02646 (11) | |
Cu2 | 0.44880 (5) | 0.61074 (3) | 0.75886 (3) | 0.02377 (11) | |
N1 | 0.3200 (3) | 0.57131 (19) | 0.9116 (2) | 0.0273 (6) | |
N2 | 0.4729 (3) | 0.46640 (18) | 0.7511 (2) | 0.0272 (6) | |
N3 | 0.2456 (4) | 0.59756 (19) | 0.6310 (3) | 0.0322 (6) | |
C12 | 0.2496 (4) | 0.3838 (2) | 0.4065 (3) | 0.0282 (7) | |
C13 | 0.0437 (4) | 0.3177 (2) | 0.6380 (3) | 0.0293 (7) | |
C1 | 0.2443 (4) | 0.6312 (3) | 0.9891 (3) | 0.0356 (8) | |
H1A | 0.2484 | 0.6967 | 0.9738 | 0.043* | |
C2 | 0.1606 (4) | 0.5987 (3) | 1.0907 (3) | 0.0402 (9) | |
H2A | 0.1075 | 0.6415 | 1.1423 | 0.048* | |
C3 | 0.1570 (5) | 0.5032 (3) | 1.1144 (3) | 0.0431 (9) | |
H3A | 0.1024 | 0.4801 | 1.1830 | 0.052* | |
C4 | 0.2352 (5) | 0.4403 (3) | 1.0356 (3) | 0.0401 (8) | |
H4A | 0.2345 | 0.3749 | 1.0511 | 0.048* | |
C5 | 0.3145 (4) | 0.4766 (2) | 0.9334 (3) | 0.0282 (7) | |
C6 | 0.3988 (4) | 0.4166 (2) | 0.8423 (3) | 0.0269 (6) | |
C7 | 0.4030 (5) | 0.3175 (2) | 0.8446 (3) | 0.0374 (8) | |
H7A | 0.3535 | 0.2841 | 0.9083 | 0.045* | |
C8 | 0.4813 (5) | 0.2692 (2) | 0.7519 (4) | 0.0428 (9) | |
H8A | 0.4853 | 0.2027 | 0.7525 | 0.051* | |
C9 | 0.5534 (5) | 0.3196 (3) | 0.6583 (4) | 0.0422 (9) | |
H9A | 0.6056 | 0.2880 | 0.5944 | 0.051* | |
C10 | 0.5469 (5) | 0.4182 (2) | 0.6612 (3) | 0.0382 (8) | |
H10A | 0.5960 | 0.4525 | 0.5980 | 0.046* | |
C11 | 0.1443 (4) | 0.5593 (2) | 0.5813 (3) | 0.0313 (7) | |
N4 | 0.3625 (4) | 0.37243 (19) | 0.3484 (3) | 0.0338 (6) | |
N5 | 0.0438 (4) | 0.2456 (2) | 0.6877 (3) | 0.0350 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0284 (2) | 0.0192 (2) | 0.0318 (2) | 0.00216 (15) | 0.00388 (15) | 0.00332 (14) |
Cu2 | 0.0269 (2) | 0.01838 (19) | 0.02610 (19) | −0.00175 (14) | 0.00628 (14) | −0.00388 (13) |
N1 | 0.0273 (14) | 0.0282 (14) | 0.0262 (13) | −0.0015 (11) | 0.0030 (10) | −0.0018 (10) |
N2 | 0.0318 (15) | 0.0206 (13) | 0.0292 (13) | −0.0009 (11) | 0.0045 (11) | −0.0020 (10) |
N3 | 0.0315 (15) | 0.0267 (14) | 0.0383 (15) | 0.0014 (12) | −0.0078 (12) | −0.0078 (11) |
C12 | 0.0302 (17) | 0.0217 (15) | 0.0329 (16) | −0.0012 (13) | 0.0062 (13) | −0.0025 (12) |
C13 | 0.0328 (18) | 0.0245 (16) | 0.0308 (16) | 0.0033 (13) | 0.0085 (13) | 0.0019 (13) |
C1 | 0.0350 (19) | 0.0338 (19) | 0.0380 (18) | 0.0014 (15) | 0.0076 (14) | −0.0052 (14) |
C2 | 0.0316 (19) | 0.058 (2) | 0.0308 (17) | 0.0021 (17) | 0.0095 (14) | −0.0071 (16) |
C3 | 0.037 (2) | 0.062 (3) | 0.0303 (18) | −0.0030 (18) | 0.0115 (15) | 0.0063 (16) |
C4 | 0.041 (2) | 0.042 (2) | 0.0374 (19) | −0.0071 (16) | 0.0013 (15) | 0.0112 (15) |
C5 | 0.0250 (16) | 0.0316 (17) | 0.0281 (16) | −0.0021 (13) | −0.0007 (12) | −0.0004 (12) |
C6 | 0.0262 (16) | 0.0259 (16) | 0.0286 (15) | −0.0036 (12) | −0.0019 (12) | 0.0006 (12) |
C7 | 0.045 (2) | 0.0251 (18) | 0.0423 (19) | −0.0033 (15) | 0.0011 (16) | 0.0067 (14) |
C8 | 0.055 (2) | 0.0163 (16) | 0.057 (2) | 0.0014 (15) | −0.0017 (18) | −0.0020 (15) |
C9 | 0.051 (2) | 0.0264 (18) | 0.049 (2) | 0.0051 (16) | 0.0104 (17) | −0.0089 (15) |
C10 | 0.048 (2) | 0.0252 (17) | 0.0418 (19) | −0.0012 (15) | 0.0150 (16) | −0.0041 (14) |
C11 | 0.0291 (17) | 0.0346 (18) | 0.0302 (16) | −0.0008 (14) | 0.0058 (13) | −0.0047 (13) |
N4 | 0.0359 (16) | 0.0244 (14) | 0.0411 (16) | −0.0030 (12) | 0.0109 (13) | −0.0021 (11) |
N5 | 0.0423 (17) | 0.0266 (15) | 0.0361 (15) | 0.0041 (12) | 0.0131 (12) | 0.0059 (11) |
Cu1—C11i | 2.094 (4) | C2—C3 | 1.359 (6) |
Cu1—C11 | 2.147 (3) | C2—H2A | 0.9300 |
Cu1—C12 | 1.977 (3) | C3—C4 | 1.387 (5) |
Cu1—C13 | 1.956 (3) | C3—H3A | 0.9300 |
Cu1—Cu1i | 2.5398 (8) | C4—C5 | 1.385 (5) |
Cu2—N1 | 2.047 (3) | C4—H4A | 0.9300 |
Cu2—N2 | 2.028 (3) | C5—C6 | 1.473 (4) |
Cu2—N3 | 2.183 (3) | C6—C7 | 1.385 (5) |
Cu2—N4ii | 1.967 (3) | C7—C8 | 1.375 (5) |
Cu2—N5iii | 1.972 (3) | C7—H7A | 0.9300 |
N1—C1 | 1.343 (4) | C8—C9 | 1.373 (5) |
N1—C5 | 1.344 (4) | C8—H8A | 0.9300 |
N2—C10 | 1.335 (4) | C9—C10 | 1.379 (5) |
N2—C6 | 1.357 (4) | C9—H9A | 0.9300 |
N3—C11 | 1.131 (4) | C10—H10A | 0.9300 |
C12—N4 | 1.143 (4) | C11—Cu1i | 2.094 (4) |
C13—N5 | 1.142 (4) | N4—Cu2ii | 1.967 (3) |
C1—C2 | 1.380 (5) | N5—Cu2iv | 1.972 (3) |
C1—H1A | 0.9300 | ||
C13—Cu1—C12 | 107.62 (13) | C2—C1—H1A | 119.0 |
C13—Cu1—C11i | 109.73 (14) | C3—C2—C1 | 119.0 (3) |
C12—Cu1—C11i | 111.61 (13) | C3—C2—H2A | 120.5 |
C13—Cu1—C11 | 118.70 (13) | C1—C2—H2A | 120.5 |
C12—Cu1—C11 | 102.58 (13) | C2—C3—C4 | 119.7 (3) |
C11i—Cu1—C11 | 106.44 (11) | C2—C3—H3A | 120.2 |
C13—Cu1—Cu1i | 133.18 (10) | C4—C3—H3A | 120.2 |
C12—Cu1—Cu1i | 119.19 (9) | C5—C4—C3 | 118.9 (3) |
C11i—Cu1—Cu1i | 54.18 (9) | C5—C4—H4A | 120.5 |
C11—Cu1—Cu1i | 52.25 (10) | C3—C4—H4A | 120.5 |
N4ii—Cu2—N5iii | 92.00 (11) | N1—C5—C4 | 121.1 (3) |
N4ii—Cu2—N2 | 90.89 (11) | N1—C5—C6 | 115.2 (3) |
N5iii—Cu2—N2 | 163.61 (12) | C4—C5—C6 | 123.6 (3) |
N4ii—Cu2—N1 | 158.12 (12) | N2—C6—C7 | 121.0 (3) |
N5iii—Cu2—N1 | 92.08 (11) | N2—C6—C5 | 114.4 (3) |
N2—Cu2—N1 | 79.50 (10) | C7—C6—C5 | 124.7 (3) |
N4ii—Cu2—N3 | 104.58 (12) | C8—C7—C6 | 119.3 (3) |
N5iii—Cu2—N3 | 106.79 (12) | C8—C7—H7A | 120.3 |
N2—Cu2—N3 | 88.05 (11) | C6—C7—H7A | 120.3 |
N1—Cu2—N3 | 94.78 (11) | C9—C8—C7 | 119.6 (3) |
Cu1i—C11—Cu1 | 73.56 (11) | C9—C8—H8A | 120.2 |
C1—N1—C5 | 119.2 (3) | C7—C8—H8A | 120.2 |
C1—N1—Cu2 | 125.7 (2) | C8—C9—C10 | 118.6 (3) |
C5—N1—Cu2 | 115.1 (2) | C8—C9—H9A | 120.7 |
C10—N2—C6 | 118.9 (3) | C10—C9—H9A | 120.7 |
C10—N2—Cu2 | 125.3 (2) | N2—C10—C9 | 122.6 (3) |
C6—N2—Cu2 | 115.8 (2) | N2—C10—H10A | 118.7 |
C11—N3—Cu2 | 155.8 (3) | C9—C10—H10A | 118.7 |
N4—C12—Cu1 | 171.4 (3) | N3—C11—Cu1i | 144.0 (3) |
N5—C13—Cu1 | 164.3 (3) | N3—C11—Cu1 | 142.2 (3) |
N1—C1—C2 | 122.0 (3) | C12—N4—Cu2ii | 164.9 (3) |
N1—C1—H1A | 119.0 | C13—N5—Cu2iv | 168.8 (3) |
N4ii—Cu2—N1—C1 | 115.0 (4) | Cu2—N1—C5—C4 | 178.2 (3) |
N5iii—Cu2—N1—C1 | 14.4 (3) | C1—N1—C5—C6 | 179.1 (3) |
N2—Cu2—N1—C1 | −179.7 (3) | Cu2—N1—C5—C6 | −1.4 (4) |
N3—Cu2—N1—C1 | −92.6 (3) | C3—C4—C5—N1 | 1.7 (5) |
N4ii—Cu2—N1—C5 | −64.5 (4) | C3—C4—C5—C6 | −178.8 (3) |
N5iii—Cu2—N1—C5 | −165.1 (2) | C10—N2—C6—C7 | 1.7 (5) |
N2—Cu2—N1—C5 | 0.7 (2) | Cu2—N2—C6—C7 | 178.2 (3) |
N3—Cu2—N1—C5 | 87.8 (2) | C10—N2—C6—C5 | −177.3 (3) |
N4ii—Cu2—N2—C10 | −23.5 (3) | Cu2—N2—C6—C5 | −0.8 (3) |
N5iii—Cu2—N2—C10 | −123.7 (4) | N1—C5—C6—N2 | 1.4 (4) |
N1—Cu2—N2—C10 | 176.3 (3) | C4—C5—C6—N2 | −178.1 (3) |
N3—Cu2—N2—C10 | 81.0 (3) | N1—C5—C6—C7 | −177.5 (3) |
N4ii—Cu2—N2—C6 | 160.3 (2) | C4—C5—C6—C7 | 3.0 (5) |
N5iii—Cu2—N2—C6 | 60.2 (5) | N2—C6—C7—C8 | −1.1 (5) |
N1—Cu2—N2—C6 | 0.1 (2) | C5—C6—C7—C8 | 177.8 (3) |
N3—Cu2—N2—C6 | −95.1 (2) | C6—C7—C8—C9 | −0.2 (6) |
N4ii—Cu2—N3—C11 | 110.5 (7) | C7—C8—C9—C10 | 0.8 (6) |
N5iii—Cu2—N3—C11 | −152.8 (7) | C6—N2—C10—C9 | −1.1 (6) |
N2—Cu2—N3—C11 | 20.1 (7) | Cu2—N2—C10—C9 | −177.1 (3) |
N1—Cu2—N3—C11 | −59.2 (7) | C8—C9—C10—N2 | −0.2 (6) |
C12—Cu1—C13—N5 | −24.5 (12) | Cu2—N3—C11—Cu1i | 160.3 (4) |
C11i—Cu1—C13—N5 | 97.1 (12) | Cu2—N3—C11—Cu1 | −28.0 (10) |
C11—Cu1—C13—N5 | −140.2 (12) | C13—Cu1—C11—N3 | 60.8 (5) |
Cu1i—Cu1—C13—N5 | 156.1 (11) | C12—Cu1—C11—N3 | −57.6 (5) |
C5—N1—C1—C2 | −0.1 (5) | C11i—Cu1—C11—N3 | −175.0 (5) |
Cu2—N1—C1—C2 | −179.6 (3) | Cu1i—Cu1—C11—N3 | −175.0 (5) |
N1—C1—C2—C3 | 1.2 (6) | C13—Cu1—C11—Cu1i | −124.25 (13) |
C1—C2—C3—C4 | −0.8 (6) | C12—Cu1—C11—Cu1i | 117.34 (12) |
C2—C3—C4—C5 | −0.6 (6) | C11i—Cu1—C11—Cu1i | 0.0 |
C1—N1—C5—C4 | −1.4 (5) | Cu1—C13—N5—Cu2iv | −16 (3) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x+1/2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(CN)3(C10H8N2)] |
Mr | 361.32 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.3009 (17), 13.972 (3), 10.814 (2) |
β (°) | 90.27 (3) |
V (Å3) | 1254.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.39 |
Crystal size (mm) | 0.10 × 0.08 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.948, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12108, 2869, 2458 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.081, 1.09 |
No. of reflections | 2869 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.60 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).
The crystal structures of some cyano-bridged CuI or CuII complexes with 2,2'-bipyridyl as co-ligand have been reported, such as catena-[(µ2-cyano)-bis(2,2'-bipyridyl)-copper(I)] hexakis[(µ2-cyano)-penta-copper(I)] (Chesnut & Zubieta, 1998); catena-[(µ2-cyano)-(2,2'-bipyridyl)-copper(I)] (He et al., 2005, Mao et al., 2005) and catena-[(µ2-cyano)-bis(2,2'-bipyridyl)-cyano-copper(II)] (Yan et al., 2006). In such complexes, one type of Cu ion either CuI or CuII appeared, and the cyano groups adopted only µ2 bridging mode. Herein, we report a new three-dimensional polymeric Cu complex, C13H8Cu2N5 (I), in which there exist both CuI and CuII ions, and µ3- and µ2- coordination cyano groups.
As shown in Fig. 1, the CuI ion [Cu1] is coordinated to four C atoms from two µ3- and two µ2-cyano groups, respectively, in a tetrahedral environment. The CuII ion [Cu2] coordinates with two N atoms of one 2,2'-bipyridyl ligand, one µ3- and two µ2-cyano N atoms in a square-pyramidal geometry. In the structure, each two CuI atoms [Cu1 and Cu1A] are bridged by two µ2-C atoms of µ3- cyano groups to form a dinuclear unit with a Cu—Cu distance of 2.5398 (8) Å. Each such dinuclear unit is further linked to six CuII ions by four µ2- and two µ3-cyano groups, to give a 4,6-connected framework, with the CuI—CuII separations of 4.864 (4) Å for Cu1—Cu2, 4.963 (4) Å for Cu1B—Cu2, 5.010 (4) Å for Cu1C—Cu2 and 5.252 (4) Å for Cu1A—Cu2, corresponding to Fig. 1.