Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026876/cv2256sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026876/cv2256Isup2.hkl |
CCDC reference: 654714
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.010 Å
- R factor = 0.069
- wR factor = 0.168
- Data-to-parameter ratio = 12.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl1 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 10
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (1) 1.29 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 12
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For the crystal structure of the orthorhombic polymorph, see: Potočňák et al. (2002). For the crystal structures of related complexes, see: Huang, Hu et al. (2003); Huang, Sun et al. (2003); Wang et al. (2007); Potočňák et al. (2001); Burcak et al. (2004).
For related literature, see: Addison et al. (1984); Garribba et al. (2000).
The title compound (I) was obtained by refluxing an ethanol solution of equal molar ratio of [bis(2,2'-bipyridine-κ2N,N1)(percholate-κO) copper(II) percholate (0.575 g, 1.0 mmol) (Garribba et al., 2000) and Na[N(CN)2] (0.089 g, 1.0 mmol) for 1 h. The blue mixture was cooled to room temperature, and blue single-crystal sample of (I) suitable for X-ray diffraction measurement was grown in one week by slow evaporation in air at room temperature. Anal. Calcd. for C22H16ClCuN7O4: C, 48.81; H, 2.98; N, 18.11%. Found: C, 48.74; H, 3.04; N, 18.19%. Main FT–IR (KBr plates, cm-1): 2279 (m), 2219 (m), 2173 (versus), 2133 (s), 1608 (m), 1602 (m), 1595 (m), 1473 (m), 1444 (s), 1154 (m), 1108 (s), 1084 (versus), 774 (s), 766 (m) and 622 (m).
All H-atoms were placed in geometrically idealized positions (C—H = 0.93 Å) and refined as riding, with Uiso(H) = 1.2eq(C).
Bis(2,2'-bipyridine-κ2N,N1)copper(II) species is a very useful building block for constructuring coordination complexes and supramolecular frameworks. We have described several bis(2,2'-bipyridine-κ2N,N1)copper(II) based complexes in our early studies (Huang, Hu et al., 2003; Huang, Sun et al., 2003; Wang et al., 2007). The crystal structures of bis(2,2'-bipyridine-κ2N,N1)(dicyanamido-κN')χopper(II) divalent cation countered by one monodentate dicyanamide anion and another uncoordinated perchlorate, tetrafluoroborate and trifluoromethanesulfonate anions have been previously reported (Potočňák et al., 2001, 2002; Burcak et al., 2004). In this paper, we report a new triclinic polymorph of [Cu(C10H8N2)2(C2N3)]ClO4.
The atom-numbering scheme of the title compound (I) is shown in Fig. 1, while selected bond distances and bond angles are given in Table 1. The title compound crystallizes in the triclinic P1 space group and the coordination configuration of Cu(II) center is distorted five-coordinate square pyramid. Atom N1 occupies the apical position with a longer Cu–N bond length of 2.163 (5) Å, while the other four Cu–N bond lengths vary within 1.978 (4)–2.019 (5) Å. The perchlorate anion is believed to be uncoordinated since the shortest distance between the oxygen atom and the central copper ion is 3.314 (10) Å (Cu1···O4).
The main difference between the title complex and the earlier reported orthorhombic polymorph (Potočňák et al., 2002) comes from the crystal symmetry and coordination geometry of the central metal ion. The reported bis(2,2'-bipyridine-κ2N,N1)(dicyanamido-κN')χopper(II) perchlorate and bis(2,2'-bipyridine-κ2N,N1)(dicyanamido-κN')χopper(II) tetrafluoroborate (Potočňák et al., 2001) are isostructural and they both crystallize in the orthorhombic Pbca space group. The values of τ parameter (Addison et al., 1984) for the two complexes are 0.508 and 0.542, respectively, showing distorted trigonal bipyramid geometry. In contrast, for the title complex, the τ value is 0.262, indicative of a distorted square pyramidal coordination sphere. As a result, the bond angle of Cu1–N5–C21 is 151.6 (5)°, which is significantly larger than that in the above-mentioned two complexes (143.5 (2)° for percholate and 141.7 (3)° for tetrafluoroborate). In addition, the coplanar monodentate dicyanamide ligand has a C21–N6–C22 bond angle of 121.1 (6)°, which is also a little bit larger than 119.4 (2)° in percholate and 119.6 (3)° in tetrafluoroborate.
For the crystal structure of the orthorhombic polymorph, see: Potočňák et al. (2002). For the crystal structures of related complexes, see: Huang, Hu et al. (2003); Huang, Sun et al. (2003); Wang et al. (2007); Potočňák et al. (2001); Burcak et al. (2004).
For related literature, see: Addison et al. (1984); Garribba et al. (2000).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. A drawing of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and the H atoms are shown as small spheres of arbitrary radii. |
[Cu(C2N3)(C10H8N2)2]ClO4 | Z = 2 |
Mr = 541.41 | F(000) = 550 |
Triclinic, P1 | Dx = 1.629 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6881 (12) Å | Cell parameters from 999 reflections |
b = 9.0059 (14) Å | θ = 2.4–20.1° |
c = 17.737 (3) Å | µ = 1.16 mm−1 |
α = 79.953 (4)° | T = 293 K |
β = 78.131 (3)° | Block, blue |
γ = 67.468 (3)° | 0.16 × 0.15 × 0.10 mm |
V = 1103.9 (3) Å3 |
Bruker 1K CCD area-detector diffractometer | 3839 independent reflections |
Radiation source: fine-focus sealed tube | 2781 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
φ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan SADABS (Bruker, 2000) | h = −9→9 |
Tmin = 0.837, Tmax = 0.893 | k = −9→10 |
5551 measured reflections | l = −21→16 |
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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0664P)2] where P = (Fo2 + 2Fc2)/3 |
3839 reflections | (Δ/σ)max < 0.001 |
317 parameters | Δρmax = 0.65 e Å−3 |
12 restraints | Δρmin = −0.38 e Å−3 |
[Cu(C2N3)(C10H8N2)2]ClO4 | γ = 67.468 (3)° |
Mr = 541.41 | V = 1103.9 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.6881 (12) Å | Mo Kα radiation |
b = 9.0059 (14) Å | µ = 1.16 mm−1 |
c = 17.737 (3) Å | T = 293 K |
α = 79.953 (4)° | 0.16 × 0.15 × 0.10 mm |
β = 78.131 (3)° |
Bruker 1K CCD area-detector diffractometer | 3839 independent reflections |
Absorption correction: multi-scan SADABS (Bruker, 2000) | 2781 reflections with I > 2σ(I) |
Tmin = 0.837, Tmax = 0.893 | Rint = 0.065 |
5551 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 12 restraints |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.65 e Å−3 |
3839 reflections | Δρmin = −0.38 e Å−3 |
317 parameters |
Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses. |
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 | 0.19003 (9) | 0.56335 (8) | 0.25165 (4) | 0.0435 (3) | |
C1 | 0.3784 (8) | 0.6567 (7) | 0.3548 (3) | 0.0448 (14) | |
C2 | 0.4336 (10) | 0.7407 (9) | 0.3973 (3) | 0.0578 (17) | |
H2 | 0.5328 | 0.6874 | 0.4260 | 0.069* | |
C3 | 0.3381 (11) | 0.9058 (10) | 0.3964 (4) | 0.071 (2) | |
H3 | 0.3694 | 0.9651 | 0.4259 | 0.085* | |
C4 | 0.1994 (11) | 0.9799 (9) | 0.3522 (4) | 0.070 (2) | |
H4 | 0.1364 | 1.0913 | 0.3503 | 0.084* | |
C5 | 0.1504 (9) | 0.8919 (8) | 0.3100 (4) | 0.0582 (17) | |
H5 | 0.0536 | 0.9448 | 0.2801 | 0.070* | |
C6 | 0.4731 (7) | 0.4797 (7) | 0.3503 (3) | 0.0439 (14) | |
C7 | 0.6032 (8) | 0.3794 (9) | 0.3970 (3) | 0.0582 (17) | |
H7 | 0.6396 | 0.4219 | 0.4327 | 0.070* | |
C8 | 0.6785 (9) | 0.2178 (9) | 0.3909 (4) | 0.0660 (19) | |
H8 | 0.7659 | 0.1494 | 0.4227 | 0.079* | |
C9 | 0.6260 (8) | 0.1568 (8) | 0.3387 (4) | 0.0591 (17) | |
H9 | 0.6778 | 0.0467 | 0.3335 | 0.071* | |
C10 | 0.4953 (9) | 0.2600 (7) | 0.2937 (3) | 0.0553 (16) | |
H10 | 0.4581 | 0.2182 | 0.2580 | 0.066* | |
C11 | 0.2155 (8) | 0.6974 (6) | 0.0944 (3) | 0.0424 (13) | |
C12 | 0.2918 (9) | 0.7448 (7) | 0.0211 (3) | 0.0547 (16) | |
H12 | 0.2116 | 0.8091 | −0.0141 | 0.066* | |
C13 | 0.4845 (10) | 0.6975 (8) | 0.0002 (4) | 0.0653 (19) | |
H13 | 0.5366 | 0.7294 | −0.0492 | 0.078* | |
C14 | 0.5998 (9) | 0.6028 (8) | 0.0526 (4) | 0.0612 (17) | |
H14 | 0.7316 | 0.5699 | 0.0396 | 0.073* | |
C15 | 0.5196 (8) | 0.5572 (8) | 0.1239 (3) | 0.0534 (16) | |
H15 | 0.5991 | 0.4919 | 0.1592 | 0.064* | |
C16 | 0.0109 (8) | 0.7505 (7) | 0.1246 (3) | 0.0437 (14) | |
C17 | −0.1305 (9) | 0.8438 (7) | 0.0818 (3) | 0.0550 (16) | |
H17 | −0.1008 | 0.8732 | 0.0292 | 0.066* | |
C18 | −0.3177 (10) | 0.8934 (8) | 0.1180 (4) | 0.0618 (18) | |
H18 | −0.4157 | 0.9558 | 0.0899 | 0.074* | |
C19 | −0.3571 (9) | 0.8500 (8) | 0.1951 (4) | 0.0613 (18) | |
H19 | −0.4820 | 0.8847 | 0.2206 | 0.074* | |
C20 | −0.2115 (9) | 0.7551 (8) | 0.2341 (4) | 0.0599 (17) | |
H20 | −0.2389 | 0.7246 | 0.2867 | 0.072* | |
C21 | 0.0205 (8) | 0.4107 (8) | 0.3986 (4) | 0.0504 (14) | |
C22 | 0.1100 (10) | 0.2596 (9) | 0.5108 (4) | 0.0620 (14) | |
Cl1 | 0.0782 (2) | 0.2387 (2) | 0.14516 (10) | 0.0672 (5) | |
N1 | 0.2396 (6) | 0.7306 (6) | 0.3109 (3) | 0.0447 (11) | |
N2 | 0.4187 (6) | 0.4198 (6) | 0.2993 (3) | 0.0446 (11) | |
N3 | 0.3321 (7) | 0.6019 (6) | 0.1455 (3) | 0.0457 (11) | |
N4 | −0.0303 (6) | 0.7041 (5) | 0.1998 (2) | 0.0435 (11) | |
N5 | 0.0378 (7) | 0.4750 (6) | 0.3393 (3) | 0.0571 (14) | |
N6 | −0.0215 (8) | 0.3402 (7) | 0.4665 (3) | 0.0688 (13) | |
N7 | 0.2105 (9) | 0.1878 (8) | 0.5522 (3) | 0.0827 (19) | |
O1 | 0.140 (2) | 0.0985 (10) | 0.1153 (5) | 0.238 (6) | |
O2 | 0.0414 (9) | 0.3627 (8) | 0.0838 (3) | 0.127 (2) | |
O3 | −0.0722 (9) | 0.2517 (12) | 0.1995 (5) | 0.202 (5) | |
O4 | 0.2253 (10) | 0.2385 (12) | 0.1770 (4) | 0.167 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0401 (4) | 0.0505 (5) | 0.0348 (4) | −0.0128 (3) | −0.0072 (3) | 0.0025 (3) |
C1 | 0.043 (3) | 0.058 (4) | 0.036 (3) | −0.027 (3) | 0.003 (3) | −0.001 (3) |
C2 | 0.067 (4) | 0.076 (5) | 0.039 (4) | −0.041 (4) | 0.002 (3) | −0.005 (3) |
C3 | 0.089 (6) | 0.085 (6) | 0.053 (4) | −0.051 (5) | 0.007 (4) | −0.021 (4) |
C4 | 0.074 (5) | 0.063 (5) | 0.071 (5) | −0.033 (4) | 0.022 (4) | −0.023 (4) |
C5 | 0.050 (4) | 0.053 (4) | 0.064 (4) | −0.017 (3) | 0.005 (3) | −0.006 (3) |
C6 | 0.037 (3) | 0.059 (4) | 0.034 (3) | −0.022 (3) | −0.002 (2) | 0.009 (3) |
C7 | 0.047 (4) | 0.080 (5) | 0.044 (4) | −0.024 (4) | −0.009 (3) | 0.005 (3) |
C8 | 0.047 (4) | 0.074 (5) | 0.061 (5) | −0.009 (4) | −0.017 (3) | 0.018 (4) |
C9 | 0.044 (4) | 0.056 (4) | 0.065 (4) | −0.011 (3) | −0.007 (3) | 0.006 (3) |
C10 | 0.052 (4) | 0.053 (4) | 0.054 (4) | −0.013 (3) | −0.008 (3) | −0.003 (3) |
C11 | 0.048 (3) | 0.038 (3) | 0.036 (3) | −0.011 (3) | −0.001 (3) | −0.004 (2) |
C12 | 0.063 (4) | 0.047 (4) | 0.044 (4) | −0.016 (3) | 0.000 (3) | 0.004 (3) |
C13 | 0.066 (5) | 0.066 (4) | 0.048 (4) | −0.023 (4) | 0.018 (3) | −0.003 (3) |
C14 | 0.051 (4) | 0.061 (4) | 0.069 (5) | −0.023 (3) | 0.007 (3) | −0.013 (3) |
C15 | 0.046 (4) | 0.065 (4) | 0.046 (4) | −0.018 (3) | 0.002 (3) | −0.012 (3) |
C16 | 0.048 (3) | 0.046 (3) | 0.035 (3) | −0.014 (3) | −0.010 (3) | −0.002 (2) |
C17 | 0.065 (4) | 0.048 (4) | 0.045 (4) | −0.014 (3) | −0.014 (3) | 0.006 (3) |
C18 | 0.060 (4) | 0.056 (4) | 0.064 (5) | −0.012 (3) | −0.026 (4) | 0.003 (3) |
C19 | 0.041 (4) | 0.060 (4) | 0.069 (5) | −0.006 (3) | −0.008 (3) | −0.001 (3) |
C20 | 0.045 (4) | 0.076 (5) | 0.046 (4) | −0.015 (3) | −0.001 (3) | 0.001 (3) |
C21 | 0.048 (3) | 0.063 (4) | 0.045 (3) | −0.026 (3) | −0.010 (3) | 0.001 (3) |
C22 | 0.062 (3) | 0.078 (3) | 0.048 (3) | −0.032 (3) | −0.011 (2) | 0.009 (2) |
Cl1 | 0.0588 (11) | 0.0839 (13) | 0.0510 (10) | −0.0225 (9) | −0.0081 (8) | 0.0050 (9) |
N1 | 0.037 (3) | 0.048 (3) | 0.046 (3) | −0.016 (2) | −0.001 (2) | −0.002 (2) |
N2 | 0.043 (3) | 0.047 (3) | 0.042 (3) | −0.016 (2) | −0.010 (2) | 0.005 (2) |
N3 | 0.045 (3) | 0.049 (3) | 0.039 (3) | −0.014 (2) | −0.004 (2) | −0.003 (2) |
N4 | 0.038 (3) | 0.046 (3) | 0.037 (3) | −0.008 (2) | −0.006 (2) | 0.003 (2) |
N5 | 0.060 (3) | 0.070 (4) | 0.042 (3) | −0.031 (3) | −0.009 (2) | 0.013 (3) |
N6 | 0.065 (3) | 0.085 (3) | 0.053 (3) | −0.031 (3) | −0.009 (2) | 0.015 (2) |
N7 | 0.084 (4) | 0.084 (5) | 0.073 (4) | −0.022 (4) | −0.031 (4) | 0.016 (3) |
O1 | 0.482 (19) | 0.125 (7) | 0.126 (7) | −0.112 (9) | −0.082 (9) | −0.011 (5) |
O2 | 0.107 (5) | 0.128 (5) | 0.098 (5) | −0.015 (4) | −0.013 (4) | 0.046 (4) |
O3 | 0.076 (5) | 0.266 (11) | 0.160 (7) | −0.019 (5) | 0.032 (5) | 0.086 (7) |
O4 | 0.119 (6) | 0.284 (11) | 0.118 (6) | −0.092 (7) | −0.058 (5) | 0.023 (6) |
Cu1—N4 | 1.978 (4) | C11—C16 | 1.469 (7) |
Cu1—N5 | 1.988 (5) | C12—C13 | 1.364 (8) |
Cu1—N2 | 1.991 (4) | C12—H12 | 0.9300 |
Cu1—N3 | 2.019 (5) | C13—C14 | 1.364 (9) |
Cu1—N1 | 2.163 (5) | C13—H13 | 0.9300 |
C1—N1 | 1.343 (7) | C14—C15 | 1.357 (8) |
C1—C2 | 1.377 (8) | C14—H14 | 0.9300 |
C1—C6 | 1.486 (8) | C15—N3 | 1.329 (7) |
C2—C3 | 1.383 (9) | C15—H15 | 0.9300 |
C2—H2 | 0.9300 | C16—N4 | 1.336 (6) |
C3—C4 | 1.346 (9) | C16—C17 | 1.372 (7) |
C3—H3 | 0.9300 | C17—C18 | 1.382 (9) |
C4—C5 | 1.372 (9) | C17—H17 | 0.9300 |
C4—H4 | 0.9300 | C18—C19 | 1.359 (8) |
C5—N1 | 1.346 (7) | C18—H18 | 0.9300 |
C5—H5 | 0.9300 | C19—C20 | 1.358 (8) |
C6—N2 | 1.336 (7) | C19—H19 | 0.9300 |
C6—C7 | 1.375 (7) | C20—N4 | 1.334 (7) |
C7—C8 | 1.359 (9) | C20—H20 | 0.9300 |
C7—H7 | 0.9300 | C21—N5 | 1.117 (7) |
C8—C9 | 1.350 (9) | C21—N6 | 1.299 (7) |
C8—H8 | 0.9300 | C22—N7 | 1.112 (7) |
C9—C10 | 1.366 (8) | C22—N6 | 1.317 (8) |
C9—H9 | 0.9300 | Cl1—O3 | 1.325 (6) |
C10—N2 | 1.343 (7) | Cl1—O1 | 1.331 (8) |
C10—H10 | 0.9300 | Cl1—O4 | 1.364 (6) |
C11—N3 | 1.355 (7) | Cl1—O2 | 1.405 (6) |
C11—C12 | 1.378 (7) | ||
N4—Cu1—N5 | 95.2 (2) | C12—C13—C14 | 119.1 (6) |
N4—Cu1—N2 | 177.48 (18) | C12—C13—H13 | 120.5 |
N5—Cu1—N2 | 86.8 (2) | C14—C13—H13 | 120.5 |
N4—Cu1—N3 | 81.29 (18) | C15—C14—C13 | 119.1 (6) |
N5—Cu1—N3 | 161.8 (2) | C15—C14—H14 | 120.5 |
N2—Cu1—N3 | 96.32 (19) | C13—C14—H14 | 120.5 |
N4—Cu1—N1 | 102.75 (18) | N3—C15—C14 | 122.8 (6) |
N5—Cu1—N1 | 98.96 (19) | N3—C15—H15 | 118.6 |
N2—Cu1—N1 | 78.38 (18) | C14—C15—H15 | 118.6 |
N3—Cu1—N1 | 99.24 (18) | N4—C16—C17 | 121.0 (5) |
N1—C1—C2 | 122.2 (6) | N4—C16—C11 | 114.5 (5) |
N1—C1—C6 | 114.6 (5) | C17—C16—C11 | 124.4 (5) |
C2—C1—C6 | 123.1 (6) | C16—C17—C18 | 119.0 (6) |
C1—C2—C3 | 118.5 (6) | C16—C17—H17 | 120.5 |
C1—C2—H2 | 120.8 | C18—C17—H17 | 120.5 |
C3—C2—H2 | 120.8 | C19—C18—C17 | 119.3 (6) |
C4—C3—C2 | 119.2 (6) | C19—C18—H18 | 120.3 |
C4—C3—H3 | 120.4 | C17—C18—H18 | 120.3 |
C2—C3—H3 | 120.4 | C20—C19—C18 | 119.0 (6) |
C3—C4—C5 | 120.4 (7) | C20—C19—H19 | 120.5 |
C3—C4—H4 | 119.8 | C18—C19—H19 | 120.5 |
C5—C4—H4 | 119.8 | N4—C20—C19 | 122.4 (6) |
N1—C5—C4 | 121.4 (6) | N4—C20—H20 | 118.8 |
N1—C5—H5 | 119.3 | C19—C20—H20 | 118.8 |
C4—C5—H5 | 119.3 | N5—C21—N6 | 172.9 (7) |
N2—C6—C7 | 120.6 (6) | N7—C22—N6 | 174.5 (8) |
N2—C6—C1 | 115.8 (5) | O3—Cl1—O1 | 110.9 (7) |
C7—C6—C1 | 123.6 (5) | O3—Cl1—O4 | 109.8 (6) |
C8—C7—C6 | 119.8 (6) | O1—Cl1—O4 | 106.1 (7) |
C8—C7—H7 | 120.1 | O3—Cl1—O2 | 113.1 (4) |
C6—C7—H7 | 120.1 | O1—Cl1—O2 | 107.6 (5) |
C9—C8—C7 | 119.8 (6) | O4—Cl1—O2 | 109.1 (5) |
C9—C8—H8 | 120.1 | C1—N1—C5 | 118.3 (5) |
C7—C8—H8 | 120.1 | C1—N1—Cu1 | 112.6 (4) |
C8—C9—C10 | 118.7 (6) | C5—N1—Cu1 | 129.1 (4) |
C8—C9—H9 | 120.6 | C6—N2—C10 | 118.8 (5) |
C10—C9—H9 | 120.6 | C6—N2—Cu1 | 117.6 (4) |
N2—C10—C9 | 122.3 (6) | C10—N2—Cu1 | 122.3 (4) |
N2—C10—H10 | 118.9 | C15—N3—C11 | 118.9 (5) |
C9—C10—H10 | 118.9 | C15—N3—Cu1 | 127.7 (4) |
N3—C11—C12 | 120.0 (5) | C11—N3—Cu1 | 113.1 (4) |
N3—C11—C16 | 115.3 (5) | C20—N4—C16 | 119.2 (5) |
C12—C11—C16 | 124.6 (5) | C20—N4—Cu1 | 125.1 (4) |
C13—C12—C11 | 120.2 (6) | C16—N4—Cu1 | 115.7 (4) |
C13—C12—H12 | 119.9 | C21—N5—Cu1 | 151.6 (5) |
C11—C12—H12 | 119.9 | C21—N6—C22 | 121.1 (6) |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2N3)(C10H8N2)2]ClO4 |
Mr | 541.41 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.6881 (12), 9.0059 (14), 17.737 (3) |
α, β, γ (°) | 79.953 (4), 78.131 (3), 67.468 (3) |
V (Å3) | 1103.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.16 |
Crystal size (mm) | 0.16 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Bruker 1K CCD area-detector |
Absorption correction | Multi-scan SADABS (Bruker, 2000) |
Tmin, Tmax | 0.837, 0.893 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5551, 3839, 2781 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.168, 1.03 |
No. of reflections | 3839 |
No. of parameters | 317 |
No. of restraints | 12 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.38 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.
Cu1—N4 | 1.978 (4) | Cu1—N3 | 2.019 (5) |
Cu1—N5 | 1.988 (5) | Cu1—N1 | 2.163 (5) |
Cu1—N2 | 1.991 (4) | ||
N4—Cu1—N2 | 177.48 (18) | N4—Cu1—N1 | 102.75 (18) |
N5—Cu1—N2 | 86.8 (2) | N5—Cu1—N1 | 98.96 (19) |
N4—Cu1—N3 | 81.29 (18) | N2—Cu1—N1 | 78.38 (18) |
N5—Cu1—N3 | 161.8 (2) | N3—Cu1—N1 | 99.24 (18) |
N2—Cu1—N3 | 96.32 (19) |
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Bis(2,2'-bipyridine-κ2N,N1)copper(II) species is a very useful building block for constructuring coordination complexes and supramolecular frameworks. We have described several bis(2,2'-bipyridine-κ2N,N1)copper(II) based complexes in our early studies (Huang, Hu et al., 2003; Huang, Sun et al., 2003; Wang et al., 2007). The crystal structures of bis(2,2'-bipyridine-κ2N,N1)(dicyanamido-κN')χopper(II) divalent cation countered by one monodentate dicyanamide anion and another uncoordinated perchlorate, tetrafluoroborate and trifluoromethanesulfonate anions have been previously reported (Potočňák et al., 2001, 2002; Burcak et al., 2004). In this paper, we report a new triclinic polymorph of [Cu(C10H8N2)2(C2N3)]ClO4.
The atom-numbering scheme of the title compound (I) is shown in Fig. 1, while selected bond distances and bond angles are given in Table 1. The title compound crystallizes in the triclinic P1 space group and the coordination configuration of Cu(II) center is distorted five-coordinate square pyramid. Atom N1 occupies the apical position with a longer Cu–N bond length of 2.163 (5) Å, while the other four Cu–N bond lengths vary within 1.978 (4)–2.019 (5) Å. The perchlorate anion is believed to be uncoordinated since the shortest distance between the oxygen atom and the central copper ion is 3.314 (10) Å (Cu1···O4).
The main difference between the title complex and the earlier reported orthorhombic polymorph (Potočňák et al., 2002) comes from the crystal symmetry and coordination geometry of the central metal ion. The reported bis(2,2'-bipyridine-κ2N,N1)(dicyanamido-κN')χopper(II) perchlorate and bis(2,2'-bipyridine-κ2N,N1)(dicyanamido-κN')χopper(II) tetrafluoroborate (Potočňák et al., 2001) are isostructural and they both crystallize in the orthorhombic Pbca space group. The values of τ parameter (Addison et al., 1984) for the two complexes are 0.508 and 0.542, respectively, showing distorted trigonal bipyramid geometry. In contrast, for the title complex, the τ value is 0.262, indicative of a distorted square pyramidal coordination sphere. As a result, the bond angle of Cu1–N5–C21 is 151.6 (5)°, which is significantly larger than that in the above-mentioned two complexes (143.5 (2)° for percholate and 141.7 (3)° for tetrafluoroborate). In addition, the coplanar monodentate dicyanamide ligand has a C21–N6–C22 bond angle of 121.1 (6)°, which is also a little bit larger than 119.4 (2)° in percholate and 119.6 (3)° in tetrafluoroborate.