Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046491/is2205sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046491/is2205Isup2.hkl |
CCDC reference: 659184
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.008 Å
- R factor = 0.050
- wR factor = 0.136
- Data-to-parameter ratio = 17.6
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.41 Ratio
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.07 Ratio PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Br1 - Cu .. 9.02 su PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C13 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C14 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C15 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C17 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C18 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C20
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 Cu (2) 1.97
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 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 6 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
All chemicals purchased were of reagent grade or better and were used without further purification. A methanol solution of K[HB(C5H7N2)3] (2 mmol) and 3,5-dimethylpyrazole (1 mmol) was added to an methanol solution of CuBr (1 mmol). The mixture was stirred for 4 h at room temperature, yielding a blue solution. This was set aside to crystallize, yielding analytically pure (I) as single crystals suitable for X-ray structure determination. Yield: 0.494 g, ca 72% (based on Cu). Anal. Calcd for C20H30N8BBrCu (FW: 536.78): C 44.69, H 5.63, N 20.86%. Found: C 44.71, H 5.59, N 20.87. IR (KBr, µ, cm-1): 3190, 2979, 2507, 2364, 1567, 1541, 1448, 1414, 1383, 1348, 1269, 1195, 1183, 1127, 1067, 1047, 1022, 984, 944, 911, 852, 808, 787, 693, 664, 644, 611, 593, 465, 436, 352, 303.
Hydrogen atoms were placed at calculated positions (C—H = 0.93–0.96, N—H = 0.86 and B—H = 0.98 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C, B, N) or 1.5Ueq(methyl C).
Since Trofimenko discovered poly(pyrazolyl)borate (Trofimenko, 1972), these ligands have been proven to be extremely popular for coordination chemists in a wide range of applications because of their ease of synthesis, ease of functionalization, and the steric protection which they afford to transition metal centers. So poly(pyrazolyl)borate ligands have been used for a number of different purposes, including modeling of metalloprotein active site (Trofimenko, 1993, 2004), mimicking metalloenzyme systems in bioinorganic chemistry (Puerta & Cohen, 2002), polymerization catalysts (Blosch et al., 1991) and C—H activation (Ghosh et al., 1988; Fernandez et al., 1989). The donor N atoms of pyrazole (or modified pyrazole) and poly(pyrazolyl)borate can coordinate to metal atoms together to form half sandwich structure. Based on these findings, we attempted to determine the structure of the title complex, (I).
The structure of (I) shows a distorting trigonal bipyramidal geometry of CuII, which is coordinated to one Br atom and four N atoms: three from tris(3,5-dimethylpyrazolyl)borate ligand [Cu—N(N2, N4, N6)] with bond lengths of 2.019 (3), 2.035 (3), 2.176 (3) Å and one from 3,5-dimethylpyrazole ligand (Cu—N8) with the bond distance of 2.067 (4) Å. In the structure, the atoms Br, N2 and N6 are in the triangle plane, and N4 and N8 are at the axial positions. The copper atom is in the center of the triangle double pyramide geometry (Fig. 1). Selected bond lengths and angles are listed in Table 1. It can be found that the Cu—N distances (from tris(pyrazolyl)borate ligand) are shorter than those of bis(hydrotris(3,5-dimethylpyrazolyl) borato-κ3N,N',N'')copper(II) (Kitajima et al., 1988) [2.034 (13), 2.085 (12), 2.296 (12) Å], longer than those of chloro(hydrotris(3-adamantyl-5-isopropyl-1-pyrazolyl) borato-κ3N,N',N'')copper(II) (Fujisawa et al., 2004) [2.125 (3), 2.005 (2), 1.961 (2) Å]. For the bond angles, the range of N—Cu—N (from tris(pyrazolyl)borate ligand) in the title complex is from 85.28 (13) to 95.06 (13)°, but in bis(hydrotris(3,5-dimethylpyrazolyl)borato-κ3N,N',N'')copper(II) (Kitajima et al., 1988) complex, the range of N—Cu—N (from tris(pyrazolyl)borate ligand) is from 86.7 (4) to 88.1 (4)°.
For related literature, see: Badura & Vahrenkamp (2002); Blosch et al. (1991); Fernandez et al. (1989); Fujisawa et al. (2004); Ghosh et al. (1988); Kitajima et al. (1988); Puerta et al. (2002); Trofimenko (1972, 1993, 2004).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
Fig. 1. The molecular structure of the title complex. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted. |
[CuBr(C15H22BN6)(C5H8N2)] | F(000) = 1100 |
Mr = 536.78 | Dx = 1.425 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2ybc | Cell parameters from 4917 reflections |
a = 17.223 (4) Å | θ = 2.2–26.0° |
b = 7.9231 (18) Å | µ = 2.49 mm−1 |
c = 19.236 (4) Å | T = 293 K |
β = 107.618 (3)° | Plate, green |
V = 2501.7 (10) Å3 | 0.21 × 0.16 × 0.13 mm |
Z = 4 |
Bruker P4 diffractometer | 4917 independent reflections |
Radiation source: fine-focus sealed tube | 3349 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ω scans | θmax = 26.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −13→21 |
Tmin = 0.626, Tmax = 0.723 | k = −9→9 |
4917 measured reflections | l = −23→21 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0625P)2] where P = (Fo2 + 2Fc2)/3 |
4917 reflections | (Δ/σ)max < 0.001 |
280 parameters | Δρmax = 0.75 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
[CuBr(C15H22BN6)(C5H8N2)] | V = 2501.7 (10) Å3 |
Mr = 536.78 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 17.223 (4) Å | µ = 2.49 mm−1 |
b = 7.9231 (18) Å | T = 293 K |
c = 19.236 (4) Å | 0.21 × 0.16 × 0.13 mm |
β = 107.618 (3)° |
Bruker P4 diffractometer | 4917 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3349 reflections with I > 2σ(I) |
Tmin = 0.626, Tmax = 0.723 | Rint = 0.055 |
4917 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.75 e Å−3 |
4917 reflections | Δρmin = −0.65 e Å−3 |
280 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 | ||
Cu | 0.23841 (3) | 0.86990 (6) | 0.30904 (3) | 0.03100 (17) | |
Br1 | 0.26691 (3) | 1.02181 (7) | 0.20786 (3) | 0.0571 (2) | |
C1 | 0.1549 (3) | 0.5592 (6) | 0.4415 (2) | 0.0433 (11) | |
C2 | 0.1719 (3) | 0.4300 (6) | 0.4000 (3) | 0.0491 (13) | |
H2A | 0.1681 | 0.3149 | 0.4079 | 0.059* | |
C3 | 0.1953 (3) | 0.5040 (6) | 0.3447 (2) | 0.0424 (11) | |
C4 | 0.0315 (3) | 1.0552 (6) | 0.3462 (2) | 0.0410 (11) | |
C5 | 0.0068 (3) | 1.1021 (6) | 0.2754 (3) | 0.0460 (12) | |
H5A | −0.0412 | 1.1581 | 0.2513 | 0.055* | |
C6 | 0.0667 (3) | 1.0510 (6) | 0.2457 (2) | 0.0390 (11) | |
C7 | 0.2787 (3) | 1.0521 (6) | 0.5238 (2) | 0.0469 (12) | |
C8 | 0.3505 (3) | 1.1191 (7) | 0.5189 (3) | 0.0557 (14) | |
H8A | 0.3902 | 1.1745 | 0.5555 | 0.067* | |
C9 | 0.3520 (3) | 1.0874 (6) | 0.4479 (3) | 0.0454 (12) | |
C10 | 0.4449 (3) | 0.6283 (8) | 0.2855 (4) | 0.0704 (17) | |
C11 | 0.4591 (3) | 0.5844 (7) | 0.3563 (4) | 0.0702 (17) | |
H11A | 0.5026 | 0.5204 | 0.3844 | 0.084* | |
C12 | 0.3964 (3) | 0.6531 (6) | 0.3791 (3) | 0.0490 (12) | |
C13 | 0.1268 (4) | 0.5499 (7) | 0.5069 (3) | 0.0633 (16) | |
H13A | 0.1204 | 0.6619 | 0.5233 | 0.095* | |
H13B | 0.1662 | 0.4897 | 0.5448 | 0.095* | |
H13C | 0.0754 | 0.4919 | 0.4948 | 0.095* | |
C14 | 0.2180 (3) | 0.4232 (7) | 0.2831 (3) | 0.0636 (15) | |
H14A | 0.2313 | 0.5092 | 0.2534 | 0.095* | |
H14B | 0.1729 | 0.3578 | 0.2540 | 0.095* | |
H14C | 0.2642 | 0.3510 | 0.3024 | 0.095* | |
C15 | −0.0100 (3) | 1.0777 (8) | 0.4035 (3) | 0.0680 (16) | |
H15A | 0.0231 | 1.0301 | 0.4486 | 0.102* | |
H15B | −0.0618 | 1.0217 | 0.3886 | 0.102* | |
H15C | −0.0180 | 1.1959 | 0.4101 | 0.102* | |
C16 | 0.0640 (3) | 1.0668 (8) | 0.1676 (2) | 0.0608 (15) | |
H16A | 0.1129 | 1.0205 | 0.1613 | 0.091* | |
H16B | 0.0596 | 1.1837 | 0.1538 | 0.091* | |
H16C | 0.0177 | 1.0063 | 0.1374 | 0.091* | |
C17 | 0.2459 (4) | 1.0483 (8) | 0.5871 (3) | 0.0795 (19) | |
H17A | 0.1942 | 0.9919 | 0.5733 | 0.119* | |
H17B | 0.2392 | 1.1617 | 0.6020 | 0.119* | |
H17C | 0.2832 | 0.9889 | 0.6269 | 0.119* | |
C18 | 0.4151 (3) | 1.1289 (8) | 0.4123 (3) | 0.0637 (16) | |
H18A | 0.3977 | 1.0894 | 0.3628 | 0.096* | |
H18B | 0.4654 | 1.0751 | 0.4383 | 0.096* | |
H18C | 0.4228 | 1.2489 | 0.4128 | 0.096* | |
C19 | 0.4902 (4) | 0.5946 (10) | 0.2306 (5) | 0.121 (3) | |
H19A | 0.4610 | 0.6447 | 0.1847 | 0.181* | |
H19B | 0.4944 | 0.4751 | 0.2245 | 0.181* | |
H19C | 0.5438 | 0.6428 | 0.2478 | 0.181* | |
C20 | 0.3829 (3) | 0.6372 (7) | 0.4518 (3) | 0.0665 (16) | |
H20A | 0.3345 | 0.6978 | 0.4515 | 0.100* | |
H20B | 0.4288 | 0.6834 | 0.4886 | 0.100* | |
H20C | 0.3767 | 0.5203 | 0.4621 | 0.100* | |
N1 | 0.1701 (2) | 0.7062 (4) | 0.41197 (17) | 0.0336 (8) | |
N2 | 0.1952 (2) | 0.6716 (4) | 0.35195 (17) | 0.0331 (8) | |
N3 | 0.1048 (2) | 0.9768 (4) | 0.35979 (17) | 0.0322 (8) | |
N4 | 0.1276 (2) | 0.9762 (4) | 0.29746 (17) | 0.0329 (8) | |
N5 | 0.2399 (2) | 0.9827 (4) | 0.45886 (17) | 0.0352 (9) | |
N6 | 0.2847 (2) | 1.0044 (4) | 0.41192 (17) | 0.0356 (9) | |
N7 | 0.3765 (2) | 0.7205 (5) | 0.2677 (2) | 0.0506 (10) | |
H7A | 0.3544 | 0.7628 | 0.2251 | 0.061* | |
N8 | 0.3461 (2) | 0.7391 (5) | 0.32409 (19) | 0.0407 (9) | |
B1 | 0.1575 (3) | 0.8903 (6) | 0.4308 (3) | 0.0339 (11) | |
H1 | 0.1291 | 0.8942 | 0.4679 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0280 (3) | 0.0343 (3) | 0.0322 (3) | 0.0016 (2) | 0.0114 (2) | 0.0010 (2) |
Br1 | 0.0572 (4) | 0.0688 (4) | 0.0551 (3) | 0.0191 (3) | 0.0319 (3) | 0.0230 (3) |
C1 | 0.040 (3) | 0.041 (3) | 0.048 (3) | −0.003 (2) | 0.012 (2) | 0.010 (2) |
C2 | 0.054 (3) | 0.027 (3) | 0.062 (3) | −0.006 (2) | 0.011 (3) | 0.014 (2) |
C3 | 0.034 (3) | 0.038 (3) | 0.051 (3) | −0.003 (2) | 0.006 (2) | −0.005 (2) |
C4 | 0.030 (2) | 0.045 (3) | 0.050 (3) | 0.003 (2) | 0.015 (2) | −0.006 (2) |
C5 | 0.028 (2) | 0.050 (3) | 0.056 (3) | 0.012 (2) | 0.007 (2) | 0.006 (2) |
C6 | 0.030 (2) | 0.043 (3) | 0.040 (2) | 0.002 (2) | 0.003 (2) | 0.006 (2) |
C7 | 0.055 (3) | 0.049 (3) | 0.033 (2) | −0.003 (3) | 0.007 (2) | −0.011 (2) |
C8 | 0.052 (3) | 0.060 (4) | 0.045 (3) | −0.020 (3) | 0.001 (2) | −0.019 (2) |
C9 | 0.041 (3) | 0.038 (3) | 0.053 (3) | −0.010 (2) | 0.009 (2) | −0.002 (2) |
C10 | 0.049 (3) | 0.061 (4) | 0.115 (5) | 0.016 (3) | 0.047 (4) | 0.016 (4) |
C11 | 0.037 (3) | 0.060 (4) | 0.112 (5) | 0.017 (3) | 0.021 (3) | 0.025 (4) |
C12 | 0.032 (3) | 0.045 (3) | 0.065 (3) | 0.003 (2) | 0.008 (2) | 0.014 (2) |
C13 | 0.078 (4) | 0.061 (4) | 0.056 (3) | −0.016 (3) | 0.028 (3) | 0.017 (3) |
C14 | 0.069 (4) | 0.043 (3) | 0.082 (4) | −0.005 (3) | 0.028 (3) | −0.024 (3) |
C15 | 0.057 (4) | 0.086 (5) | 0.071 (4) | 0.024 (3) | 0.035 (3) | 0.002 (3) |
C16 | 0.045 (3) | 0.089 (4) | 0.041 (3) | 0.006 (3) | 0.002 (2) | 0.014 (3) |
C17 | 0.090 (5) | 0.109 (5) | 0.040 (3) | −0.020 (4) | 0.021 (3) | −0.028 (3) |
C18 | 0.041 (3) | 0.078 (4) | 0.070 (3) | −0.021 (3) | 0.014 (3) | −0.002 (3) |
C19 | 0.104 (6) | 0.118 (7) | 0.179 (8) | 0.062 (5) | 0.101 (6) | 0.037 (6) |
C20 | 0.048 (3) | 0.074 (4) | 0.061 (3) | 0.005 (3) | −0.009 (3) | 0.014 (3) |
N1 | 0.0305 (19) | 0.035 (2) | 0.0337 (18) | −0.0037 (16) | 0.0079 (15) | 0.0022 (16) |
N2 | 0.033 (2) | 0.033 (2) | 0.0360 (18) | −0.0016 (16) | 0.0138 (16) | −0.0001 (15) |
N3 | 0.030 (2) | 0.035 (2) | 0.0342 (18) | 0.0026 (16) | 0.0135 (16) | −0.0002 (15) |
N4 | 0.030 (2) | 0.037 (2) | 0.0340 (18) | 0.0004 (16) | 0.0130 (16) | 0.0008 (15) |
N5 | 0.039 (2) | 0.038 (2) | 0.0291 (18) | −0.0030 (17) | 0.0106 (16) | −0.0055 (15) |
N6 | 0.034 (2) | 0.037 (2) | 0.0339 (19) | −0.0065 (16) | 0.0083 (16) | −0.0034 (16) |
N7 | 0.040 (2) | 0.050 (3) | 0.071 (3) | 0.010 (2) | 0.030 (2) | 0.007 (2) |
N8 | 0.032 (2) | 0.043 (2) | 0.048 (2) | 0.0019 (18) | 0.0134 (18) | 0.0019 (18) |
B1 | 0.032 (3) | 0.041 (3) | 0.032 (2) | −0.001 (2) | 0.014 (2) | −0.002 (2) |
Cu—N2 | 2.019 (3) | C13—H13A | 0.9600 |
Cu—N4 | 2.035 (3) | C13—H13B | 0.9600 |
Cu—N8 | 2.067 (4) | C13—H13C | 0.9600 |
Cu—N6 | 2.176 (3) | C14—H14A | 0.9600 |
Cu—Br1 | 2.4607 (8) | C14—H14B | 0.9600 |
C1—N1 | 1.355 (5) | C14—H14C | 0.9600 |
C1—C2 | 1.383 (7) | C15—H15A | 0.9600 |
C1—C13 | 1.480 (6) | C15—H15B | 0.9600 |
C2—C3 | 1.378 (7) | C15—H15C | 0.9600 |
C2—H2A | 0.9300 | C16—H16A | 0.9600 |
C3—N2 | 1.335 (5) | C16—H16B | 0.9600 |
C3—C14 | 1.499 (7) | C16—H16C | 0.9600 |
C4—C5 | 1.350 (6) | C17—H17A | 0.9600 |
C4—N3 | 1.360 (5) | C17—H17B | 0.9600 |
C4—C15 | 1.495 (6) | C17—H17C | 0.9600 |
C5—C6 | 1.382 (6) | C18—H18A | 0.9600 |
C5—H5A | 0.9300 | C18—H18B | 0.9600 |
C6—N4 | 1.346 (5) | C18—H18C | 0.9600 |
C6—C16 | 1.494 (6) | C19—H19A | 0.9600 |
C7—N5 | 1.343 (5) | C19—H19B | 0.9600 |
C7—C8 | 1.374 (7) | C19—H19C | 0.9600 |
C7—C17 | 1.491 (6) | C20—H20A | 0.9600 |
C8—C9 | 1.396 (6) | C20—H20B | 0.9600 |
C8—H8A | 0.9300 | C20—H20C | 0.9600 |
C9—N6 | 1.331 (5) | N1—N2 | 1.378 (4) |
C9—C18 | 1.485 (6) | N1—B1 | 1.534 (6) |
C10—N7 | 1.340 (6) | N3—N4 | 1.370 (4) |
C10—C11 | 1.353 (8) | N3—B1 | 1.552 (6) |
C10—C19 | 1.514 (8) | N5—N6 | 1.364 (4) |
C11—C12 | 1.394 (7) | N5—B1 | 1.542 (6) |
C11—H11A | 0.9300 | N7—N8 | 1.348 (5) |
C12—N8 | 1.333 (5) | N7—H7A | 0.8600 |
C12—C20 | 1.491 (7) | B1—H1 | 0.9800 |
N2—Cu—N4 | 85.28 (13) | H15A—C15—H15C | 109.5 |
N2—Cu—N8 | 88.77 (14) | H15B—C15—H15C | 109.5 |
N4—Cu—N8 | 174.01 (14) | C6—C16—H16A | 109.5 |
N2—Cu—N6 | 95.06 (13) | C6—C16—H16B | 109.5 |
N4—Cu—N6 | 88.27 (13) | H16A—C16—H16B | 109.5 |
N8—Cu—N6 | 92.99 (14) | C6—C16—H16C | 109.5 |
N2—Cu—Br1 | 152.93 (10) | H16A—C16—H16C | 109.5 |
N4—Cu—Br1 | 96.65 (9) | H16B—C16—H16C | 109.5 |
N8—Cu—Br1 | 88.31 (10) | C7—C17—H17A | 109.5 |
N6—Cu—Br1 | 111.97 (10) | C7—C17—H17B | 109.5 |
N1—C1—C2 | 107.1 (4) | H17A—C17—H17B | 109.5 |
N1—C1—C13 | 123.6 (4) | C7—C17—H17C | 109.5 |
C2—C1—C13 | 129.3 (5) | H17A—C17—H17C | 109.5 |
C3—C2—C1 | 107.0 (4) | H17B—C17—H17C | 109.5 |
C3—C2—H2A | 126.5 | C9—C18—H18A | 109.5 |
C1—C2—H2A | 126.5 | C9—C18—H18B | 109.5 |
N2—C3—C2 | 109.4 (4) | H18A—C18—H18B | 109.5 |
N2—C3—C14 | 121.1 (4) | C9—C18—H18C | 109.5 |
C2—C3—C14 | 129.5 (5) | H18A—C18—H18C | 109.5 |
C5—C4—N3 | 108.0 (4) | H18B—C18—H18C | 109.5 |
C5—C4—C15 | 129.5 (4) | C10—C19—H19A | 109.5 |
N3—C4—C15 | 122.5 (4) | C10—C19—H19B | 109.5 |
C4—C5—C6 | 106.9 (4) | H19A—C19—H19B | 109.5 |
C4—C5—H5A | 126.5 | C10—C19—H19C | 109.5 |
C6—C5—H5A | 126.5 | H19A—C19—H19C | 109.5 |
N4—C6—C5 | 109.5 (4) | H19B—C19—H19C | 109.5 |
N4—C6—C16 | 124.1 (4) | C12—C20—H20A | 109.5 |
C5—C6—C16 | 126.3 (4) | C12—C20—H20B | 109.5 |
N5—C7—C8 | 107.5 (4) | H20A—C20—H20B | 109.5 |
N5—C7—C17 | 123.1 (5) | C12—C20—H20C | 109.5 |
C8—C7—C17 | 129.4 (4) | H20A—C20—H20C | 109.5 |
C7—C8—C9 | 106.3 (4) | H20B—C20—H20C | 109.5 |
C7—C8—H8A | 126.8 | C1—N1—N2 | 109.2 (3) |
C9—C8—H8A | 126.8 | C1—N1—B1 | 131.2 (4) |
N6—C9—C8 | 109.0 (4) | N2—N1—B1 | 119.3 (3) |
N6—C9—C18 | 120.9 (4) | C3—N2—N1 | 107.2 (3) |
C8—C9—C18 | 130.1 (4) | C3—N2—Cu | 136.0 (3) |
N7—C10—C11 | 106.0 (5) | N1—N2—Cu | 115.8 (2) |
N7—C10—C19 | 121.1 (6) | C4—N3—N4 | 109.2 (3) |
C11—C10—C19 | 133.0 (6) | C4—N3—B1 | 129.2 (4) |
C10—C11—C12 | 107.1 (5) | N4—N3—B1 | 121.5 (3) |
C10—C11—H11A | 126.4 | C6—N4—N3 | 106.3 (3) |
C12—C11—H11A | 126.4 | C6—N4—Cu | 139.3 (3) |
N8—C12—C11 | 109.2 (5) | N3—N4—Cu | 114.4 (2) |
N8—C12—C20 | 122.6 (4) | C7—N5—N6 | 109.9 (4) |
C11—C12—C20 | 128.2 (5) | C7—N5—B1 | 131.8 (4) |
C1—C13—H13A | 109.5 | N6—N5—B1 | 118.2 (3) |
C1—C13—H13B | 109.5 | C9—N6—N5 | 107.3 (3) |
H13A—C13—H13B | 109.5 | C9—N6—Cu | 137.4 (3) |
C1—C13—H13C | 109.5 | N5—N6—Cu | 114.6 (2) |
H13A—C13—H13C | 109.5 | C10—N7—N8 | 112.3 (4) |
H13B—C13—H13C | 109.5 | C10—N7—H7A | 123.9 |
C3—C14—H14A | 109.5 | N8—N7—H7A | 123.9 |
C3—C14—H14B | 109.5 | C12—N8—N7 | 105.4 (4) |
H14A—C14—H14B | 109.5 | C12—N8—Cu | 135.0 (3) |
C3—C14—H14C | 109.5 | N7—N8—Cu | 119.5 (3) |
H14A—C14—H14C | 109.5 | N1—B1—N5 | 110.7 (4) |
H14B—C14—H14C | 109.5 | N1—B1—N3 | 107.4 (3) |
C4—C15—H15A | 109.5 | N5—B1—N3 | 109.2 (4) |
C4—C15—H15B | 109.5 | N1—B1—H1 | 109.8 |
H15A—C15—H15B | 109.5 | N5—B1—H1 | 109.8 |
C4—C15—H15C | 109.5 | N3—B1—H1 | 109.8 |
Experimental details
Crystal data | |
Chemical formula | [CuBr(C15H22BN6)(C5H8N2)] |
Mr | 536.78 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 17.223 (4), 7.9231 (18), 19.236 (4) |
β (°) | 107.618 (3) |
V (Å3) | 2501.7 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.49 |
Crystal size (mm) | 0.21 × 0.16 × 0.13 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.626, 0.723 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4917, 4917, 3349 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.136, 1.03 |
No. of reflections | 4917 |
No. of parameters | 280 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.75, −0.65 |
Computer programs: APEX2 (Bruker, 2005), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
Cu—N2 | 2.019 (3) | Cu—N6 | 2.176 (3) |
Cu—N4 | 2.035 (3) | Cu—Br1 | 2.4607 (8) |
Cu—N8 | 2.067 (4) | ||
N2—Cu—N4 | 85.28 (13) | N8—Cu—N6 | 92.99 (14) |
N2—Cu—N8 | 88.77 (14) | N2—Cu—Br1 | 152.93 (10) |
N4—Cu—N8 | 174.01 (14) | N4—Cu—Br1 | 96.65 (9) |
N2—Cu—N6 | 95.06 (13) | N8—Cu—Br1 | 88.31 (10) |
N4—Cu—N6 | 88.27 (13) | N6—Cu—Br1 | 111.97 (10) |
Since Trofimenko discovered poly(pyrazolyl)borate (Trofimenko, 1972), these ligands have been proven to be extremely popular for coordination chemists in a wide range of applications because of their ease of synthesis, ease of functionalization, and the steric protection which they afford to transition metal centers. So poly(pyrazolyl)borate ligands have been used for a number of different purposes, including modeling of metalloprotein active site (Trofimenko, 1993, 2004), mimicking metalloenzyme systems in bioinorganic chemistry (Puerta & Cohen, 2002), polymerization catalysts (Blosch et al., 1991) and C—H activation (Ghosh et al., 1988; Fernandez et al., 1989). The donor N atoms of pyrazole (or modified pyrazole) and poly(pyrazolyl)borate can coordinate to metal atoms together to form half sandwich structure. Based on these findings, we attempted to determine the structure of the title complex, (I).
The structure of (I) shows a distorting trigonal bipyramidal geometry of CuII, which is coordinated to one Br atom and four N atoms: three from tris(3,5-dimethylpyrazolyl)borate ligand [Cu—N(N2, N4, N6)] with bond lengths of 2.019 (3), 2.035 (3), 2.176 (3) Å and one from 3,5-dimethylpyrazole ligand (Cu—N8) with the bond distance of 2.067 (4) Å. In the structure, the atoms Br, N2 and N6 are in the triangle plane, and N4 and N8 are at the axial positions. The copper atom is in the center of the triangle double pyramide geometry (Fig. 1). Selected bond lengths and angles are listed in Table 1. It can be found that the Cu—N distances (from tris(pyrazolyl)borate ligand) are shorter than those of bis(hydrotris(3,5-dimethylpyrazolyl) borato-κ3N,N',N'')copper(II) (Kitajima et al., 1988) [2.034 (13), 2.085 (12), 2.296 (12) Å], longer than those of chloro(hydrotris(3-adamantyl-5-isopropyl-1-pyrazolyl) borato-κ3N,N',N'')copper(II) (Fujisawa et al., 2004) [2.125 (3), 2.005 (2), 1.961 (2) Å]. For the bond angles, the range of N—Cu—N (from tris(pyrazolyl)borate ligand) in the title complex is from 85.28 (13) to 95.06 (13)°, but in bis(hydrotris(3,5-dimethylpyrazolyl)borato-κ3N,N',N'')copper(II) (Kitajima et al., 1988) complex, the range of N—Cu—N (from tris(pyrazolyl)borate ligand) is from 86.7 (4) to 88.1 (4)°.