Bromido(3,5-dimethyl­pyrazole-κN)[hydro­tris(3,5-dimethyl­pyrazol­yl)borato-κ³N,N′,N′′]copper(II)

In the title copper complex, [CuBr(C₁₅H₂₂BN₆)(C₅H₈N₂)], the Cu^II atom is coordinated by one Br atom, three N atoms from the hydro­tris(3,5-dimethyl­pyrazol­yl)borate ligand and one N atom from the 3,5-dimethyl­pyrazole ligand, forming a distorted trigonal–bipyramidal geometry. The equatorial positions are occupied by the Br atom and the N atoms of the hydro­tris(3,5-dimethyl­pyrazol­yl)borate ligand.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

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S1. Comment

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 Cu^II, 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)°.

Related literature

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).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2U_eq(C, B, N) or 1.5U_eq(methyl C).

Computing details

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).

Figures

Fig. 1. The molecular structure of the title complex. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted.

Bromido(3,5-dimethylpyrazole-κN)[hydrotris(3,5-dimethylpyrazolyl)βorato-κ³N,N',N'']copper(II)

Crystal data

[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) Å^3	0.21 × 0.16 × 0.13 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0625P)^2] where P = (Fo^2 + 2Fc^2)/3
4917 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.75 e Å^−3
0 restraints	Δρmin = −0.65 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7A···Br1	0.86	2.51	3.045 (4)	121