The triclinic polymorph of di­bromo[(–)-sparteine-κ²N,N′]­zinc(II)

The title compound, [ZnBr₂(C₁₅H₂₆N₂)], when synthesized starting from Zn⁰, is obtained in two polymorphic forms, one belonging to space group P2₁2₁2₁ and one to P1. The present contribution deals with the triclinic phase, which is isostructural with the orthorhombic form but presents a larger metal–metal intermolecular separation; the Zn...Zn distance is 7.4715 (6) Å for the triclinic polymorph as opposed to 6.534 Å for the orthorhombic polymorph.

S1. Comment

The correlation between the tetrahedral coordination of the Cu^II ion in type 1 blue copper proteins and some unique spectroscopic features reported for these proteins is a well established fact (Krishnan, 1978; Colman et al., 1978; Solomon et al., 1992; Holland & Tolman, 2000). Well studied examples are the intense absorption observed in electronic spectra near 600 nm (ε ≈ 5000 M⁻¹ cm⁻¹) and the small Cu hyperfine splitting observed in EPR spectra (A_// < 70 × 10⁻⁴ cm⁻¹), which is reduced to less than half the value observed in common Cu^II coordination complexes.

In this context, numerous Cu^II complexes containing sparteine as a ligand have been synthesized, with the hope of accurately modeling spectroscopic and structural features of the catalytic center of these proteins (Boschmann et al., 1974; Choi et al., 1975; Kim et al., 2001). For the X-ray-characterized complexes, the expected distorted tetrahedral geometry has been observed in most cases, although the spectroscopic characteristics of these complexes did not always fit correctly with those of the proteins (Childers et al., 1975; Lopez et al., 1998; Choi et al., 1995; Lee et al., 2000).

During the course of our work dealing with this class of compounds, we prepared by direct synthesis a series of complexes with the general formula M(SP)X₂ where SP is the naturally occurring (-)-sparteine ligand, X = Cl or Br, and M = Cu^II or Zn^II. The Cu^II complexes are intended to be used for modeling the active site of type 1 blue copper proteins (structurally and spectroscopically), while the Zn^II complexes are used as diluting agents for measuring the hyperfine, and eventually the super-hyperfine, coupling by electron paramagnetic resonance (EPR) on powdered samples. To validate the EPR, isostructurality between Cu and Zn complexes has first to be established by X-ray diffraction. In the case of X = Br, both metals yielded two isomorphous polymorphic crystalline phases, one in space group P1 and one in P2₁2₁2₁, when a direct synthesis was used, i.e. using metallic copper or zinc as a starting material (see experimental section). The Zn complex here described, (I), corresponds to the triclinic polymorph of Zn(SP)Br₂. The orthorhombic phase, which is synthesized using zinc(II) bromide as a starting material, was reported very recently by Lee et al. (2002).

The molecular structure of (I) is, within the experimental s.u. values, identical (Fig. 1) to that of the reported orthorhombic phase: the r.m.s. deviation between the two structures is 0.0362 Å (excluding H atoms). The largest observed deviation for the fit, 0.082 Å, arises from the Br atoms.

In contrast, the symmetry change induces dramatic differences for the packing structures. The orthorhombic phase is stabilized through two intermolecular contacts involving both the Br atoms and the methylene or methine H atoms belonging to the SP ligands of symmetry-related molecules: Zn—Br1···H15Bⁱ [contact = 2.910 Å, angle = 156.0°; (i) 1/2 − x, 1 − y, −1/2 + z] and Zn—Br2···H7ⁱⁱ (contact = 2.933 Å, angle = 160.0°; (ii) 1/2 − x, −y, −1/2 + z). The Br···H separations are then 0.14 and 0.12 Å shorter than the van der Waals distance. This arrangement generates layers of connected molecules, with the layers normal to the a axis of the orthorhombic cell (Fig. 2).

In the case of (I), the only operators available for connecting molecules are axis translations. A single short Br···H contact is observed (Table 1), which corresponds to a relatively weak interaction, with a difference from the van der Waals distance of 0.06 Å; the resulting network of interconnected molecules is one dimensional (Fig. 3). In spite of these weak contacts, the packing index (Spek, 2003) is lowered from 0.683 for the orthorhombic phase to 0.681 for (I). This more efficient packing for (I) is confirmed by the analysis of the intermolecular H···H contacts. The shortest contact observed for the orthorhombic phase is H3A···H11Bⁱ = 2.403 Å [(i) 1 + x, y, z], i.e. a separation equal to the van der Waals distance. However, for (I), the shortest H···H separation is 2.317 Å (Table 1), which corresponds to an actual H···H contact (Fig. 3).

Finally, the metal–metal separations are significantly affected by the symmetry. The observed distances are Zn···Znⁱ = 6.534 Å [(i) 1/2 + x, 1/2 − y, −z] in the orthorhombic case versus Zn···Znⁱⁱ = 7.4715 (6) Å [(ii) 1 + x, y, z] for (I). This difference of ca 1 Å is unimportant for the Zn^II-based compounds but essential for the corresponding Cu^II-based compounds that are intended for modeling. Considering that the metal centers should be magnetically isolated in the native proteins, the triclinic phase seems to be a more suitable magnetic model than the orthorhombic one.

S2. Experimental

Equimolar amounts of zinc (0.123 g), CBr₄ (0.626 g) and (-)sparteine (0.433 ml) were mixed in DMSO (5.376 ml). The mixture was heated at 333 K for 30 min and then filtered. The first drop of crystals was collected after 2 days (0.219 g, yield 25.3%, m.p. 566 K). These crystals exhibited a characteristic hexagonal plate habit and were identified as (I). Further crystallization produced small quantities of the orthorhombic polymorph, which can be distinguished from (I) on the basis of its quite isotropic block habit.

S3. Refinement

H atoms were treated as riding atoms with C—H distances 0.97 Å (CH₂) or 0.98 Å (CH).

Computing details

Data collection: XSCANS 2.21 (Siemens, 1996); cell refinement: XSCANS 2.21 (Siemens, 1996); data reduction: XSCANS 2.21 (Siemens, 1996); program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 1998); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1998) and Mercury 1.1 (CCDC, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The structure of (I) with displacement ellipsoids at the 40% probability level. The numbering scheme is identical to that adopted by Lee et al. (2002) for the orthorhombic phase.
	Fig. 2. One layer of interconnected Zn(SP)Br2 molecules in the packing structure of the orthorhombic polymorph, viewed down the a axis. Nine molecules are represented. The capped sticks representation of the bottom molecule is given with the numbering scheme for non-C atoms, and H atoms not involved in the network have been omitted for clarity. For the remaining molecules, Br1, Br2, H7 and H15B atoms that connect molecules are represented as van der Waals radii spheres (CCDC, 2002), making obvious the two-dimensional character of the network.
	Fig. 3. The packing structure for (I) viewed down the a axis. As in Fig. 2, nine molecules are represented, one of which (bottom left) includes labels for non-C atoms. The retained H atoms are those that give short non-bonding H···H intermolecular contacts. For the remaining molecules, Br2 and H8A atoms that connect molecules are represented as van der Waals radii spheres (CCDC, 2002), while dotted lines join H atoms that are participating in the H···H contacts network (see Table 1).

dibromo[(6R,7S,8S,14S)-1,3,4,7,7a,8,9,10,11,13,14,14a-dodecahydro-7,14- methano-2H,6H-dipyrido[1,2 − a;1',2'-e][1,5]diazocine-κ²N,N']zinc(II)

Crystal data

[ZnBr2(C15H26N2)]	Z = 1
Mr = 459.57	F(000) = 230
Triclinic, P1	Dx = 1.766 Mg m^−3
Hall symbol: P 1	Melting point: 566 K
a = 7.4715 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.7082 (7) Å	Cell parameters from 84 reflections
c = 9.1435 (6) Å	θ = 5.0–13.0°
α = 97.429 (6)°	µ = 6.04 mm^−1
β = 112.808 (5)°	T = 296 K
γ = 110.666 (6)°	Prism, colorless
V = 432.02 (7) Å^3	0.60 × 0.24 × 0.16 mm

Data collection

Bruker P4 diffractometer	4244 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.048
Graphite monochromator	θmax = 30.0°, θmin = 2.5°
2θ/ω scans	h = −9→10
Absorption correction: ψ-scan XSCANS 2.21 (Siemens, 1996)	k = −10→10
Tmin = 0.254, Tmax = 0.381	l = −12→12
4908 measured reflections	3 standard reflections every 97 reflections
4908 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.0364P)^2 + 0.6283P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.097	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.53 e Å^−3
4908 reflections	Δρmin = −0.77 e Å^−3
182 parameters	Extinction correction: SHELXL97, Fc^* = kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.0083 (17)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983); 2436 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.016 (13)

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
Zn1	0.64020 (6)	0.60790 (6)	0.13464 (5)	0.03135 (13)
Br1	0.94293 (9)	0.90078 (8)	0.19208 (8)	0.05669 (18)
Br2	0.31099 (9)	0.57007 (9)	−0.07858 (7)	0.05857 (18)
N1	0.7406 (6)	0.3888 (5)	0.1528 (5)	0.0310 (7)
C2	0.7964 (10)	0.3414 (8)	0.0173 (7)	0.0465 (12)
H2A	0.8568	0.2488	0.0362	0.056*
H2B	0.9056	0.4589	0.0204	0.056*
C3	0.6019 (11)	0.2570 (9)	−0.1510 (7)	0.0509 (13)
H3A	0.6430	0.2234	−0.2352	0.061*
H3B	0.5501	0.3544	−0.1742	0.061*
C4	0.4189 (11)	0.0749 (9)	−0.1623 (7)	0.0585 (16)
H4A	0.2899	0.0351	−0.2671	0.070*
H4B	0.4605	−0.0310	−0.1595	0.070*
C5	0.3705 (8)	0.1160 (7)	−0.0182 (6)	0.0412 (11)
H5A	0.2676	−0.0045	−0.0193	0.049*
H5B	0.3050	0.2053	−0.0322	0.049*
C6	0.5745 (7)	0.2039 (6)	0.1488 (6)	0.0330 (9)
H6A	0.6362	0.1103	0.1578	0.040*
C7	0.5350 (8)	0.2371 (7)	0.3007 (6)	0.0350 (9)
H7A	0.4297	0.1122	0.2937	0.042*
C8	0.9051 (7)	0.4956 (7)	0.4687 (6)	0.0366 (10)
H8A	1.0435	0.5350	0.5675	0.044*
N9	0.6050 (6)	0.5912 (5)	0.3492 (4)	0.0282 (7)
C10	0.5210 (8)	0.7348 (7)	0.3770 (6)	0.0387 (10)
H10A	0.3732	0.6851	0.2901	0.046*
H10B	0.6058	0.8552	0.3649	0.046*
C11	0.5246 (10)	0.7812 (9)	0.5452 (7)	0.0511 (13)
H11A	0.4759	0.8814	0.5544	0.061*
H11B	0.4263	0.6655	0.5538	0.061*
C12	0.7514 (11)	0.8511 (10)	0.6861 (7)	0.0550 (15)
H12A	0.7504	0.8720	0.7926	0.066*
H12B	0.8478	0.9734	0.6845	0.066*
C13	0.8302 (9)	0.6960 (9)	0.6631 (6)	0.0452 (13)
H13A	0.7398	0.5777	0.6743	0.054*
H13B	0.9771	0.7416	0.7504	0.054*
C14	0.8245 (7)	0.6492 (6)	0.4918 (5)	0.0315 (8)
H14A	0.9245	0.7695	0.4878	0.038*
C15	0.9415 (7)	0.4698 (7)	0.3149 (6)	0.0374 (10)
H15A	1.0399	0.5955	0.3198	0.045*
H15B	1.0109	0.3840	0.3192	0.045*
C16	0.4477 (7)	0.3884 (6)	0.3169 (5)	0.0322 (9)
H16A	0.3164	0.3525	0.2149	0.039*
H16B	0.4104	0.3852	0.4074	0.039*
C17	0.7462 (9)	0.2974 (7)	0.4580 (6)	0.0408 (10)
H17A	0.8019	0.2021	0.4514	0.049*
H17B	0.7233	0.3076	0.5555	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0304 (3)	0.0336 (3)	0.0299 (2)	0.0126 (2)	0.0142 (2)	0.0132 (2)
Br1	0.0473 (3)	0.0442 (3)	0.0787 (4)	0.0112 (2)	0.0343 (3)	0.0297 (3)
Br2	0.0509 (3)	0.0706 (4)	0.0441 (3)	0.0325 (3)	0.0055 (2)	0.0242 (3)
N1	0.0305 (17)	0.0320 (18)	0.0334 (18)	0.0116 (15)	0.0196 (15)	0.0106 (15)
C2	0.057 (3)	0.048 (3)	0.056 (3)	0.027 (3)	0.043 (3)	0.020 (2)
C3	0.069 (4)	0.051 (3)	0.043 (3)	0.021 (3)	0.040 (3)	0.014 (2)
C4	0.070 (4)	0.049 (3)	0.042 (3)	0.009 (3)	0.032 (3)	0.000 (2)
C5	0.039 (2)	0.034 (2)	0.032 (2)	0.0028 (19)	0.0141 (19)	0.0004 (18)
C6	0.037 (2)	0.028 (2)	0.041 (2)	0.0143 (17)	0.0235 (19)	0.0094 (17)
C7	0.037 (2)	0.033 (2)	0.036 (2)	0.0103 (18)	0.0216 (19)	0.0135 (18)
C8	0.030 (2)	0.045 (3)	0.031 (2)	0.018 (2)	0.0086 (17)	0.0164 (19)
N9	0.0254 (16)	0.0323 (18)	0.0232 (15)	0.0118 (14)	0.0092 (13)	0.0071 (13)
C10	0.035 (2)	0.040 (3)	0.037 (2)	0.018 (2)	0.0152 (19)	0.0048 (19)
C11	0.054 (3)	0.058 (3)	0.044 (3)	0.026 (3)	0.027 (3)	0.005 (2)
C12	0.062 (4)	0.056 (4)	0.033 (2)	0.021 (3)	0.018 (2)	−0.001 (2)
C13	0.040 (3)	0.052 (3)	0.025 (2)	0.011 (2)	0.0095 (19)	0.003 (2)
C14	0.0234 (18)	0.034 (2)	0.0262 (18)	0.0062 (16)	0.0075 (15)	0.0075 (16)
C15	0.027 (2)	0.044 (3)	0.044 (2)	0.0180 (19)	0.0156 (18)	0.016 (2)
C16	0.0245 (19)	0.036 (2)	0.030 (2)	0.0067 (17)	0.0148 (16)	0.0072 (17)
C17	0.049 (3)	0.040 (2)	0.039 (2)	0.021 (2)	0.021 (2)	0.022 (2)

Geometric parameters (Å, º)

Zn1—N1	2.077 (4)	C8—C14	1.532 (7)
Zn1—N9	2.092 (3)	C8—C15	1.534 (7)
Zn1—Br2	2.3590 (7)	C8—H8A	0.9800
Zn1—Br1	2.3784 (7)	N9—C10	1.492 (6)
N1—C15	1.488 (6)	N9—C16	1.492 (6)
N1—C2	1.494 (6)	N9—C14	1.504 (5)
N1—C6	1.508 (6)	C10—C11	1.521 (7)
C2—C3	1.498 (9)	C10—H10A	0.9700
C2—H2A	0.9700	C10—H10B	0.9700
C2—H2B	0.9700	C11—C12	1.518 (9)
C3—C4	1.533 (8)	C11—H11A	0.9700
C3—H3A	0.9700	C11—H11B	0.9700
C3—H3B	0.9700	C12—C13	1.532 (9)
C4—C5	1.520 (7)	C12—H12A	0.9700
C4—H4A	0.9700	C12—H12B	0.9700
C4—H4B	0.9700	C13—C14	1.542 (6)
C5—C6	1.521 (7)	C13—H13A	0.9700
C5—H5A	0.9700	C13—H13B	0.9700
C5—H5B	0.9700	C14—H14A	0.9800
C6—C7	1.537 (6)	C15—H15A	0.9700
C6—H6A	0.9800	C15—H15B	0.9700
C7—C17	1.525 (7)	C16—H16A	0.9700
C7—C16	1.541 (7)	C16—H16B	0.9700
C7—H7A	0.9800	C17—H17A	0.9700
C8—C17	1.531 (7)	C17—H17B	0.9700
Br2···H8A^i	2.986	H5A···H13B^iii	2.317
H3A···H17B^ii	2.319	H10B···H17A^iv	2.390
N1—Zn1—N9	88.66 (14)	C10—N9—C16	111.5 (3)
N1—Zn1—Br2	124.28 (11)	C10—N9—C14	110.6 (3)
N9—Zn1—Br2	108.51 (10)	C16—N9—C14	112.5 (3)
N1—Zn1—Br1	107.81 (10)	C10—N9—Zn1	105.3 (3)
N9—Zn1—Br1	110.88 (10)	C16—N9—Zn1	108.5 (2)
Br2—Zn1—Br1	113.69 (3)	C14—N9—Zn1	108.1 (2)
C15—N1—C2	108.0 (4)	N9—C10—C11	115.6 (4)
C15—N1—C6	110.0 (3)	N9—C10—H10A	108.4
C2—N1—C6	108.7 (4)	C11—C10—H10A	108.4
C15—N1—Zn1	105.6 (3)	N9—C10—H10B	108.4
C2—N1—Zn1	111.5 (3)	C11—C10—H10B	108.4
C6—N1—Zn1	112.9 (3)	H10A—C10—H10B	107.5
N1—C2—C3	111.5 (5)	C12—C11—C10	110.5 (5)
N1—C2—H2A	109.3	C12—C11—H11A	109.5
C3—C2—H2A	109.3	C10—C11—H11A	109.5
N1—C2—H2B	109.3	C12—C11—H11B	109.5
C3—C2—H2B	109.3	C10—C11—H11B	109.5
H2A—C2—H2B	108.0	H11A—C11—H11B	108.1
C2—C3—C4	112.1 (5)	C11—C12—C13	108.7 (5)
C2—C3—H3A	109.2	C11—C12—H12A	110.0
C4—C3—H3A	109.2	C13—C12—H12A	110.0
C2—C3—H3B	109.2	C11—C12—H12B	110.0
C4—C3—H3B	109.2	C13—C12—H12B	110.0
H3A—C3—H3B	107.9	H12A—C12—H12B	108.3
C5—C4—C3	110.5 (4)	C12—C13—C14	112.2 (4)
C5—C4—H4A	109.6	C12—C13—H13A	109.2
C3—C4—H4A	109.6	C14—C13—H13A	109.2
C5—C4—H4B	109.6	C12—C13—H13B	109.2
C3—C4—H4B	109.6	C14—C13—H13B	109.2
H4A—C4—H4B	108.1	H13A—C13—H13B	107.9
C4—C5—C6	111.5 (5)	N9—C14—C8	110.7 (3)
C4—C5—H5A	109.3	N9—C14—C13	112.5 (4)
C6—C5—H5A	109.3	C8—C14—C13	112.5 (4)
C4—C5—H5B	109.3	N9—C14—H14A	106.9
C6—C5—H5B	109.3	C8—C14—H14A	106.9
H5A—C5—H5B	108.0	C13—C14—H14A	106.9
N1—C6—C5	110.7 (4)	N1—C15—C8	114.4 (4)
N1—C6—C7	111.1 (3)	N1—C15—H15A	108.7
C5—C6—C7	114.2 (4)	C8—C15—H15A	108.7
N1—C6—H6A	106.8	N1—C15—H15B	108.7
C5—C6—H6A	106.8	C8—C15—H15B	108.7
C7—C6—H6A	106.8	H15A—C15—H15B	107.6
C17—C7—C6	108.4 (4)	N9—C16—C7	113.3 (3)
C17—C7—C16	109.1 (4)	N9—C16—H16A	108.9
C6—C7—C16	115.8 (4)	C7—C16—H16A	108.9
C17—C7—H7A	107.7	N9—C16—H16B	108.9
C6—C7—H7A	107.7	C7—C16—H16B	108.9
C16—C7—H7A	107.7	H16A—C16—H16B	107.7
C17—C8—C14	110.3 (4)	C7—C17—C8	106.6 (4)
C17—C8—C15	108.3 (4)	C7—C17—H17A	110.4
C14—C8—C15	114.7 (4)	C8—C17—H17A	110.4
C17—C8—H8A	107.8	C7—C17—H17B	110.4
C14—C8—H8A	107.8	C8—C17—H17B	110.4
C15—C8—H8A	107.8	H17A—C17—H17B	108.6
N9—Zn1—N1—C15	−61.8 (3)	Br2—Zn1—N9—C14	−170.5 (2)
Br2—Zn1—N1—C15	−173.4 (2)	Br1—Zn1—N9—C14	−44.9 (3)
Br1—Zn1—N1—C15	49.7 (3)	C16—N9—C10—C11	74.6 (5)
N9—Zn1—N1—C2	−178.8 (3)	C14—N9—C10—C11	−51.5 (5)
Br2—Zn1—N1—C2	69.6 (4)	Zn1—N9—C10—C11	−168.0 (4)
Br1—Zn1—N1—C2	−67.3 (3)	N9—C10—C11—C12	55.6 (7)
N9—Zn1—N1—C6	58.4 (3)	C10—C11—C12—C13	−55.8 (7)
Br2—Zn1—N1—C6	−53.2 (3)	C11—C12—C13—C14	56.8 (6)
Br1—Zn1—N1—C6	170.0 (2)	C10—N9—C14—C8	176.6 (4)
C15—N1—C2—C3	179.5 (4)	C16—N9—C14—C8	51.1 (4)
C6—N1—C2—C3	60.2 (6)	Zn1—N9—C14—C8	−68.7 (4)
Zn1—N1—C2—C3	−64.9 (5)	C10—N9—C14—C13	49.7 (5)
N1—C2—C3—C4	−56.7 (7)	C16—N9—C14—C13	−75.7 (5)
C2—C3—C4—C5	51.6 (7)	Zn1—N9—C14—C13	164.5 (3)
C3—C4—C5—C6	−51.9 (7)	C17—C8—C14—N9	−58.9 (5)
C15—N1—C6—C5	−178.4 (4)	C15—C8—C14—N9	63.6 (5)
C2—N1—C6—C5	−60.3 (5)	C17—C8—C14—C13	67.9 (5)
Zn1—N1—C6—C5	64.0 (4)	C15—C8—C14—C13	−169.6 (4)
C15—N1—C6—C7	53.7 (5)	C12—C13—C14—N9	−54.7 (5)
C2—N1—C6—C7	171.7 (4)	C12—C13—C14—C8	179.5 (4)
Zn1—N1—C6—C7	−64.0 (4)	C2—N1—C15—C8	−170.7 (4)
C4—C5—C6—N1	57.4 (5)	C6—N1—C15—C8	−52.2 (5)
C4—C5—C6—C7	−176.3 (4)	Zn1—N1—C15—C8	69.9 (4)
N1—C6—C7—C17	−62.0 (5)	C17—C8—C15—N1	57.3 (5)
C5—C6—C7—C17	172.0 (4)	C14—C8—C15—N1	−66.3 (5)
N1—C6—C7—C16	61.0 (5)	C10—N9—C16—C7	−175.6 (4)
C5—C6—C7—C16	−65.0 (5)	C14—N9—C16—C7	−50.7 (5)
N1—Zn1—N9—C10	−178.1 (3)	Zn1—N9—C16—C7	68.9 (4)
Br2—Zn1—N9—C10	−52.2 (3)	C17—C7—C16—N9	56.4 (5)
Br1—Zn1—N9—C10	73.3 (3)	C6—C7—C16—N9	−66.2 (5)
N1—Zn1—N9—C16	−58.6 (3)	C6—C7—C17—C8	65.4 (5)
Br2—Zn1—N9—C16	67.3 (3)	C16—C7—C17—C8	−61.6 (5)
Br1—Zn1—N9—C16	−167.2 (2)	C14—C8—C17—C7	64.2 (5)
N1—Zn1—N9—C14	63.6 (3)	C15—C8—C17—C7	−62.0 (5)

Symmetry codes: (i) x−1, y, z−1; (ii) x, y, z−1; (iii) x−1, y−1, z−1; (iv) x, y+1, z.