1,8-Di-aza-bicyclo-[5.4.0]undec-7-en-8-ium bromido-(phthalocyaninato)zincate.

The title compound, (C9H17N2)[ZnBr(C32H16N8)], contains a bromido-(phthalocyaninato)zincate anion and a protonated 1,8-di-aza-bicyclo-[5.4.0]undece-7-ene cation, [DBUH](+). The central Zn(II) atom has a distorted square-pyramidal geometry, with four iso-indole N atoms of the macrocycle in equatorial positions and a bromide ion in the axial position. The latter has a relatively high displacement parameter, but no evidence for disorder was obtained. The central Zn(II) atom is displaced by 0.488 (3) Å from the mean plane defined by the four iso-indole N atoms. The [DBUH](+) cation is involved in an almost linear N-H⋯Br hydrogen bond. In the crystal, π-π inter-actions lead to a relatively short distance of 3.366 (3) Å between the phthalocyaninate rings.

Related literature

For background information on phthalocyanines, see: n class="Chemical">Nyokong et al. (1987 ▶); Gregory (2000 ▶); Leznoff & Lever (1996 ▶); Tedesco et al. (2003 ▶); Ormond & Freeman (2013 ▶). For related structures, see: Kobayashi et al. (1971 ▶); Mossoyan-Deneux et al. (1985 ▶); Zeng et al. (2005 ▶); Del Sole et al. (2005 ▶); Kubiak et al. (2007 ▶); Yang et al. (2008 ▶); Janczak et al. (2009 ▶, 2011 ▶); Janczak & Kubiak (2009 ▶); Li et al. (2011 ▶); Przybył & Janczak (2014 ▶).

Experimental

Crystal data

(C9H17N2)[ZnBr(C32H16N8)]

M = 811.05

Monoclinic,

a = 12.4336 (8) Å

b = 22.9278 (16) Å

c = 13.3267 (9) Å

β = 113.266 (4)°

V = 3490.2 (4) Å3

Z = 4

Mo Kα radiation

μ = 1.90 mm−1

T = 295 K

0.35 × 0.21 × 0.19 mm

Data collection

Kuma KM-4 with CCD detector diffractometer

Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2008 ▶) T min = 0.562, T max = 0.725

42041 measured reflections

8492 independent reflections

4908 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.143

S = 1.00

8492 reflections

478 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.76 e Å−3

Δρmin = −1.26 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data n class="Disease">reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681401157X/fj2673sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401157X/fj2673Isup2.hkl

CCDC reference: 1003951

Additional supporting information: crystallographic information; 3D view; checkCIF report

(C9H17N2)[ZnBr(C32H16N8)]	F(000) = 1656
Mr = 811.05	Dx = 1.544 Mg m−3Dm = 1.54 Mg m−3Dm measured by floatation
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3452 reflections
a = 12.4336 (8) Å	θ = 2.6–27.5°
b = 22.9278 (16) Å	µ = 1.90 mm−1
c = 13.3267 (9) Å	T = 295 K
β = 113.266 (4)°	Parallelepiped, blue-violet
V = 3490.2 (4) Å3	0.35 × 0.21 × 0.19 mm
Z = 4

Kuma KM-4 with CCD detector diffractometer	8492 independent reflections
Radiation source: fine-focus sealed tube	4908 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scan	θmax = 28.8°, θmin = 2.6°
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2008)	h = −16→12
Tmin = 0.562, Tmax = 0.725	k = −30→30
42041 measured reflections	l = −17→17

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.076P)2] where P = (Fo2 + 2Fc2)/3
8492 reflections	(Δ/σ)max < 0.001
478 parameters	Δρmax = 0.76 e Å−3
0 restraints	Δρmin = −1.26 e Å−3

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
Zn1	0.45113 (3)	0.025014 (16)	0.31931 (3)	0.02443 (12)
Br1	0.34125 (5)	0.06134 (3)	0.13296 (5)	0.07214 (19)
N1	0.4406 (2)	0.14541 (12)	0.4657 (2)	0.0260 (6)
N2	0.3569 (2)	0.04946 (12)	0.4069 (2)	0.0262 (6)
N3	0.2243 (2)	−0.03246 (12)	0.3688 (2)	0.0266 (6)
N4	0.3855 (2)	−0.05667 (12)	0.3176 (2)	0.0257 (6)
N5	0.5072 (2)	−0.11056 (12)	0.2462 (2)	0.0274 (7)
N6	0.5907 (2)	−0.01490 (11)	0.3055 (2)	0.0241 (6)
N7	0.7220 (2)	0.06751 (12)	0.3406 (2)	0.0255 (6)
N8	0.5615 (2)	0.09175 (12)	0.3933 (2)	0.0255 (6)
C1	0.3601 (3)	0.10425 (14)	0.4491 (3)	0.0241 (7)
C2	0.2578 (3)	0.11214 (15)	0.4761 (3)	0.0254 (7)
C3	0.2179 (3)	0.15852 (16)	0.5191 (3)	0.0360 (9)
H3	0.2594	0.1934	0.5376	0.043*
C4	0.1140 (3)	0.15119 (18)	0.5335 (3)	0.0392 (10)
H4	0.0851	0.1817	0.5615	0.047*
C5	0.0527 (3)	0.09887 (18)	0.5065 (3)	0.0374 (9)
H5	−0.0170	0.0953	0.5163	0.045*
C6	0.0927 (3)	0.05206 (16)	0.4655 (3)	0.0310 (8)
H6	0.0522	0.0169	0.4497	0.037*
C7	0.1959 (3)	0.05924 (15)	0.4485 (3)	0.0257 (8)
C8	0.2596 (3)	0.02122 (15)	0.4053 (3)	0.0257 (7)
C9	0.2820 (3)	−0.06799 (14)	0.3283 (3)	0.0259 (8)
C10	0.2418 (3)	−0.12622 (15)	0.2871 (3)	0.0282 (8)
C11	0.1426 (3)	−0.15806 (16)	0.2767 (3)	0.0351 (9)
H11	0.0886	−0.1438	0.3030	0.042*
C12	0.1275 (4)	−0.21193 (17)	0.2256 (4)	0.0445 (11)
H12	0.0614	−0.2339	0.2167	0.053*
C13	0.2086 (4)	−0.23419 (18)	0.1871 (4)	0.0460 (11)
H13	0.1959	−0.2707	0.1542	0.055*
C14	0.3078 (3)	−0.20285 (15)	0.1971 (3)	0.0376 (9)
H14	0.3614	−0.2172	0.1704	0.045*
C15	0.3235 (3)	−0.14865 (15)	0.2493 (3)	0.0282 (8)
C16	0.4146 (3)	−0.10403 (14)	0.2715 (3)	0.0274 (8)
C17	0.5885 (3)	−0.06958 (14)	0.2633 (3)	0.0260 (8)
C18	0.6887 (3)	−0.07754 (16)	0.2344 (3)	0.0295 (8)
C19	0.7285 (3)	−0.12345 (17)	0.1915 (3)	0.0371 (9)
H19	0.6885	−0.1588	0.1745	0.044*
C20	0.8312 (4)	−0.11469 (19)	0.1750 (4)	0.0459 (11)
H20	0.8592	−0.1448	0.1453	0.055*
C21	0.8930 (3)	−0.06286 (18)	0.2010 (3)	0.0402 (10)
H21	0.9618	−0.0591	0.1897	0.048*
C22	0.8530 (3)	−0.01619 (17)	0.2442 (3)	0.0324 (8)
H22	0.8930	0.0191	0.2604	0.039*
C23	0.7526 (3)	−0.02415 (15)	0.2619 (3)	0.0285 (8)
C24	0.6867 (3)	0.01334 (14)	0.3065 (3)	0.0240 (7)
C25	0.6642 (3)	0.10279 (14)	0.3824 (3)	0.0238 (7)
C26	0.7048 (3)	0.16120 (14)	0.4240 (3)	0.0259 (8)
C27	0.8037 (3)	0.19329 (16)	0.4326 (3)	0.0325 (9)
H27	0.8576	0.1789	0.4064	0.039*
C28	0.8176 (3)	0.24766 (17)	0.4819 (3)	0.0388 (10)
H28	0.8823	0.2702	0.4885	0.047*
C29	0.7384 (3)	0.26927 (16)	0.5212 (3)	0.0386 (9)
H29	0.7520	0.3054	0.5556	0.046*
C30	0.6399 (3)	0.23853 (15)	0.5107 (3)	0.0343 (9)
H30	0.5853	0.2538	0.5351	0.041*
C31	0.6246 (3)	0.18372 (14)	0.4624 (3)	0.0253 (8)
C32	0.5330 (3)	0.13890 (14)	0.4404 (3)	0.0226 (7)
N9	0.2108 (3)	−0.14631 (15)	−0.0847 (3)	0.0429 (8)
C34	0.3084 (4)	−0.1587 (2)	−0.1199 (4)	0.0594 (13)
H34A	0.3181	−0.2006	−0.1233	0.089*
H34B	0.2896	−0.1429	−0.1923	0.089*
C35	0.4196 (4)	−0.1325 (2)	−0.0422 (4)	0.0561 (12)
H35A	0.4797	−0.1363	−0.0710	0.084*
H35B	0.4458	−0.1530	0.0271	0.084*
C36	0.4004 (4)	−0.0697 (2)	−0.0254 (4)	0.0532 (12)
H36A	0.4691	−0.0541	0.0332	0.080*
H36B	0.3888	−0.0480	−0.0914	0.080*
N10	0.3005 (3)	−0.06292 (16)	0.0010 (3)	0.0476 (9)
H10	0.2977 (9)	−0.0324 (8)	0.0388 (8)	0.057*
C37	0.2124 (3)	−0.09974 (18)	−0.0279 (3)	0.0395 (10)
C38	0.1153 (4)	−0.0872 (2)	0.0084 (4)	0.0559 (12)
H38A	0.1389	−0.0553	0.0602	0.084*
H38B	0.1036	−0.1212	0.0461	0.084*
C39	−0.0027 (4)	−0.0713 (2)	−0.0856 (4)	0.0540 (12)
H39A	−0.0530	−0.0533	−0.0543	0.081*
H39B	0.0121	−0.0426	−0.1321	0.081*
C40	−0.0669 (4)	−0.1216 (2)	−0.1551 (4)	0.0629 (14)
H40A	−0.0897	−0.1479	−0.1100	0.094*
H40B	−0.1382	−0.1068	−0.2117	0.094*
C41	−0.0026 (4)	−0.1557 (2)	−0.2082 (4)	0.0668 (15)
H41A	0.0188	−0.1299	−0.2549	0.100*
H41B	−0.0548	−0.1852	−0.2545	0.100*
C42	0.1090 (4)	−0.18605 (19)	−0.1279 (4)	0.0546 (12)
H42A	0.0936	−0.2018	−0.0673	0.082*
H42B	0.1281	−0.2184	−0.1648	0.082*

	U11	U22	U33	U12	U13	U23
Zn1	0.0227 (2)	0.0204 (2)	0.0316 (2)	−0.00134 (17)	0.01218 (17)	−0.00316 (18)
Br1	0.0702 (4)	0.0754 (4)	0.0621 (4)	0.0065 (3)	0.0168 (3)	0.0066 (3)
N1	0.0239 (15)	0.0223 (15)	0.0314 (17)	0.0007 (12)	0.0104 (13)	−0.0021 (13)
N2	0.0263 (15)	0.0239 (15)	0.0305 (16)	−0.0017 (12)	0.0136 (13)	0.0001 (13)
N3	0.0244 (15)	0.0224 (15)	0.0341 (17)	−0.0033 (12)	0.0128 (13)	−0.0002 (13)
N4	0.0275 (16)	0.0212 (15)	0.0307 (16)	−0.0026 (12)	0.0141 (13)	−0.0024 (13)
N5	0.0256 (15)	0.0246 (15)	0.0293 (17)	0.0032 (13)	0.0079 (13)	−0.0016 (13)
N6	0.0220 (14)	0.0210 (15)	0.0287 (16)	0.0013 (11)	0.0094 (13)	−0.0008 (12)
N7	0.0227 (15)	0.0253 (15)	0.0293 (16)	0.0009 (12)	0.0111 (13)	−0.0002 (13)
N8	0.0237 (15)	0.0221 (14)	0.0309 (17)	−0.0018 (12)	0.0111 (13)	−0.0019 (13)
C1	0.0236 (17)	0.0230 (17)	0.0250 (18)	0.0022 (14)	0.0089 (15)	0.0004 (15)
C2	0.0193 (17)	0.0291 (18)	0.0270 (19)	0.0036 (14)	0.0083 (15)	0.0006 (15)
C3	0.035 (2)	0.028 (2)	0.043 (2)	0.0000 (17)	0.0139 (19)	−0.0059 (18)
C4	0.033 (2)	0.042 (2)	0.048 (3)	0.0118 (18)	0.022 (2)	−0.001 (2)
C5	0.028 (2)	0.048 (2)	0.039 (2)	0.0058 (18)	0.0154 (18)	0.0071 (19)
C6	0.0262 (19)	0.035 (2)	0.034 (2)	−0.0013 (16)	0.0144 (17)	0.0067 (17)
C7	0.0234 (18)	0.0280 (19)	0.0252 (19)	0.0026 (15)	0.0088 (15)	0.0022 (15)
C8	0.0224 (17)	0.0276 (18)	0.0277 (18)	−0.0003 (15)	0.0104 (15)	0.0063 (16)
C9	0.0239 (18)	0.0228 (17)	0.0289 (19)	−0.0020 (14)	0.0082 (16)	0.0025 (15)
C10	0.0273 (19)	0.0231 (18)	0.030 (2)	−0.0029 (15)	0.0061 (16)	0.0034 (15)
C11	0.035 (2)	0.030 (2)	0.036 (2)	−0.0078 (17)	0.0096 (18)	0.0049 (17)
C12	0.037 (2)	0.035 (2)	0.052 (3)	−0.0131 (18)	0.007 (2)	0.002 (2)
C13	0.053 (3)	0.030 (2)	0.049 (3)	−0.012 (2)	0.015 (2)	−0.011 (2)
C14	0.041 (2)	0.0218 (19)	0.044 (2)	−0.0011 (17)	0.0099 (19)	−0.0040 (17)
C15	0.0302 (19)	0.0231 (18)	0.0266 (19)	−0.0028 (15)	0.0063 (16)	0.0011 (15)
C16	0.0285 (19)	0.0202 (17)	0.0297 (19)	0.0030 (15)	0.0074 (16)	0.0030 (15)
C17	0.0262 (18)	0.0240 (17)	0.0233 (18)	0.0032 (15)	0.0051 (15)	−0.0005 (15)
C18	0.0252 (19)	0.0313 (19)	0.0268 (19)	0.0051 (15)	0.0049 (16)	−0.0023 (16)
C19	0.036 (2)	0.034 (2)	0.041 (2)	0.0067 (17)	0.0140 (19)	−0.0100 (18)
C20	0.046 (3)	0.043 (2)	0.053 (3)	0.009 (2)	0.025 (2)	−0.014 (2)
C21	0.034 (2)	0.050 (3)	0.041 (2)	0.0038 (19)	0.019 (2)	−0.002 (2)
C22	0.0306 (19)	0.035 (2)	0.034 (2)	0.0060 (16)	0.0157 (17)	0.0019 (17)
C23	0.0282 (18)	0.0276 (18)	0.0288 (19)	0.0018 (16)	0.0102 (16)	0.0024 (16)
C24	0.0234 (17)	0.0253 (18)	0.0240 (18)	0.0027 (14)	0.0101 (15)	0.0008 (14)
C25	0.0205 (17)	0.0227 (17)	0.0287 (19)	−0.0007 (14)	0.0102 (15)	0.0011 (15)
C26	0.0233 (17)	0.0208 (17)	0.0295 (19)	−0.0021 (14)	0.0062 (15)	0.0028 (15)
C27	0.0269 (19)	0.032 (2)	0.039 (2)	−0.0040 (16)	0.0133 (17)	0.0049 (17)
C28	0.033 (2)	0.029 (2)	0.049 (3)	−0.0078 (17)	0.0103 (19)	0.0070 (19)
C29	0.038 (2)	0.0238 (19)	0.047 (2)	−0.0064 (17)	0.009 (2)	−0.0039 (18)
C30	0.035 (2)	0.0235 (19)	0.042 (2)	0.0027 (16)	0.0131 (18)	−0.0008 (17)
C31	0.0243 (18)	0.0190 (17)	0.0286 (19)	−0.0013 (14)	0.0062 (15)	0.0015 (14)
C32	0.0195 (16)	0.0198 (16)	0.0267 (18)	0.0012 (13)	0.0071 (15)	−0.0004 (14)
N9	0.043 (2)	0.043 (2)	0.041 (2)	0.0002 (17)	0.0150 (17)	0.0038 (17)
C34	0.070 (3)	0.060 (3)	0.059 (3)	0.004 (3)	0.038 (3)	−0.002 (3)
C35	0.047 (3)	0.066 (3)	0.059 (3)	0.008 (2)	0.025 (2)	0.013 (3)
C36	0.034 (2)	0.072 (3)	0.044 (3)	−0.006 (2)	0.005 (2)	0.014 (2)
N10	0.046 (2)	0.050 (2)	0.037 (2)	−0.0004 (18)	0.0054 (17)	0.0001 (17)
C37	0.036 (2)	0.045 (2)	0.031 (2)	0.0023 (19)	0.0059 (18)	0.0049 (19)
C38	0.055 (3)	0.070 (3)	0.044 (3)	0.015 (2)	0.021 (2)	0.007 (2)
C39	0.045 (3)	0.054 (3)	0.067 (3)	0.007 (2)	0.026 (3)	0.019 (2)
C40	0.042 (3)	0.057 (3)	0.078 (4)	−0.003 (2)	0.011 (3)	0.021 (3)
C41	0.053 (3)	0.050 (3)	0.070 (4)	−0.014 (2)	−0.005 (3)	0.002 (3)
C42	0.056 (3)	0.039 (2)	0.061 (3)	−0.009 (2)	0.015 (2)	0.006 (2)

Zn1—N2	2.032 (3)	C19—H19	0.9300
Zn1—N8	2.032 (3)	C20—C21	1.383 (6)
Zn1—N6	2.034 (3)	C20—H20	0.9300
Zn1—N4	2.040 (3)	C21—C22	1.396 (5)
Zn1—Br1	2.4591 (7)	C21—H21	0.9300
N1—C32	1.327 (4)	C22—C23	1.370 (5)
N1—C1	1.328 (4)	C22—H22	0.9300
N2—C8	1.366 (4)	C23—C24	1.466 (5)
N2—C1	1.370 (4)	C25—C26	1.461 (5)
N3—C8	1.332 (4)	C26—C31	1.388 (5)
N3—C9	1.333 (4)	C26—C27	1.398 (5)
N4—C16	1.365 (4)	C27—C28	1.388 (5)
N4—C9	1.374 (4)	C27—H27	0.9300
N5—C16	1.330 (4)	C28—C29	1.378 (5)
N5—C17	1.332 (4)	C28—H28	0.9300
N6—C24	1.353 (4)	C29—C30	1.371 (5)
N6—C17	1.370 (4)	C29—H29	0.9300
N7—C24	1.336 (4)	C30—C31	1.390 (5)
N7—C25	1.341 (4)	C30—H30	0.9300
N8—C32	1.365 (4)	C31—C32	1.475 (4)
N8—C25	1.365 (4)	N9—C37	1.304 (5)
C1—C2	1.465 (4)	N9—C42	1.479 (5)
C2—C3	1.389 (5)	N9—C34	1.492 (5)
C2—C7	1.405 (5)	C34—C35	1.488 (6)
C3—C4	1.389 (5)	C34—H34A	0.9700
C3—H3	0.9300	C34—H34B	0.9700
C4—C5	1.390 (6)	C35—C36	1.491 (6)
C4—H4	0.9300	C35—H35A	0.9700
C5—C6	1.383 (5)	C35—H35B	0.9700
C5—H5	0.9300	C36—N10	1.428 (5)
C6—C7	1.397 (5)	C36—H36A	0.9700
C6—H6	0.9300	C36—H36B	0.9700
C7—C8	1.442 (5)	N10—C37	1.314 (5)
C9—C10	1.455 (5)	N10—H10	0.87 (2)
C10—C11	1.393 (5)	C37—C38	1.495 (6)
C10—C15	1.398 (5)	C38—C39	1.551 (6)
C11—C12	1.387 (5)	C38—H38A	0.9700
C11—H11	0.9300	C38—H38B	0.9700
C12—C13	1.396 (6)	C39—C40	1.496 (7)
C12—H12	0.9300	C39—H39A	0.9700
C13—C14	1.388 (5)	C39—H39B	0.9700
C13—H13	0.9300	C40—C41	1.483 (7)
C14—C15	1.400 (5)	C40—H40A	0.9700
C14—H14	0.9300	C40—H40B	0.9700
C15—C16	1.467 (5)	C41—C42	1.544 (6)
C17—C18	1.454 (5)	C41—H41A	0.9700
C18—C19	1.379 (5)	C41—H41B	0.9700
C18—C23	1.426 (5)	C42—H42A	0.9700
C19—C20	1.393 (5)	C42—H42B	0.9700
N2—Zn1—N8	86.86 (11)	C23—C22—H22	121.1
N2—Zn1—N6	151.95 (12)	C21—C22—H22	121.1
N8—Zn1—N6	86.90 (11)	C22—C23—C18	121.5 (3)
N2—Zn1—N4	86.61 (11)	C22—C23—C24	133.2 (3)
N8—Zn1—N4	152.57 (12)	C18—C23—C24	105.3 (3)
N6—Zn1—N4	86.44 (11)	N7—C24—N6	128.2 (3)
N2—Zn1—Br1	105.68 (8)	N7—C24—C23	121.5 (3)
N8—Zn1—Br1	103.56 (8)	N6—C24—C23	110.3 (3)
N6—Zn1—Br1	102.38 (8)	N7—C25—N8	127.6 (3)
N4—Zn1—Br1	103.85 (8)	N7—C25—C26	123.3 (3)
C32—N1—C1	123.2 (3)	N8—C25—C26	109.0 (3)
C8—N2—C1	108.8 (3)	C31—C26—C27	120.7 (3)
C8—N2—Zn1	124.7 (2)	C31—C26—C25	106.9 (3)
C1—N2—Zn1	124.0 (2)	C27—C26—C25	132.3 (3)
C8—N3—C9	124.1 (3)	C28—C27—C26	116.9 (3)
C16—N4—C9	108.8 (3)	C28—C27—H27	121.5
C16—N4—Zn1	124.0 (2)	C26—C27—H27	121.5
C9—N4—Zn1	124.0 (2)	C29—C28—C27	121.9 (3)
C16—N5—C17	123.4 (3)	C29—C28—H28	119.0
C24—N6—C17	108.5 (3)	C27—C28—H28	119.0
C24—N6—Zn1	124.4 (2)	C30—C29—C28	121.3 (4)
C17—N6—Zn1	124.7 (2)	C30—C29—H29	119.3
C24—N7—C25	123.0 (3)	C28—C29—H29	119.3
C32—N8—C25	109.0 (3)	C29—C30—C31	117.7 (4)
C32—N8—Zn1	124.8 (2)	C29—C30—H30	121.1
C25—N8—Zn1	124.6 (2)	C31—C30—H30	121.1
N1—C1—N2	128.1 (3)	C26—C31—C30	121.3 (3)
N1—C1—C2	122.8 (3)	C26—C31—C32	106.1 (3)
N2—C1—C2	109.1 (3)	C30—C31—C32	132.5 (3)
C3—C2—C7	121.4 (3)	N1—C32—N8	127.9 (3)
C3—C2—C1	133.0 (3)	N1—C32—C31	123.3 (3)
C7—C2—C1	105.6 (3)	N8—C32—C31	108.9 (3)
C2—C3—C4	117.8 (3)	C37—N9—C42	123.1 (4)
C2—C3—H3	121.1	C37—N9—C34	120.7 (4)
C4—C3—H3	121.1	C42—N9—C34	115.9 (4)
C3—C4—C5	120.9 (3)	C35—C34—N9	110.6 (4)
C3—C4—H4	119.6	C35—C34—H34A	109.5
C5—C4—H4	119.6	N9—C34—H34A	109.5
C6—C5—C4	121.7 (3)	C35—C34—H34B	109.5
C6—C5—H5	119.1	N9—C34—H34B	109.5
C4—C5—H5	119.1	H34A—C34—H34B	108.1
C5—C6—C7	117.9 (3)	C34—C35—C36	109.6 (4)
C5—C6—H6	121.0	C34—C35—H35A	109.8
C7—C6—H6	121.0	C36—C35—H35A	109.8
C6—C7—C2	120.2 (3)	C34—C35—H35B	109.8
C6—C7—C8	132.7 (3)	C36—C35—H35B	109.8
C2—C7—C8	107.2 (3)	H35A—C35—H35B	108.2
N3—C8—N2	127.3 (3)	N10—C36—C35	110.4 (4)
N3—C8—C7	123.4 (3)	N10—C36—H36A	109.6
N2—C8—C7	109.3 (3)	C35—C36—H36A	109.6
N3—C9—N4	127.1 (3)	N10—C36—H36B	109.6
N3—C9—C10	123.6 (3)	C35—C36—H36B	109.6
N4—C9—C10	109.3 (3)	H36A—C36—H36B	108.1
C11—C10—C15	120.8 (3)	C37—N10—C36	124.3 (4)
C11—C10—C9	132.6 (3)	C37—N10—H10	118 (1)
C15—C10—C9	106.5 (3)	C36—N10—H10	118 (1)
C12—C11—C10	117.3 (4)	N9—C37—N10	121.2 (4)
C12—C11—H11	121.4	N9—C37—C38	121.0 (4)
C10—C11—H11	121.4	N10—C37—C38	117.9 (4)
C11—C12—C13	121.9 (4)	C37—C38—C39	114.3 (4)
C11—C12—H12	119.0	C37—C38—H38A	108.7
C13—C12—H12	119.0	C39—C38—H38A	108.7
C14—C13—C12	121.3 (4)	C37—C38—H38B	108.7
C14—C13—H13	119.4	C39—C38—H38B	108.7
C12—C13—H13	119.4	H38A—C38—H38B	107.6
C13—C14—C15	116.8 (4)	C40—C39—C38	114.9 (4)
C13—C14—H14	121.6	C40—C39—H39A	108.5
C15—C14—H14	121.6	C38—C39—H39A	108.5
C10—C15—C14	121.8 (3)	C40—C39—H39B	108.5
C10—C15—C16	106.5 (3)	C38—C39—H39B	108.5
C14—C15—C16	131.6 (3)	H39A—C39—H39B	107.5
N5—C16—N4	127.9 (3)	C41—C40—C39	116.5 (4)
N5—C16—C15	123.2 (3)	C41—C40—H40A	108.2
N4—C16—C15	109.0 (3)	C39—C40—H40A	108.2
N5—C17—N6	127.4 (3)	C41—C40—H40B	108.2
N5—C17—C18	122.5 (3)	C39—C40—H40B	108.2
N6—C17—C18	110.0 (3)	H40A—C40—H40B	107.3
C19—C18—C23	120.4 (3)	C40—C41—C42	114.4 (5)
C19—C18—C17	133.7 (3)	C40—C41—H41A	108.7
C23—C18—C17	105.9 (3)	C42—C41—H41A	108.7
C18—C19—C20	117.2 (4)	C40—C41—H41B	108.7
C18—C19—H19	121.4	C42—C41—H41B	108.7
C20—C19—H19	121.4	H41A—C41—H41B	107.6
C21—C20—C19	122.5 (4)	N9—C42—C41	112.9 (3)
C21—C20—H20	118.8	N9—C42—H42A	109.0
C19—C20—H20	118.8	C41—C42—H42A	109.0
C20—C21—C22	120.6 (4)	N9—C42—H42B	109.0
C20—C21—H21	119.7	C41—C42—H42B	109.0
C22—C21—H21	119.7	H42A—C42—H42B	107.8
C23—C22—C21	117.7 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10···Br1	0.87 (2)	2.44 (2)	3.281 (4)	163 (2)

Compound	Zn—L	Zn—N4	Ref.
ZnPc—(DBU)	2.063 (2)	0.614 (2)	Janczak et al., 2011
ZnPc—(4-picoline)	2.166 (3)	0.352 (2)	Kubiak et al., 2007
ZnPc—(2-amino-3-picoline)	2.157 (2)	0.470 (2)	Janczak et al., 2009
ZnPc—(n-buthylamine)	2.073 (4)	0.494 (4)	Przybył & Janczak, 2014
ZnPc—(n-amylamine)	2.087 (3)	0.498 (4)	Przybył & Janczak, 2014
ZnPc—(n-heptylamine)	2.097 (2)	0.477 (4)	Przybył & Janczak, 2014
ZnPc—(n-hexylamine)	2.178	0.480	Kobayashi et al., 1971
ZnPc—(pyrazine)	2.178 (2)	0.371 (2)	Janczak & Kubiak, 2009
(ZnPc)2—(pyrazine)	2.207 (2)	0.296 (2)	Janczak & Kubiak, 2009
ZnPc—(4-aminopyridine)	2.092 (3)	0.446 (1)	Yang et al., 2008
ZnPc—(1,3-bis(4-pyridyl)propane)	2.130 (5)	0.375 (3)	Zeng et al., 2005
(ZnPc)2—(µ2-1,2-bis(4-pyridyl)ethane)	2.125 (7)	0.483 (4)	Zeng et al., 2005
(ZnPc)2—(µ2-1,2-bis(4-pyridyl)ethylene)	2.156 (2)	0.347 (2)	Zeng et al., 2005
(ZnPc)2—(µ2-N,N'-bis((pyridin-3-yl)methyl)ethanediamide)	2.147 (3)	0.377 (3)	Li et al., 2011
ZnPc—Cl	2.35	0.59	Mossoyan-Deneux et al., 1985
ZnPc—Br	2.459 (3)	0.488 (3)	this work

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10—H10⋯Br1	0.87 (2)	2.44 (2)	3.281 (4)	163 (2)