Charge-assisted hydrogen bonding in three di­amino­benzene salts

Hydrogen-bonding inter­actions play an important role in the rational design of crystal systems with desirable architectures. The crystal structures of benzene-1,2-diaminium sulfate sesquihydrate, C₆H₂₀N₂²⁺·SO₄²⁻·1.5H₂O, (1), benzene-1,3-diaminium tetra­chlorido­zincate(II), (C₆H₂₀N₂)[ZnCl₄], (3), and 3-amino­anilinium perchlorate, C₆H₉N₂⁺·ClO₄⁻, (4), are reported. Hydrated salt (1) is a polymorph (space group C2/c) of a previously reported [Anderson et al. (2011). Cryst. Growth Des. 11, 4904–4919] crystalline modification of salt (2) (space group P2₁/c). The contents of the asymmetric unit of (2) are twice that of (1). In each, the extended structures exhibit hydrogen bonds, resulting in chains of ions and hydrogen-bonded rings with an R₄⁴(8) motif involving water mol­ecules. Hirshfeld surface analysis shows that a significant difference between the two is the degree of C...C inter­action. Salt (3) exhibits an extended structure having hydrogen-bonded rings and parallel benzene rings, with a centroid-to-centroid separation of 3.860 (2) Å. Salt (4) displays a three-dimensional superstructure that results from linked planes of ions joined by an extensive hydrogen-bonding network involving N—H...O, N—H...N and C—H...π inter­actions. The cation–anion and N—H...N inter­action energies in (4), determined using density functional theory (DFT), show significantly stronger aminium–per­chlorate than amine–perchlorate inter­actions.

Computing details

For all structures, data collection: APEX2 (Bruker, 2015); cell refinement: APEX2 (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Benzene-1,2-diaminium sulfate sesquihydrate (1)

Crystal data

2C6H10N2^2+·2SO4^2^−·3H2O	F(000) = 984
Mr = 466.49	Dx = 1.535 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 28.348 (3) Å	Cell parameters from 6495 reflections
b = 9.6720 (9) Å	θ = 3.4–27.0°
c = 7.5667 (8) Å	µ = 0.33 mm^−1
β = 103.308 (4)°	T = 300 K
V = 2018.9 (4) Å^3	Plate, clear colourless
Z = 4	0.50 × 0.30 × 0.05 mm

Data collection

Bruker SMART X2S benchtop diffractometer	2218 independent reflections
Radiation source: XOS X-beam microfocus source	1881 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromator	Rint = 0.044
Detector resolution: 8.3330 pixels mm^-1	θmax = 27.1°, θmin = 2.2°
ω scans	h = −35→36
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −12→11
Tmin = 0.908, Tmax = 1.000	l = −9→9
15241 measured reflections

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)] = 0.043	Hydrogen site location: mixed
wR(F^2) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0539P)^2 + 4.0638P] where P = (Fo^2 + 2Fc^2)/3
2218 reflections	(Δ/σ)max = 0.001
166 parameters	Δρmax = 0.45 e Å^−3
2 restraints	Δρmin = −0.38 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.19815 (2)	0.83419 (6)	0.25370 (7)	0.01861 (18)
O1	0.21519 (8)	0.7412 (2)	0.1272 (3)	0.0371 (5)
O2	0.18628 (8)	0.75257 (18)	0.4004 (3)	0.0359 (5)
O3	0.15528 (7)	0.9103 (2)	0.1546 (3)	0.0432 (5)
O4	0.23676 (6)	0.93470 (18)	0.3279 (2)	0.0276 (4)
O5	0.0000	1.0132 (5)	0.2500	0.0638 (11)
H5A	−0.0168 (19)	0.957 (5)	0.290 (8)	0.096*
O6	0.05449 (9)	0.8495 (3)	0.0646 (4)	0.0635 (7)
H6A	0.0836 (8)	0.858 (5)	0.111 (6)	0.095*
H6B	0.0429 (18)	0.898 (5)	−0.021 (5)	0.095*
N1	0.17746 (9)	0.1850 (2)	0.2465 (3)	0.0284 (5)
H1A	0.1952 (11)	0.194 (3)	0.156 (4)	0.032 (8)*
H1B	0.1670 (11)	0.102 (4)	0.226 (4)	0.034 (8)*
H1C	0.1959 (15)	0.191 (4)	0.348 (6)	0.055 (11)*
N2	0.19378 (7)	0.4664 (2)	0.3650 (3)	0.0219 (4)
H2A	0.2019 (11)	0.423 (3)	0.472 (5)	0.038 (9)*
H2B	0.1947 (11)	0.558 (4)	0.396 (4)	0.033 (8)*
H2C	0.2147 (11)	0.458 (3)	0.291 (4)	0.033 (8)*
C1	0.13737 (8)	0.2826 (2)	0.2197 (3)	0.0210 (5)
C2	0.14542 (8)	0.4196 (2)	0.2727 (3)	0.0208 (5)
C3	0.10709 (9)	0.5115 (3)	0.2437 (4)	0.0331 (6)
H3	0.1123	0.6034	0.2791	0.040*
C4	0.06090 (10)	0.4666 (3)	0.1619 (5)	0.0457 (8)
H4	0.0351	0.5285	0.1420	0.055*
C5	0.05289 (10)	0.3299 (3)	0.1094 (5)	0.0463 (8)
H5	0.0217	0.2999	0.0552	0.056*
C6	0.09125 (10)	0.2379 (3)	0.1375 (4)	0.0344 (6)
H6	0.0860	0.1462	0.1011	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0193 (3)	0.0137 (3)	0.0223 (3)	−0.0008 (2)	0.0037 (2)	−0.0017 (2)
O1	0.0463 (11)	0.0339 (11)	0.0340 (10)	−0.0007 (9)	0.0153 (9)	−0.0141 (8)
O2	0.0537 (13)	0.0241 (10)	0.0351 (10)	−0.0082 (9)	0.0210 (9)	0.0008 (8)
O3	0.0267 (10)	0.0255 (10)	0.0668 (14)	0.0023 (8)	−0.0112 (9)	0.0049 (9)
O4	0.0251 (9)	0.0249 (9)	0.0308 (9)	−0.0069 (7)	0.0020 (7)	−0.0034 (7)
O5	0.054 (2)	0.073 (3)	0.069 (3)	0.000	0.0233 (18)	0.000
O6	0.0384 (13)	0.071 (2)	0.0768 (19)	−0.0040 (13)	0.0054 (13)	−0.0044 (15)
N1	0.0307 (12)	0.0162 (11)	0.0355 (13)	0.0036 (9)	0.0021 (10)	−0.0031 (9)
N2	0.0229 (10)	0.0187 (11)	0.0224 (10)	−0.0017 (8)	0.0019 (8)	0.0000 (8)
C1	0.0229 (11)	0.0184 (11)	0.0209 (10)	0.0016 (9)	0.0035 (8)	0.0025 (9)
C2	0.0203 (11)	0.0216 (12)	0.0201 (10)	−0.0001 (9)	0.0038 (8)	0.0014 (9)
C3	0.0292 (13)	0.0240 (13)	0.0434 (16)	0.0060 (11)	0.0031 (11)	−0.0037 (11)
C4	0.0227 (13)	0.0413 (18)	0.068 (2)	0.0096 (12)	−0.0003 (13)	−0.0018 (15)
C5	0.0226 (13)	0.0439 (18)	0.065 (2)	−0.0044 (12)	−0.0056 (13)	0.0000 (15)
C6	0.0304 (13)	0.0229 (14)	0.0449 (16)	−0.0064 (11)	−0.0019 (11)	−0.0006 (11)

Geometric parameters (Å, º)

S1—O2	1.4629 (18)	N2—H2B	0.92 (3)
S1—O3	1.4699 (19)	N2—H2C	0.91 (3)
S1—O1	1.4737 (18)	C1—C6	1.382 (3)
S1—O4	1.4750 (17)	C1—C2	1.388 (3)
O5—H5A	0.83 (5)	C2—C3	1.382 (3)
O6—H6A	0.82 (2)	C3—C4	1.383 (4)
O6—H6B	0.805 (19)	C3—H3	0.9300
N1—C1	1.455 (3)	C4—C5	1.385 (5)
N1—H1A	0.94 (3)	C4—H4	0.9300
N1—H1B	0.86 (3)	C5—C6	1.383 (4)
N1—H1C	0.83 (4)	C5—H5	0.9300
N2—C2	1.460 (3)	C6—H6	0.9300
N2—H2A	0.89 (3)
O2—S1—O3	110.46 (13)	C6—C1—C2	120.3 (2)
O2—S1—O1	109.30 (12)	C6—C1—N1	119.2 (2)
O3—S1—O1	109.29 (13)	C2—C1—N1	120.5 (2)
O2—S1—O4	110.30 (11)	C3—C2—C1	119.8 (2)
O3—S1—O4	108.56 (11)	C3—C2—N2	119.6 (2)
O1—S1—O4	108.90 (11)	C1—C2—N2	120.5 (2)
H6A—O6—H6B	118 (5)	C2—C3—C4	119.8 (3)
C1—N1—H1A	111.8 (19)	C2—C3—H3	120.1
C1—N1—H1B	111 (2)	C4—C3—H3	120.1
H1A—N1—H1B	100 (3)	C3—C4—C5	120.3 (3)
C1—N1—H1C	113 (3)	C3—C4—H4	119.9
H1A—N1—H1C	110 (3)	C5—C4—H4	119.9
H1B—N1—H1C	111 (3)	C6—C5—C4	119.9 (3)
C2—N2—H2A	108 (2)	C6—C5—H5	120.0
C2—N2—H2B	113.1 (19)	C4—C5—H5	120.0
H2A—N2—H2B	104 (3)	C1—C6—C5	119.8 (3)
C2—N2—H2C	110.5 (19)	C1—C6—H6	120.1
H2A—N2—H2C	117 (3)	C5—C6—H6	120.1
H2B—N2—H2C	105 (3)
C6—C1—C2—C3	0.3 (4)	C2—C3—C4—C5	0.2 (5)
N1—C1—C2—C3	179.0 (2)	C3—C4—C5—C6	−0.5 (5)
C6—C1—C2—N2	178.0 (2)	C2—C1—C6—C5	−0.6 (4)
N1—C1—C2—N2	−3.3 (3)	N1—C1—C6—C5	−179.3 (3)
C1—C2—C3—C4	−0.1 (4)	C4—C5—C6—C1	0.7 (5)
N2—C2—C3—C4	−177.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6^i	0.83 (5)	1.99 (5)	2.803 (4)	167 (5)
O6—H6A···O3	0.82 (2)	2.05 (2)	2.842 (3)	162 (5)
O6—H6B···O5^ii	0.81 (2)	2.06 (2)	2.851 (4)	166 (5)
N1—H1A···O2^iii	0.94 (3)	1.96 (3)	2.755 (3)	140 (3)
N1—H1B···O3^iv	0.86 (3)	1.94 (4)	2.782 (3)	167 (3)
N1—H1C···O1^v	0.83 (4)	2.53 (4)	3.022 (3)	119 (3)
N1—H1C···O1^vi	0.83 (4)	2.16 (4)	2.921 (3)	154 (4)
N2—H2A···O1^vi	0.89 (3)	1.96 (3)	2.789 (3)	154 (3)
N2—H2B···O2	0.92 (3)	1.90 (3)	2.794 (3)	166 (3)
N2—H2C···O4^v	0.91 (3)	1.82 (3)	2.725 (3)	172 (3)

Symmetry codes: (i) −x, y, −z+1/2; (ii) −x, −y+2, −z; (iii) x, −y+1, z−1/2; (iv) x, y−1, z; (v) −x+1/2, y−1/2, −z+1/2; (vi) x, −y+1, z+1/2.

3-Aminoanilinium perchlorate (4)

Crystal data

C6H9N2^+·ClO4^−	Dx = 1.571 Mg m^−3
Mr = 208.60	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 6504 reflections
a = 5.7979 (19) Å	θ = 2.5–27.4°
b = 9.866 (4) Å	µ = 0.42 mm^−1
c = 15.421 (6) Å	T = 200 K
V = 882.1 (6) Å^3	Plate, clear colourless
Z = 4	0.60 × 0.48 × 0.20 mm
F(000) = 432

Data collection

Bruker SMART X2S benchtop diffractometer	1898 independent reflections
Radiation source: XOS X-beam microfocus source	1783 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromator	Rint = 0.030
Detector resolution: 8.3330 pixels mm^-1	θmax = 27.1°, θmin = 2.5°
ω scans	h = −7→5
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −12→12
Tmin = 0.75, Tmax = 0.92	l = −19→19
5983 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.029	w = 1/[σ^2(Fo^2) + (0.0445P)^2 + 0.1509P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.077	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.23 e Å^−3
1898 reflections	Δρmin = −0.27 e Å^−3
139 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015)
0 restraints	Extinction coefficient: 0.061 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack x determined using 678 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.03 (3)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cl1	0.08993 (10)	0.32402 (6)	0.37637 (3)	0.03545 (19)
O1	0.2989 (4)	0.3778 (3)	0.41188 (17)	0.0652 (7)
O2	0.0379 (5)	0.3889 (2)	0.29567 (13)	0.0597 (6)
O3	0.1136 (4)	0.17999 (19)	0.36341 (16)	0.0586 (6)
O4	−0.0963 (4)	0.3466 (2)	0.43551 (14)	0.0633 (6)
N1	0.2940 (4)	0.6659 (2)	0.28748 (14)	0.0396 (5)
H1A	0.268 (6)	0.589 (4)	0.312 (2)	0.064 (11)*
H1B	0.168 (8)	0.708 (4)	0.294 (2)	0.075 (13)*
N2	0.6047 (5)	1.0979 (2)	0.38845 (15)	0.0358 (5)
H2A	0.630 (7)	1.131 (3)	0.337 (2)	0.065 (11)*
H2B	0.701 (6)	1.133 (3)	0.423 (2)	0.053 (10)*
H2C	0.457 (8)	1.124 (4)	0.405 (2)	0.073 (12)*
C1	0.4605 (4)	0.7387 (2)	0.33616 (13)	0.0298 (5)
C2	0.4484 (4)	0.8800 (2)	0.34173 (14)	0.0277 (5)
H2	0.3249	0.9278	0.3152	0.033*
C3	0.6179 (4)	0.9490 (2)	0.38614 (13)	0.0277 (5)
C4	0.8014 (5)	0.8841 (3)	0.42598 (16)	0.0358 (5)
H4	0.9168	0.9338	0.456	0.043*
C5	0.8108 (5)	0.7433 (3)	0.42049 (16)	0.0399 (6)
H5	0.9335	0.6961	0.4479	0.048*
C6	0.6437 (4)	0.6708 (2)	0.37561 (15)	0.0360 (5)
H6	0.6541	0.5749	0.3718	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0362 (3)	0.0308 (3)	0.0394 (3)	−0.0059 (2)	−0.0053 (3)	0.0020 (2)
O1	0.0536 (13)	0.0594 (14)	0.0828 (16)	−0.0218 (12)	−0.0247 (13)	−0.0001 (12)
O2	0.0785 (16)	0.0548 (12)	0.0459 (10)	−0.0150 (12)	−0.0114 (11)	0.0145 (9)
O3	0.0493 (12)	0.0308 (9)	0.0958 (16)	−0.0012 (9)	−0.0123 (12)	−0.0022 (10)
O4	0.0627 (14)	0.0737 (16)	0.0536 (11)	−0.0018 (14)	0.0136 (11)	−0.0073 (10)
N1	0.0455 (13)	0.0297 (10)	0.0436 (11)	−0.0084 (10)	0.0000 (10)	−0.0041 (9)
N2	0.0393 (12)	0.0273 (10)	0.0407 (11)	−0.0047 (9)	0.0032 (11)	−0.0032 (8)
C1	0.0354 (13)	0.0280 (11)	0.0261 (9)	−0.0036 (9)	0.0053 (9)	−0.0003 (8)
C2	0.0281 (12)	0.0269 (10)	0.0281 (9)	0.0014 (9)	0.0002 (9)	0.0016 (8)
C3	0.0316 (11)	0.0268 (10)	0.0247 (9)	−0.0021 (9)	0.0040 (10)	0.0008 (7)
C4	0.0311 (12)	0.0459 (14)	0.0304 (11)	−0.0006 (11)	−0.0011 (10)	0.0009 (9)
C5	0.0375 (13)	0.0467 (15)	0.0355 (12)	0.0120 (12)	−0.0018 (11)	0.0079 (10)
C6	0.0449 (14)	0.0264 (10)	0.0366 (11)	0.0080 (10)	0.0065 (10)	0.0049 (10)

Geometric parameters (Å, º)

Cl1—O4	1.431 (2)	C1—C6	1.396 (3)
Cl1—O2	1.431 (2)	C1—C2	1.398 (3)
Cl1—O1	1.432 (2)	C2—C3	1.378 (3)
Cl1—O3	1.442 (2)	C2—H2	0.95
N1—C1	1.418 (3)	C3—C4	1.385 (4)
N1—H1A	0.86 (4)	C4—C5	1.392 (4)
N1—H1B	0.85 (4)	C4—H4	0.95
N2—C3	1.471 (3)	C5—C6	1.389 (4)
N2—H2A	0.87 (4)	C5—H5	0.95
N2—H2B	0.85 (4)	C6—H6	0.95
N2—H2C	0.93 (5)
O4—Cl1—O2	109.01 (15)	C2—C1—N1	120.2 (2)
O4—Cl1—O1	109.70 (15)	C3—C2—C1	119.2 (2)
O2—Cl1—O1	110.19 (15)	C3—C2—H2	120.4
O4—Cl1—O3	108.28 (14)	C1—C2—H2	120.4
O2—Cl1—O3	109.88 (14)	C2—C3—C4	122.7 (2)
O1—Cl1—O3	109.75 (14)	C2—C3—N2	117.9 (2)
C1—N1—H1A	109 (2)	C4—C3—N2	119.4 (2)
C1—N1—H1B	106 (3)	C3—C4—C5	117.6 (2)
H1A—N1—H1B	103 (3)	C3—C4—H4	121.2
C3—N2—H2A	110 (2)	C5—C4—H4	121.2
C3—N2—H2B	113 (2)	C6—C5—C4	121.1 (3)
H2A—N2—H2B	108 (3)	C6—C5—H5	119.4
C3—N2—H2C	109 (2)	C4—C5—H5	119.4
H2A—N2—H2C	107 (4)	C5—C6—C1	120.1 (2)
H2B—N2—H2C	109 (3)	C5—C6—H6	120.0
C6—C1—C2	119.3 (2)	C1—C6—H6	120.0
C6—C1—N1	120.4 (2)
C6—C1—C2—C3	0.0 (3)	N2—C3—C4—C5	−178.4 (2)
N1—C1—C2—C3	−177.1 (2)	C3—C4—C5—C6	0.9 (4)
C1—C2—C3—C4	−0.1 (3)	C4—C5—C6—C1	−1.0 (4)
C1—C2—C3—N2	178.0 (2)	C2—C1—C6—C5	0.5 (3)
C2—C3—C4—C5	−0.4 (4)	N1—C1—C6—C5	177.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86 (4)	2.60 (4)	3.429 (4)	163 (3)
N1—H1A···O2	0.86 (4)	2.40 (4)	3.113 (3)	141 (3)
N1—H1B···O2^i	0.85 (4)	2.55 (4)	3.191 (3)	134 (3)
N2—H2A···N1^ii	0.87 (4)	2.00 (4)	2.856 (3)	168 (3)
N2—H2B···O1^iii	0.85 (4)	2.61 (3)	3.287 (4)	138 (3)
N2—H2B···O3^iv	0.85 (4)	2.61 (4)	3.084 (4)	117 (3)
N2—H2B···O4^iv	0.85 (4)	2.42 (4)	3.091 (4)	137 (3)
N2—H2C···O3^v	0.93 (5)	2.16 (4)	2.985 (4)	147 (3)
N2—H2C···O4^iii	0.93 (5)	2.50 (4)	3.004 (3)	114 (3)

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x+1/2, −y+3/2, −z+1; (iv) x+1, y+1, z; (v) x, y+1, z.

benzene-1,3-diaminium tetrachloridozincate(II) (3)

Crystal data

(C6H10N2)[ZnCl4]	Dx = 1.793 Mg m^−3
Mr = 317.35	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 7163 reflections
a = 14.0070 (11) Å	θ = 2.3–26.2°
b = 11.6085 (9) Å	µ = 2.96 mm^−1
c = 7.2286 (5) Å	T = 300 K
V = 1175.37 (15) Å^3	Plate, clear brown
Z = 4	0.60 × 0.40 × 0.15 mm
F(000) = 632

Data collection

Bruker SMART X2S benchtop diffractometer	2373 independent reflections
Radiation source: XOS X-beam microfocus source	2242 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromator	Rint = 0.047
Detector resolution: 8.3330 pixels mm^-1	θmax = 26.4°, θmin = 2.9°
ω scans	h = −17→12
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −14→14
Tmin = 0.39, Tmax = 0.73	l = −8→8
13300 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.057	w = 1/[σ^2(Fo^2) + (0.0302P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2373 reflections	Δρmax = 0.23 e Å^−3
137 parameters	Δρmin = −0.43 e Å^−3
7 restraints	Absolute structure: Refined as an inversion twin.
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.217 (16)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.62942 (2)	0.59599 (3)	0.11294 (8)	0.03168 (13)
Cl1	0.70069 (7)	0.71712 (8)	−0.09310 (14)	0.0427 (2)
Cl2	0.69054 (6)	0.41969 (7)	0.05242 (16)	0.0444 (3)
Cl3	0.67671 (7)	0.66110 (9)	0.39359 (15)	0.0481 (3)
Cl4	0.47047 (7)	0.60647 (10)	0.0747 (2)	0.0586 (3)
N1	0.7761 (2)	0.4550 (3)	0.6358 (6)	0.0440 (8)
H1A	0.771 (4)	0.390 (3)	0.565 (6)	0.066*
H1B	0.737 (3)	0.500 (4)	0.570 (7)	0.066*
H1C	0.749 (4)	0.448 (4)	0.743 (5)	0.066*
N2	0.9972 (2)	0.7825 (3)	0.6528 (6)	0.0435 (9)
H2B	0.948 (3)	0.827 (4)	0.607 (7)	0.065*
H2C	1.046 (3)	0.804 (4)	0.577 (6)	0.065*
H2A	1.003 (4)	0.820 (4)	0.758 (5)	0.065*
C1	0.8746 (2)	0.4998 (3)	0.6432 (6)	0.0338 (8)
C2	0.8882 (2)	0.6177 (3)	0.6437 (6)	0.0337 (9)
H2	0.8367	0.6684	0.6414	0.04*
C3	0.9809 (2)	0.6573 (3)	0.6477 (5)	0.0332 (8)
C4	1.0589 (3)	0.5835 (3)	0.6496 (6)	0.0393 (10)
H4	1.1208	0.6124	0.651	0.047*
C5	1.0425 (3)	0.4662 (4)	0.6495 (6)	0.0433 (10)
H5	1.0939	0.4154	0.6507	0.052*
C6	0.9499 (3)	0.4235 (3)	0.6476 (6)	0.0402 (10)
H6	0.9389	0.3445	0.6494	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0333 (2)	0.0277 (2)	0.0340 (2)	0.00183 (13)	−0.00168 (19)	−0.0002 (2)
Cl1	0.0495 (5)	0.0401 (5)	0.0386 (5)	0.0033 (4)	0.0126 (4)	0.0072 (4)
Cl2	0.0390 (4)	0.0277 (4)	0.0664 (7)	0.0060 (3)	0.0081 (4)	0.0031 (4)
Cl3	0.0561 (6)	0.0528 (6)	0.0354 (5)	−0.0058 (5)	−0.0074 (5)	−0.0064 (5)
Cl4	0.0299 (4)	0.0692 (7)	0.0768 (10)	0.0000 (4)	−0.0001 (5)	0.0125 (6)
N1	0.0363 (15)	0.0399 (17)	0.056 (2)	−0.0068 (13)	0.0070 (17)	−0.0011 (19)
N2	0.0355 (16)	0.0373 (19)	0.058 (3)	−0.0016 (13)	−0.0073 (15)	−0.0106 (17)
C1	0.0301 (15)	0.0373 (19)	0.034 (2)	−0.0008 (13)	0.0029 (14)	−0.0022 (17)
C2	0.0269 (15)	0.0366 (18)	0.037 (3)	0.0043 (13)	0.0015 (15)	−0.0037 (17)
C3	0.0311 (16)	0.0338 (19)	0.035 (2)	−0.0003 (13)	−0.0021 (14)	−0.0070 (16)
C4	0.0299 (16)	0.045 (2)	0.043 (3)	0.0045 (14)	−0.0031 (16)	−0.0096 (17)
C5	0.0383 (18)	0.046 (2)	0.046 (3)	0.0155 (15)	−0.0048 (17)	−0.0086 (18)
C6	0.048 (2)	0.0332 (19)	0.040 (3)	0.0031 (15)	−0.0017 (18)	−0.0021 (17)

Geometric parameters (Å, º)

Zn1—Cl4	2.2469 (10)	N2—H2A	0.88 (3)
Zn1—Cl2	2.2611 (9)	C1—C6	1.378 (5)
Zn1—Cl3	2.2640 (12)	C1—C2	1.383 (5)
Zn1—Cl1	2.2785 (10)	C2—C3	1.378 (5)
N1—C1	1.474 (4)	C2—H2	0.93
N1—H1A	0.92 (3)	C3—C4	1.389 (5)
N1—H1B	0.90 (3)	C4—C5	1.381 (6)
N1—H1C	0.87 (3)	C4—H4	0.93
N2—C3	1.473 (5)	C5—C6	1.389 (5)
N2—H2B	0.92 (2)	C5—H5	0.93
N2—H2C	0.92 (3)	C6—H6	0.93
Cl4—Zn1—Cl2	113.60 (4)	C6—C1—C2	122.0 (3)
Cl4—Zn1—Cl3	112.46 (5)	C6—C1—N1	119.4 (3)
Cl2—Zn1—Cl3	111.39 (4)	C2—C1—N1	118.6 (3)
Cl4—Zn1—Cl1	108.68 (4)	C3—C2—C1	117.4 (3)
Cl2—Zn1—Cl1	105.44 (4)	C3—C2—H2	121.3
Cl3—Zn1—Cl1	104.57 (4)	C1—C2—H2	121.3
C1—N1—H1A	112 (3)	C2—C3—C4	122.5 (3)
C1—N1—H1B	113 (3)	C2—C3—N2	118.4 (3)
H1A—N1—H1B	98 (5)	C4—C3—N2	119.1 (3)
C1—N1—H1C	114 (4)	C5—C4—C3	118.5 (3)
H1A—N1—H1C	113 (5)	C5—C4—H4	120.7
H1B—N1—H1C	105 (5)	C3—C4—H4	120.7
C3—N2—H2B	115 (3)	C4—C5—C6	120.5 (3)
C3—N2—H2C	112 (3)	C4—C5—H5	119.8
H2B—N2—H2C	102 (4)	C6—C5—H5	119.8
C3—N2—H2A	121 (4)	C1—C6—C5	119.1 (4)
H2B—N2—H2A	96 (5)	C1—C6—H6	120.4
H2C—N2—H2A	108 (5)	C5—C6—H6	120.4

Hydrogen-bond geometry (Å, º)

The N–H bond distances were restrained to 0.89 Å. See section 2.2 for details.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1^i	0.92 (3)	2.34 (3)	3.236 (4)	166 (4)
N1—H1B···Cl3	0.90 (3)	2.41 (3)	3.276 (4)	162 (4)
N1—H1C···Cl2^ii	0.87 (3)	2.40 (3)	3.267 (4)	174 (5)
N2—H2B···Cl2^iii	0.92 (2)	2.25 (3)	3.158 (3)	167 (5)
N2—H2C···Cl3^iv	0.92 (3)	2.29 (3)	3.203 (4)	174 (4)
N2—H2A···Cl1^v	0.88 (3)	3.00 (5)	3.391 (4)	109 (4)
N2—H2A···Cl4^v	0.88 (3)	2.49 (3)	3.332 (4)	161 (5)
C2—H2···Cl1^ii	0.93	2.76	3.442 (4)	131
C2—H2···Cl3	0.93	2.87	3.506 (4)	127
C4—H4···Cl1^v	0.93	2.93	3.572 (4)	127
C4—H4···Cl2^vi	0.93	2.76	3.580 (4)	147

Symmetry codes: (i) −x+3/2, y−1/2, z+1/2; (ii) x, y, z+1; (iii) −x+3/2, y+1/2, z+1/2; (iv) x+1/2, −y+3/2, z; (v) x+1/2, −y+3/2, z+1; (vi) −x+2, −y+1, z+1/2.