Octa­kis(dimethyl­ammonium) hexa-μ₂-chlorido-hexa­chloridotrinickelate(II) dichloride: a linear trinickel complex with asymmetric bridging

The title compound, (C₂H₈N)₈[Ni₃Cl₁₂]Cl₂, crystallizes as linear [Ni₃Cl₁₂]⁶⁻ complex anions with inversion symmetry, separated from one another by dimethyl­ammonium cations and noncoordinated chloride ions. The gross structural arrangement of the trinickel complex is as a segment of face-sharing NiCl₆ octa­hedra similar to the (NiCl₃)_n chains of CsNiCl₃-type compounds. On closer inspection, the regular coordination geometry of the complex consists of octa­hedral NiCl₆ in the center linked by two symmetrically bridging chloride ions to square-pyramidal NiCl₅ on each end. A long semicoordinate bond is formed by each of the terminal Ni^II cations, to give a 5+1 coordination geometry and form an asymmetric bridge to the central Ni^II cation. The dimethyl­ammonium cations surround the complex with an extensive hydrogen-bonding network, linking the complex to the noncoordinated chloride ions. Asymmetric bridging in the complex arises from short hydrogen bonds from the same dimethyl­ammonium cation to the apical and asymmetric bridging chloride ions, causing the complex to scissor outward.

S1. Comment

The CsNiCl₃ structure type, consisting of parallel chains of face-sharing NiCl₆ octahedra, is a dominant motif of nickel(II) chloride structural chemistry. ANiCl₃ compounds of this type are readily formed with a variety of organic cations, and are found to exhibit only minor distortions from regular octahedral coordination and to contain tri-µ₂-symmetric chloride bridges between neighbors (Bond, 1990). This structure type is even found for a different stoichiometric combination of ACl and NiCl₂, specifically for (piperidinium)₂NiCl₄, which consists of parallel (NiCl₃)_n chains and noncoordinated chloride ions rather than the isolated tetrahedral or square-planar [NiCl₄]^2- complexes one might first expect (Bond & Willett, 1993). This predictable structural regularity is in marked contrast to copper(II) chloride compounds, the structures and compositions of which are extremely dependent on the structure of the organic counter-ion (Willett, 1991). Copper(II) chloride chain structures are frequently found with a mixture of symmetric and asymmetric chloride bridges, the latter a result of long semicoordinate bonding produced by the Jahn–Teller-distorted Cu^II coordination polyhedra. The title compound, (I), contains a linear trinickel complex which appears similar to a chain segment from an ANiCl₃ compound, but with some intriguing differences which suggest that a more complicated structural chemistry for nickel(II) chlorides remains to be explored.

The linear trinickel complex of (I) consists of an octahedral NiCl₆ group (Ni1) located at the center of the complex, and also on an inversion center, and two terminal NiCl₅ groups. The central Ni^II cation exhibits minor distortions from octahedral coordination: the Ni1—Cl bond lengths are in the range ~2.40–2.45 Å, with the Ni1—Cl1 bond the longest, and the Cl—Ni1—Cl angles deviate by only 4–5° from right angles (Table 1). The interior Cl—Ni1—Cl angles are acute, a consequence of elongation of the octahedron along its trigonal axis, which results from electrostatic repulsion between neighboring metal cations. The coordinate bonds of the terminal nickel ions form a square-pyramidal arrangement, with atom Cl6 as the apical ligand. The Ni2—Cl coordinate bond lengths fall in the narrow range ~2.36–2.38 Å, except for Ni—Cl3 which is ~0.10 Å longer. Deviations in the Ni—Cl coordinate bond of this magnitude resulting from crystal packing strains have been observed previously for the [NiCl₆]^4- complex in (3-chloroanilinium)₈NiCl₁₀ (Wei & Willett, 1995). Atom Ni2 is 0.2172 (2) Å above the basal plane and completes its coordination environment by forming a long semi-coordinate bond (0.3–0.4 Å longer than the coordinate bonds) to atom Cl1, to give it a 5+1 coordination geometry, while also forming an asymmetric bridge to atom Ni1. The bond lengths and angles within the dimethylammonium cations conform to expected values (Ladd & Palmer, 1994). Fig. 1 shows the complex anion grouped with other ions of the asymmetric unit. Bond lengths and angles of the complex anion are presented in Table 1.

The extended structure of (I) can be envisioned as square-packed layers of trinickel complexes parallel to the ac plane and stacked along the b axis, with all complexes within a layer translationally equivalent. The axis of the complex centered at the origin of the unit cell (as determined by the Ni1—Ni2 vector) points approximately along the [212] line and forms angles of 59.60 (1), 44.49 (1) and 49.43 (1)° with the a, b and c axes, respectively. Neighboring layers are related by a c-glide operation, which reverses the orientation of the complex and places the complexes at inversion centers on the corners and in the centers of the bc faces of the unit cell. Complex ions, dimethylammonium cations and noncoordinated chloride ions can be envisioned as forming parallel lines of translationally equivalent ions along the a axis. A packing diagram viewed down the c axis is shown in Fig. 2.

Each complex is surrounded by a cage of eight dimethylammonium cations. Cation 1 (N1) is found deepest within the square-packed layers of complexes and forms hydrogen bonds to atom Cl5 in the complex and to the noncoordinated chloride ion Cl7. Cation 2 (N2) forms hydrogen bonds to chloride ions Cl1 and Cl6 in the same complex, while cation 3 (N3) forms a hydrogen bond to Cl7 and a bifurcated hydrogen bond to Cl3 and Cl4. Cation 4 (N4) is the one most exterior to the layer, and forms a bifurcated hydrogen bond to two terminal chloride ions and one hydrogen bond to Cl7. The hydrogen bonds involving the chloride ions in the complex and the noncoordinated chloride ions form a network that indirectly links the complexes into a chain parallel to [110] in the same layer. Significant hydrogen-bonding interactions are summarized in Table 2.

Noncoordinated chloride ions are sequestered close to the x = 1/2 plane in the unit cell and between the complexes. This packing arrangement is similar to the sequestration of noncoordinated iodide ions in [Co(en)₆]₄(Sn₃I₁₂)I₂ (en is ethylenediamine; Lode & Krautscheid, 2007), the only other [M₃X₁₂]^n- compound with noncoordinated halides. However, in the iodide compound the [Co(en)₆]²⁺ ions form more clearly defined channels for the noncoordinated iodide anions to reside in.

The complex in (I) bears a strong resemblance to the structure of the complex in (dimethylammonium)₆Cr₃Cl₁₂ [Babar et al., 1981; refcode BAHVOV in the Cambridge Structural Database (Allen, 2002)]. The trichromium complex can also be considered to have two symmetric bridges and one asymmetric bridge from the central to each terminal metal atom. Here, the distortions of the bridging and coordination geometries were attributed to the strong Jahn–Teller activity expected for Cr^II. The coordination geometries of Ni^II in (I) do show less distortion than found for Cr^II in [Cr₃Cl₁₂]^6-, almost certainly a consequence of the absence of Jahn–Teller activity expected for Ni^II. But why does [Ni₃Cl₁₂]^6- show any distortion at all? In this case it appears that the complex distorts so as to better accommodate the hydrogen bonding established by the organic cation `cage' that surrounds it. It is notable that the shortest and most direct hydrogen bond made to the complex is to the apical chloride ion of one terminal Ni^II ion [H2A···Cl6(-x, -y, -z)]. This same cation also forms a short hydrogen bond to the asymmetrically bridged chloride ion of the other terminal Ni^II ion (H2B···Cl1). In this way. the hydrogen bonding from cation 2 induces a scissoring action on the complex that opens it up and establishes the asymmetric bridge. A similar hydrogen-bonding arrangement is present in BAHVOV, with N···Cl distances to the apical and asymmetric bridge chloride ions (3.163 and 3.210 Å, respectively) that are comparable to those in (I). Thus, while much of the distortion in the [Cr₃Cl₁₂]^6- complex can be attributed to the Jahn–Teller effect, a significant contribution to the distortion of the bridging geometry is probably induced by hydrogen bonding. Dramatic distortions in bridging geometry caused by hydrogen bonding are known. For example, the V—O—V bridging angle in (µ₂-oxo)tetrakis(l-histidine)divanadium(III) is reduced by almost 30° as a result of hydrogen bonding between histidine ligands on neighboring V^III cations (Czernuszewicz et al., 1994).

S2. Experimental

Crystals of (I) were grown by slow evaporation of an approximately 6 M HCl solution containing dimethylammonium chloride and nickel(II) chloride dissolved in a 3:1 molar ratio. The solution was maintained at at a temperature of 323 K. While small crystals of (I) are orange in color under the microscope, the bulk sample is dark burgundy red.

S3. Refinement

All H atoms were visible in difference maps. The positions of the methyl group H atoms were calculated and constrained during refinement using a riding model [C—H = 0.96 Å and U_iso(H) = 1.5U_iso(C)]. The positions and isotropic displacement parameters of H atoms bound to N atoms were freely refined. The refined N—H bond lengths are in the range 0.837 (14)–0.868 (14) Å and the displacement parameters are in the range 0.021 (3)–0.030 (4) Ų.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The [Ni3Cl12]^6- complex anion of (I), surrounded by the chloride anion and dimethylammonium cations of the asymmetric unit, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Significant hydrogen-bonding interactions are shown as dashed lines.
	Fig. 2. A packing diagram for (I), viewed along the a axis. Hydrogen bonding that establishes the layered packing arrangement of the trinickel complexes is shown as dashed lines.

Octakis(dimethylammonium) hexa-µ₂-chlorido-hexachloridotrinickelate(II) dichloride

Crystal data

(C2H8N)8[Ni3Cl12]Cl2	F(000) = 1076
Mr = 1041.18	Dx = 1.571 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.0058 (2) Å	Cell parameters from 18336 reflections
b = 20.0564 (4) Å	θ = 2.9–45.3°
c = 10.9787 (2) Å	µ = 2.14 mm^−1
β = 92.464 (1)°	T = 100 K
V = 2201.17 (7) Å^3	Block, red-orange
Z = 2	0.27 × 0.24 × 0.21 mm

Data collection

Bruker KappaCCD diffractometer	18194 independent reflections
Radiation source: Enraf Nonius FR590	13786 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 9 pixels mm^-1	θmax = 45.3°, θmin = 4.2°
CCD rotation images, thick slices scans	h = −19→19
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	k = −39→39
Tmin = 0.564, Tmax = 0.635	l = −21→21
34160 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.052	w = 1/[σ^2(Fo^2) + (0.0077P)^2 + 0.5877P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
18194 reflections	Δρmax = 0.57 e Å^−3
228 parameters	Δρmin = −0.76 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00392 (16)

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
Ni1	0	0	0	0.00970 (2)
Ni2	0.170357 (9)	−0.090178 (5)	0.189259 (9)	0.01014 (2)
Cl1	0.212498 (17)	0.038234 (10)	0.094353 (17)	0.01373 (3)
Cl2	0.107830 (17)	−0.106424 (9)	−0.019692 (15)	0.01103 (3)
Cl3	−0.050149 (17)	−0.035794 (9)	0.202549 (15)	0.01116 (3)
Cl4	0.242340 (18)	−0.053441 (9)	0.385613 (16)	0.01251 (3)
Cl5	0.393097 (17)	−0.124654 (9)	0.158320 (17)	0.01278 (3)
Cl6	0.086807 (18)	−0.195572 (9)	0.251269 (17)	0.01370 (3)
Cl7	0.39837 (2)	0.149958 (11)	0.37714 (2)	0.01977 (4)
N1	0.50274 (7)	0.01805 (4)	0.24324 (6)	0.01417 (11)
H1A	0.4514 (13)	0.0480 (7)	0.2739 (12)	0.024 (3)*
H1B	0.4516 (13)	−0.0137 (7)	0.2162 (11)	0.021 (3)*
C11	0.59345 (10)	−0.00849 (5)	0.34183 (9)	0.02310 (17)
H11A	0.6574	−0.038	0.3076	0.035*
H11B	0.5422	−0.0325	0.3994	0.035*
H11C	0.6395	0.0278	0.3824	0.035*
C12	0.57451 (10)	0.04842 (5)	0.14189 (9)	0.02410 (17)
H12A	0.6309	0.0838	0.173	0.036*
H12B	0.5108	0.066	0.0824	0.036*
H12C	0.6283	0.0151	0.1046	0.036*
N2	0.16117 (7)	0.17268 (4)	−0.06657 (7)	0.01570 (11)
H2A	0.0891 (13)	0.1819 (7)	−0.1101 (12)	0.022 (3)*
H2B	0.1464 (13)	0.1343 (7)	−0.0404 (12)	0.026 (3)*
C21	0.17977 (10)	0.21879 (5)	0.03864 (9)	0.02329 (17)
H21A	0.2122	0.2609	0.0108	0.035*
H21B	0.2434	0.2001	0.097	0.035*
H21C	0.0958	0.2252	0.0761	0.035*
C22	0.27635 (10)	0.17174 (6)	−0.14659 (12)	0.0317 (2)
H22A	0.3533	0.154	−0.1024	0.048*
H22B	0.2951	0.2163	−0.1728	0.048*
H22C	0.2555	0.1443	−0.2164	0.048*
N3	0.10944 (7)	0.08865 (4)	0.37537 (6)	0.01377 (10)
H3A	0.1909 (13)	0.1017 (7)	0.3667 (12)	0.024 (3)*
H3B	0.1051 (14)	0.0494 (7)	0.3452 (13)	0.030 (4)*
C31	0.08948 (10)	0.08381 (5)	0.50790 (8)	0.02051 (15)
H31A	0.1043	0.1267	0.545	0.031*
H31B	0.1515	0.0521	0.5437	0.031*
H31C	−0.0003	0.0695	0.521	0.031*
C32	0.01298 (11)	0.13344 (5)	0.31142 (9)	0.02584 (19)
H32A	−0.076	0.1164	0.3187	0.039*
H32B	0.0331	0.136	0.2268	0.039*
H32C	0.019	0.1771	0.3471	0.039*
N4	0.37176 (7)	−0.20105 (4)	0.43693 (7)	0.01610 (12)
H4A	0.4407 (14)	−0.1833 (7)	0.4729 (12)	0.025 (3)*
H4B	0.3420 (13)	−0.1732 (7)	0.3856 (12)	0.024 (3)*
C41	0.41061 (11)	−0.26238 (5)	0.37261 (9)	0.02460 (18)
H41A	0.4482	−0.2938	0.4305	0.037*
H41B	0.4758	−0.2516	0.314	0.037*
H41C	0.3331	−0.2815	0.3316	0.037*
C42	0.27166 (9)	−0.21381 (5)	0.53031 (8)	0.02131 (16)
H42A	0.1903	−0.23	0.4912	0.032*
H42B	0.2539	−0.1731	0.5728	0.032*
H42C	0.3061	−0.2466	0.5872	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01002 (5)	0.01070 (5)	0.00835 (5)	0.00167 (4)	−0.00009 (4)	0.00111 (4)
Ni2	0.00907 (3)	0.01186 (4)	0.00939 (4)	0.00064 (3)	−0.00070 (3)	−0.00112 (3)
Cl1	0.01029 (6)	0.01714 (8)	0.01358 (7)	0.00048 (5)	−0.00159 (5)	−0.00139 (6)
Cl2	0.01129 (6)	0.01193 (6)	0.00982 (6)	0.00150 (5)	−0.00003 (5)	−0.00018 (5)
Cl3	0.01144 (6)	0.01248 (7)	0.00964 (6)	0.00114 (5)	0.00113 (5)	0.00111 (5)
Cl4	0.01400 (7)	0.01300 (7)	0.01030 (6)	0.00182 (5)	−0.00206 (5)	−0.00130 (5)
Cl5	0.00967 (6)	0.01362 (7)	0.01500 (7)	0.00137 (5)	0.00009 (5)	−0.00215 (6)
Cl6	0.01448 (7)	0.01191 (7)	0.01458 (7)	−0.00057 (5)	−0.00102 (5)	0.00221 (5)
Cl7	0.01487 (7)	0.01741 (8)	0.02709 (10)	−0.00085 (6)	0.00169 (7)	−0.00645 (7)
N1	0.0115 (2)	0.0155 (3)	0.0155 (3)	−0.0010 (2)	0.0003 (2)	−0.0018 (2)
C11	0.0210 (4)	0.0284 (5)	0.0193 (4)	0.0036 (3)	−0.0064 (3)	−0.0022 (3)
C12	0.0235 (4)	0.0266 (4)	0.0227 (4)	−0.0041 (3)	0.0075 (3)	0.0021 (3)
N2	0.0113 (2)	0.0137 (3)	0.0220 (3)	−0.0015 (2)	−0.0002 (2)	0.0008 (2)
C21	0.0256 (4)	0.0201 (4)	0.0241 (4)	−0.0046 (3)	−0.0003 (3)	−0.0032 (3)
C22	0.0193 (4)	0.0282 (5)	0.0489 (7)	−0.0069 (3)	0.0154 (4)	−0.0131 (5)
N3	0.0146 (3)	0.0134 (3)	0.0135 (3)	0.0022 (2)	0.0023 (2)	0.0005 (2)
C31	0.0256 (4)	0.0218 (4)	0.0145 (3)	0.0026 (3)	0.0052 (3)	0.0026 (3)
C32	0.0298 (4)	0.0277 (5)	0.0194 (4)	0.0136 (4)	−0.0062 (3)	−0.0018 (3)
N4	0.0175 (3)	0.0144 (3)	0.0163 (3)	0.0023 (2)	0.0002 (2)	0.0026 (2)
C41	0.0321 (5)	0.0213 (4)	0.0203 (4)	0.0088 (3)	−0.0008 (3)	−0.0025 (3)
C42	0.0195 (3)	0.0260 (4)	0.0186 (4)	0.0005 (3)	0.0027 (3)	0.0047 (3)

Geometric parameters (Å, º)

Ni1—Cl1	2.4480 (2)	C21—H21C	0.96
Ni1—Cl2	2.4056 (2)	C22—H22A	0.96
Ni1—Cl3	2.4100 (2)	C22—H22B	0.96
Ni2—Cl1	2.8168 (2)	C22—H22C	0.96
Ni2—Cl2	2.3742 (2)	N3—C31	1.4803 (11)
Ni2—Cl3	2.4712 (2)	N3—C32	1.4743 (11)
Ni2—Cl4	2.3612 (2)	N3—H3A	0.865 (13)
Ni2—Cl5	2.3718 (2)	N3—H3B	0.855 (15)
Ni2—Cl6	2.3832 (2)	C31—H31A	0.96
N1—C11	1.4812 (11)	C31—H31B	0.96
N1—C12	1.4810 (11)	C31—H31C	0.96
N1—H1A	0.868 (14)	C32—H32A	0.96
N1—H1B	0.862 (13)	C32—H32B	0.96
C11—H11A	0.96	C32—H32C	0.96
C11—H11B	0.96	N4—C41	1.4787 (12)
C11—H11C	0.96	N4—C42	1.4859 (11)
C12—H12A	0.96	N4—H4A	0.857 (14)
C12—H12B	0.96	N4—H4B	0.840 (14)
C12—H12C	0.96	C41—H41A	0.96
N2—C21	1.4852 (12)	C41—H41B	0.96
N2—C22	1.4790 (12)	C41—H41C	0.96
N2—H2A	0.868 (13)	C42—H42A	0.96
N2—H2B	0.837 (14)	C42—H42B	0.96
C21—H21A	0.96	C42—H42C	0.96
C21—H21B	0.96
Cl1—Ni1—Cl2	86.056 (6)	H21A—C21—H21B	109.5
Cl1—Ni1—Cl3	85.088 (6)	N2—C21—H21C	109.5
Cl2—Ni1—Cl3	86.020 (6)	H21A—C21—H21C	109.5
Cl2—Ni2—Cl3	85.341 (6)	H21B—C21—H21C	109.5
Cl1—Ni2—Cl2	78.784 (6)	N2—C22—H22A	109.5
Cl1—Ni2—Cl3	76.496 (6)	N2—C22—H22B	109.5
Cl1—Ni2—Cl4	90.445 (7)	H22A—C22—H22B	109.5
Cl1—Ni2—Cl5	93.271 (7)	N2—C22—H22C	109.5
Cl1—Ni2—Cl6	167.577 (7)	H22A—C22—H22C	109.5
Cl2—Ni2—Cl4	169.218 (8)	H22B—C22—H22C	109.5
Cl2—Ni2—Cl5	91.823 (7)	C32—N3—C31	113.26 (7)
Cl2—Ni2—Cl6	94.197 (7)	C32—N3—H3A	111.4 (9)
Cl3—Ni2—Cl4	92.661 (7)	C31—N3—H3A	107.2 (9)
Cl3—Ni2—Cl5	169.726 (8)	C32—N3—H3B	110.8 (10)
Cl3—Ni2—Cl6	92.842 (7)	C31—N3—H3B	108.3 (10)
Cl4—Ni2—Cl5	88.287 (7)	H3A—N3—H3B	105.5 (12)
Cl4—Ni2—Cl6	96.485 (7)	N3—C31—H31A	109.5
Cl5—Ni2—Cl6	97.218 (7)	N3—C31—H31B	109.5
Ni1—Cl1—Ni2	74.277 (5)	H31A—C31—H31B	109.5
Ni1—Cl2—Ni2	83.798 (6)	N3—C31—H31C	109.5
Ni1—Cl3—Ni2	81.672 (6)	H31A—C31—H31C	109.5
C12—N1—C11	113.27 (7)	H31B—C31—H31C	109.5
C12—N1—H1A	108.7 (9)	N3—C32—H32A	109.5
C11—N1—H1A	108.6 (9)	N3—C32—H32B	109.5
C12—N1—H1B	110.2 (8)	H32A—C32—H32B	109.5
C11—N1—H1B	108.7 (9)	N3—C32—H32C	109.5
H1A—N1—H1B	107.1 (12)	H32A—C32—H32C	109.5
N1—C11—H11A	109.5	H32B—C32—H32C	109.5
N1—C11—H11B	109.5	C41—N4—C42	112.65 (8)
H11A—C11—H11B	109.5	C41—N4—H4A	110.0 (9)
N1—C11—H11C	109.5	C42—N4—H4A	107.9 (9)
H11A—C11—H11C	109.5	C41—N4—H4B	109.0 (9)
H11B—C11—H11C	109.5	C42—N4—H4B	110.3 (9)
N1—C12—H12A	109.5	H4A—N4—H4B	106.7 (13)
N1—C12—H12B	109.5	N4—C41—H41A	109.5
H12A—C12—H12B	109.5	N4—C41—H41B	109.5
N1—C12—H12C	109.5	H41A—C41—H41B	109.5
H12A—C12—H12C	109.5	N4—C41—H41C	109.5
H12B—C12—H12C	109.5	H41A—C41—H41C	109.5
C22—N2—C21	113.27 (7)	H41B—C41—H41C	109.5
C22—N2—H2A	109.0 (9)	N4—C42—H42A	109.5
C21—N2—H2A	111.6 (9)	N4—C42—H42B	109.5
C22—N2—H2B	110.2 (9)	H42A—C42—H42B	109.5
C21—N2—H2B	108.9 (9)	N4—C42—H42C	109.5
H2A—N2—H2B	103.3 (12)	H42A—C42—H42C	109.5
N2—C21—H21A	109.5	H42B—C42—H42C	109.5
N2—C21—H21B	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl7	0.868 (14)	2.407 (14)	3.2222 (8)	156.5 (12)
N1—H1B···Cl5	0.862 (13)	2.380 (14)	3.1901 (8)	156.8 (11)
N2—H2A···Cl6^i	0.868 (13)	2.311 (13)	3.1696 (8)	170.2 (12)
N2—H2B···Cl1	0.837 (14)	2.501 (14)	3.2525 (8)	149.9 (12)
N3—H3A···Cl7	0.865 (13)	2.289 (14)	3.1409 (7)	168.2 (12)
N3—H3B···Cl3	0.855 (15)	2.752 (15)	3.4812 (8)	144.2 (12)
N3—H3B···Cl4	0.855 (15)	2.507 (14)	3.1448 (7)	132.1 (12)
N4—H4A···Cl7^ii	0.857 (14)	2.351 (14)	3.1786 (8)	162.6 (12)
N4—H4B···Cl4	0.840 (14)	2.600 (14)	3.2705 (7)	137.7 (12)
N4—H4B···Cl5	0.840 (14)	2.746 (14)	3.4360 (8)	140.5 (11)

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