4,4'-(Azinodimethyl­ene)dipyridinium bis­(tetra­fluoro­borate) and 4-[(4-pyri­dylmethyl­ene)hydrazonomethyl]­pyridinium perchlorate: two different hydrogen-bonding motifs

In the crystal structures of the title compounds, C₁₂H₁₂N₄²⁺·2BF₄^-, (I), and C₁₂H₁₁N₄⁺·ClO₄^-, (II), respectively, infinite two- and one-dimensional architectures are built up via N-H...F [in (I)] and conventional N-H...N [in (II)] hydrogen bonding. The N-N single bond in (I) lies on a crystallographic centre of symmetry; as a result, the two pyridinium rings are parallel. In (II), the pyridinium and pyridyl ring planes are inclined with a dihedral angle of 14.45 (3)°.

S1. Comment

Neutral 4,4'-bis-pyridinyl methylenehydrazine has been known as an antitumour precursor (Hirayama et al., 1980) as well as an analytical reagent for the determination of Fe²⁺ concentration in solution (Luque de Castro & Valcarcel, 1978). Recent interest in this and related molecules stems from their use as a linear organic mono- or bidentate bridging ligands in the crystal engineering of multi-dimensional coordination polymers (Ciurtin et al., 2001; Patra & Goldberg, 2003; Kennedy et al., 2005; Granifo et al., 2006). The characterization of 4,4'-bis-pyridinyl methylenehydrazine (El-Rayyes & Katrib, 1983) and its crystal structure (Shanmuga Sundara Raj et al., 2000; Ciurtin et al., 2001), as well as the crystal structure of 4,4'-pyridinyl pyridinium methylenehydrazine diperchlorate, C₁₂H₁₂N₄²⁺·2ClO₄^- (Chen et al., 1997), have been reported. The geometric features of the non-isostructural compounds 4,4'-bis-pyridinium methylenehydrazine ditetrafluoroborate C₁₂H₁₂N₄²⁺·2BF₄^-, (I), and 4,4'-pyridinyl pyridinium methylenehydrazine perchlorate, C₁₂H₁₂N₄⁺·ClO₄^-, (II), are discussed here.

The bond distances of N1—N1ⁱ [symmetry code: (i) -x, -y + 2, -z + 2] and N1═C1 in (I), and N1A—N1B, N1A═C1A and N1B═C1B in (II), are longer than those of the diperchlorate salt [1.400 (4) and 1.260 (4) Å; Chen et al., 1997] but agree well with those reported for the 4,4-dipyridinium azinodimethylene chloranilate dichloromethane disolvate [1.411 (6) and 1.278 (5) Å; Kennedy & Waterson, 2003] (Table 1). Perspective drawings of compounds (I) and (II), with the atomic numbering schemes, are shown in Figs. 1 and 2, respectively.

The two pyridine rings in (I) are coplanar, with an interplanar distance of 0.104 (2) Å and a dihedral angle of 1.21 (9)° with the mean plane of the —CH═N—N═CH— zigzag-like spacer, which exhibits an ideal antiperiplanar conformation with a torsion angle of 180° and the N—N bond lying on a crystallographic centre of symmetry. In (II), the molecule has no crystallographic centre of symmetry, the two ring planes are inclined by an angle of 14.45 (3)° and the antiperiplanar —CH═N—N═ CH— spacer exhibits a torsion angle of -170.34 (2)°.

The parallel molecular stacks in (I) are arranged along the b axis (Fig. 3), maintained via π–π stacking at an interplanar distance of 3.335 (3) Å and supported by a bifurcated N—H···F hydrogen bond building up an extended two-dimensional architecture along the (100) plane and S-like molecular sheets along the c axis. On the first-level graph set, as defined by Bernstein et al. (1995) and Grell et al. (1999), D(2) and D₂²(16) finite patterns are formed via hydrogen bonds a and b, respectively. On the second-level graph set, C₂¹(4) and C₂²(17) chains and an R₆⁶(43) ring can be recognized (Table 2 and Fig. 5).

In (II), no profound π–π stacking exists. However, the zigzag-like molecular stacks built up along the a axis direction (Fig. 4) are cemented by a conventional N—H···N^iv [symmetry code: (iv) x, y - 1, z + 1] hydrogen-bond, (Table 3 and Fig. 6), giving rise to an infinite one-dimensional C(13) chain along the vector [011]. Assignments and graph-set analyses were performed using PLUTO (Motherwell et al., 1999).

Related literature

For related literature, see: Bernstein et al. (1995); Chen et al. (1997); Ciurtin et al. (2001); El-Rayyes & Katrib (1983); Granifo et al. (2006); Grell et al. (1999); Hirayama et al. (1980); Kennedy & Waterson (2003); Kennedy et al. (2005); Luque & Valcarcel (1978); Motherwell et al. (1999); Patra & Goldberg (2003); Shanmuga Sundara Raj, Fun, Zhang, Xiong & You (2000).

S2. Experimental

Compound (I) was prepared as follows. Fe(BF₄)₂·6H₂O (1 mmol; Aldrich), NH₂NH₂·H₂O (1 mmol; Aldrich) and 4-pyridylcarboxaldehyde (2 mmol; Aldrich) were stirred under N₂ flow in EtOH (95%) at 350–355 K for 2 h. The resulting solution was allowed to cool, and was then filtered and evaporated at room temperature for a few days. The yellow crystals were collected by filtration, washed with MeOH and dried in vacuo.

Compound (II) was prepared as follows. 4,4'-Bis-pyridinyl methylenehydrazine (1 mmol), prepared as described by El-Rayyes & Katrib (1983), was added to an ethanolic solution of Fe(ClO₄)₂·H₂O (1 mmol; Aldrich). The solution was stirred at 350–355 K for 1 h. The resulting solution was cooled, and was then filtered and evaporated at room temperature for a few days. The red crystals were collected by filtration, washed with MeOH and dried in vacuo.

S3. Refinement

H atoms were refined isotropically and were constrained to the ideal geometry using an appropriate riding model, with C—H = 0.95 Å and N—H = 0.88 Å [Please check added text], and with U_iso(H) = 1.2U_eq(C,N).

Computing details

For both compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT and SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A perspective drawing of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code (i) and unlabelled atoms: -x, -y + 2, -z + 2]
	Fig. 2. A perspective drawing of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. A packing pattern for (I), projected along the b axis.
	Fig. 4. A packing pattern for (II), projected along the a axis.
	Fig. 5. The hydrogen-bonding pattern of (I) along the a and c axes, with hydrogen bonds shown as dashed lines. For notation, see Table 2.
	Fig. 6. The hydrogen-bonding chains of (II) along the b axis, with hydrogen bonds shown as dashed lines. For symmetry code, see Table 3.

(I) 4,4'-(Azinodimethylene)dipyridinium bis(tetrafluoroborate)

Crystal data

C12H12N4^2+·2BF4^−	F(000) = 388
Mr = 385.88	Dx = 1.591 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4759 reflections
a = 5.1056 (3) Å	θ = 2.5–31.6°
b = 16.5856 (10) Å	µ = 0.16 mm^−1
c = 9.6587 (6) Å	T = 153 K
β = 99.962 (1)°	Drop-like, yellow
V = 805.56 (8) Å^3	0.46 × 0.26 × 0.12 mm
Z = 2

Data collection

Siemens SMART CCD area-detector diffractometer	2925 independent reflections
Radiation source: fine-focus sealed tube	2154 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 33.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −7→7
Tmin = 0.588, Tmax = 0.981	k = −25→25
14300 measured reflections	l = −14→14

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0649P)^2 + 0.1823P] where P = (Fo^2 + 2Fc^2)/3
2925 reflections	(Δ/σ)max = 0.001
118 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.19 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
N1	0.07148 (19)	0.96973 (6)	0.97141 (10)	0.0257 (2)
C1	0.2071 (2)	0.99914 (6)	0.88416 (11)	0.0229 (2)
H1	0.2027	1.0554	0.8650	0.027*
C2	0.37040 (19)	0.94479 (6)	0.81355 (10)	0.02068 (19)
C3	0.3844 (2)	0.86229 (7)	0.84199 (12)	0.0266 (2)
H3	0.2844	0.8394	0.9064	0.032*
C4	0.5451 (2)	0.81444 (7)	0.77541 (13)	0.0295 (2)
H4	0.5568	0.7582	0.7937	0.035*
N5	0.68489 (19)	0.84768 (6)	0.68465 (11)	0.0268 (2)
H5	0.7877	0.8163	0.6436	0.032*
C6	0.6751 (2)	0.92628 (7)	0.65367 (11)	0.0258 (2)
H6	0.7763	0.9472	0.5881	0.031*
C7	0.5174 (2)	0.97680 (6)	0.71743 (11)	0.0238 (2)
H7	0.5090	1.0328	0.6962	0.029*
B1	0.0878 (3)	0.65814 (7)	0.89064 (14)	0.0248 (2)
F1	0.36132 (15)	0.65972 (5)	0.89689 (9)	0.0380 (2)
F2	−0.03732 (17)	0.68835 (5)	0.76275 (8)	0.0391 (2)
F3	0.00672 (15)	0.57898 (4)	0.90612 (8)	0.03481 (19)
F4	0.01973 (18)	0.70520 (5)	0.99962 (9)	0.0411 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0272 (4)	0.0250 (4)	0.0277 (4)	0.0053 (3)	0.0126 (4)	−0.0017 (3)
C1	0.0236 (5)	0.0231 (5)	0.0231 (5)	0.0035 (4)	0.0069 (4)	−0.0011 (4)
C2	0.0197 (4)	0.0226 (4)	0.0207 (4)	0.0018 (3)	0.0061 (3)	−0.0014 (3)
C3	0.0274 (5)	0.0239 (5)	0.0314 (5)	0.0022 (4)	0.0136 (4)	0.0015 (4)
C4	0.0301 (5)	0.0224 (5)	0.0392 (6)	0.0022 (4)	0.0149 (5)	−0.0004 (4)
N5	0.0246 (4)	0.0270 (4)	0.0313 (5)	0.0016 (3)	0.0122 (4)	−0.0071 (4)
C6	0.0248 (5)	0.0306 (5)	0.0242 (5)	−0.0027 (4)	0.0103 (4)	−0.0025 (4)
C7	0.0255 (5)	0.0237 (5)	0.0239 (5)	−0.0005 (4)	0.0088 (4)	0.0000 (4)
B1	0.0278 (6)	0.0203 (5)	0.0290 (6)	−0.0009 (4)	0.0123 (4)	0.0015 (4)
F1	0.0269 (4)	0.0399 (4)	0.0491 (5)	−0.0023 (3)	0.0123 (3)	0.0068 (3)
F2	0.0450 (4)	0.0385 (4)	0.0344 (4)	0.0144 (3)	0.0090 (3)	0.0073 (3)
F3	0.0420 (4)	0.0230 (3)	0.0439 (4)	−0.0054 (3)	0.0198 (3)	0.0011 (3)
F4	0.0554 (5)	0.0345 (4)	0.0405 (4)	−0.0119 (4)	0.0283 (4)	−0.0122 (3)

Geometric parameters (Å, º)

N1—C1	1.276 (1)	N5—C6	1.3366 (15)
N1—N1^i	1.409 (2)	N5—H5	0.8800
C1—C2	1.4729 (14)	C6—C7	1.3788 (15)
C1—H1	0.9500	C6—H6	0.9500
C2—C3	1.3950 (15)	C7—H7	0.9500
C2—C7	1.3960 (14)	B1—F2	1.3828 (15)
C3—C4	1.3780 (15)	B1—F1	1.3873 (15)
C3—H3	0.9500	B1—F3	1.3926 (14)
C4—N5	1.3410 (15)	B1—F4	1.4016 (14)
C4—H4	0.9500
C1—N1—N1^i	111.30 (11)	C6—N5—H5	118.5
N1—C1—C2	119.14 (9)	C4—N5—H5	118.5
N1—C1—H1	120.4	N5—C6—C7	119.66 (10)
C2—C1—H1	120.4	N5—C6—H6	120.2
C3—C2—C7	119.26 (9)	C7—C6—H6	120.2
C3—C2—C1	121.53 (9)	C6—C7—C2	119.26 (10)
C7—C2—C1	119.20 (9)	C6—C7—H7	120.4
C4—C3—C2	119.17 (10)	C2—C7—H7	120.4
C4—C3—H3	120.4	F2—B1—F1	109.76 (9)
C2—C3—H3	120.4	F2—B1—F3	109.72 (10)
N5—C4—C3	119.70 (10)	F1—B1—F3	109.20 (10)
N5—C4—H4	120.1	F2—B1—F4	109.43 (10)
C3—C4—H4	120.1	F1—B1—F4	109.60 (10)
C6—N5—C4	122.95 (9)	F3—B1—F4	109.11 (9)
N1^i—N1—C1—C2	179.91 (11)	C3—C4—N5—C6	−0.56 (18)
N1—C1—C2—C3	−1.32 (16)	C4—N5—C6—C7	0.57 (18)
N1—C1—C2—C7	179.59 (10)	N5—C6—C7—C2	0.02 (16)
C7—C2—C3—C4	0.58 (17)	C3—C2—C7—C6	−0.58 (16)
C1—C2—C3—C4	−178.50 (11)	C1—C2—C7—C6	178.53 (10)
C2—C3—C4—N5	−0.03 (18)	C1^i—N1^i—N1—C1	−180.00 (10)

Symmetry code: (i) −x, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···F1	0.95	2.24	3.0369 (14)	141
C4—H4···F2^ii	0.95	2.44	3.0040 (14)	118
C6—H6···F3^iii	0.95	2.45	3.1161 (14)	127
C6—H6···F3^iv	0.95	2.32	3.1609 (13)	147
C7—H7···F1^iii	0.95	2.43	3.3231 (14)	157

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

(II) 4-[4-pyridylmethylene)hydrazonomethyl]pyridinium perchlorate

Crystal data

C12H11N4^+·ClO4^−	F(000) = 640
Mr = 310.70	Dx = 1.504 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 5650 reflections
a = 15.0896 (6) Å	θ = 3.2–28.2°
b = 11.5525 (5) Å	µ = 0.30 mm^−1
c = 7.8694 (3) Å	T = 153 K
V = 1371.81 (10) Å^3	Plate, dark red
Z = 4	0.18 × 0.12 × 0.08 mm

Data collection

Siemens SMART CCD area-detector diffractometer	3440 independent reflections
Radiation source: fine-focus sealed tube	2994 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ω scans	θmax = 28.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −20→20
Tmin = 0.795, Tmax = 0.976	k = −15→15
18851 measured reflections	l = −10→10

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-atom parameters constrained
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0484P)^2 + 0.1706P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
3440 reflections	Δρmax = 0.24 e Å^−3
190 parameters	Δρmin = −0.21 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 1594 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (5)

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
Cl1	0.98221 (3)	0.76602 (3)	0.00534 (6)	0.02777 (11)
O1	0.92927 (10)	0.69864 (14)	0.12131 (19)	0.0396 (4)
O2	1.01859 (10)	0.69249 (14)	−0.1247 (2)	0.0428 (4)
O3	0.92716 (9)	0.85251 (13)	−0.0748 (2)	0.0403 (4)
O4	1.05271 (10)	0.82178 (15)	0.0958 (2)	0.0440 (4)
N1A	0.81434 (11)	0.08944 (13)	0.1570 (2)	0.0262 (3)
C1A	0.87944 (12)	0.04458 (16)	0.2366 (2)	0.0237 (4)
H1A	0.9372	0.0759	0.2235	0.028*
C2A	0.86515 (12)	−0.05595 (15)	0.3491 (2)	0.0221 (4)
C3A	0.93832 (12)	−0.10634 (15)	0.4283 (2)	0.0238 (4)
H3A	0.9959	−0.0748	0.4126	0.029*
C4A	0.92612 (11)	−0.20199 (15)	0.5293 (2)	0.0244 (4)
H4A	0.9754	−0.2365	0.5848	0.029*
N5A	0.84507 (10)	−0.24675 (12)	0.5495 (2)	0.0243 (3)
H5A	0.8387	−0.3095	0.6117	0.029*
C6A	0.77331 (12)	−0.19892 (15)	0.4779 (2)	0.0261 (4)
H6A	0.7166	−0.2320	0.4972	0.031*
C7A	0.78106 (12)	−0.10232 (15)	0.3766 (2)	0.0239 (4)
H7A	0.7302	−0.0680	0.3265	0.029*
N1B	0.84225 (10)	0.18383 (12)	0.0567 (2)	0.0254 (3)
C1B	0.77652 (11)	0.23963 (14)	−0.0032 (3)	0.0238 (3)
H1B	0.7179	0.2126	0.0158	0.029*
C2B	0.79149 (12)	0.34610 (15)	−0.1022 (2)	0.0233 (4)
C3B	0.71989 (12)	0.41495 (16)	−0.1477 (3)	0.0269 (4)
H3B	0.6611	0.3915	−0.1215	0.032*
C4B	0.73543 (14)	0.51879 (15)	−0.2322 (3)	0.0289 (4)
H4B	0.6862	0.5657	−0.2624	0.035*
N5B	0.81684 (11)	0.55534 (14)	−0.2726 (2)	0.0294 (4)
C6B	0.88550 (14)	0.48630 (17)	−0.2334 (3)	0.0338 (5)
H6B	0.9435	0.5103	−0.2647	0.041*
C7B	0.87559 (12)	0.38182 (16)	−0.1495 (3)	0.0306 (4)
H7B	0.9258	0.3352	−0.1247	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.02195 (18)	0.0298 (2)	0.0315 (2)	0.00091 (17)	0.0014 (2)	0.0009 (2)
O1	0.0384 (8)	0.0394 (9)	0.0411 (9)	−0.0076 (7)	0.0059 (7)	0.0089 (7)
O2	0.0429 (9)	0.0440 (9)	0.0414 (9)	0.0135 (7)	0.0038 (7)	−0.0066 (8)
O3	0.0289 (7)	0.0381 (8)	0.0538 (10)	0.0070 (6)	0.0042 (7)	0.0108 (7)
O4	0.0321 (8)	0.0554 (10)	0.0446 (9)	−0.0114 (7)	−0.0046 (7)	−0.0019 (8)
N1A	0.0295 (8)	0.0209 (7)	0.0282 (8)	−0.0037 (6)	0.0017 (7)	0.0069 (6)
C1A	0.0251 (9)	0.0212 (8)	0.0248 (9)	−0.0037 (7)	0.0014 (7)	0.0011 (7)
C2A	0.0264 (9)	0.0190 (8)	0.0208 (8)	−0.0019 (7)	0.0013 (7)	−0.0021 (7)
C3A	0.0226 (8)	0.0243 (9)	0.0246 (9)	−0.0033 (7)	−0.0003 (7)	−0.0008 (7)
C4A	0.0244 (8)	0.0253 (8)	0.0236 (9)	0.0024 (6)	−0.0033 (7)	0.0003 (8)
N5A	0.0287 (7)	0.0188 (7)	0.0255 (8)	−0.0013 (5)	0.0010 (6)	0.0042 (6)
C6A	0.0238 (9)	0.0258 (8)	0.0288 (10)	−0.0038 (6)	0.0005 (8)	0.0042 (8)
C7A	0.0233 (8)	0.0217 (8)	0.0268 (9)	0.0011 (7)	−0.0018 (7)	0.0024 (7)
N1B	0.0286 (8)	0.0207 (7)	0.0270 (8)	−0.0036 (6)	0.0015 (6)	0.0048 (6)
C1B	0.0274 (8)	0.0200 (7)	0.0240 (8)	−0.0030 (6)	0.0018 (9)	0.0023 (8)
C2B	0.0294 (9)	0.0189 (8)	0.0216 (9)	−0.0023 (7)	−0.0014 (7)	0.0003 (7)
C3B	0.0262 (9)	0.0268 (9)	0.0278 (9)	−0.0016 (7)	0.0002 (8)	0.0038 (8)
C4B	0.0356 (12)	0.0225 (9)	0.0287 (10)	0.0037 (8)	−0.0034 (8)	0.0025 (8)
N5B	0.0347 (9)	0.0221 (8)	0.0314 (9)	−0.0034 (7)	−0.0025 (7)	0.0068 (7)
C6B	0.0288 (11)	0.0303 (10)	0.0423 (13)	−0.0040 (8)	0.0005 (9)	0.0136 (9)
C7B	0.0265 (10)	0.0256 (9)	0.0396 (11)	0.0032 (8)	−0.0012 (9)	0.0096 (9)

Geometric parameters (Å, º)

Cl1—O4	1.4330 (15)	C6A—C7A	1.376 (3)
Cl1—O2	1.4386 (16)	C6A—H6A	0.9500
Cl1—O1	1.4412 (15)	C7A—H7A	0.9500
Cl1—O3	1.4444 (15)	N1B—C1B	1.273 (2)
N1A—C1A	1.275 (2)	C1B—C2B	1.473 (2)
N1A—N1B	1.410 (2)	C1B—H1B	0.9500
C1A—C2A	1.476 (3)	C2B—C7B	1.385 (3)
C1A—H1A	0.9500	C2B—C3B	1.388 (2)
C2A—C7A	1.394 (2)	C3B—C4B	1.392 (3)
C2A—C3A	1.395 (2)	C3B—H3B	0.9500
C3A—C4A	1.373 (3)	C4B—N5B	1.337 (3)
C3A—H3A	0.9500	C4B—H4B	0.9500
C4A—N5A	1.337 (2)	N5B—C6B	1.343 (3)
C4A—H4A	0.9500	C6B—C7B	1.384 (3)
N5A—C6A	1.340 (2)	C6B—H6B	0.9500
N5A—H5A	0.8800	C7B—H7B	0.9500
O4—Cl1—O2	109.61 (10)	C7A—C6A—H6A	119.7
O4—Cl1—O1	109.86 (10)	C6A—C7A—C2A	118.61 (16)
O2—Cl1—O1	110.05 (9)	C6A—C7A—H7A	120.7
O4—Cl1—O3	109.45 (10)	C2A—C7A—H7A	120.7
O2—Cl1—O3	108.50 (9)	C1B—N1B—N1A	111.48 (15)
O1—Cl1—O3	109.35 (9)	N1B—C1B—C2B	119.93 (15)
C1A—N1A—N1B	111.04 (15)	N1B—C1B—H1B	120.0
N1A—C1A—C2A	120.12 (16)	C2B—C1B—H1B	120.0
N1A—C1A—H1A	119.9	C7B—C2B—C3B	118.22 (16)
C2A—C1A—H1A	119.9	C7B—C2B—C1B	122.09 (16)
C7A—C2A—C3A	119.37 (16)	C3B—C2B—C1B	119.68 (16)
C7A—C2A—C1A	121.90 (16)	C4B—C3B—C2B	119.07 (17)
C3A—C2A—C1A	118.73 (16)	C4B—C3B—H3B	120.5
C4A—C3A—C2A	119.22 (16)	C2B—C3B—H3B	120.5
C4A—C3A—H3A	120.4	N5B—C4B—C3B	122.72 (18)
C2A—C3A—H3A	120.4	N5B—C4B—H4B	118.6
N5A—C4A—C3A	120.17 (16)	C3B—C4B—H4B	118.6
N5A—C4A—H4A	119.9	C4B—N5B—C6B	117.81 (16)
C3A—C4A—H4A	119.9	N5B—C6B—C7B	122.96 (19)
C6A—N5A—C4A	121.98 (15)	N5B—C6B—H6B	118.5
C6A—N5A—H5A	119.0	C7B—C6B—H6B	118.5
C4A—N5A—H5A	119.0	C6B—C7B—C2B	119.14 (18)
N5A—C6A—C7A	120.61 (16)	C6B—C7B—H7B	120.4
N5A—C6A—H6A	119.7	C2B—C7B—H7B	120.4
N1B—N1A—C1A—C2A	−179.83 (16)	N1A—N1B—C1B—C2B	175.91 (17)
N1A—C1A—C2A—C7A	−2.2 (3)	N1B—C1B—C2B—C7B	7.4 (3)
N1A—C1A—C2A—C3A	177.12 (18)	N1B—C1B—C2B—C3B	−171.35 (19)
C7A—C2A—C3A—C4A	1.2 (3)	C7B—C2B—C3B—C4B	−2.6 (3)
C1A—C2A—C3A—C4A	−178.10 (16)	C1B—C2B—C3B—C4B	176.15 (17)
C2A—C3A—C4A—N5A	0.7 (3)	C2B—C3B—C4B—N5B	0.3 (3)
C3A—C4A—N5A—C6A	−2.1 (3)	C3B—C4B—N5B—C6B	2.0 (3)
C4A—N5A—C6A—C7A	1.5 (3)	C4B—N5B—C6B—C7B	−1.9 (3)
N5A—C6A—C7A—C2A	0.5 (3)	N5B—C6B—C7B—C2B	−0.4 (3)
C3A—C2A—C7A—C6A	−1.8 (3)	C3B—C2B—C7B—C6B	2.7 (3)
C1A—C2A—C7A—C6A	177.48 (17)	C1B—C2B—C7B—C6B	−176.08 (18)
C1A—N1A—N1B—C1B	−170.36 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5A—H5A···N5B^i	0.88	1.84	2.715 (2)	174
C3B—H3B···O2^ii	0.95	2.36	3.286 (2)	165
C4A—H4A···O2^i	0.95	2.51	3.294 (2)	139
C4B—H4B···O1^iii	0.95	2.50	3.438 (2)	171
C6A—H6A···O1^iv	0.95	2.54	3.467 (2)	166
C6A—H6A···O3^iv	0.95	2.44	3.111 (2)	127

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