A two-dimensional layer in N,N′-bis­[2-(hydroxy­meth­yl)benz­yl]ethyl­ene­diamine and a three-dimensional network in N,N′-bis­[2-(hydroxy­methyl)benz­yl]ethyl­enediammonium bis­(perchlorate)

In both title compounds, C₁₈H₂₄N₂O₂, (Ia), and C₁₈H₂₆­N₂O₂²⁺·2ClO₄⁻, (II), respectively, the two aryl rings are strictly parallel, with an inversion centre lying at the mid-point of each central CH₂—CH₂ bond. Mol­ecules in (Ia) are linked into two-dimensional layers by N—H...O hydrogen bonds. The component ions in (II) are joined together by a combination of N/O/C—H...O hydrogen bonds and C—H...π and anion...π inter­actions, forming a three-dimensional network. A structural understanding of (Ia) and (II) may provide some useful information about how and why their metal–organic complexes display various biological activities and function in catalytic processes.

S1. Comment

In recent decades, tetradentate Schiff bases known generally as SalenH₂ (Kahwa et al., 1986) have been studied extensively owing to their potential biological activities, e.g. antibacterial, antitumour (Santos et al., 2001; Viswanathan et al., 1998; García-Zarracino et al., 2002) and catalytic (Mohebbi et al., 2005). They not only offer greater flexibility than the corresponding Schiff bases, but also adopt two additional sites capable of σ-bonding which should be helpful in designing new useful inorganic complexes (Atwood & Rutherford, 1995; Xu et al., 2004; Tinoco et al., 2007). In order to gain more insight into these analogues, we have synthesized a new tetradentate ligand, (Ia), containing an N₂O₂ donor set, and its diammonium bis(perchlorate), (II), and we report their molecular and supramolecular structures.

Both title compounds crystallize in space group P2₁/c, with only one-half of the molecule representing the asymmetric unit (Fig. 1). The conformation of the central chain in (Ia) is described by the torsion angles of C3—C2—N1—C1 = -72.6 (1)°, C2—N1—C1—C1ⁱ = 175.5 (1)° and N1—C1—C1ⁱ—N1ⁱ constrained by symmetry to be 180° [symmetry code: (i) -x, 1 - y, -z], resulting in the less common gauche–trans–trans conformation (Xia et al., 2006). The corresponding angles in (II) are -178.9 (3), -168.1 (3) and 180°, respectively, forming the general trans–trans–trans conformation (Palladino et al., 2006; Matiková-Maľarová et al., 2007; Yang, Wang et al., 2007; Yang, Han et al., 2007; Liu et al., 2007). Both N atoms in the tetradentate ligand can be potentially coordinated to a metal ion, according to previously reported analogues (Panda et al., 2004; Ghosh et al., 1994), giving rise to many other conformations. This indicates that these highly flexible molecules can freely rotate about all the σ bonds. However, when (II) is coordinated to a metal ion, it should first be deprotonated using a moderately basic medium.

Although a similar C(7) motif (Bernstein et al., 1995) exists in both compounds, in (Ia) it is formed by intramolecular O1—H1E···N1 hydrogen bonds, and in (II) by N1—H1C···O1 hydrogen bonds. In order to investigate further the reason for this, the hydrogen-bonding energy and the total molecular energy of the two practical and one posulated conformations were calculated according to our earlier method (Hu et al., 1999; Hu, 1998) using the program GAUSSIAN03W (Frisch et al., 2004) at the RB3LYP/6-31G(d) level. It can be seen from Table 1 that the dication has the lowest total molecular energy and the postulated form (Ib) has the highest one. The Mulliken charges on the N atoms in (Ia) and (Ib) are -0.594 and -0.569, respectively. This indicates that the neutral N atoms in (Ia) may be more easily protonated than those in (Ib). We also have found that when Lewis acids are absent, the neutral molecules preferentially adopt conformation (Ia). Some contrast experiments have been carried out by displacing the solvent with ethanol, acetone and water. However, no crystals adopting conformation (Ib) were obtained.

In the crystal structure of (Ia), the molecules are linked by means of N—H···O hydrogen bonds into two-dimensional layers. Amino atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atom H1C, to the hydroxyl atom O1 in the molecule at (-x, 1/2 + y, 1/2 - z), forming a one-dimensional C(7) chain running parallel to the [010] direction, which is generated by the 2₁ screw axis at (0, y, 1/4). Adjacent C(7) chains related by the inversion centres at the mid-point of the CH₂—CH₂ unit thus link the molecules into two-dimensional layers (Fig. 2) running parallel to the (100) plane. There are two halves of such a layer passing through the unit cell, with the reference layer in the domain -0.474 < x < 0.474 and the other in the domain 0.526 < x < 1.474. No C—H···π or π–π stacking interactions are observed between adjacent layers.

In the crystal structure of (II), the component ions are linked into a three-dimensional network by a combination of N/O/C—H···O hydrogen bonds and C—H···π and anion···π interactions, which can be readily analysed in terms of two simple substructures. First, the combined actions of five inter-ion hydrogen bonds (Table 2) and their respective equivalents result in two-dimensional layers running parallel to the (100) plane. The reference two-dimensional layer lies within the domain -0.065< x < 1.065 and there is only one such layer passing through the unit cell (Fig. 3). Analysis by PLATON (Spek, 2003) indicates that a rather weak anion···π interaction exists within the two-dimensional layer formed between the perchlorate anion at (x, y, z) and the phenyl ring at (x, y - 1, z) [O3···Cg1 = 3.849 (6) Å and Cl1—O3···Cg1 = 117.5 (3)°; Cg1 denotes the centroid of the C3–C8 ring]. Secondly, neighbouring layers are interlinked by weak C—H···π interactions (Table 2) into a three-dimensional network. In more detail, aromatic atom C7 in the molecule at (x, y, z) acts as donor to the phenyl ring at (2 - x, 1/2 + y, 3/2 - z), so producing a two-dimensional layer parallel to the (102) plane generated by cooperative action between the 2₁ screw axis and the inversion centre (Fig. 4). These two types of (100) and (102) layers are joined together to form a three-dimensional network in (II).

In summary, the crystal structures of a ligand with an N₂O₂ donor set and its ammonium perchlorate have been reported. In (Ia), the neutral molecules are linked into a two-dimensional layer. The component ions in (II) are joined together, forming a three-dimensional network. Further research on the synthesis of metal–organic complexes containing the ligand and their potential application is underway in our laboratory.

S2. Experimental

All reagents and solvents were used as obtained without further purification. A mixture of ethylenediamine (2 g, 0.03 mol) and 2-(hydroxymethyl)benzaldehyde (8 g, 0.06 mol) was stirred at 348 K for 10 h, and then the resulting white precipitate was removed by filtration and dried in a vacuum. The white precipitate (4 g, 0.013 mol), LiAlH₄ (1 g, 0.026 mol) and THF (50 ml) were stirred at 333 K for 6 h. The solvent was removed by rotary evaporation to yield 6.7 g of a powder. Plate colourless crystals of (Ia) suitable for single-crystal X-ray diffraction analysis were grown by slow evaporation of its methanol solution (10 ml) at room temperature. To prepare compound (II), the powder of (Ia) (2 g) was dissolved in methanol (15 ml) adjusted to pH 5 using HClO₄. Block colourless crystals of (II) were obtained by slow evaporation of the solvent over several days.

S3. Refinement

For both compounds, H atoms bonded to C atoms were positioned geometrically, with C—H = 0.93 Å (aromatic) or 0.97 Å (methylene), and refined as riding, with U_iso(H) = 1.2U_eq(C). H atoms bonded to N and O atoms were found in difference Fourier maps, with N—H and O—H distances refined freely [Please give ranges] and with U_iso(H) = 1.2U_eq(N) or 1.5U_eq(O).

Computing details

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (Ia), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Some hydrogen bonds are shown in dashed lines. [Symmetry codes: (i) -x, 1 - y, -z.]
	Fig. 2. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Some hydrogen bonds are shown in dashed lines. [Symmetry codes: (ii) 1 - x, 1 - y, 1 - z.]
	Fig. 3. Part of the crystal structure of (Ia), showing the formation of the two-dimensional network running parallel to the (100) plane. Hydrogen bonds are shown as dashed lines.
	Fig. 4. Part of the crystal structure of (II), showing the formation of the two-dimensional network running parallel to the (100) plane. Hydrogen bonds are shown as dashed lines.
	Fig. 5. Part of the crystal structure of (II), showing the formation of the two-dimensional network running parallel to the (102) plane built up from C—H···π interactions. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms and perchlorate anions not involved in the motif have been omitted.

(Ia) N,N'-bis[2-(hydroxymethyl)benzyl]ethylenediamine

Crystal data

C18H24N2O2	F(000) = 324
Mr = 300.39	Dx = 1.190 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2040 reflections
a = 14.0939 (2) Å	θ = 2.4–26.7°
b = 6.9520 (6) Å	µ = 0.08 mm^−1
c = 8.6661 (7) Å	T = 294 K
β = 99.226 (3)°	Plate, colourless
V = 838.13 (10) Å^3	0.30 × 0.15 × 0.04 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer	1645 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	1314 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
0.3° wide ω exposures scans	θmax = 26.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.947, Tmax = 0.996	k = −7→8
6213 measured reflections	l = −10→10

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0861P)^2 + 0.049P] where P = (Fo^2 + 2Fc^2)/3
1645 reflections	(Δ/σ)max < 0.001
106 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.16 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
C1	0.03897 (10)	0.5581 (2)	0.04839 (17)	0.0434 (4)
H1A	0.0961	0.5573	−0.0009	0.052*
H1B	0.0178	0.6904	0.0539	0.052*
C2	0.14354 (11)	0.5793 (2)	0.30179 (18)	0.0496 (4)
H2A	0.1460	0.5439	0.4106	0.059*
H2B	0.1333	0.7171	0.2932	0.059*
C3	0.23822 (10)	0.5299 (2)	0.25108 (16)	0.0418 (4)
C4	0.28947 (12)	0.6709 (2)	0.18559 (19)	0.0574 (5)
H4	0.2643	0.7944	0.1720	0.069*
C5	0.37728 (13)	0.6309 (3)	0.1402 (2)	0.0703 (6)
H5	0.4105	0.7269	0.0965	0.084*
C6	0.41484 (12)	0.4495 (4)	0.1601 (2)	0.0751 (6)
H6	0.4742	0.4222	0.1313	0.090*
C7	0.36465 (11)	0.3079 (3)	0.2225 (2)	0.0608 (5)
H7	0.3906	0.1847	0.2342	0.073*
C8	0.27637 (10)	0.3429 (2)	0.26864 (16)	0.0438 (4)
C9	0.22174 (11)	0.1824 (2)	0.33094 (18)	0.0524 (4)
H9A	0.2649	0.0751	0.3604	0.063*
H9B	0.1981	0.2262	0.4240	0.063*
N1	0.06208 (8)	0.47920 (18)	0.20610 (14)	0.0438 (4)
H1C	0.0101 (12)	0.497 (2)	0.2493 (19)	0.053*
O1	0.14228 (8)	0.11842 (16)	0.21829 (13)	0.0527 (4)
H1E	0.1056 (14)	0.227 (3)	0.197 (2)	0.079*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0409 (8)	0.0429 (8)	0.0478 (8)	0.0047 (6)	0.0109 (6)	0.0057 (6)
C2	0.0550 (9)	0.0485 (9)	0.0456 (8)	0.0067 (7)	0.0093 (7)	−0.0080 (7)
C3	0.0409 (8)	0.0451 (8)	0.0374 (7)	−0.0046 (6)	−0.0001 (5)	−0.0065 (6)
C4	0.0610 (10)	0.0497 (10)	0.0586 (10)	−0.0140 (8)	0.0002 (7)	−0.0041 (8)
C5	0.0520 (10)	0.0879 (15)	0.0707 (12)	−0.0296 (10)	0.0083 (8)	0.0019 (10)
C6	0.0381 (9)	0.1099 (17)	0.0779 (13)	−0.0065 (10)	0.0111 (8)	−0.0042 (11)
C7	0.0390 (8)	0.0722 (11)	0.0689 (11)	0.0091 (8)	0.0010 (7)	−0.0021 (9)
C8	0.0380 (8)	0.0511 (9)	0.0397 (7)	0.0026 (6)	−0.0020 (5)	−0.0029 (6)
C9	0.0559 (9)	0.0483 (9)	0.0507 (9)	0.0056 (7)	0.0016 (7)	0.0081 (7)
N1	0.0378 (7)	0.0516 (8)	0.0440 (7)	0.0063 (5)	0.0127 (5)	0.0044 (5)
O1	0.0534 (7)	0.0436 (7)	0.0602 (7)	−0.0045 (5)	0.0062 (5)	0.0034 (5)

Geometric parameters (Å, º)

C1—N1	1.4603 (18)	C5—C6	1.368 (3)
C1—C1^i	1.506 (3)	C5—H5	0.9300
C1—H1A	0.9700	C6—C7	1.373 (3)
C1—H1B	0.9700	C6—H6	0.9300
C2—N1	1.4781 (19)	C7—C8	1.388 (2)
C2—C3	1.510 (2)	C7—H7	0.9300
C2—H2A	0.9700	C8—C9	1.504 (2)
C2—H2B	0.9700	C9—O1	1.4332 (19)
C3—C4	1.391 (2)	C9—H9A	0.9700
C3—C8	1.406 (2)	C9—H9B	0.9700
C4—C5	1.385 (3)	N1—H1C	0.883 (17)
C4—H4	0.9300	O1—H1E	0.92 (2)
N1—C1—C1^i	110.67 (14)	C4—C5—H5	120.2
N1—C1—H1A	109.5	C5—C6—C7	119.82 (16)
C1^i—C1—H1A	109.5	C5—C6—H6	120.1
N1—C1—H1B	109.5	C7—C6—H6	120.1
C1^i—C1—H1B	109.5	C6—C7—C8	122.00 (17)
H1A—C1—H1B	108.1	C6—C7—H7	119.0
N1—C2—C3	111.89 (11)	C8—C7—H7	119.0
N1—C2—H2A	109.2	C7—C8—C3	118.43 (14)
C3—C2—H2A	109.2	C7—C8—C9	120.49 (14)
N1—C2—H2B	109.2	C3—C8—C9	121.06 (13)
C3—C2—H2B	109.2	O1—C9—C8	112.00 (12)
H2A—C2—H2B	107.9	O1—C9—H9A	109.2
C4—C3—C8	118.75 (14)	C8—C9—H9A	109.2
C4—C3—C2	119.95 (14)	O1—C9—H9B	109.2
C8—C3—C2	121.30 (13)	C8—C9—H9B	109.2
C5—C4—C3	121.36 (17)	H9A—C9—H9B	107.9
C5—C4—H4	119.3	C1—N1—C2	112.63 (12)
C3—C4—H4	119.3	C1—N1—H1C	105.5 (11)
C6—C5—C4	119.63 (16)	C2—N1—H1C	108.5 (11)
C6—C5—H5	120.2	C9—O1—H1E	103.6 (13)
N1—C2—C3—C4	113.77 (15)	C4—C3—C8—C7	1.2 (2)
N1—C2—C3—C8	−66.27 (17)	C2—C3—C8—C7	−178.75 (13)
C8—C3—C4—C5	−1.0 (2)	C4—C3—C8—C9	−176.80 (14)
C2—C3—C4—C5	178.94 (14)	C2—C3—C8—C9	3.2 (2)
C3—C4—C5—C6	−0.1 (3)	C7—C8—C9—O1	−104.33 (16)
C4—C5—C6—C7	1.0 (3)	C3—C8—C9—O1	73.64 (18)
C5—C6—C7—C8	−0.8 (3)	C1^i—C1—N1—C2	175.49 (13)
C6—C7—C8—C3	−0.3 (2)	C3—C2—N1—C1	−72.65 (15)
C6—C7—C8—C9	177.69 (16)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1E···N1	0.92 (2)	1.86 (2)	2.7461 (16)	161.0 (18)
N1—H1C···O1^ii	0.883 (17)	2.366 (17)	3.2042 (15)	158.6 (14)

Symmetry code: (ii) −x, y+1/2, −z+1/2.

(II) N,N'-bis[2-(hydroxymethyl)benzyl]ethylenediammonium bis(perchlorate)

Crystal data

C18H26N2O2^2+·2ClO4^−	F(000) = 524
Mr = 501.31	Dx = 1.527 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3251 reflections
a = 12.8926 (12) Å	θ = 2.5–25.4°
b = 5.8332 (6) Å	µ = 0.36 mm^−1
c = 15.1397 (15) Å	T = 294 K
β = 106.779 (2)°	Plate, colourless
V = 1090.11 (19) Å^3	0.20 × 0.10 × 0.06 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2133 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	1806 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
0.3° wide ω exposures scans	θmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.931, Tmax = 0.983	k = −7→7
8763 measured reflections	l = −18→18

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0783P)^2 + 1.0643P] where P = (Fo^2 + 2Fc^2)/3
2133 reflections	(Δ/σ)max < 0.001
151 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.36 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
C1	0.5448 (2)	0.4711 (5)	0.5433 (2)	0.0529 (9)
H1A	0.5195	0.4936	0.5971	0.064*
H1B	0.5656	0.3117	0.5416	0.064*
C2	0.7397 (2)	0.5438 (5)	0.6218 (2)	0.0506 (8)
H2A	0.7585	0.3901	0.6074	0.061*
H2B	0.7253	0.5392	0.6812	0.061*
C3	0.8330 (2)	0.7026 (5)	0.62696 (18)	0.0389 (6)
C4	0.9080 (3)	0.6466 (6)	0.5808 (2)	0.0540 (8)
H4	0.8995	0.5117	0.5468	0.065*
C5	0.9955 (3)	0.7885 (7)	0.5845 (2)	0.0600 (9)
H5	1.0460	0.7470	0.5542	0.072*
C6	1.0074 (2)	0.9878 (6)	0.6326 (2)	0.0516 (8)
H6	1.0653	1.0844	0.6343	0.062*
C7	0.9335 (2)	1.0474 (5)	0.67897 (19)	0.0405 (6)
H7	0.9425	1.1843	0.7118	0.049*
C8	0.8462 (2)	0.9071 (5)	0.67762 (17)	0.0356 (6)
C9	0.7701 (2)	0.9747 (5)	0.7316 (2)	0.0492 (7)
H9A	0.7705	0.8593	0.7778	0.059*
H9B	0.7925	1.1196	0.7626	0.059*
Cl1	0.64645 (6)	0.09372 (14)	0.37511 (5)	0.0516 (3)
N1	0.6399 (2)	0.6218 (4)	0.5493 (2)	0.0564 (8)
H1C	0.626 (3)	0.755 (4)	0.562 (2)	0.068*
H1D	0.647 (3)	0.620 (7)	0.4949 (16)	0.068*
O1	0.66378 (17)	0.9952 (4)	0.6685 (2)	0.0641 (7)
H1E	0.622 (3)	1.013 (8)	0.699 (3)	0.096*
O2	0.6913 (4)	0.3043 (7)	0.4111 (3)	0.1308 (16)
O3	0.7272 (3)	−0.0674 (9)	0.3860 (4)	0.157 (2)
O4	0.5951 (5)	0.1165 (10)	0.2816 (3)	0.160 (2)
O5	0.5710 (2)	0.0198 (5)	0.4198 (2)	0.0811 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0446 (16)	0.0295 (14)	0.067 (2)	0.0004 (12)	−0.0129 (15)	−0.0070 (13)
C2	0.0444 (16)	0.0296 (14)	0.0619 (19)	0.0027 (12)	−0.0100 (14)	0.0001 (13)
C3	0.0357 (13)	0.0348 (14)	0.0373 (13)	0.0069 (11)	−0.0034 (11)	−0.0012 (11)
C4	0.076 (2)	0.0448 (17)	0.0398 (15)	0.0155 (16)	0.0135 (15)	−0.0050 (13)
C5	0.068 (2)	0.071 (2)	0.0516 (18)	0.0199 (19)	0.0333 (16)	0.0069 (17)
C6	0.0448 (16)	0.060 (2)	0.0509 (17)	0.0014 (15)	0.0158 (14)	0.0125 (15)
C7	0.0369 (13)	0.0388 (15)	0.0401 (14)	−0.0013 (12)	0.0021 (11)	−0.0012 (12)
C8	0.0308 (12)	0.0360 (14)	0.0355 (13)	0.0055 (10)	0.0023 (10)	−0.0013 (11)
C9	0.0410 (15)	0.0443 (17)	0.0636 (19)	0.0036 (13)	0.0174 (14)	−0.0079 (14)
Cl1	0.0509 (5)	0.0518 (5)	0.0548 (5)	−0.0030 (3)	0.0195 (3)	0.0028 (3)
N1	0.0470 (15)	0.0289 (12)	0.0719 (18)	−0.0006 (11)	−0.0165 (14)	−0.0007 (13)
O1	0.0354 (11)	0.0512 (13)	0.104 (2)	0.0073 (10)	0.0182 (12)	−0.0122 (13)
O2	0.174 (4)	0.102 (3)	0.148 (3)	−0.080 (3)	0.096 (3)	−0.052 (2)
O3	0.092 (3)	0.180 (5)	0.208 (5)	0.052 (3)	0.057 (3)	−0.046 (4)
O4	0.203 (5)	0.180 (5)	0.069 (2)	−0.065 (4)	−0.005 (3)	0.023 (3)
O5	0.0816 (18)	0.0708 (18)	0.105 (2)	−0.0135 (15)	0.0498 (17)	0.0022 (15)

Geometric parameters (Å, º)

C1—N1	1.489 (4)	C6—H6	0.9300
C1—C1^i	1.514 (6)	C7—C8	1.387 (4)
C1—H1A	0.9700	C7—H7	0.9300
C1—H1B	0.9700	C8—C9	1.499 (4)
C2—N1	1.500 (4)	C9—O1	1.432 (4)
C2—C3	1.502 (4)	C9—H9A	0.9700
C2—H2A	0.9700	C9—H9B	0.9700
C2—H2B	0.9700	Cl1—O3	1.377 (4)
C3—C4	1.386 (4)	Cl1—O4	1.386 (4)
C3—C8	1.401 (4)	Cl1—O2	1.399 (3)
C4—C5	1.388 (5)	Cl1—O5	1.403 (3)
C4—H4	0.9300	N1—H1C	0.832 (19)
C5—C6	1.356 (5)	N1—H1D	0.856 (18)
C5—H5	0.9300	O1—H1E	0.81 (4)
C6—C7	1.381 (4)
N1—C1—C1^i	109.3 (3)	C6—C7—H7	119.3
N1—C1—H1A	109.8	C8—C7—H7	119.3
C1^i—C1—H1A	109.8	C7—C8—C3	118.7 (3)
N1—C1—H1B	109.8	C7—C8—C9	119.5 (2)
C1^i—C1—H1B	109.8	C3—C8—C9	121.8 (3)
H1A—C1—H1B	108.3	O1—C9—C8	108.0 (3)
N1—C2—C3	110.8 (2)	O1—C9—H9A	110.1
N1—C2—H2A	109.5	C8—C9—H9A	110.1
C3—C2—H2A	109.5	O1—C9—H9B	110.1
N1—C2—H2B	109.5	C8—C9—H9B	110.1
C3—C2—H2B	109.5	H9A—C9—H9B	108.4
H2A—C2—H2B	108.1	O3—Cl1—O4	108.0 (4)
C4—C3—C8	119.0 (3)	O3—Cl1—O2	109.9 (3)
C4—C3—C2	119.5 (3)	O4—Cl1—O2	109.6 (3)
C8—C3—C2	121.5 (3)	O3—Cl1—O5	109.8 (3)
C3—C4—C5	121.1 (3)	O4—Cl1—O5	109.2 (3)
C3—C4—H4	119.4	O2—Cl1—O5	110.4 (2)
C5—C4—H4	119.4	C1—N1—C2	112.5 (2)
C6—C5—C4	119.8 (3)	C1—N1—H1C	110 (3)
C6—C5—H5	120.1	C2—N1—H1C	108 (3)
C4—C5—H5	120.1	C1—N1—H1D	104 (3)
C5—C6—C7	120.1 (3)	C2—N1—H1D	113 (3)
C5—C6—H6	120.0	H1C—N1—H1D	109 (4)
C7—C6—H6	120.0	C9—O1—H1E	107 (4)
C6—C7—C8	121.3 (3)
N1—C2—C3—C4	−97.3 (3)	C4—C3—C8—C7	0.6 (4)
N1—C2—C3—C8	82.8 (3)	C2—C3—C8—C7	−179.4 (2)
C8—C3—C4—C5	0.4 (4)	C4—C3—C8—C9	−178.1 (3)
C2—C3—C4—C5	−179.6 (3)	C2—C3—C8—C9	1.9 (4)
C3—C4—C5—C6	−1.3 (5)	C7—C8—C9—O1	120.9 (3)
C4—C5—C6—C7	1.1 (5)	C3—C8—C9—O1	−60.5 (3)
C5—C6—C7—C8	−0.1 (4)	C1^i—C1—N1—C2	−168.1 (3)
C6—C7—C8—C3	−0.8 (4)	C3—C2—N1—C1	−178.9 (3)
C6—C7—C8—C9	177.9 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O5^ii	0.83 (2)	2.57 (4)	3.004 (4)	113 (3)
O1—H1E···O4^iii	0.81 (4)	2.57 (4)	3.118 (5)	126 (4)
C9—H9A···O3^iv	0.97	2.53	3.487 (5)	168
N1—H1C···O1	0.83 (2)	2.09 (3)	2.788 (4)	142 (3)
N1—H1D···O2	0.86 (2)	2.39 (4)	3.008 (5)	129 (3)
C1—H1B···O5	0.97	2.53	3.302 (4)	137

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