4-(4-Chloro­benzyl­ideneamino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one and 4-(2-chloro­benzyl­idene­amino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one

The two title compounds, both with formula C₁₈H₁₆ClN₃O, are structurally similar Schiff bases derived from the condensation of 4-chloro­benzaldehyde or 2-chloro­benzaldehyde with 4-amino­anti­pyrine in methanol solution. As expected, both compounds adopt trans configurations about the central C=N bonds. In the crystal structure of the 4-chloro analogue, mol­ecules are linked through weak C-H...O hydrogen bonds, forming chains running along the a axis. In the crystal structure of the 2-chloro analogue, mol­ecules are linked through weak C-H...O and C-H...Cl hydrogen bonds, forming layers parallel to the ab plane.

S1. Comment

Antipyrine and its derivatives exhibit a wide range of biological activities and applications (Yadav et al., 2003; Ismail, 2000; Abd El Rehim et al., 2001). A few crystal structures of antipyrine derivatives have been investigated (Liang et al., 2002; Li & Zhang, 2004, 2005; Zhang & Li, 2005). Schiff bases have demonstrated significant biological activity and new examples are being tested for their antitumor, antimicrobial and antiviral activities (Tarafder et al., 2002; Cukurovali et al., 2002; Ali et al., 2002). Recently, the crystal structure of 4-[(2,4-dichlorobenzylidene)amino]-1,5-dimethyl-2-phenyl-1,2- dihydropyrazol-3-one, (III), has been reported (Jing et al., 2005). However, the crystal structures of antipyrine derivatives influenced by the substituent groups have seldom been reported. In this paper, the crystal structures and the substituent effects of the two structurally similar title antipyrine derivatives, viz. the para-substituted compound (I) and the ortho-substituted compound (II), are reported.

The structures of (I) and (II) (Figs. 1 and 2) are analogous to those of ortho- and para-substituted (III). The bond lengths and angles in (I) and (II) are comparable to one another and to the corresponding values in (III), and all lie within normal ranges (Allen et al., 1987). The main difference between the two structures is the position of the Cl atoms. In (I), the Cl1 atom is located at the para position, and thus it cannot participate in the forming of intramolecular hydrogen bonds, while in (II), the Cl1 atom is located at the ortho position, forming an intramolecular C7—H7···Cl1 hydrogen bond (Table 1). In each of the compounds, the C7═N1 bond lengths [1.276 (2) Å in (I) and 1.278 (3) Å in (II)] conform to the value for double bonds. The distance between atoms C8 and N1 [1.392 (2) Å in both (I) and (II)] is intermediate between a C—N single bond and a C═N double bond length, because of conjugation effects in each of the molecules. The conjugation effects also cause the pyrazoline and C1–C6 phenyl rings to be nearly coplanar, with a mean deviation from the overall plane of 0.0672 Å in (I) and 0.1125 Å in (II). The dihedral angle between the C1–C6 phenyl ring and the pyrazoline ring is 8.7 (2)° for (I) and 13.2 (2)° for (II). The dihedral angle between the C13–C18 phenyl ring and the pyrazoline ring is 51.6 (2)° for (I) and 75.5 (2)° for (II). As expected, the molecular structures adopt trans configurations about the central C═N bonds, which is also observed in (III).

In the crystal structure of (I), molecules are linked through weak C—H···O hydrogen bonds (Table 1), forming chains running along the a axis (Fig. 3). In the crystal structure of (II), molecules are linked through weak C—H···O and C—H···Cl hydrogen bonds, forming layers parallel to the ab plane (Fig. 4). The same pattern can be observed in (III), in which the ortho-positional Cl1 atom participates in the formation of intermolecular C—H···Cl hydrogen bonds, while the para-positional Cl2 atom does not participate in any hydrogen bonds.

In conclusion, in the chloro-substituted antipyrine Schiff bases, the ortho-positional Cl atom can participate in the formation of both intramolecular and intermolecular hydrogen bonds; however, the para-positional Cl atom cannot participate in any hydrogen bonds. The positions of substituent groups can significantly influence the final structures.

S2. Experimental

For the preparation of (I), a mixture of 4-chlorobenzylaldehyde (0.1 mmol, 14.1 mg) and 4-aminoantipyrine (0.1 mmol, 20.3 mg) were dissolved in methanol (10 ml). The mixture was stirred for about 1 h at room temperature to give a clear yellow solution. After the solution had been kept in air for 3 d, yellow prism-shaped crystals were formed. Compound (II) was prepared by a procedure similar to that described for (I), with 4-chlorobenzylaldehyde replaced by 2-chlorobenzylaldehyde (0.1 mmol, 14.1 mg). Yellow prism-shaped crystals of (II) were obtained after evaporating the solution in air for 6 d.

S3. Refinement

All H atoms in (I) and (II) were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.96 Å and with U_iso(H) values of 1.2 or 1.5 times U_eq(C). The Flack (1983) parameter value of (II) is based on an `on-the-cheap' refinement.

Computing details

For both compounds, data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2002); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The intramolecular hydrogen bond is shown as a dashed line.
	Fig. 2. The structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 3. The molecular packing of (I), viewed along the a axis. Intramolecular hydrogen bonds are shown as dashed lines. H atoms not involved in the interactions shown have been omitted.
	Fig. 4. The molecular packing of (II), viewed along the a axis. Intramolecular hydrogen bonds are shown as dashed lines. H atoms not involved in the interactions shown have been omitted.

(I) 4-(4-Chlorobenzylideneamino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one

Crystal data

C18H16ClN3O	F(000) = 1360
Mr = 325.79	Dx = 1.318 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5083 reflections
a = 6.971 (1) Å	θ = 2.4–24.5°
b = 17.508 (1) Å	µ = 0.24 mm^−1
c = 26.905 (2) Å	T = 298 K
V = 3283.7 (6) Å^3	Prism, yellow
Z = 8	0.35 × 0.20 × 0.17 mm

Data collection

Bruker SMART APEX area-detector diffractometer	3402 independent reflections
Radiation source: fine-focus sealed tube	2620 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ϕ and ω scans	θmax = 26.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
Tmin = 0.921, Tmax = 0.960	k = −21→21
24843 measured reflections	l = −33→33

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0573P)^2 + 0.8176P] where P = (Fo^2 + 2Fc^2)/3
3402 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.28 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
Cl1	0.66199 (12)	1.04863 (5)	0.28220 (2)	0.0999 (3)
O1	0.76288 (18)	0.87648 (8)	0.58652 (5)	0.0652 (4)
N1	1.0174 (2)	0.88957 (8)	0.49072 (5)	0.0498 (4)
N2	1.19968 (19)	0.78390 (9)	0.59305 (6)	0.0487 (4)
N3	1.02877 (19)	0.81017 (9)	0.61493 (5)	0.0499 (4)
C1	0.9432 (3)	0.94939 (12)	0.39332 (8)	0.0633 (5)
H1	1.0617	0.9261	0.3981	0.076*
C2	0.8964 (3)	0.97778 (13)	0.34713 (8)	0.0708 (6)
H2	0.9821	0.9735	0.3208	0.085*
C3	0.7216 (3)	1.01242 (12)	0.34052 (8)	0.0629 (5)
C4	0.5927 (3)	1.01929 (11)	0.37853 (8)	0.0613 (5)
H4	0.4750	1.0431	0.3735	0.074*
C5	0.6408 (3)	0.99016 (11)	0.42441 (8)	0.0566 (5)
H5	0.5536	0.9941	0.4505	0.068*
C6	0.8162 (3)	0.95506 (10)	0.43265 (7)	0.0497 (4)
C7	0.8611 (3)	0.92509 (10)	0.48203 (7)	0.0519 (4)
H7	0.7736	0.9321	0.5077	0.062*
C8	1.0520 (2)	0.85825 (10)	0.53743 (6)	0.0449 (4)
C9	1.2152 (2)	0.81793 (10)	0.54810 (7)	0.0457 (4)
C10	0.9273 (2)	0.85325 (10)	0.57957 (7)	0.0481 (4)
C11	1.3897 (3)	0.81000 (12)	0.51708 (8)	0.0653 (6)
H11A	1.4943	0.8366	0.5326	0.098*
H11B	1.3663	0.8314	0.4848	0.098*
H11C	1.4217	0.7569	0.5138	0.098*
C12	1.3602 (3)	0.76816 (12)	0.62631 (8)	0.0618 (5)
H12A	1.4668	0.7493	0.6074	0.093*
H12B	1.3226	0.7305	0.6503	0.093*
H12C	1.3968	0.8143	0.6431	0.093*
C13	0.9352 (2)	0.76378 (11)	0.65078 (6)	0.0506 (5)
C14	0.9495 (3)	0.68508 (13)	0.64998 (8)	0.0614 (5)
H14	1.0240	0.6609	0.6260	0.074*
C15	0.8520 (3)	0.64253 (15)	0.68512 (9)	0.0757 (6)
H15	0.8626	0.5896	0.6850	0.091*
C16	0.7401 (4)	0.67757 (19)	0.72015 (9)	0.0833 (7)
H16	0.6749	0.6486	0.7437	0.100*
C17	0.7245 (3)	0.75551 (19)	0.72040 (8)	0.0787 (7)
H17	0.6465	0.7791	0.7438	0.094*
C18	0.8230 (3)	0.79949 (14)	0.68635 (7)	0.0629 (5)
H18	0.8141	0.8525	0.6873	0.076*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1167 (6)	0.1139 (6)	0.0690 (4)	0.0311 (4)	−0.0041 (4)	0.0246 (3)
O1	0.0394 (7)	0.0882 (10)	0.0679 (9)	0.0190 (7)	0.0047 (6)	0.0037 (7)
N1	0.0477 (8)	0.0462 (8)	0.0556 (9)	−0.0020 (7)	−0.0013 (7)	−0.0052 (7)
N2	0.0323 (7)	0.0569 (9)	0.0570 (9)	0.0057 (6)	0.0007 (6)	−0.0049 (7)
N3	0.0352 (7)	0.0613 (9)	0.0533 (9)	0.0072 (7)	0.0017 (6)	−0.0044 (7)
C1	0.0553 (12)	0.0663 (13)	0.0683 (13)	0.0135 (10)	0.0039 (10)	0.0063 (10)
C2	0.0688 (14)	0.0782 (14)	0.0653 (13)	0.0156 (11)	0.0142 (11)	0.0101 (11)
C3	0.0744 (14)	0.0557 (12)	0.0586 (12)	0.0086 (10)	−0.0033 (10)	0.0041 (9)
C4	0.0599 (12)	0.0550 (11)	0.0689 (13)	0.0141 (10)	−0.0038 (10)	−0.0007 (10)
C5	0.0559 (11)	0.0547 (11)	0.0593 (11)	0.0071 (9)	0.0044 (9)	−0.0050 (9)
C6	0.0511 (10)	0.0404 (9)	0.0576 (11)	0.0002 (8)	−0.0006 (8)	−0.0041 (8)
C7	0.0492 (10)	0.0488 (10)	0.0576 (11)	−0.0010 (8)	0.0020 (8)	−0.0052 (8)
C8	0.0393 (9)	0.0444 (9)	0.0509 (10)	−0.0014 (7)	−0.0019 (7)	−0.0097 (7)
C9	0.0380 (9)	0.0433 (9)	0.0557 (10)	−0.0023 (7)	0.0013 (8)	−0.0116 (8)
C10	0.0368 (9)	0.0529 (10)	0.0545 (10)	0.0017 (8)	−0.0014 (8)	−0.0084 (8)
C11	0.0496 (11)	0.0704 (13)	0.0759 (14)	0.0078 (10)	0.0144 (10)	−0.0046 (11)
C12	0.0396 (10)	0.0681 (13)	0.0776 (13)	0.0080 (9)	−0.0110 (9)	0.0025 (10)
C13	0.0349 (9)	0.0726 (13)	0.0442 (10)	0.0017 (8)	−0.0052 (7)	−0.0052 (9)
C14	0.0512 (11)	0.0716 (13)	0.0613 (12)	−0.0030 (10)	0.0033 (9)	−0.0075 (10)
C15	0.0619 (13)	0.0842 (16)	0.0809 (16)	−0.0115 (12)	0.0040 (12)	0.0097 (13)
C16	0.0592 (14)	0.123 (2)	0.0683 (15)	−0.0130 (15)	0.0059 (11)	0.0173 (15)
C17	0.0527 (13)	0.133 (2)	0.0507 (12)	0.0100 (14)	0.0079 (10)	−0.0072 (13)
C18	0.0500 (11)	0.0891 (15)	0.0496 (11)	0.0115 (10)	−0.0022 (9)	−0.0114 (10)

Geometric parameters (Å, º)

Cl1—C3	1.743 (2)	C8—C9	1.369 (2)
O1—C10	1.230 (2)	C8—C10	1.432 (2)
N1—C7	1.276 (2)	C9—C11	1.482 (2)
N1—C8	1.392 (2)	C11—H11A	0.9600
N2—C9	1.353 (2)	C11—H11B	0.9600
N2—N3	1.4062 (19)	C11—H11C	0.9600
N2—C12	1.459 (2)	C12—H12A	0.9600
N3—C10	1.405 (2)	C12—H12B	0.9600
N3—C13	1.420 (2)	C12—H12C	0.9600
C1—C2	1.378 (3)	C13—C14	1.382 (3)
C1—C6	1.383 (3)	C13—C18	1.385 (3)
C1—H1	0.9300	C14—C15	1.382 (3)
C2—C3	1.372 (3)	C14—H14	0.9300
C2—H2	0.9300	C15—C16	1.369 (3)
C3—C4	1.367 (3)	C15—H15	0.9300
C4—C5	1.377 (3)	C16—C17	1.369 (4)
C4—H4	0.9300	C16—H16	0.9300
C5—C6	1.386 (3)	C17—C18	1.380 (3)
C5—H5	0.9300	C17—H17	0.9300
C6—C7	1.462 (3)	C18—H18	0.9300
C7—H7	0.9300
C7—N1—C8	120.33 (16)	O1—C10—N3	122.94 (17)
C9—N2—N3	107.33 (13)	O1—C10—C8	131.75 (17)
C9—N2—C12	124.78 (15)	N3—C10—C8	105.26 (14)
N3—N2—C12	117.05 (15)	C9—C11—H11A	109.5
C10—N3—N2	108.59 (14)	C9—C11—H11B	109.5
C10—N3—C13	122.39 (14)	H11A—C11—H11B	109.5
N2—N3—C13	119.12 (14)	C9—C11—H11C	109.5
C2—C1—C6	120.84 (19)	H11A—C11—H11C	109.5
C2—C1—H1	119.6	H11B—C11—H11C	109.5
C6—C1—H1	119.6	N2—C12—H12A	109.5
C3—C2—C1	119.1 (2)	N2—C12—H12B	109.5
C3—C2—H2	120.4	H12A—C12—H12B	109.5
C1—C2—H2	120.4	N2—C12—H12C	109.5
C4—C3—C2	121.71 (19)	H12A—C12—H12C	109.5
C4—C3—Cl1	118.99 (17)	H12B—C12—H12C	109.5
C2—C3—Cl1	119.29 (17)	C14—C13—C18	120.11 (19)
C3—C4—C5	118.54 (19)	C14—C13—N3	121.78 (17)
C3—C4—H4	120.7	C18—C13—N3	118.08 (18)
C5—C4—H4	120.7	C13—C14—C15	119.4 (2)
C4—C5—C6	121.50 (19)	C13—C14—H14	120.3
C4—C5—H5	119.2	C15—C14—H14	120.3
C6—C5—H5	119.2	C16—C15—C14	120.6 (2)
C1—C6—C5	118.28 (18)	C16—C15—H15	119.7
C1—C6—C7	122.15 (17)	C14—C15—H15	119.7
C5—C6—C7	119.56 (17)	C15—C16—C17	119.7 (2)
N1—C7—C6	121.61 (17)	C15—C16—H16	120.2
N1—C7—H7	119.2	C17—C16—H16	120.2
C6—C7—H7	119.2	C16—C17—C18	120.9 (2)
C9—C8—N1	122.42 (16)	C16—C17—H17	119.5
C9—C8—C10	107.88 (16)	C18—C17—H17	119.5
N1—C8—C10	129.34 (16)	C17—C18—C13	119.2 (2)
N2—C9—C8	110.38 (15)	C17—C18—H18	120.4
N2—C9—C11	121.85 (16)	C13—C18—H18	120.4
C8—C9—C11	127.76 (18)
C9—N2—N3—C10	7.73 (18)	C10—C8—C9—N2	3.35 (19)
C12—N2—N3—C10	153.86 (16)	N1—C8—C9—C11	9.8 (3)
C9—N2—N3—C13	154.27 (15)	C10—C8—C9—C11	−176.47 (17)
C12—N2—N3—C13	−59.6 (2)	N2—N3—C10—O1	171.89 (17)
C6—C1—C2—C3	0.4 (3)	C13—N3—C10—O1	26.7 (3)
C1—C2—C3—C4	−0.2 (4)	N2—N3—C10—C8	−5.59 (18)
C1—C2—C3—Cl1	179.85 (18)	C13—N3—C10—C8	−150.81 (16)
C2—C3—C4—C5	−0.3 (3)	C9—C8—C10—O1	−175.67 (19)
Cl1—C3—C4—C5	179.69 (16)	N1—C8—C10—O1	−2.5 (3)
C3—C4—C5—C6	0.6 (3)	C9—C8—C10—N3	1.50 (19)
C2—C1—C6—C5	−0.1 (3)	N1—C8—C10—N3	174.66 (16)
C2—C1—C6—C7	179.63 (19)	C10—N3—C13—C14	112.9 (2)
C4—C5—C6—C1	−0.4 (3)	N2—N3—C13—C14	−28.9 (2)
C4—C5—C6—C7	179.89 (18)	C10—N3—C13—C18	−65.3 (2)
C8—N1—C7—C6	−176.68 (15)	N2—N3—C13—C18	152.91 (16)
C1—C6—C7—N1	−2.7 (3)	C18—C13—C14—C15	−0.4 (3)
C5—C6—C7—N1	177.04 (17)	N3—C13—C14—C15	−178.59 (18)
C7—N1—C8—C9	178.21 (16)	C13—C14—C15—C16	0.8 (3)
C7—N1—C8—C10	5.9 (3)	C14—C15—C16—C17	0.0 (4)
N3—N2—C9—C8	−6.84 (19)	C15—C16—C17—C18	−1.2 (4)
C12—N2—C9—C8	−149.65 (17)	C16—C17—C18—C13	1.6 (3)
N3—N2—C9—C11	173.00 (16)	C14—C13—C18—C17	−0.7 (3)
C12—N2—C9—C11	30.2 (3)	N3—C13—C18—C17	177.48 (17)
N1—C8—C9—N2	−170.39 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1^i	0.93	2.43	3.219 (2)	143
C7—H7···O1	0.93	2.33	3.016 (2)	130
C11—H11A···O1^ii	0.96	2.47	3.407 (5)	165

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

(II) 4-(2-chlorobenzylideneamino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one

Crystal data

C18H16ClN3O	F(000) = 680
Mr = 325.79	Dx = 1.317 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4187 reflections
a = 6.848 (1) Å	θ = 2.3–24.3°
b = 13.654 (2) Å	µ = 0.24 mm^−1
c = 17.567 (2) Å	T = 298 K
V = 1642.6 (4) Å^3	Prism, yellow
Z = 4	0.25 × 0.18 × 0.18 mm

Data collection

Bruker SMART APEX area-detector diffractometer	3377 independent reflections
Radiation source: fine-focus sealed tube	2979 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ϕ and ω scans	θmax = 26.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→7
Tmin = 0.942, Tmax = 0.958	k = −17→17
11680 measured reflections	l = −22→22

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + (0.0492P)^2 + 0.2996P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.107	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.29 e Å^−3
3377 reflections	Δρmin = −0.25 e Å^−3
211 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.043 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1415 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.01 (10)

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	0.51175 (17)	0.34774 (7)	0.23537 (7)	0.1339 (5)
O1	0.7916 (2)	0.09926 (11)	0.35265 (10)	0.0628 (4)
N1	1.0447 (3)	0.29069 (11)	0.36027 (10)	0.0499 (4)
N2	1.2339 (3)	0.07475 (13)	0.44531 (10)	0.0522 (4)
N3	1.0634 (2)	0.03550 (12)	0.41396 (10)	0.0518 (4)
C1	0.6710 (4)	0.43838 (18)	0.26717 (14)	0.0643 (6)
C2	0.6187 (4)	0.5352 (2)	0.25421 (14)	0.0710 (7)
H2	0.5014	0.5502	0.2302	0.085*
C3	0.7411 (5)	0.60775 (19)	0.27698 (14)	0.0735 (8)
H3	0.7078	0.6729	0.2685	0.088*
C4	0.9136 (5)	0.58507 (19)	0.31242 (16)	0.0759 (8)
H4	0.9975	0.6350	0.3275	0.091*
C5	0.9633 (4)	0.48913 (16)	0.32579 (14)	0.0660 (6)
H5	1.0805	0.4751	0.3502	0.079*
C6	0.8419 (4)	0.41237 (16)	0.30363 (12)	0.0525 (5)
C7	0.8915 (4)	0.31063 (15)	0.32170 (12)	0.0548 (5)
H7	0.8109	0.2602	0.3050	0.066*
C8	1.0818 (3)	0.19456 (14)	0.38230 (11)	0.0462 (5)
C9	0.9576 (3)	0.11015 (14)	0.37798 (11)	0.0480 (5)
C10	1.2474 (3)	0.16885 (15)	0.42139 (11)	0.0481 (5)
C11	1.4217 (4)	0.22941 (18)	0.43757 (16)	0.0695 (7)
H11A	1.4525	0.2255	0.4908	0.104*
H11B	1.3955	0.2963	0.4241	0.104*
H11C	1.5302	0.2057	0.4083	0.104*
C12	1.3986 (3)	0.00933 (18)	0.45745 (15)	0.0660 (6)
H12A	1.4410	−0.0167	0.4094	0.099*
H12B	1.3596	−0.0434	0.4902	0.099*
H12C	1.5038	0.0449	0.4807	0.099*
C13	0.9699 (3)	−0.04389 (14)	0.45148 (12)	0.0484 (5)
C14	0.9714 (3)	−0.05216 (16)	0.52989 (13)	0.0587 (5)
H14	1.0378	−0.0065	0.5594	0.070*
C15	0.8734 (4)	−0.12879 (18)	0.56389 (15)	0.0681 (7)
H15	0.8745	−0.1351	0.6166	0.082*
C16	0.7742 (4)	−0.19594 (18)	0.52028 (17)	0.0722 (7)
H16	0.7077	−0.2473	0.5435	0.087*
C17	0.7732 (4)	−0.18725 (17)	0.44238 (16)	0.0702 (7)
H17	0.7050	−0.2324	0.4130	0.084*
C18	0.8727 (3)	−0.11203 (15)	0.40760 (14)	0.0595 (6)
H18	0.8743	−0.1071	0.3548	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1217 (8)	0.0993 (6)	0.1807 (10)	−0.0330 (5)	−0.0983 (8)	0.0483 (6)
O1	0.0423 (9)	0.0624 (9)	0.0838 (11)	−0.0041 (7)	−0.0165 (8)	0.0131 (8)
N1	0.0490 (10)	0.0496 (9)	0.0512 (9)	0.0013 (8)	0.0011 (8)	−0.0005 (7)
N2	0.0369 (9)	0.0575 (10)	0.0621 (10)	0.0010 (8)	−0.0053 (8)	0.0025 (8)
N3	0.0394 (9)	0.0526 (9)	0.0633 (10)	−0.0017 (8)	−0.0075 (8)	0.0057 (8)
C1	0.0632 (15)	0.0681 (15)	0.0616 (13)	−0.0051 (12)	−0.0120 (12)	0.0163 (11)
C2	0.0761 (17)	0.0809 (17)	0.0561 (13)	0.0180 (14)	−0.0031 (13)	0.0176 (12)
C3	0.104 (2)	0.0562 (13)	0.0606 (14)	0.0226 (15)	0.0079 (15)	0.0048 (11)
C4	0.093 (2)	0.0523 (13)	0.0820 (17)	0.0015 (14)	−0.0043 (16)	−0.0003 (12)
C5	0.0673 (16)	0.0556 (12)	0.0753 (14)	0.0015 (12)	−0.0073 (13)	0.0005 (11)
C6	0.0577 (13)	0.0513 (11)	0.0485 (11)	0.0005 (10)	0.0021 (10)	0.0046 (9)
C7	0.0571 (13)	0.0522 (12)	0.0553 (11)	−0.0049 (10)	−0.0060 (10)	0.0053 (9)
C8	0.0422 (11)	0.0490 (10)	0.0472 (10)	0.0006 (8)	−0.0006 (8)	−0.0033 (8)
C9	0.0398 (11)	0.0518 (11)	0.0523 (11)	−0.0001 (9)	−0.0015 (9)	0.0041 (9)
C10	0.0425 (11)	0.0543 (11)	0.0474 (10)	0.0015 (9)	0.0013 (9)	−0.0061 (9)
C11	0.0529 (15)	0.0749 (15)	0.0807 (16)	−0.0108 (12)	−0.0139 (12)	−0.0040 (13)
C12	0.0443 (13)	0.0746 (15)	0.0789 (16)	0.0108 (11)	−0.0096 (11)	0.0122 (12)
C13	0.0346 (10)	0.0485 (10)	0.0620 (12)	0.0066 (9)	−0.0028 (9)	0.0057 (9)
C14	0.0519 (13)	0.0599 (13)	0.0645 (13)	0.0005 (11)	−0.0013 (11)	0.0011 (10)
C15	0.0604 (15)	0.0753 (15)	0.0687 (14)	0.0017 (13)	0.0056 (12)	0.0141 (12)
C16	0.0526 (14)	0.0620 (14)	0.102 (2)	−0.0066 (11)	0.0037 (14)	0.0226 (13)
C17	0.0602 (15)	0.0563 (13)	0.0940 (18)	−0.0062 (12)	−0.0120 (14)	−0.0008 (13)
C18	0.0527 (13)	0.0565 (12)	0.0692 (14)	−0.0004 (11)	−0.0067 (11)	−0.0001 (11)

Geometric parameters (Å, º)

Cl1—C1	1.742 (3)	C8—C10	1.372 (3)
O1—C9	1.230 (2)	C8—C9	1.434 (3)
N1—C7	1.278 (3)	C10—C11	1.480 (3)
N1—C8	1.392 (2)	C11—H11A	0.9600
N2—C10	1.355 (3)	C11—H11B	0.9600
N2—N3	1.398 (2)	C11—H11C	0.9600
N2—C12	1.454 (3)	C12—H12A	0.9600
N3—C9	1.401 (2)	C12—H12B	0.9600
N3—C13	1.421 (3)	C12—H12C	0.9600
C1—C6	1.381 (3)	C13—C18	1.380 (3)
C1—C2	1.389 (3)	C13—C14	1.382 (3)
C2—C3	1.358 (4)	C14—C15	1.379 (3)
C2—H2	0.9300	C14—H14	0.9300
C3—C4	1.371 (4)	C15—C16	1.375 (4)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.374 (3)	C16—C17	1.374 (4)
C4—H4	0.9300	C16—H16	0.9300
C5—C6	1.393 (3)	C17—C18	1.376 (3)
C5—H5	0.9300	C17—H17	0.9300
C6—C7	1.465 (3)	C18—H18	0.9300
C7—H7	0.9300
C7—N1—C8	119.87 (18)	N2—C10—C8	109.97 (18)
C10—N2—N3	107.36 (16)	N2—C10—C11	121.7 (2)
C10—N2—C12	125.09 (19)	C8—C10—C11	128.3 (2)
N3—N2—C12	118.05 (17)	C10—C11—H11A	109.5
N2—N3—C9	109.31 (15)	C10—C11—H11B	109.5
N2—N3—C13	119.07 (16)	H11A—C11—H11B	109.5
C9—N3—C13	122.11 (16)	C10—C11—H11C	109.5
C6—C1—C2	122.7 (2)	H11A—C11—H11C	109.5
C6—C1—Cl1	119.79 (18)	H11B—C11—H11C	109.5
C2—C1—Cl1	117.6 (2)	N2—C12—H12A	109.5
C3—C2—C1	119.2 (2)	N2—C12—H12B	109.5
C3—C2—H2	120.4	H12A—C12—H12B	109.5
C1—C2—H2	120.4	N2—C12—H12C	109.5
C2—C3—C4	120.1 (2)	H12A—C12—H12C	109.5
C2—C3—H3	120.0	H12B—C12—H12C	109.5
C4—C3—H3	120.0	C18—C13—C14	120.3 (2)
C3—C4—C5	120.4 (3)	C18—C13—N3	118.21 (19)
C3—C4—H4	119.8	C14—C13—N3	121.43 (19)
C5—C4—H4	119.8	C15—C14—C13	119.4 (2)
C4—C5—C6	121.5 (3)	C15—C14—H14	120.3
C4—C5—H5	119.3	C13—C14—H14	120.3
C6—C5—H5	119.3	C16—C15—C14	120.4 (2)
C1—C6—C5	116.2 (2)	C16—C15—H15	119.8
C1—C6—C7	122.8 (2)	C14—C15—H15	119.8
C5—C6—C7	121.0 (2)	C17—C16—C15	120.0 (2)
N1—C7—C6	120.5 (2)	C17—C16—H16	120.0
N1—C7—H7	119.8	C15—C16—H16	120.0
C6—C7—H7	119.8	C16—C17—C18	120.3 (2)
C10—C8—N1	122.10 (18)	C16—C17—H17	119.8
C10—C8—C9	108.13 (17)	C18—C17—H17	119.8
N1—C8—C9	129.41 (18)	C17—C18—C13	119.6 (2)
O1—C9—N3	123.58 (18)	C17—C18—H18	120.2
O1—C9—C8	131.63 (19)	C13—C18—H18	120.2
N3—C9—C8	104.73 (16)
C10—N2—N3—C9	−7.5 (2)	C10—C8—C9—O1	175.3 (2)
C12—N2—N3—C9	−155.6 (2)	N1—C8—C9—O1	2.1 (4)
C10—N2—N3—C13	−154.52 (18)	C10—C8—C9—N3	−1.9 (2)
C12—N2—N3—C13	57.4 (3)	N1—C8—C9—N3	−175.07 (19)
C6—C1—C2—C3	1.1 (4)	N3—N2—C10—C8	6.2 (2)
Cl1—C1—C2—C3	−178.8 (2)	C12—N2—C10—C8	151.4 (2)
C1—C2—C3—C4	−0.1 (4)	N3—N2—C10—C11	−173.61 (19)
C2—C3—C4—C5	−0.6 (4)	C12—N2—C10—C11	−28.4 (3)
C3—C4—C5—C6	0.4 (4)	N1—C8—C10—N2	171.09 (18)
C2—C1—C6—C5	−1.3 (4)	C9—C8—C10—N2	−2.7 (2)
Cl1—C1—C6—C5	178.63 (19)	N1—C8—C10—C11	−9.1 (3)
C2—C1—C6—C7	176.0 (2)	C9—C8—C10—C11	177.1 (2)
Cl1—C1—C6—C7	−4.1 (3)	N2—N3—C13—C18	−147.86 (19)
C4—C5—C6—C1	0.5 (4)	C9—N3—C13—C18	69.4 (3)
C4—C5—C6—C7	−176.8 (2)	N2—N3—C13—C14	33.7 (3)
C8—N1—C7—C6	174.81 (19)	C9—N3—C13—C14	−109.0 (2)
C1—C6—C7—N1	−175.0 (2)	C18—C13—C14—C15	−0.5 (3)
C5—C6—C7—N1	2.1 (3)	N3—C13—C14—C15	177.93 (19)
C7—N1—C8—C10	177.7 (2)	C13—C14—C15—C16	−0.4 (4)
C7—N1—C8—C9	−10.0 (3)	C14—C15—C16—C17	0.4 (4)
N2—N3—C9—O1	−171.8 (2)	C15—C16—C17—C18	0.6 (4)
C13—N3—C9—O1	−25.9 (3)	C16—C17—C18—C13	−1.5 (4)
N2—N3—C9—C8	5.7 (2)	C14—C13—C18—C17	1.4 (3)
C13—N3—C9—C8	151.56 (18)	N3—C13—C18—C17	−177.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1^i	0.93	2.57	3.491 (3)	172
C3—H3···Cl1^i	0.93	2.82	3.713 (3)	161
C7—H7···Cl1	0.93	2.67	3.053 (3)	106
C7—H7···O1	0.93	2.35	3.015 (3)	128
C11—H11C···O1^ii	0.96	2.50	3.435 (3)	163

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