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Two structural isomers, 3,6-bis(2-chloro­phenyl)-1,4-di­hydro-1,2,4,5-tetrazine, (I), and 3,5-bis(2-chloro­phenyl)-4-amino-1H-1,2,4-triazole, (II), both C14H10Cl2N4, form chain-like structures in the solid state, stabilized by N-H...N and N-H...Cl hydrogen bonds. A contribution from weak interactions to the strong hydrogen-bond network is observed in both structures. The secondary graph sets for intermolecular hydrogen bonds [R_2^2(11) for (I) and R_2^2(12) for (II)] indicate the similarity between the networks.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103026945/sk1670sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103026945/sk1670Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103026945/sk1670IIsup3.hkl
Contains datablock II

CCDC references: 231074; 231075

Comment top

The compound of general formulae C2H2N4(C6H4Cl)2 crystallizes as 3,6-bis(2-chlorophenyl)-1,4-dihydro-1,2,4,5-tetrazine, (I), in the form of yellow–orange needles. It undergoes irreversible isomerization above 353 K in acidic water solution, forming the structural isomer 3,5-bis (2-chlorophenyl)-4-amino-1,2,4-triazol, (II).

X-ray structure determination revealed that isomer (I) crystallizes in the monoclinic space group C2/c, while isomer (II) crystallizes in the orthorhombic space group Pbca. The molecular structures of (I) and (II), with the atom-numbering schemes, are shown in Figs. 1 and 2, respectively.

Since both molecules retain potential strong proton-donor groups [–NH in (I) and –NH2 in (II)] and proton acceptors (N and Cl atoms) we undertook a detailed analysis of the hydrogen-bonded networks. Analysis of intra- and intermolecular contacts occurring in crystalline isomers indicated that, in both cases, the weaker –CH donor groups are also important in the formation of the hydrogen-bonded network (Taylor & Kennard, 1982; Desiraju & Steiner, 1999). To attempt a consistent characterization of the differences and similarities of the solid-state structures of the studied compounds, we have used the Etter (1990, 1991) graph-set descriptors.

The molecule of (I) consists of a six-membered central tetrazine ring and two chlorophenyl rings. As a twofold axis passes through the centre of the tetrazine ring, the molecule exhibits crystallographic C2 point-group symmetry, so the chlorophenyl rings are symmetry equivalent. The central ring is folded along the N1—N1i vector and exhibits a boat conformation [puckering parameters Q = 0.513 (2)°, θ = 90.0 (2)° and ϕ = 175.7 (2)°; Cremer & Pople, 1975]. An analysis of structures deposited in the Cambridge Structural Database (Version 5.24 of April 2003; Allen, 2002) showed that a boat conformation is observed for all structurally characterized tetrazine derivatives. The chlorophenyl rings are twisted to one another with a dihedral angle of 77.94 (7)°. The Cl atoms lie on the same side of the C10—N2—C10i—N2i plane [symmetry code: (i) −x, y, 1/2 − z]. Atoms N1 and N1i lie above this plane, and atoms H1 and H1i are located in equatorial positions. Such an arrangement enables the formation of a pair of strong intermolecular N—H···N hydrogen bonds between centrosymmetrically related neighbouring molecules [H···N = 2.29 (2) Å, N···N = 3.052 (2) Å and N—H···N = 145 (2)°; hydrogen-bond motif R22(6) (Bernstein et al., 1995); motif a in Fig.3], leading to the formation of an infinite C(4)[R22(6)] chain of rings along the c axis.

The molecule of (II) consists of a five-membered (heterocyclic) aromatic triazole ring and two chlorophenyl rings (Ph1 and Ph2). The main difference from the molecule of (I) is the asymmetry of the molecule of (II), which is a result of the postions of the H atoms of the –NH2 amine group. They lie on the same side of the quasi-mirror plane that passes through the amine N atom and the ring N—N bond, and is perpendicular to the ring plane. Excluding these H atoms, the molecule displays almost Cm point-group symmetry. The main reason for the asymmetry of the molecule is the strong N4—H4B···N2i intermolecular hydrogen bond [H···N = 2.19 (3) Å, N···N = 3.016 (3) Å and N—H···N 154 (2)°]. The observed infinite zigzag C(5) chain (motif a in Fig. 4) is formed by molecules related by a b-glide plane. As atoms H4A and H4B are both directed towards ring Ph1, the formation of an intramolecular hydrogen bond between the N4—H4A donor group and atom Cl1 is observed. The proton–acceptor distance is 2.66 (3) Å and the N4—H4A···Cl1 angle is 137 (2)°. The corresponding graph-set descriptor is S(7) (motif b in Fig. 4). This interaction is also evidenced by the significantly different thermal parameters of atoms Cl1 and Cl2, the Ueq values being 0.0503 (2) and 0.0908 (3), respectively. The dihedral angles between the triazole plane and the planes of the chlorophenyl rings Ph1 and Ph2 are 60.06 (7) and 65.21 (8)°, respectively. The larger value for ring Ph2 is a consequence of the repulsion between atoms Cl2 and N4 [Cl2···N4 = 3.378 (3) Å].

The observed one-dimensional assemblies formed by strong hydrogen bonding are enforced by weaker intermolecular interactions. C—H···Cl contacts are observed along the main chains, between the chlorophenyl rings of adjacent molecules. The H···Cl distances [2.83 (3) Å in (I) and 2.85 (2) Å in (II)] typify relatively strong C—H···Cl bonding (Taylor & Kennard, 1982). The assigned graph-set descriptors are C(5) for both compounds (motif b in Fig. 3 and motif c in Fig. 4). Motifs a, b and c constitute primary graph sets given as N1 = C(5) C(4)[R22(6)] [for (I)] and N1= C(5)S(7) C(5) [for (II)] (Etter, et al., 1990). The first-level graph sets are different because of the presence of symmetry-equivalent atoms in (I) and intramolecular hydrogen bonding in (II). Secondary graph sets for intermolecular bonding are N2(ab) = R22(11) [(I)] and N2(ac) = R22(12) [(II)], indicating the similarity of the main structural features.

Detailed analysis of the molecular packing shows that the main chains form close-packed structures. In the case of (II), the zigzag chains are connected together via C24—H24···N4v and C13—H13···N2vi weak hydrogen bonds, with motifs R22(16) and C(6), respectively. There is no evidence of weak hydrogen bonding between the chains of (I), but by analogy to the crystal structure of (II), the long C3—H3···N1iv contact [H···N = 2.98 (3) Å] can be regarded as an atractive interaction. The same graph-set descriptor, C(6), is applicable.

Experimental top

Compound (I) was prepared using a modification of the procedure described by Brooker et al. (1987), by reacting bis-(α,2-dichlorobenzilidene)hydrazine and hydrazine hydrate at low temperature. Crystals suitable for X-ray diffraction were crystallized from ethanol, precipitating in the form of yellow–orange needles (m.p. 482–483 K). Compound (I) was dissolved in an acidic water solution and heated to above 353 K, giving the structural isomer (II). The isomerization reaction is irreversible. Well shaped crystals of (II), in the form of colourless prisms (m.p. 441–442 K), were obtained from ethanol. Detailed descriptions of the products and synthesis routes are given elsewhere (Włostowski & Olszewski, 2003).

Refinement top

Since the absorption coefficients of both compounds were comparatively high, a numerical correction (Gaussian integration) based on a well defined crystal shape was applied using SHELX76 (Sheldrick, 1976). For both compounds, H atoms were found from a difference Fourier map and their positional and isotropic displacement parameters were refined.

Computing details top

For both compounds, data collection: P3/P4-PC Software (Siemens, 1991). Cell refinement: P3/P4-PC Software for (I); P3/P4-PC for (II). For both compounds, data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecule of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level·[Symmetry code: (i) −x, y, 1/2 − z.]
[Figure 2] Fig. 2. The molecule of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. A map of the hydrogen-bond patterns in the main structural feature of (I). Hydrogen bonds are shown as dashed and dotted lines. For motif a, a full description of the pattern is C(4)[R22(6)] (Bernstein et al., 1995). The two motifs together constitute the first-order hydrogen-bonded network described as N1 = C(5) C(4)[R22(6)].
[Figure 4] Fig. 4. A map of the hydrogen-bond patterns in the main structural feature of (II). Hygrogen bonds are shown as dashed and dotted lines. The three motifs together constitute the first-order hydrogen-bonded network described as N1 = C(5)S(7) C(5).
(I) 3,6-bis(2-chlorophenyl)-1,4-dihydro-1,2,4,5-tetrazine top
Crystal data top
C14H10Cl2N4F(000) = 624
Mr = 305.16Dx = 1.495 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 30 reflections
a = 16.0020 (12) Åθ = 7.7–16.4°
b = 9.4123 (8) ŵ = 0.47 mm1
c = 10.5752 (7) ÅT = 293 K
β = 121.664 (5)°Needle, yellow–orange
V = 1355.69 (18) Å30.62 × 0.09 × 0.09 mm
Z = 4
Data collection top
Siemens, P3
diffractometer
996 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.014
Graphite monochromatorθmax = 25.0°, θmin = 2.6°
profile data from ω–2θ scansh = 1818
Absorption correction: gaussian
SHELX76 (Sheldrick, 1976)
k = 1111
Tmin = 0.936, Tmax = 0.960l = 1212
2496 measured reflections1 standard reflections every 70 reflections
1203 independent reflections intensity decay: 1.8%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036All H-atom parameters refined
wR(F2) = 0.099 w = 1/[σ2(Fo2) + (0.0452P)2 + 1.4393P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
1203 reflectionsΔρmax = 0.39 e Å3
112 parametersΔρmin = 0.43 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0047 (12)
Crystal data top
C14H10Cl2N4V = 1355.69 (18) Å3
Mr = 305.16Z = 4
Monoclinic, C2/cMo Kα radiation
a = 16.0020 (12) ŵ = 0.47 mm1
b = 9.4123 (8) ÅT = 293 K
c = 10.5752 (7) Å0.62 × 0.09 × 0.09 mm
β = 121.664 (5)°
Data collection top
Siemens, P3
diffractometer
996 reflections with I > 2σ(I)
Absorption correction: gaussian
SHELX76 (Sheldrick, 1976)
Rint = 0.014
Tmin = 0.936, Tmax = 0.9601 standard reflections every 70 reflections
2496 measured reflections intensity decay: 1.8%
1203 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.099All H-atom parameters refined
S = 1.04Δρmax = 0.39 e Å3
1203 reflectionsΔρmin = 0.43 e Å3
112 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Cl10.16401 (5)0.74870 (6)0.21918 (8)0.0646 (3)
N10.04530 (12)0.4499 (2)0.18150 (18)0.0376 (4)
N20.05456 (12)0.49908 (19)0.40415 (17)0.0372 (4)
C10.20247 (14)0.5248 (2)0.4027 (2)0.0359 (5)
C20.24122 (16)0.6321 (2)0.3587 (2)0.0439 (5)
C30.3429 (2)0.6493 (3)0.4296 (3)0.0618 (8)
C40.4044 (2)0.5597 (4)0.5428 (3)0.0646 (8)
C50.36748 (18)0.4549 (3)0.5887 (3)0.0589 (7)
C60.26745 (15)0.4384 (3)0.5202 (2)0.0434 (5)
C100.09617 (14)0.4949 (2)0.3295 (2)0.0334 (5)
H10.0749 (15)0.470 (2)0.134 (2)0.036 (5)*
H30.362 (2)0.720 (3)0.398 (3)0.072 (9)*
H40.475 (2)0.568 (4)0.593 (3)0.094 (10)*
H50.412 (2)0.391 (3)0.670 (3)0.078 (9)*
H60.2407 (16)0.363 (3)0.552 (2)0.049 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0958 (6)0.0467 (4)0.0745 (5)0.0089 (3)0.0608 (4)0.0122 (3)
N10.0339 (9)0.0530 (11)0.0309 (9)0.0034 (8)0.0204 (8)0.0022 (8)
N20.0340 (9)0.0513 (10)0.0298 (8)0.0032 (7)0.0191 (7)0.0000 (7)
C10.0388 (11)0.0407 (11)0.0350 (10)0.0041 (9)0.0242 (9)0.0080 (8)
C20.0558 (13)0.0434 (12)0.0480 (12)0.0080 (10)0.0380 (11)0.0100 (10)
C30.0720 (18)0.0631 (16)0.0756 (18)0.0309 (15)0.0560 (16)0.0241 (15)
C40.0409 (14)0.091 (2)0.0577 (16)0.0135 (14)0.0232 (13)0.0206 (15)
C50.0424 (13)0.0792 (19)0.0461 (13)0.0030 (13)0.0172 (11)0.0095 (13)
C60.0378 (12)0.0531 (14)0.0372 (11)0.0024 (10)0.0181 (10)0.0040 (10)
C100.0370 (11)0.0366 (10)0.0309 (10)0.0004 (8)0.0208 (9)0.0004 (8)
Geometric parameters (Å, º) top
Cl1—C21.730 (2)C2—C31.399 (3)
N1—C101.398 (2)C3—C41.369 (4)
N1—N2i1.438 (2)C3—H30.87 (3)
N1—H10.88 (2)C4—C51.363 (4)
N2—C101.273 (2)C4—H40.97 (3)
N2—N1i1.438 (2)C5—C61.376 (3)
C10—C11.480 (3)C5—H50.98 (3)
C1—C21.388 (3)C6—H60.98 (2)
C1—C61.389 (3)
C10—N1—N2i114.14 (15)C4—C3—C2119.8 (3)
C10—N1—H1114.1 (14)C4—C3—H3125 (2)
N2i—N1—H1109.0 (13)C2—C3—H3115 (2)
C10—N2—N1i111.68 (16)C5—C4—C3120.7 (2)
N2—C10—N1121.13 (18)C5—C4—H4117 (2)
N2—C10—C1120.07 (17)C3—C4—H4122 (2)
N1—C10—C1118.55 (16)C4—C5—C6119.7 (3)
C2—C1—C6118.02 (19)C4—C5—H5120.6 (17)
C2—C1—C10123.78 (19)C6—C5—H5119.7 (17)
C6—C1—C10118.17 (18)C5—C6—C1121.5 (2)
C1—C2—C3120.2 (2)C5—C6—H6120.0 (13)
C1—C2—Cl1120.20 (17)C1—C6—H6118.4 (13)
C3—C2—Cl1119.56 (19)
N1i—N2—C10—N11.4 (3)C6—C1—C2—Cl1176.82 (16)
N1i—N2—C10—C1172.72 (17)C10—C1—C2—Cl14.8 (3)
N2i—N1—C10—N239.8 (2)C1—C2—C3—C40.0 (4)
N2i—N1—C10—C1146.05 (18)Cl1—C2—C3—C4178.2 (2)
N2—C10—C1—C2121.8 (2)C2—C3—C4—C50.9 (4)
N1—C10—C1—C263.9 (3)C3—C4—C5—C60.2 (4)
N2—C10—C1—C659.8 (3)C4—C5—C6—C11.2 (4)
N1—C10—C1—C6114.4 (2)C2—C1—C6—C52.0 (3)
C6—C1—C2—C31.3 (3)C10—C1—C6—C5176.5 (2)
C10—C1—C2—C3177.05 (19)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2ii0.88 (2)2.29 (2)3.052 (2)145 (2)
C6—H6···Cl1iii0.98 (2)2.83 (2)3.732 (2)154 (2)
Symmetry codes: (ii) x, y+1, z1/2; (iii) x, y+1, z+1/2.
(II) 3,5-bis(2-chlorophenyl)-4-amino-1H-1,2,4-triazole top
Crystal data top
C14H10Cl2N4F(000) = 1248
Mr = 305.16Dx = 1.458 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 29 reflections
a = 12.3382 (14) Åθ = 4.1–10.3°
b = 8.6777 (9) ŵ = 0.46 mm1
c = 25.968 (4) ÅT = 293 K
V = 2780.3 (6) Å3Prism, colourless
Z = 80.49 × 0.18 × 0.12 mm
Data collection top
Siemens, P3
diffractometer
1662 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.000
Graphite monochromatorθmax = 25.1°, θmin = 2.3°
profile data from ω–2θ scansh = 014
Absorption correction: gaussian
SHELX76 (Sheldrick, 1976)
k = 010
Tmin = 0.913, Tmax = 0.952l = 300
2461 measured reflections2 standard reflections every 70 reflections
2461 independent reflections intensity decay: 0.0%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036All H-atom parameters refined
wR(F2) = 0.098 w = 1/[σ2(Fo2) + (0.0497P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2461 reflectionsΔρmax = 0.22 e Å3
222 parametersΔρmin = 0.23 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0016 (4)
Crystal data top
C14H10Cl2N4V = 2780.3 (6) Å3
Mr = 305.16Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 12.3382 (14) ŵ = 0.46 mm1
b = 8.6777 (9) ÅT = 293 K
c = 25.968 (4) Å0.49 × 0.18 × 0.12 mm
Data collection top
Siemens, P3
diffractometer
1662 reflections with I > 2σ(I)
Absorption correction: gaussian
SHELX76 (Sheldrick, 1976)
Rint = 0.000
Tmin = 0.913, Tmax = 0.9522 standard reflections every 70 reflections
2461 measured reflections intensity decay: 0.0%
2461 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.098All H-atom parameters refined
S = 1.02Δρmax = 0.22 e Å3
2461 reflectionsΔρmin = 0.23 e Å3
222 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Cl10.50422 (5)0.13786 (7)0.26922 (2)0.0503 (2)
Cl20.48752 (7)0.13503 (11)0.43241 (3)0.0908 (3)
N10.78855 (15)0.2046 (2)0.38776 (7)0.0518 (6)
N20.79746 (15)0.1982 (2)0.33424 (7)0.0473 (5)
N30.65026 (13)0.3238 (2)0.35401 (6)0.0343 (4)
N40.55912 (17)0.4213 (3)0.35109 (8)0.0416 (5)
C10.71345 (16)0.2705 (2)0.31492 (8)0.0362 (5)
C20.69952 (17)0.2803 (2)0.39847 (8)0.0396 (5)
C110.69218 (16)0.2990 (2)0.26003 (8)0.0350 (5)
C120.59812 (17)0.2490 (2)0.23554 (8)0.0367 (5)
C130.5780 (2)0.2813 (3)0.18424 (9)0.0462 (6)
C140.6538 (2)0.3637 (3)0.15663 (9)0.0515 (7)
C150.7480 (2)0.4125 (3)0.17992 (9)0.0564 (7)
C160.76670 (19)0.3809 (3)0.23107 (9)0.0454 (6)
C210.65961 (19)0.3180 (3)0.45040 (8)0.0432 (6)
C220.5635 (2)0.2598 (3)0.46946 (9)0.0535 (7)
C230.5276 (3)0.2992 (4)0.51846 (12)0.0696 (9)
C240.5879 (3)0.3959 (4)0.54759 (11)0.0777 (11)
C250.6840 (3)0.4539 (4)0.53002 (11)0.0760 (9)
C260.7199 (2)0.4152 (3)0.48162 (10)0.0587 (7)
H4A0.512 (2)0.375 (3)0.3340 (10)0.065 (9)*
H4B0.586 (2)0.508 (3)0.3383 (10)0.071 (10)*
H130.5124 (18)0.251 (3)0.1703 (9)0.047 (7)*
H140.6408 (19)0.383 (3)0.1202 (10)0.064 (8)*
H150.800 (2)0.471 (3)0.1614 (10)0.070 (8)*
H160.8318 (18)0.414 (2)0.2493 (8)0.045 (6)*
H230.460 (2)0.262 (3)0.5265 (11)0.077 (10)*
H240.561 (2)0.425 (3)0.5811 (12)0.086 (10)*
H250.730 (2)0.529 (4)0.5505 (12)0.096 (11)*
H260.789 (2)0.454 (3)0.4679 (10)0.064 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0436 (3)0.0512 (4)0.0561 (4)0.0137 (3)0.0032 (3)0.0011 (3)
Cl20.0859 (6)0.0964 (6)0.0902 (6)0.0431 (5)0.0163 (5)0.0045 (5)
N10.0455 (12)0.0693 (14)0.0407 (12)0.0152 (11)0.0017 (9)0.0066 (10)
N20.0387 (11)0.0658 (13)0.0375 (11)0.0138 (10)0.0020 (8)0.0034 (10)
N30.0303 (9)0.0368 (10)0.0356 (10)0.0053 (8)0.0002 (8)0.0008 (8)
N40.0341 (11)0.0426 (12)0.0482 (12)0.0070 (10)0.0028 (10)0.0031 (11)
C10.0311 (11)0.0391 (13)0.0384 (12)0.0000 (10)0.0030 (9)0.0001 (10)
C20.0370 (12)0.0451 (13)0.0367 (13)0.0033 (10)0.0009 (10)0.0035 (11)
C110.0335 (11)0.0344 (11)0.0371 (13)0.0044 (10)0.0010 (10)0.0034 (10)
C120.0377 (12)0.0291 (11)0.0435 (13)0.0004 (9)0.0029 (11)0.0021 (10)
C130.0477 (14)0.0474 (15)0.0433 (14)0.0014 (12)0.0081 (12)0.0040 (12)
C140.0642 (17)0.0547 (16)0.0357 (13)0.0010 (14)0.0017 (12)0.0034 (12)
C150.0608 (16)0.0624 (18)0.0461 (14)0.0128 (14)0.0098 (14)0.0090 (13)
C160.0376 (13)0.0527 (15)0.0458 (12)0.0081 (12)0.0040 (11)0.0002 (12)
C210.0476 (14)0.0454 (14)0.0364 (13)0.0096 (12)0.0002 (11)0.0049 (11)
C220.0579 (16)0.0561 (17)0.0464 (15)0.0051 (13)0.0071 (12)0.0101 (12)
C230.074 (2)0.084 (2)0.0504 (18)0.0169 (19)0.0204 (16)0.0230 (17)
C240.107 (3)0.090 (3)0.0355 (17)0.038 (2)0.0059 (18)0.0045 (17)
C250.096 (2)0.088 (2)0.0443 (18)0.012 (2)0.0170 (18)0.0105 (17)
C260.0573 (17)0.074 (2)0.0444 (15)0.0060 (16)0.0094 (13)0.0007 (14)
Geometric parameters (Å, º) top
Cl1—C121.743 (2)C14—C151.376 (4)
Cl2—C221.725 (3)C14—H140.97 (3)
N1—C21.310 (3)C15—C161.376 (3)
N1—N21.395 (3)C15—H150.95 (3)
N2—C11.311 (3)C16—H160.98 (2)
N3—C21.358 (2)C2—C211.473 (3)
N3—C11.361 (3)C21—C221.381 (3)
N3—N41.410 (2)C21—C261.387 (3)
N4—H4A0.83 (3)C22—C231.390 (4)
N4—H4B0.88 (3)C23—C241.352 (5)
C1—C111.470 (3)C23—H230.92 (3)
C11—C161.384 (3)C24—C251.367 (5)
C11—C121.393 (3)C24—H240.96 (3)
C12—C131.384 (3)C25—C261.374 (4)
C13—C141.379 (4)C25—H251.02 (3)
C13—H130.93 (2)C26—H260.98 (3)
C2—N1—N2107.30 (18)C14—C15—H15120.6 (16)
C1—N2—N1107.46 (17)C15—C16—C11121.0 (2)
C2—N3—C1106.45 (17)C15—C16—H16123.2 (13)
C2—N3—N4124.73 (17)C11—C16—H16115.8 (13)
C1—N3—N4128.39 (17)N1—C2—N3109.53 (18)
N3—N4—H4A107.3 (18)N1—C2—C21125.9 (2)
N3—N4—H4B103.6 (17)N3—C2—C21124.55 (19)
H4A—N4—H4B118 (2)C22—C21—C26118.3 (2)
N2—C1—N3109.26 (19)C22—C21—C2122.3 (2)
N2—C1—C11126.33 (19)C26—C21—C2119.4 (2)
N3—C1—C11124.31 (18)C21—C22—C23120.8 (3)
C16—C11—C12117.74 (19)C21—C22—Cl2119.75 (19)
C16—C11—C1119.6 (2)C23—C22—Cl2119.5 (2)
C12—C11—C1122.62 (19)C24—C23—C22119.3 (3)
C13—C12—C11121.7 (2)C24—C23—H23126.2 (18)
C13—C12—Cl1118.42 (18)C22—C23—H23114.2 (19)
C11—C12—Cl1119.81 (16)C23—C24—C25121.3 (3)
C14—C13—C12119.0 (2)C23—C24—H24118.9 (19)
C14—C13—H13122.6 (15)C25—C24—H24119.9 (19)
C12—C13—H13118.3 (15)C24—C25—C26119.7 (3)
C15—C14—C13120.2 (2)C24—C25—H25123.2 (17)
C15—C14—H14120.8 (15)C26—C25—H25117.0 (18)
C13—C14—H14118.9 (15)C25—C26—C21120.7 (3)
C14—C15—C16120.3 (2)C25—C26—H26121.7 (16)
C16—C15—H15119.0 (16)C21—C26—H26117.6 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4B···N2i0.88 (3)2.19 (3)3.016 (3)154 (2)
N4—H4B···N1i0.88 (3)2.64 (3)3.238 (3)126 (2)
N4—H4A···Cl10.83 (3)2.66 (3)3.321 (2)137 (2)
C16—H16···Cl1i0.98 (2)2.85 (2)3.734 (2)151 (2)
C24—H24···N4ii0.96 (3)2.66 (3)3.567 (4)157 (2)
C13—H13···N2iii0.93 (2)2.69 (2)3.568 (3)158 (2)
Symmetry codes: (i) x+3/2, y+1/2, z; (ii) x+1, y+1, z+1; (iii) x1/2, y, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H10Cl2N4C14H10Cl2N4
Mr305.16305.16
Crystal system, space groupMonoclinic, C2/cOrthorhombic, Pbca
Temperature (K)293293
a, b, c (Å)16.0020 (12), 9.4123 (8), 10.5752 (7)12.3382 (14), 8.6777 (9), 25.968 (4)
α, β, γ (°)90, 121.664 (5), 9090, 90, 90
V3)1355.69 (18)2780.3 (6)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.470.46
Crystal size (mm)0.62 × 0.09 × 0.090.49 × 0.18 × 0.12
Data collection
DiffractometerSiemens, P3
diffractometer
Siemens, P3
diffractometer
Absorption correctionGaussian
SHELX76 (Sheldrick, 1976)
Gaussian
SHELX76 (Sheldrick, 1976)
Tmin, Tmax0.936, 0.9600.913, 0.952
No. of measured, independent and
observed [I > 2σ(I)] reflections
2496, 1203, 996 2461, 2461, 1662
Rint0.0140.000
(sin θ/λ)max1)0.5950.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.099, 1.04 0.036, 0.098, 1.02
No. of reflections12032461
No. of parameters112222
H-atom treatmentAll H-atom parameters refinedAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.39, 0.430.22, 0.23

Computer programs: P3/P4-PC Software (Siemens, 1991), P3/P4-PC Software, P3/P4-PC, XDISK (Siemens, 1991), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97 and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) for (I) top
Cl1—C21.730 (2)N2—C101.273 (2)
N1—C101.398 (2)C10—C11.480 (3)
N1—N2i1.438 (2)
C10—N1—N2i114.14 (15)C2—C1—C10123.78 (19)
C10—N2—N1i111.68 (16)C6—C1—C10118.17 (18)
N2—C10—N1121.13 (18)C1—C2—Cl1120.20 (17)
N2—C10—C1120.07 (17)C3—C2—Cl1119.56 (19)
N1—C10—C1118.55 (16)
N1i—N2—C10—N11.4 (3)N2i—N1—C10—N239.8 (2)
N1i—N2—C10—C1172.72 (17)N2i—N1—C10—C1146.05 (18)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2ii0.88 (2)2.29 (2)3.052 (2)145 (2)
C6—H6···Cl1iii0.98 (2)2.83 (2)3.732 (2)154 (2)
Symmetry codes: (ii) x, y+1, z1/2; (iii) x, y+1, z+1/2.
Selected geometric parameters (Å, º) for (II) top
Cl1—C121.743 (2)N3—C21.358 (2)
Cl2—C221.725 (3)N3—C11.361 (3)
N1—C21.310 (3)N3—N41.410 (2)
N1—N21.395 (3)C1—C111.470 (3)
N2—C11.311 (3)C2—C211.473 (3)
C2—N1—N2107.30 (18)N2—C1—C11126.33 (19)
C1—N2—N1107.46 (17)N3—C1—C11124.31 (18)
C2—N3—C1106.45 (17)N1—C2—N3109.53 (18)
C2—N3—N4124.73 (17)N1—C2—C21125.9 (2)
C1—N3—N4128.39 (17)N3—C2—C21124.55 (19)
N2—C1—N3109.26 (19)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N4—H4B···N2i0.88 (3)2.19 (3)3.016 (3)154 (2)
N4—H4A···Cl10.83 (3)2.66 (3)3.321 (2)137 (2)
C16—H16···Cl1i0.98 (2)2.85 (2)3.734 (2)151 (2)
C24—H24···N4ii0.96 (3)2.66 (3)3.567 (4)157 (2)
C13—H13···N2iii0.93 (2)2.69 (2)3.568 (3)158 (2)
Symmetry codes: (i) x+3/2, y+1/2, z; (ii) x+1, y+1, z+1; (iii) x1/2, y, z+1/2.
 

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