Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807017175/ci2355sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807017175/ci2355Isup2.hkl |
CCDC reference: 642405
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- R factor = 0.076
- wR factor = 0.286
- Data-to-parameter ratio = 13.7
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for O1 - C20 .. 12.06 su
Alert level C RFACR01_ALERT_3_C The value of the weighted R factor is > 0.25 Weighted R factor given 0.286 PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 47 Perc. PLAT084_ALERT_2_C High R2 Value .................................. 0.29 PLAT230_ALERT_2_C Hirshfeld Test Diff for C14 - C19 .. 6.63 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C18 - C19 .. 6.14 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C34 - C39 .. 6.67 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O1 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C13 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C16 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C19 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C14 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C17 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C34 PLAT334_ALERT_2_C Small Average Benzene C-C Dist. C27 -C32 1.35 Ang. PLAT335_ALERT_2_C Large Benzene C-C Range ....... C14 -C19 0.23 Ang. PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 6 PLAT363_ALERT_2_C Long C(sp3)-C(sp2) Bond C33 - C34 ... 1.62 Ang. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C18 - C19 ... 1.56 Ang.
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 18 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 16 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
With sulfur (1.0 g) as catalyst, 85% hydrazine hydrate (10 ml, 170 mmol) was added dropwise to an anhydrous ethanol solution (15 ml) of p-methoxybenzyl cyanide (50 mmol) and p-chlorobenzonitrile (50 mmol) at 295 K. After refluxing for 3 h, the mixture was cooled to room temperature and the resulting solid product was filtered off. The solid product was then dissolved in diethyl ether (15 ml), and oxided by sodium nitrate (14 mmol) and acetic acid (14 mmol) over a period of 2 h to afford the product which were purified by preparative thin-layer chromatography over silica gel PF254 (2 mm) (cyclohexane-dichloromethane, 1:1) to give red single crystals of (I). The solid product was dissolved in tetrahydrofuran-anhydrous ethanol (4:1 v/v) and the solution evaporated gradually at room temperature to afford single crystals of (I) (m.p. 426–428 K).
Methyl H atoms were placed in calculated positions, with C—H = 0.96 Å, and torsion angles were refined to fit the electron density [Uiso(H) = 1.5Ueq(C)]. Other H atoms were placed in calculated positions, with C—H = 0.93 Å, and refined in riding mode, with Uiso(H) = 1.2Ueq(C). Owing to the large number of weak high-angle reflections, the ratio of observed to unique reflections is low (47%). The slightly large Ueq values and some longer C—-C distances may be as a result of the poor data set.
1,2,4,5-Tetrazine derivatives have high potential for biological activity, possessing a wide spectrum of antiviral and antitumor properties. They have been widely used in pesticides and herbicides (Sauer, 1996). In continuation of our work on the structure-activity relationship of 1,2,4,5-tetrazine derivatives (Hu et al., 2004, 2005), we present here the structure of the title compound, (I).
Compound (I) crystallizes with two unique molecules in the asymmetric unit that differ in the orientation of the methoxy group (Fig. 1). In both molecules the chlorophenyl ring is almost coplanar with the central tetrazine ring, but the methoxyphenyl ring is twisted. The C7—C12 and C14—C19 benzene rings form dihedral angles of 2.32 (3) and 76.74 (2)°, respectively, with the N1/N2/N4/N5/C3/C6 plane. The C27—C32 and C34—C39 benzene rings for dihedral angles of 2.37 (3) and 80.47 (2)°, respectively, with the N21/N22/N24/N25/C23/C26 plane.
A C—H···Cl hydrogen bonding is observed between the two independent molecules. In the crystal structure, pair of C—H···π interactions involving the C34—C39 ring (centroid Cg1) link the molecules into a dimer (Table 1).
For related literature, see: Hu et al. (2004); Hu et al. (2005); Sauer (1996).
Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL.
Fig. 1. The asymmetric unit of (I), with the atomic numbering. Displacement ellipsoids are drawn at the 30% probability level. |
C16H13ClN4O | Z = 4 |
Mr = 312.75 | F(000) = 648 |
Triclinic, P1 | Dx = 1.390 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.471 (3) Å | Cell parameters from 1325 reflections |
b = 10.170 (3) Å | θ = 2.2–25.1° |
c = 16.911 (7) Å | µ = 0.26 mm−1 |
α = 101.429 (6)° | T = 293 K |
β = 97.597 (6)° | Prism, red |
γ = 107.012 (4)° | 0.25 × 0.20 × 0.15 mm |
V = 1495.0 (9) Å3 |
Bruker SMART APEXII CCD area-detector diffractometer | 5475 independent reflections |
Radiation source: fine-focus sealed tube | 2567 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
φ and ω scans | θmax = 25.5°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.937, Tmax = 0.952 | k = −12→11 |
8415 measured reflections | l = −16→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.076 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.286 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.1771P)2] where P = (Fo2 + 2Fc2)/3 |
5475 reflections | (Δ/σ)max = 0.001 |
399 parameters | Δρmax = 0.63 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C16H13ClN4O | γ = 107.012 (4)° |
Mr = 312.75 | V = 1495.0 (9) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.471 (3) Å | Mo Kα radiation |
b = 10.170 (3) Å | µ = 0.26 mm−1 |
c = 16.911 (7) Å | T = 293 K |
α = 101.429 (6)° | 0.25 × 0.20 × 0.15 mm |
β = 97.597 (6)° |
Bruker SMART APEXII CCD area-detector diffractometer | 5475 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2567 reflections with I > 2σ(I) |
Tmin = 0.937, Tmax = 0.952 | Rint = 0.023 |
8415 measured reflections |
R[F2 > 2σ(F2)] = 0.076 | 0 restraints |
wR(F2) = 0.286 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.63 e Å−3 |
5475 reflections | Δρmin = −0.31 e Å−3 |
399 parameters |
Experimental. IR:(KBr cm-1): 3089, 2930, 1388, 715. Analysis calculated for C16H13Cl1N4O1 (312.75): C 61.44,H 4.19,N 17.91%; found: C 61.14, H 4.13,N 17.55. |
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 > 2σ(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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.47728 (14) | 1.08559 (13) | 0.78131 (7) | 0.1003 (5) | |
O1 | −0.0674 (5) | 0.1630 (5) | 0.0080 (3) | 0.1402 (15) | |
N1 | 0.4097 (4) | 0.4999 (4) | 0.3715 (2) | 0.0863 (11) | |
N2 | 0.4047 (4) | 0.5804 (4) | 0.4406 (2) | 0.0790 (10) | |
C3 | 0.5042 (4) | 0.7185 (4) | 0.4728 (2) | 0.0597 (9) | |
N4 | 0.6093 (4) | 0.7780 (4) | 0.4411 (2) | 0.0781 (10) | |
N5 | 0.6143 (4) | 0.6963 (4) | 0.3725 (2) | 0.0833 (10) | |
C6 | 0.5145 (4) | 0.5607 (5) | 0.3392 (3) | 0.0754 (11) | |
C7 | 0.4969 (4) | 0.8087 (4) | 0.5488 (2) | 0.0604 (9) | |
C8 | 0.3928 (4) | 0.7512 (4) | 0.5873 (2) | 0.0689 (11) | |
H8 | 0.3274 | 0.6585 | 0.5670 | 0.083* | |
C9 | 0.3869 (4) | 0.8352 (4) | 0.6580 (3) | 0.0754 (11) | |
H9 | 0.3140 | 0.7980 | 0.6867 | 0.091* | |
C10 | 0.4855 (4) | 0.9785 (4) | 0.6922 (2) | 0.0692 (10) | |
C11 | 0.5891 (4) | 1.0384 (4) | 0.6552 (3) | 0.0733 (11) | |
H11 | 0.6546 | 1.1310 | 0.6760 | 0.088* | |
C12 | 0.5928 (4) | 0.9531 (4) | 0.5836 (3) | 0.0709 (11) | |
H12 | 0.6638 | 0.9916 | 0.5542 | 0.085* | |
C13 | 0.5203 (5) | 0.4704 (6) | 0.2623 (3) | 0.0964 (15) | |
H13A | 0.5548 | 0.3948 | 0.2753 | 0.116* | |
H13B | 0.5960 | 0.5263 | 0.2379 | 0.116* | |
C14 | 0.3661 (5) | 0.3984 (5) | 0.1933 (3) | 0.0733 (11) | |
C15 | 0.2766 (5) | 0.2587 (5) | 0.1800 (3) | 0.0869 (13) | |
H15 | 0.3107 | 0.2069 | 0.2131 | 0.104* | |
C16 | 0.1376 (6) | 0.1833 (6) | 0.1216 (3) | 0.1084 (17) | |
H16 | 0.0870 | 0.0887 | 0.1189 | 0.130* | |
C17 | 0.0815 (6) | 0.2496 (6) | 0.0713 (3) | 0.0905 (14) | |
C18 | 0.1558 (6) | 0.3874 (6) | 0.0769 (3) | 0.0924 (15) | |
H18 | 0.1167 | 0.4350 | 0.0427 | 0.111* | |
C19 | 0.3072 (7) | 0.4672 (6) | 0.1404 (4) | 0.1093 (18) | |
H19 | 0.3586 | 0.5616 | 0.1430 | 0.131* | |
C20 | −0.1294 (8) | 0.2308 (8) | −0.0434 (4) | 0.143 (3) | |
H20A | −0.2000 | 0.2673 | −0.0184 | 0.214* | |
H20B | −0.1805 | 0.1644 | −0.0953 | 0.214* | |
H20C | −0.0508 | 0.3076 | −0.0521 | 0.214* | |
Cl2 | 0.02128 (15) | −0.08105 (12) | 0.23099 (7) | 0.0954 (5) | |
O2 | 0.5539 (4) | 0.7113 (4) | 1.0099 (2) | 0.1058 (11) | |
N21 | 0.0947 (4) | 0.5168 (4) | 0.6356 (2) | 0.0788 (10) | |
N22 | 0.0969 (4) | 0.4333 (3) | 0.5668 (2) | 0.0726 (9) | |
C23 | −0.0032 (4) | 0.2965 (4) | 0.5359 (2) | 0.0581 (9) | |
N24 | −0.1086 (4) | 0.2389 (4) | 0.5692 (2) | 0.0751 (10) | |
N25 | −0.1113 (4) | 0.3232 (4) | 0.6379 (2) | 0.0789 (10) | |
C26 | −0.0098 (4) | 0.4583 (5) | 0.6694 (2) | 0.0655 (10) | |
C27 | 0.0023 (4) | 0.2033 (4) | 0.4610 (2) | 0.0561 (9) | |
C28 | 0.1065 (4) | 0.2588 (4) | 0.4221 (2) | 0.0617 (10) | |
H28 | 0.1722 | 0.3516 | 0.4415 | 0.074* | |
C29 | 0.1117 (4) | 0.1718 (4) | 0.3517 (2) | 0.0683 (10) | |
H29 | 0.1846 | 0.2072 | 0.3226 | 0.082* | |
C30 | 0.0125 (4) | 0.0287 (4) | 0.3190 (2) | 0.0647 (10) | |
C31 | −0.0902 (4) | −0.0287 (4) | 0.3568 (2) | 0.0699 (10) | |
H31 | −0.1548 | −0.1219 | 0.3371 | 0.084* | |
C32 | −0.0957 (4) | 0.0578 (4) | 0.4268 (2) | 0.0677 (10) | |
H32 | −0.1685 | 0.0211 | 0.4558 | 0.081* | |
C33 | −0.0099 (4) | 0.5533 (5) | 0.7470 (3) | 0.0795 (12) | |
H33A | −0.0948 | 0.5064 | 0.7692 | 0.095* | |
H33B | −0.0254 | 0.6381 | 0.7351 | 0.095* | |
C34 | 0.1426 (4) | 0.6006 (4) | 0.8172 (2) | 0.0635 (10) | |
C35 | 0.2527 (5) | 0.7364 (4) | 0.8449 (3) | 0.0747 (12) | |
H35 | 0.2357 | 0.8071 | 0.8213 | 0.090* | |
C36 | 0.3924 (5) | 0.7774 (4) | 0.9077 (3) | 0.0740 (11) | |
H36 | 0.4598 | 0.8696 | 0.9217 | 0.089* | |
C37 | 0.4201 (5) | 0.6799 (5) | 0.9440 (3) | 0.0774 (12) | |
C38 | 0.3144 (6) | 0.5426 (5) | 0.9179 (3) | 0.0918 (14) | |
H38 | 0.3327 | 0.4727 | 0.9418 | 0.110* | |
C39 | 0.1764 (5) | 0.5032 (5) | 0.8549 (3) | 0.0837 (12) | |
H39 | 0.1108 | 0.4102 | 0.8404 | 0.100* | |
C40 | 0.6673 (6) | 0.8493 (6) | 1.0380 (3) | 0.1141 (18) | |
H40A | 0.6217 | 0.9186 | 1.0582 | 0.171* | |
H40B | 0.7131 | 0.8732 | 0.9931 | 0.171* | |
H40C | 0.7429 | 0.8482 | 1.0815 | 0.171* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1142 (10) | 0.0969 (9) | 0.0768 (8) | 0.0206 (8) | 0.0258 (7) | 0.0097 (6) |
O1 | 0.157 (4) | 0.141 (4) | 0.111 (3) | 0.046 (3) | 0.035 (3) | 0.004 (3) |
N1 | 0.080 (2) | 0.081 (2) | 0.088 (3) | 0.0081 (19) | 0.038 (2) | 0.013 (2) |
N2 | 0.076 (2) | 0.072 (2) | 0.081 (2) | 0.0028 (18) | 0.0387 (18) | 0.0193 (18) |
C3 | 0.047 (2) | 0.063 (2) | 0.069 (2) | 0.0066 (18) | 0.0169 (17) | 0.0313 (19) |
N4 | 0.075 (2) | 0.078 (2) | 0.081 (2) | 0.0075 (18) | 0.0341 (18) | 0.034 (2) |
N5 | 0.075 (2) | 0.097 (3) | 0.080 (2) | 0.014 (2) | 0.0372 (19) | 0.033 (2) |
C6 | 0.055 (2) | 0.086 (3) | 0.085 (3) | 0.011 (2) | 0.028 (2) | 0.030 (2) |
C7 | 0.051 (2) | 0.060 (2) | 0.071 (2) | 0.0093 (18) | 0.0165 (18) | 0.030 (2) |
C8 | 0.064 (2) | 0.067 (2) | 0.069 (3) | 0.0021 (19) | 0.0187 (19) | 0.028 (2) |
C9 | 0.070 (3) | 0.078 (3) | 0.072 (3) | 0.006 (2) | 0.027 (2) | 0.025 (2) |
C10 | 0.066 (2) | 0.071 (3) | 0.071 (3) | 0.018 (2) | 0.015 (2) | 0.024 (2) |
C11 | 0.068 (3) | 0.059 (2) | 0.083 (3) | 0.007 (2) | 0.014 (2) | 0.017 (2) |
C12 | 0.065 (2) | 0.065 (3) | 0.083 (3) | 0.009 (2) | 0.025 (2) | 0.032 (2) |
C13 | 0.075 (3) | 0.120 (4) | 0.091 (3) | 0.027 (3) | 0.039 (2) | 0.012 (3) |
C14 | 0.079 (3) | 0.078 (3) | 0.078 (3) | 0.030 (2) | 0.048 (2) | 0.028 (2) |
C15 | 0.102 (4) | 0.087 (3) | 0.077 (3) | 0.029 (3) | 0.045 (3) | 0.017 (2) |
C16 | 0.134 (5) | 0.097 (4) | 0.099 (4) | 0.034 (4) | 0.049 (4) | 0.025 (3) |
C17 | 0.110 (4) | 0.091 (4) | 0.080 (3) | 0.042 (3) | 0.047 (3) | 0.013 (3) |
C18 | 0.125 (4) | 0.110 (4) | 0.085 (3) | 0.072 (4) | 0.053 (3) | 0.048 (3) |
C19 | 0.139 (5) | 0.102 (4) | 0.124 (4) | 0.055 (4) | 0.084 (4) | 0.049 (4) |
C20 | 0.191 (7) | 0.200 (7) | 0.088 (4) | 0.125 (6) | 0.036 (4) | 0.053 (4) |
Cl2 | 0.1259 (10) | 0.0808 (8) | 0.0714 (8) | 0.0269 (7) | 0.0256 (7) | 0.0077 (6) |
O2 | 0.121 (3) | 0.120 (3) | 0.088 (2) | 0.055 (2) | 0.016 (2) | 0.029 (2) |
N21 | 0.082 (2) | 0.073 (2) | 0.076 (2) | 0.0093 (18) | 0.0368 (18) | 0.0158 (18) |
N22 | 0.078 (2) | 0.063 (2) | 0.065 (2) | 0.0000 (17) | 0.0345 (16) | 0.0142 (16) |
C23 | 0.052 (2) | 0.063 (2) | 0.061 (2) | 0.0102 (18) | 0.0145 (17) | 0.0321 (19) |
N24 | 0.075 (2) | 0.072 (2) | 0.077 (2) | 0.0077 (18) | 0.0347 (18) | 0.0277 (19) |
N25 | 0.074 (2) | 0.093 (3) | 0.072 (2) | 0.016 (2) | 0.0353 (18) | 0.029 (2) |
C26 | 0.056 (2) | 0.079 (3) | 0.067 (2) | 0.019 (2) | 0.0234 (19) | 0.027 (2) |
C27 | 0.055 (2) | 0.057 (2) | 0.057 (2) | 0.0101 (17) | 0.0182 (17) | 0.0246 (17) |
C28 | 0.062 (2) | 0.059 (2) | 0.061 (2) | 0.0044 (18) | 0.0206 (18) | 0.0239 (18) |
C29 | 0.080 (3) | 0.067 (3) | 0.061 (2) | 0.017 (2) | 0.0271 (19) | 0.0226 (19) |
C30 | 0.075 (3) | 0.060 (2) | 0.058 (2) | 0.016 (2) | 0.0141 (19) | 0.0212 (19) |
C31 | 0.075 (3) | 0.053 (2) | 0.071 (3) | 0.004 (2) | 0.014 (2) | 0.017 (2) |
C32 | 0.062 (2) | 0.060 (2) | 0.075 (3) | 0.0027 (19) | 0.0199 (19) | 0.027 (2) |
C33 | 0.074 (3) | 0.106 (3) | 0.070 (3) | 0.037 (2) | 0.033 (2) | 0.025 (2) |
C34 | 0.079 (3) | 0.067 (2) | 0.061 (2) | 0.034 (2) | 0.0362 (19) | 0.0231 (19) |
C35 | 0.095 (3) | 0.071 (3) | 0.077 (3) | 0.038 (3) | 0.039 (2) | 0.031 (2) |
C36 | 0.084 (3) | 0.060 (2) | 0.077 (3) | 0.019 (2) | 0.031 (2) | 0.012 (2) |
C37 | 0.093 (3) | 0.091 (3) | 0.063 (3) | 0.045 (3) | 0.029 (2) | 0.022 (2) |
C38 | 0.120 (4) | 0.096 (4) | 0.084 (3) | 0.052 (3) | 0.034 (3) | 0.041 (3) |
C39 | 0.098 (3) | 0.075 (3) | 0.082 (3) | 0.024 (2) | 0.037 (3) | 0.024 (2) |
C40 | 0.100 (4) | 0.136 (5) | 0.097 (4) | 0.046 (4) | 0.012 (3) | −0.001 (3) |
Cl1—C10 | 1.701 (4) | Cl2—C30 | 1.703 (4) |
O1—C20 | 1.384 (6) | O2—C40 | 1.438 (6) |
O1—C17 | 1.552 (6) | O2—C37 | 1.482 (5) |
N1—C6 | 1.259 (5) | N21—C26 | 1.266 (5) |
N1—N2 | 1.303 (5) | N21—N22 | 1.303 (4) |
N2—C3 | 1.394 (5) | N22—C23 | 1.385 (5) |
C3—N4 | 1.250 (4) | C23—N24 | 1.263 (4) |
C3—C7 | 1.446 (5) | C23—C27 | 1.441 (5) |
N4—N5 | 1.302 (5) | N24—N25 | 1.308 (5) |
N5—C6 | 1.379 (5) | N25—C26 | 1.377 (5) |
C6—C13 | 1.454 (6) | C26—C33 | 1.467 (5) |
C7—C8 | 1.312 (5) | C27—C28 | 1.311 (5) |
C7—C12 | 1.437 (5) | C27—C32 | 1.449 (5) |
C8—C9 | 1.343 (5) | C28—C29 | 1.351 (5) |
C8—H8 | 0.93 | C28—H28 | 0.93 |
C9—C10 | 1.434 (6) | C29—C30 | 1.431 (5) |
C9—H9 | 0.93 | C29—H29 | 0.93 |
C10—C11 | 1.299 (5) | C30—C31 | 1.294 (5) |
C11—C12 | 1.354 (5) | C31—C32 | 1.345 (5) |
C11—H11 | 0.93 | C31—H31 | 0.93 |
C12—H12 | 0.93 | C32—H32 | 0.93 |
C13—C14 | 1.617 (6) | C33—C34 | 1.625 (5) |
C13—H13A | 0.97 | C33—H33A | 0.97 |
C13—H13B | 0.97 | C33—H33B | 0.97 |
C14—C15 | 1.380 (6) | C34—C39 | 1.370 (6) |
C14—C19 | 1.394 (6) | C34—C35 | 1.409 (5) |
C15—C16 | 1.435 (6) | C35—C36 | 1.478 (6) |
C15—H15 | 0.93 | C35—H35 | 0.93 |
C16—C17 | 1.334 (7) | C36—C37 | 1.334 (6) |
C16—H16 | 0.93 | C36—H36 | 0.93 |
C17—C18 | 1.349 (7) | C37—C38 | 1.403 (6) |
C18—C19 | 1.560 (7) | C38—C39 | 1.469 (6) |
C18—H18 | 0.93 | C38—H38 | 0.93 |
C19—H19 | 0.93 | C39—H39 | 0.93 |
C20—H20A | 0.96 | C40—H40A | 0.96 |
C20—H20B | 0.96 | C40—H40B | 0.96 |
C20—H20C | 0.96 | C40—H40C | 0.96 |
C20—O1—C17 | 118.8 (5) | C40—O2—C37 | 122.4 (4) |
C6—N1—N2 | 112.2 (4) | C26—N21—N22 | 112.0 (3) |
N1—N2—C3 | 122.7 (3) | N21—N22—C23 | 123.3 (3) |
N4—C3—N2 | 125.0 (4) | N24—C23—N22 | 124.6 (4) |
N4—C3—C7 | 112.4 (4) | N24—C23—C27 | 112.3 (3) |
N2—C3—C7 | 122.6 (3) | N22—C23—C27 | 123.1 (3) |
C3—N4—N5 | 111.9 (4) | C23—N24—N25 | 112.0 (3) |
N4—N5—C6 | 123.6 (3) | N24—N25—C26 | 123.3 (3) |
N1—C6—N5 | 124.6 (4) | N21—C26—N25 | 124.8 (4) |
N1—C6—C13 | 112.1 (4) | N21—C26—C33 | 111.3 (4) |
N5—C6—C13 | 123.3 (4) | N25—C26—C33 | 124.0 (3) |
C8—C7—C12 | 119.0 (4) | C28—C27—C23 | 115.1 (3) |
C8—C7—C3 | 115.8 (4) | C28—C27—C32 | 119.1 (4) |
C12—C7—C3 | 125.2 (3) | C23—C27—C32 | 125.8 (3) |
C7—C8—C9 | 115.6 (4) | C27—C28—C29 | 115.3 (4) |
C7—C8—H8 | 122.2 | C27—C28—H28 | 122.4 |
C9—C8—H8 | 122.2 | C29—C28—H28 | 122.4 |
C8—C9—C10 | 124.4 (4) | C28—C29—C30 | 124.4 (3) |
C8—C9—H9 | 117.8 | C28—C29—H29 | 117.8 |
C10—C9—H9 | 117.8 | C30—C29—H29 | 117.8 |
C11—C10—C9 | 121.4 (4) | C31—C30—C29 | 121.4 (4) |
C11—C10—Cl1 | 114.1 (3) | C31—C30—Cl2 | 114.4 (3) |
C9—C10—Cl1 | 124.5 (3) | C29—C30—Cl2 | 124.1 (3) |
C10—C11—C12 | 113.6 (4) | C30—C31—C32 | 114.3 (4) |
C10—C11—H11 | 123.2 | C30—C31—H31 | 122.8 |
C12—C11—H11 | 123.2 | C32—C31—H31 | 122.8 |
C11—C12—C7 | 126.0 (4) | C31—C32—C27 | 125.5 (3) |
C11—C12—H12 | 117.0 | C31—C32—H32 | 117.3 |
C7—C12—H12 | 117.0 | C27—C32—H32 | 117.3 |
C6—C13—C14 | 117.5 (3) | C26—C33—C34 | 115.0 (3) |
C6—C13—H13A | 107.9 | C26—C33—H33A | 108.5 |
C14—C13—H13A | 107.9 | C34—C33—H33A | 108.5 |
C6—C13—H13B | 107.9 | C26—C33—H33B | 108.5 |
C14—C13—H13B | 107.9 | C34—C33—H33B | 108.5 |
H13A—C13—H13B | 107.2 | H33A—C33—H33B | 107.5 |
C15—C14—C19 | 111.8 (5) | C39—C34—C35 | 113.0 (4) |
C15—C14—C13 | 123.0 (4) | C39—C34—C33 | 120.1 (4) |
C19—C14—C13 | 125.2 (5) | C35—C34—C33 | 126.9 (4) |
C14—C15—C16 | 128.3 (5) | C34—C35—C36 | 126.3 (4) |
C14—C15—H15 | 115.8 | C34—C35—H35 | 116.9 |
C16—C15—H15 | 115.8 | C36—C35—H35 | 116.9 |
C17—C16—C15 | 119.7 (5) | C37—C36—C35 | 118.9 (4) |
C17—C16—H16 | 120.2 | C37—C36—H36 | 120.6 |
C15—C16—H16 | 120.2 | C35—C36—H36 | 120.6 |
C16—C17—C18 | 119.2 (5) | C36—C37—C38 | 116.9 (4) |
C16—C17—O1 | 117.9 (5) | C36—C37—O2 | 123.2 (4) |
C18—C17—O1 | 122.9 (5) | C38—C37—O2 | 119.9 (4) |
C17—C18—C19 | 120.3 (5) | C37—C38—C39 | 123.6 (4) |
C17—C18—H18 | 119.9 | C37—C38—H38 | 118.2 |
C19—C18—H18 | 119.9 | C39—C38—H38 | 118.2 |
C14—C19—C18 | 120.7 (5) | C34—C39—C38 | 121.3 (4) |
C14—C19—H19 | 119.7 | C34—C39—H39 | 119.4 |
C18—C19—H19 | 119.7 | C38—C39—H39 | 119.4 |
O1—C20—H20A | 109.5 | O2—C40—H40A | 109.5 |
O1—C20—H20B | 109.5 | O2—C40—H40B | 109.5 |
H20A—C20—H20B | 109.5 | H40A—C40—H40B | 109.5 |
O1—C20—H20C | 109.5 | O2—C40—H40C | 109.5 |
H20A—C20—H20C | 109.5 | H40A—C40—H40C | 109.5 |
H20B—C20—H20C | 109.5 | H40B—C40—H40C | 109.5 |
C6—N1—N2—C3 | 0.9 (6) | C26—N21—N22—C23 | −0.6 (6) |
N1—N2—C3—N4 | −2.0 (6) | N21—N22—C23—N24 | 1.7 (6) |
N1—N2—C3—C7 | 178.9 (4) | N21—N22—C23—C27 | −178.3 (3) |
N2—C3—N4—N5 | 1.2 (6) | N22—C23—N24—N25 | −1.1 (6) |
C7—C3—N4—N5 | −179.6 (3) | C27—C23—N24—N25 | 178.9 (3) |
C3—N4—N5—C6 | 0.3 (6) | C23—N24—N25—C26 | −0.3 (6) |
N2—N1—C6—N5 | 0.6 (6) | N22—N21—C26—N25 | −0.8 (6) |
N2—N1—C6—C13 | 179.7 (4) | N22—N21—C26—C33 | 179.6 (3) |
N4—N5—C6—N1 | −1.3 (7) | N24—N25—C26—N21 | 1.3 (6) |
N4—N5—C6—C13 | 179.7 (4) | N24—N25—C26—C33 | −179.1 (4) |
N4—C3—C7—C8 | −177.4 (3) | N24—C23—C27—C28 | 177.8 (3) |
N2—C3—C7—C8 | 1.7 (6) | N22—C23—C27—C28 | −2.2 (5) |
N4—C3—C7—C12 | 3.0 (5) | N24—C23—C27—C32 | −2.2 (5) |
N2—C3—C7—C12 | −177.8 (3) | N22—C23—C27—C32 | 177.8 (3) |
C12—C7—C8—C9 | −0.6 (6) | C23—C27—C28—C29 | −179.9 (3) |
C3—C7—C8—C9 | 179.8 (3) | C32—C27—C28—C29 | 0.1 (5) |
C7—C8—C9—C10 | −0.4 (6) | C27—C28—C29—C30 | 0.4 (6) |
C8—C9—C10—C11 | 0.7 (7) | C28—C29—C30—C31 | −1.1 (6) |
C8—C9—C10—Cl1 | 179.5 (3) | C28—C29—C30—Cl2 | −179.2 (3) |
C9—C10—C11—C12 | 0.1 (6) | C29—C30—C31—C32 | 1.0 (6) |
Cl1—C10—C11—C12 | −178.8 (3) | Cl2—C30—C31—C32 | 179.3 (3) |
C10—C11—C12—C7 | −1.2 (6) | C30—C31—C32—C27 | −0.5 (6) |
C8—C7—C12—C11 | 1.6 (6) | C28—C27—C32—C31 | −0.1 (6) |
C3—C7—C12—C11 | −178.9 (4) | C23—C27—C32—C31 | 179.9 (4) |
N1—C6—C13—C14 | 52.1 (6) | N21—C26—C33—C34 | −61.4 (5) |
N5—C6—C13—C14 | −128.8 (4) | N25—C26—C33—C34 | 118.9 (4) |
C6—C13—C14—C15 | −101.2 (5) | C26—C33—C34—C39 | −69.2 (5) |
C6—C13—C14—C19 | 78.9 (6) | C26—C33—C34—C35 | 109.4 (4) |
C19—C14—C15—C16 | −0.7 (6) | C39—C34—C35—C36 | −0.1 (5) |
C13—C14—C15—C16 | 179.4 (4) | C33—C34—C35—C36 | −178.8 (3) |
C14—C15—C16—C17 | 0.6 (7) | C34—C35—C36—C37 | −1.0 (6) |
C15—C16—C17—C18 | −0.8 (7) | C35—C36—C37—C38 | 1.5 (6) |
C15—C16—C17—O1 | 178.9 (4) | C35—C36—C37—O2 | −177.7 (3) |
C20—O1—C17—C16 | 178.4 (5) | C40—O2—C37—C36 | −2.1 (6) |
C20—O1—C17—C18 | −1.9 (7) | C40—O2—C37—C38 | 178.8 (4) |
C16—C17—C18—C19 | 1.1 (7) | C36—C37—C38—C39 | −1.1 (6) |
O1—C17—C18—C19 | −178.5 (4) | O2—C37—C38—C39 | 178.0 (4) |
C15—C14—C19—C18 | 0.9 (6) | C35—C34—C39—C38 | 0.5 (5) |
C13—C14—C19—C18 | −179.2 (3) | C33—C34—C39—C38 | 179.3 (3) |
C17—C18—C19—C14 | −1.3 (6) | C37—C38—C39—C34 | 0.1 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···Cl2 | 0.93 | 2.82 | 3.555 (6) | 137 |
C20—H20A···Cg1i | 0.96 | 2.64 | 3.482 (8) | 147 |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H13ClN4O |
Mr | 312.75 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.471 (3), 10.170 (3), 16.911 (7) |
α, β, γ (°) | 101.429 (6), 97.597 (6), 107.012 (4) |
V (Å3) | 1495.0 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.25 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.937, 0.952 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8415, 5475, 2567 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.076, 0.286, 0.95 |
No. of reflections | 5475 |
No. of parameters | 399 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.63, −0.31 |
Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2005), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···Cl2 | 0.93 | 2.82 | 3.555 (6) | 137 |
C20—H20A···Cg1i | 0.96 | 2.64 | 3.482 (8) | 147 |
Symmetry code: (i) −x, −y+1, −z+1. |
1,2,4,5-Tetrazine derivatives have high potential for biological activity, possessing a wide spectrum of antiviral and antitumor properties. They have been widely used in pesticides and herbicides (Sauer, 1996). In continuation of our work on the structure-activity relationship of 1,2,4,5-tetrazine derivatives (Hu et al., 2004, 2005), we present here the structure of the title compound, (I).
Compound (I) crystallizes with two unique molecules in the asymmetric unit that differ in the orientation of the methoxy group (Fig. 1). In both molecules the chlorophenyl ring is almost coplanar with the central tetrazine ring, but the methoxyphenyl ring is twisted. The C7—C12 and C14—C19 benzene rings form dihedral angles of 2.32 (3) and 76.74 (2)°, respectively, with the N1/N2/N4/N5/C3/C6 plane. The C27—C32 and C34—C39 benzene rings for dihedral angles of 2.37 (3) and 80.47 (2)°, respectively, with the N21/N22/N24/N25/C23/C26 plane.
A C—H···Cl hydrogen bonding is observed between the two independent molecules. In the crystal structure, pair of C—H···π interactions involving the C34—C39 ring (centroid Cg1) link the molecules into a dimer (Table 1).