Ethyl 3,6-di­phenyl-1,4-di­hydro-1,2,4,5-tetrazine-1-carboxylate

The title compound, C₁₇H₁₆N₄O₂, was prepared from ethyl chloro­formate and 3,6-di­phenyl­di­hydro-1,2,4,5-tetrazine. The central six-membered ring has an asymmetric boat conformation.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.034
• wR factor = 0.098
• Data-to-parameter ratio = 7.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C4     -   C5      ..       7.40 su

Alert level C
STRVA01_ALERT_4_C           Flack parameter is too small
           From the CIF: _refine_ls_abs_structure_Flack   -1.000
           From the CIF: _refine_ls_abs_structure_Flack_su    2.000
PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ...       2.00
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......      -1.00
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       6.99
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     -   C15     ..       6.50 su
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C17 H16 N4 O2

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.17
           From the CIF: _reflns_number_total               1468
           Count of symmetry unique reflns         1468
           Completeness (_total/calc)            100.00%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present           no

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: CAD-4 EXPRESS (Enraf0-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Version 1.05; Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Ethyl 3,6-diphenyl-1,4-dihydro-1,2,4,5-tetrazine-1-carbonate

Crystal data

C17H16N4O2	Dx = 1.298 Mg m^−3
Mr = 308.34	Melting point: 412 K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 25 reflections
a = 10.175 (2) Å	θ = 11.5–12.5°
b = 9.219 (2) Å	µ = 0.09 mm^−1
c = 16.814 (4) Å	T = 293 K
V = 1577.2 (6) Å^3	Prism, yellow
Z = 4	0.35 × 0.30 × 0.20 mm
F(000) = 648

Data collection

Enraf–Nonius CAD-4 diffractometer	1159 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Graphite monochromator	θmax = 25.2°, θmin = 2.4°
ω/2θ scans	h = −1→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = 0→11
Tmin = 0.970, Tmax = 0.983	l = −20→0
1633 measured reflections	3 standard reflections every 60 min
1468 independent reflections	intensity decay: 0.3%

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)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0519P)^2 + 0.3521P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.098	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.24 e Å^−3
1468 reflections	Δρmin = −0.17 e Å^−3
210 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0283 (14)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −1 (2)

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
O1	0.23976 (12)	0.91687 (14)	0.30370 (9)	0.0636 (4)
O2	0.10564 (13)	0.85240 (14)	0.40356 (8)	0.0577 (4)
N1	0.08852 (13)	1.07443 (15)	0.35228 (8)	0.0465 (4)
N2	0.11734 (12)	1.17047 (15)	0.28787 (8)	0.0426 (4)
N4	−0.10754 (13)	1.20704 (17)	0.29793 (9)	0.0501 (4)
H4	−0.1800	1.2035	0.2717	0.060*
N5	−0.10587 (13)	1.19339 (17)	0.38082 (8)	0.0495 (4)
C2	−0.09304 (19)	1.1116 (2)	0.54438 (11)	0.0569 (5)
H2	−0.1775	1.1146	0.5233	0.068*
C4	−0.0761 (2)	1.1071 (2)	0.62534 (12)	0.0618 (6)
H6	−0.1489	1.1075	0.6588	0.074*
C5	0.0479 (2)	1.1022 (2)	0.65672 (12)	0.0645 (6)
H5	0.0592	1.0993	0.7116	0.077*
C7	0.1562 (2)	1.1015 (2)	0.60726 (11)	0.0625 (6)
H7	0.2404	1.0973	0.6287	0.075*
C8	0.13909 (19)	1.1070 (2)	0.52624 (11)	0.0547 (5)
H8	0.2121	1.1076	0.4930	0.066*
C1	0.01420 (17)	1.11175 (19)	0.49359 (10)	0.0462 (4)
C6	−0.00612 (15)	1.1247 (2)	0.40698 (10)	0.0444 (4)
C3	0.01043 (14)	1.22630 (18)	0.26001 (10)	0.0400 (4)
C9	0.01554 (15)	1.31349 (18)	0.18654 (10)	0.0413 (4)
C10	0.10280 (19)	1.2749 (2)	0.12715 (12)	0.0541 (5)
H10	0.1576	1.1951	0.1337	0.065*
C11	0.1081 (2)	1.3554 (2)	0.05808 (13)	0.0687 (6)
H11	0.1664	1.3290	0.0180	0.082*
C12	0.0285 (2)	1.4740 (3)	0.04784 (12)	0.0622 (6)
H12	0.0328	1.5276	0.0011	0.075*
C13	−0.05719 (19)	1.5130 (2)	0.10673 (13)	0.0587 (6)
H13	−0.1105	1.5941	0.1002	0.070*
C14	−0.06503 (17)	1.4325 (2)	0.17579 (11)	0.0494 (5)
H14	−0.1247	1.4585	0.2152	0.059*
C15	0.15298 (16)	0.94427 (19)	0.34967 (10)	0.0454 (4)
C16	0.1652 (2)	0.7090 (2)	0.40140 (14)	0.0641 (6)
H16A	0.1569	0.6640	0.4533	0.077*
H16B	0.2580	0.7183	0.3895	0.077*
C17	0.1024 (3)	0.6146 (3)	0.34083 (18)	0.0943 (9)
H17A	0.1198	0.6525	0.2887	0.141*
H17B	0.0093	0.6119	0.3497	0.141*
H17C	0.1376	0.5182	0.3449	0.141*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0615 (7)	0.0697 (7)	0.0595 (7)	0.0188 (6)	0.0176 (6)	0.0075 (7)
O2	0.0638 (7)	0.0527 (6)	0.0567 (7)	−0.0009 (6)	0.0106 (7)	0.0037 (6)
N1	0.0438 (7)	0.0559 (8)	0.0398 (7)	0.0054 (6)	0.0062 (7)	0.0053 (7)
N2	0.0377 (6)	0.0520 (7)	0.0382 (7)	0.0025 (6)	0.0035 (6)	0.0031 (6)
N4	0.0320 (6)	0.0772 (9)	0.0412 (7)	−0.0005 (7)	0.0004 (6)	0.0060 (7)
N5	0.0376 (7)	0.0710 (9)	0.0398 (7)	0.0036 (7)	0.0050 (6)	0.0046 (7)
C2	0.0493 (9)	0.0668 (11)	0.0546 (10)	0.0005 (10)	0.0121 (9)	0.0093 (9)
C4	0.0633 (11)	0.0755 (13)	0.0465 (10)	−0.0012 (10)	0.0156 (9)	0.0114 (10)
C5	0.0868 (13)	0.0658 (11)	0.0409 (9)	0.0015 (12)	0.0055 (10)	0.0092 (9)
C7	0.0638 (11)	0.0751 (13)	0.0485 (11)	0.0071 (11)	−0.0098 (10)	−0.0014 (10)
C8	0.0464 (9)	0.0658 (11)	0.0519 (10)	0.0038 (9)	0.0061 (8)	−0.0028 (9)
C1	0.0488 (9)	0.0484 (9)	0.0414 (8)	0.0014 (8)	0.0039 (8)	0.0058 (8)
C6	0.0344 (7)	0.0545 (9)	0.0443 (8)	−0.0016 (7)	0.0040 (8)	0.0018 (8)
C3	0.0315 (7)	0.0492 (9)	0.0392 (8)	0.0001 (7)	−0.0005 (6)	−0.0033 (8)
C9	0.0373 (7)	0.0462 (8)	0.0403 (8)	−0.0032 (7)	−0.0017 (7)	−0.0045 (8)
C10	0.0584 (10)	0.0515 (10)	0.0524 (10)	0.0059 (9)	0.0112 (9)	0.0028 (9)
C11	0.0794 (14)	0.0752 (13)	0.0516 (11)	0.0031 (11)	0.0211 (11)	0.0050 (11)
C12	0.0667 (12)	0.0714 (12)	0.0485 (10)	−0.0117 (11)	−0.0049 (10)	0.0130 (9)
C13	0.0491 (10)	0.0573 (11)	0.0697 (12)	0.0001 (9)	−0.0157 (9)	0.0090 (10)
C14	0.0412 (8)	0.0597 (10)	0.0472 (10)	0.0050 (8)	−0.0026 (8)	−0.0041 (9)
C15	0.0432 (8)	0.0517 (9)	0.0414 (8)	−0.0023 (8)	−0.0043 (8)	0.0004 (8)
C16	0.0706 (12)	0.0549 (11)	0.0666 (13)	−0.0022 (10)	−0.0010 (11)	0.0059 (10)
C17	0.1062 (17)	0.0743 (14)	0.1023 (19)	−0.0049 (14)	−0.0242 (17)	−0.0199 (15)

Geometric parameters (Å, º)

O1—C15	1.200 (2)	C8—H8	0.9300
O2—C15	1.331 (2)	C1—C6	1.476 (2)
O2—C16	1.455 (2)	C3—C9	1.475 (2)
N1—C15	1.368 (2)	C9—C14	1.382 (2)
N1—C6	1.410 (2)	C9—C10	1.383 (3)
N1—N2	1.429 (2)	C10—C11	1.379 (3)
N2—C3	1.291 (2)	C10—H10	0.9300
N4—C3	1.371 (2)	C11—C12	1.371 (3)
N4—N5	1.399 (2)	C11—H11	0.9300
N4—H4	0.8600	C12—C13	1.368 (3)
N5—C6	1.274 (2)	C12—H12	0.9300
C2—C4	1.373 (3)	C13—C14	1.380 (3)
C2—C1	1.386 (3)	C13—H13	0.9300
C2—H2	0.9300	C14—H14	0.9300
C4—C5	1.368 (3)	C16—C17	1.484 (3)
C4—H6	0.9300	C16—H16A	0.9700
C5—C7	1.381 (3)	C16—H16B	0.9700
C5—H5	0.9300	C17—H17A	0.9600
C7—C8	1.374 (3)	C17—H17B	0.9600
C7—H7	0.9300	C17—H17C	0.9600
C8—C1	1.385 (3)
C15—O2—C16	114.26 (15)	C14—C9—C10	119.40 (17)
C15—N1—C6	129.55 (15)	C14—C9—C3	121.44 (15)
C15—N1—N2	114.88 (13)	C10—C9—C3	119.16 (15)
C6—N1—N2	115.50 (13)	C11—C10—C9	119.65 (18)
C3—N2—N1	110.42 (13)	C11—C10—H10	120.2
C3—N4—N5	117.66 (13)	C9—C10—H10	120.2
C3—N4—H4	121.2	C12—C11—C10	120.8 (2)
N5—N4—H4	121.2	C12—C11—H11	119.6
C6—N5—N4	113.45 (14)	C10—C11—H11	119.6
C4—C2—C1	120.83 (18)	C13—C12—C11	119.7 (2)
C4—C2—H2	119.6	C13—C12—H12	120.2
C1—C2—H2	119.6	C11—C12—H12	120.2
C5—C4—C2	119.92 (19)	C12—C13—C14	120.32 (18)
C5—C4—H6	120.0	C12—C13—H13	119.8
C2—C4—H6	120.0	C14—C13—H13	119.8
C4—C5—C7	120.28 (18)	C13—C14—C9	120.17 (17)
C4—C5—H5	119.9	C13—C14—H14	119.9
C7—C5—H5	119.9	C9—C14—H14	119.9
C8—C7—C5	119.7 (2)	O1—C15—O2	124.81 (16)
C8—C7—H7	120.2	O1—C15—N1	123.91 (16)
C5—C7—H7	120.2	O2—C15—N1	111.28 (15)
C7—C8—C1	120.70 (18)	O2—C16—C17	111.79 (19)
C7—C8—H8	119.6	O2—C16—H16A	109.3
C1—C8—H8	119.6	C17—C16—H16A	109.3
C8—C1—C2	118.57 (17)	O2—C16—H16B	109.3
C8—C1—C6	121.49 (15)	C17—C16—H16B	109.3
C2—C1—C6	119.86 (16)	H16A—C16—H16B	107.9
N5—C6—N1	118.82 (16)	C16—C17—H17A	109.5
N5—C6—C1	119.50 (15)	C16—C17—H17B	109.5
N1—C6—C1	121.42 (14)	H17A—C17—H17B	109.5
N2—C3—N4	121.15 (15)	C16—C17—H17C	109.5
N2—C3—C9	119.43 (14)	H17A—C17—H17C	109.5
N4—C3—C9	119.41 (14)	H17B—C17—H17C	109.5
C15—N1—N2—C3	134.40 (15)	N1—N2—C3—C9	−171.94 (14)
C6—N1—N2—C3	−42.86 (18)	N5—N4—C3—N2	31.3 (2)
C3—N4—N5—C6	−36.0 (2)	N5—N4—C3—C9	−148.07 (16)
C1—C2—C4—C5	−0.3 (3)	N2—C3—C9—C14	−144.84 (17)
C2—C4—C5—C7	−0.1 (3)	N4—C3—C9—C14	34.6 (2)
C4—C5—C7—C8	0.6 (3)	N2—C3—C9—C10	35.3 (2)
C5—C7—C8—C1	−0.7 (3)	N4—C3—C9—C10	−145.32 (17)
C7—C8—C1—C2	0.4 (3)	C14—C9—C10—C11	−0.1 (3)
C7—C8—C1—C6	177.06 (19)	C3—C9—C10—C11	179.80 (17)
C4—C2—C1—C8	0.1 (3)	C9—C10—C11—C12	0.5 (3)
C4—C2—C1—C6	−176.63 (19)	C10—C11—C12—C13	0.0 (3)
N4—N5—C6—N1	1.0 (2)	C11—C12—C13—C14	−0.8 (3)
N4—N5—C6—C1	175.28 (15)	C12—C13—C14—C9	1.2 (3)
C15—N1—C6—N5	−137.65 (19)	C10—C9—C14—C13	−0.7 (3)
N2—N1—C6—N5	39.1 (2)	C3—C9—C14—C13	179.36 (16)
C15—N1—C6—C1	48.2 (3)	C16—O2—C15—O1	−2.1 (3)
N2—N1—C6—C1	−135.02 (16)	C16—O2—C15—N1	176.99 (15)
C8—C1—C6—N5	−147.50 (18)	C6—N1—C15—O1	−173.92 (17)
C2—C1—C6—N5	29.2 (3)	N2—N1—C15—O1	9.3 (2)
C8—C1—C6—N1	26.6 (3)	C6—N1—C15—O2	7.0 (2)
C2—C1—C6—N1	−156.74 (17)	N2—N1—C15—O2	−169.78 (13)
N1—N2—C3—N4	8.7 (2)	C15—O2—C16—C17	−83.8 (2)