Bispyrazolone

Structure determination of Bispyrazolone with the Bruker SMART X2S benchtop crystallographic system

A colorless crystal of Bispyrazolone with the dimensions of 0.20 mm x 0.50 mm x 0.50 mm mounted on a Mitegen Micromount was automatically centered on a Bruker SMART X2S benchtop crystallographic system. Intensity measurements were performed using a monochromated (Doubly Curved Silicon Crystal) Mo-K_α-radiation (0.71073 Å) from a sealed MicroFocus tube. Generator settings were 50 kV, 1 mA. Data collection temperature was 23°C.
Data were acquired using three sets of Omega scans at different Phi settings. The frame width was 0.5° with an exposure time of 60.0 s.

The detailed data collection strategy was as follows:
Detector distance: 40 mm
Detector swing angle (fixed 2 Theta): -20°.

Run	Omega (start)	Omega (end)	Phi	Frames
1	-20.0	-200.0	0.0	360
2	-20.0	-140.0	120.0	240
3	-20.0	-80.0	240.0	120

APEX2 software was used for preliminary determination of the unit cell. Determination of integral intensities and unit cell refinement were performed using SAINT. The integration of the data yielded a total of 21223 reflections to a maximum θ angle of 25.25° (0.83 Å resolution).
The constants for the orthorhombic unit cell are a = 8.7369(10) Å, b = 18.8533(18) Å, c = 21.174(2) Å, V = 3487.8(6) Å³. They are based upon the refinement of the XYZ-centroids of 4259 reflections above 20.0 I/σ(I) with 2.74° ≤ θ ≤ 24.66°.
Data were corrected for absorption effects with SADABS using the multiscan technique. The ratio of minimum to maximum apparent transmission is 80.9:100. The average residual for symmetry equivalent reflections is R_int = 6.75% and R_σ = 3.97%. XPREP determined the space group to be P b c a, with Z = 8 for the formula unit, C₂₀H₁₈N₄O₂.
The structure was solved with XS and subsequent structure refinements were performed with XL. The final anisotropic full-matrix least-squares refinement on F_o² with 237 variables converged at R₁ = 5.17% for the observed data and wR₂ = 18.35% for all data. The goodness-of-fit was 1.027. The largest peak on the final difference electron density synthesis was 0.47 e^-/Å³ and the deepest hole was -0.53 e^-/Å³ with an RMS deviation of 0.09 e^-/Å³. On the basis of the final model, the calculated density is 1.319 g/cm³ and F(000) = 1456.

APEX2 Version 2.2 (Bruker AXS Inc., 2007)
SAINT Version 7.34a (Bruker AXS Inc., 2007)
SADABS Version 2007/2 (Sheldrick, Bruker AXS Inc.)
XPREP Version 2005/2 (Sheldrick, Bruker AXS Inc.)
XS Version 2008/1 (George M. Sheldrick, Acta Cryst. (2008). A64, 112-122)
XL Version 2008/1 (George M. Sheldrick, Acta Cryst. (2008). A64, 112-122)

Table 1. Crystal data and structure refinement for Bispyrazolone.

Identification code	Bispyrazolone
Empirical formula	C20 H18 N4 O2
Formula weight	346.38
Temperature	296(2) K
Wavelength	0.71073 Å
Crystal system	Orthorhombic
Space group	P b c a
Unit cell dimensions	a = 8.7369(10) Å	α = 90°
	b = 18.8533(18) Å	β = 90°
	c = 21.174(2) Å	γ = 90°
Volume	3487.8(6) Å³
Z	8
Density (calculated)	1.319 Mg/cm³
Absorption coefficient	0.088 mm^-1
F(000)	1456
Crystal size	0.20 x 0.50 x 0.50 mm³
Theta range for data collection	2.74 to 24.66°
Index ranges	-10<=h<=10, -22<=k<=21, -25<=l<=25
Reflections collected	21223
Independent reflections	3147 [R(int) = 0.0675]
Completeness to theta = 24.66°	99.6%
Absorption correction	Multiscan
Max. and min. transmission	0.9826 and 0.7952
Refinement method	Full-matrix least-squares on F²
Data / restraints / parameters	3147 / 0 / 237
Goodness-of-fit on F²	1.027
Final R indices [I>2sigma(I)]	R1 = 0.0517, wR2 = 0.1500
R indices (all data)	R1 = 0.0822, wR2 = 0.1835
Largest diff. peak and hole	0.471 and -0.525

R_int = Σ|F_o² - F_o²(mean)| / Σ[F_o²]
R₁ = Σ||F_o| - |F_c|| / Σ|F_o|
GOOF = S = {Σ[w(F_o² - F_c²)²] / (n - p)}^1/2
wR₂ = {Σ[w(F_o² - F_c²)²] / Σ[w(F_o²)²]}^1/2
w = 1 / [σ(F_o²) + (aP)² + bP] where P is [2F_c² + Max(F_o², 0)] / 3

Table 2. Atomic coordinates (x10⁴) and equivalent isotropic displacement parameters (Å²x10³) for Bispyrazolone.

U(eq) is defined as one third of the trace of the orthogonalized U^ij tensor.

	x	y	z	U(eq)
O1	6725(2)	954(1)	4746(1)	38(1)
O2	9169(2)	1220(1)	6161(1)	43(1)
N1	9930(2)	2384(1)	5952(1)	37(1)
N2	8279(2)	183(1)	4178(1)	32(1)
N3	10312(3)	2754(1)	5413(1)	49(1)
N4	9820(2)	144(1)	4030(1)	32(1)
C1	9300(5)	3422(2)	7680(1)	74(1)
C2	8739(5)	2753(2)	7590(1)	85(1)
C3	8932(5)	2415(2)	7022(1)	70(1)
C4	9726(3)	2737(1)	6542(1)	38(1)
C5	9587(3)	1690(1)	5779(1)	32(1)
C6	9804(3)	1656(1)	5114(1)	33(1)
C7	9512(3)	1034(1)	4714(1)	31(1)
C8	8026(3)	755(1)	4579(1)	29(1)
C9	7197(2)	-181(1)	3795(1)	32(1)
C10	5784(3)	-368(1)	4040(1)	37(1)
C11	4742(3)	-718(1)	3660(1)	45(1)
C12	5108(3)	-891(1)	3048(1)	49(1)
C13	10027(4)	3760(2)	7196(2)	72(1)
C14	10235(4)	3417(2)	6621(1)	62(1)
C15	10264(3)	2315(1)	4918(1)	42(1)
C16	10672(5)	2576(2)	4276(1)	71(1)
C17	10555(3)	637(1)	4383(1)	32(1)
C18	12247(3)	692(1)	4357(1)	48(1)
C19	7559(3)	-343(1)	3175(1)	42(1)
C20	6509(3)	-698(1)	2804(1)	52(1)

Table 3. Bond lengths (Å) and angles (°) for Bispyrazolone.

O1-C8	1.249(3)
O2-C5	1.255(3)
N1-N3	1.379(3)
N1-C5	1.393(3)
N1-C4	1.427(3)
N2-N4	1.385(3)
N2-C8	1.389(3)
N2-C9	1.422(3)
N3-C15	1.336(3)
N4-C17	1.354(3)
C1-C13	1.364(5)
C1-C2	1.366(5)
C2-C3	1.372(4)
C3-C4	1.373(4)
C4-C14	1.366(4)
C5-C6	1.422(3)
C6-C15	1.369(3)
C6-C7	1.470(3)
C7-C17	1.372(3)
C7-C8	1.429(3)
C9-C19	1.385(3)
C9-C10	1.385(3)
C10-C11	1.383(3)
C11-C12	1.375(4)
C12-C20	1.378(4)
C13-C14	1.392(4)
C15-C16	1.490(4)
C17-C18	1.483(3)
C19-C20	1.381(4)

N3-N1-C5	108.00(17)
N3-N1-C4	121.3(2)
C5-N1-C4	130.0(2)
N4-N2-C8	109.49(17)
N4-N2-C9	119.45(17)
C8-N2-C9	128.06(18)
C15-N3-N1	109.2(2)
C17-N4-N2	107.45(17)
C13-C1-C2	119.5(3)
C1-C2-C3	120.5(3)
C2-C3-C4	120.3(3)
C14-C4-C3	119.4(2)
C14-C4-N1	120.2(2)
C3-C4-N1	120.3(2)
O2-C5-N1	123.8(2)
O2-C5-C6	130.3(2)
N1-C5-C6	105.9(2)
C15-C6-C5	107.4(2)
C15-C6-C7	126.9(2)
C5-C6-C7	125.7(2)
C17-C7-C8	107.5(2)
C17-C7-C6	127.9(2)
C8-C7-C6	124.5(2)
O1-C8-N2	123.5(2)
O1-C8-C7	131.3(2)
N2-C8-C7	105.26(18)
C19-C9-C10	120.2(2)
C19-C9-N2	119.7(2)
C10-C9-N2	120.1(2)
C11-C10-C9	119.3(2)
C12-C11-C10	120.7(2)
C11-C12-C20	119.8(2)
C1-C13-C14	120.1(3)
C4-C14-C13	120.0(3)
N3-C15-C6	109.5(2)
N3-C15-C16	120.2(2)
C6-C15-C16	130.3(2)
N4-C17-C7	109.9(2)
N4-C17-C18	120.0(2)
C7-C17-C18	130.0(2)
C20-C19-C9	119.6(2)
C12-C20-C19	120.4(3)

Table 4. Anisotropic displacement parameters (Å²x10³) for Bispyrazolone.

The anisotropic displacement factor exponent takes the form: -2π²[ h² a^*2 U¹¹ + ... + 2 h k a^* b^* U¹² ]

	U¹¹	U²²	U³³	U²³	U¹³	U¹²
O1	39(1)	33(1)	42(1)	-6(1)	5(1)	6(1)
O2	65(1)	23(1)	40(1)	-2(1)	13(1)	-3(1)
N1	55(1)	26(1)	32(1)	-2(1)	-1(1)	-8(1)
N2	32(1)	27(1)	36(1)	-9(1)	2(1)	-0(1)
N3	87(2)	27(1)	33(1)	-2(1)	-2(1)	-20(1)
N4	33(1)	29(1)	36(1)	-9(1)	6(1)	1(1)
C1	127(3)	56(2)	40(2)	-18(2)	6(2)	-0(2)
C2	159(4)	53(2)	43(2)	-7(2)	27(2)	-17(2)
C3	125(3)	37(2)	47(2)	-8(1)	19(2)	-18(2)
C4	53(2)	30(1)	31(1)	-4(1)	-6(1)	1(1)
C5	39(1)	21(1)	36(1)	-5(1)	2(1)	-1(1)
C6	42(1)	24(1)	35(1)	-4(1)	-1(1)	-4(1)
C7	42(1)	23(1)	29(1)	-2(1)	1(1)	-2(1)
C8	38(1)	21(1)	27(1)	-1(1)	3(1)	1(1)
C9	36(1)	23(1)	38(1)	-7(1)	-2(1)	2(1)
C10	39(1)	31(1)	40(1)	-2(1)	2(1)	1(1)
C11	36(1)	36(1)	61(2)	-1(1)	-2(1)	-2(1)
C12	47(2)	40(2)	60(2)	-13(1)	-16(1)	2(1)
C13	111(3)	46(2)	58(2)	-24(2)	11(2)	-23(2)
C14	86(2)	47(2)	52(2)	-15(1)	16(2)	-23(2)
C15	64(2)	31(1)	32(1)	-4(1)	-1(1)	-12(1)
C16	132(3)	43(2)	37(2)	0(1)	8(2)	-30(2)
C17	39(1)	25(1)	33(1)	1(1)	-1(1)	-1(1)
C18	39(1)	48(2)	56(2)	-5(1)	2(1)	-4(1)
C19	42(1)	44(2)	41(1)	-13(1)	5(1)	-5(1)
C20	57(2)	54(2)	45(2)	-20(1)	-4(1)	0(1)

Table 5. Hydrogen coordinates (x10⁴) and isotropic displacement parameters (Å²x10³) for Bispyrazolone.

	x	y	z	U(eq)
H3	10543	3197	5397	59
H4	10235	-140	3762	39
H1	9187	3645	8069	89
H2	8222	2526	7916	102
H3A	8522	1964	6962	84
H10	5538	-260	4457	44
H11	3785	-837	3820	54
H12	4411	-1138	2799	58
H13	10384	4220	7251	86
H14	10720	3650	6289	74
H16A	9774	2761	4073	106
H16B	11077	2191	4030	106
H16C	11427	2944	4311	106
H18A	12692	233	4427	71
H18B	12595	1015	4677	71
H18C	12551	865	3949	71
H19	8505	-213	3009	50
H20	6749	-807	2387	62