chloropropham

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

A colorless crystal of chloropropham with the dimensions of 0.50 mm x 0.60 mm x 1.00 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 41266 reflections to a maximum θ angle of 25.05° (0.84 Å resolution).
The constants for the orthorhombic unit cell are a = 20.9518(9) Å, b = 14.2690(7) Å, c = 22.5186(11) Å, V = 6732.2(5) Å³. They are based upon the refinement of the XYZ-centroids of 9978 reflections above 20.0 I/σ(I) with 2.50° ≤ θ ≤ 24.98°.
Data were corrected for absorption effects with SADABS using the multiscan technique. The ratio of minimum to maximum apparent transmission is 87.4:100. The average residual for symmetry equivalent reflections is R_int = 2.87% and R_σ = 1.82%. XPREP determined the space group to be P b c a, with Z = 24 for the formula unit, C₁₀H₁₂ClNO₂.
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 385 variables converged at R₁ = 4.43% for the observed data and wR₂ = 19.95% for all data. The goodness-of-fit was 1.013. The largest peak on the final difference electron density synthesis was 0.45 e^-/Å³ and the deepest hole was -0.33 e^-/Å³ with an RMS deviation of 0.13 e^-/Å³. On the basis of the final model, the calculated density is 1.265 g/cm³ and F(000) = 2688.

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 chloropropham.

Identification code	chloropropham
Empirical formula	C10 H12 Cl N O2
Formula weight	213.66
Temperature	296(2) K
Wavelength	0.71073 Å
Crystal system	Orthorhombic
Space group	P b c a
Unit cell dimensions	a = 20.9518(9) Å	α = 90°
	b = 14.2690(7) Å	β = 90°
	c = 22.5186(11) Å	γ = 90°
Volume	6732.2(5) Å³
Z	24
Density (calculated)	1.265 Mg/cm³
Absorption coefficient	0.316 mm^-1
F(000)	2688
Crystal size	0.50 x 0.60 x 1.00 mm³
Theta range for data collection	2.50 to 24.98°
Index ranges	-24<=h<=23, -16<=k<=16, -26<=l<=25
Reflections collected	41266
Independent reflections	5935 [R(int) = 0.0287]
Completeness to theta = 24.98°	99.6%
Absorption correction	Multiscan
Max. and min. transmission	0.8582 and 0.7498
Refinement method	Full-matrix least-squares on F²
Data / restraints / parameters	5935 / 0 / 385
Goodness-of-fit on F²	1.013
Final R indices [I>2sigma(I)]	R1 = 0.0443, wR2 = 0.1388
R indices (all data)	R1 = 0.0742, wR2 = 0.1995
Largest diff. peak and hole	0.451 and -0.329

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 chloropropham.

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

	x	y	z	U(eq)
Cl1	1524(1)	2636(1)	745(1)	99(1)
Cl2	157(1)	7210(1)	1397(1)	128(1)
Cl3	4842(1)	5713(1)	-3300(1)	109(1)
O1	2653(1)	3083(1)	-2098(1)	70(1)
O2	2647(1)	2323(1)	-1222(1)	69(1)
O3	2790(1)	5576(1)	-97(1)	65(1)
O4	2204(1)	5685(1)	744(1)	62(1)
O5	1484(1)	4601(2)	-3231(1)	69(1)
O6	1754(1)	5033(1)	-2299(1)	68(1)
N1	1985(1)	3557(2)	-1416(1)	68(1)
N2	1897(1)	6366(2)	-127(1)	59(1)
N3	2484(1)	4989(2)	-3056(1)	55(1)
C1	958(1)	4033(2)	148(1)	70(1)
C2	1392(1)	3322(2)	118(1)	63(1)
C3	1737(1)	3119(2)	-388(1)	59(1)
C4	1644(1)	3671(2)	-885(1)	54(1)
C5	2450(1)	2931(2)	-1545(1)	55(1)
C6	3183(2)	2514(2)	-2316(1)	71(1)
C7	3073(2)	2426(3)	-2972(2)	96(1)
C8	3803(2)	2989(3)	-2151(2)	97(1)
C9	1196(1)	4395(2)	-869(1)	64(1)
C10	858(1)	4563(2)	-361(1)	72(1)
C11	474(2)	7200(2)	682(2)	80(1)
C12	1056(1)	6775(2)	586(1)	62(1)
C13	1305(1)	6759(2)	19(1)	57(1)
C14	2288(1)	5858(2)	226(1)	51(1)
C15	3305(1)	5091(2)	214(1)	65(1)
C16	3875(2)	5203(4)	-185(2)	103(1)
C17	3129(2)	4086(3)	327(2)	97(1)
C18	961(2)	7150(2)	-451(2)	81(1)
C19	385(2)	7566(3)	-341(3)	107(2)
C20	135(2)	7603(3)	222(3)	102(1)
C21	4152(1)	5676(2)	-2872(1)	68(1)
C22	3597(1)	5346(2)	-3116(1)	58(1)
C23	3043(1)	5318(2)	-2774(1)	54(1)
C24	1899(1)	4883(2)	-2814(1)	55(1)
C25	821(2)	4435(3)	-3041(2)	84(1)
C26	768(2)	3450(4)	-2809(2)	123(2)
C27	417(2)	4625(4)	-3579(2)	110(1)
C28	3062(2)	5625(2)	-2187(1)	74(1)
C29	3638(2)	5955(3)	-1963(2)	87(1)
C30	4184(2)	5984(3)	-2293(2)	82(1)

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

Cl1-C2	1.741(3)
Cl2-C11	1.741(4)
Cl3-C21	1.739(3)
O1-C5	1.333(3)
O1-C6	1.461(4)
O2-C5	1.204(3)
O3-C14	1.341(3)
O3-C15	1.459(3)
O4-C14	1.206(3)
O5-C24	1.342(3)
O5-C25	1.472(4)
O6-C24	1.218(3)
N1-C5	1.355(4)
N1-C4	1.402(3)
N2-C14	1.352(3)
N2-C13	1.399(4)
N3-C24	1.349(3)
N3-C23	1.413(3)
C1-C2	1.364(4)
C1-C10	1.389(5)
C2-C3	1.379(4)
C3-C4	1.382(4)
C4-C9	1.395(4)
C6-C7	1.500(5)
C6-C8	1.512(6)
C9-C10	1.369(4)
C11-C12	1.379(4)
C11-C20	1.381(6)
C12-C13	1.380(4)
C13-C18	1.396(4)
C15-C17	1.503(5)
C15-C16	1.504(5)
C18-C19	1.367(6)
C19-C20	1.374(7)
C21-C30	1.377(5)
C21-C22	1.371(4)
C22-C23	1.392(4)
C23-C28	1.394(4)
C25-C26	1.504(6)
C25-C27	1.502(6)
C28-C29	1.390(5)
C29-C30	1.366(5)

C5-O1-C6	117.8(2)
C14-O3-C15	117.5(2)
C24-O5-C25	117.1(2)
C5-N1-C4	128.8(2)
C14-N2-C13	127.9(2)
C24-N3-C23	127.5(2)
C2-C1-C10	117.8(3)
C1-C2-C3	123.1(3)
C1-C2-Cl1	119.0(2)
C3-C2-Cl1	117.9(2)
C4-C3-C2	118.4(3)
C3-C4-C9	119.7(3)
C3-C4-N1	123.6(2)
C9-C4-N1	116.7(2)
O2-C5-O1	124.9(3)
O2-C5-N1	126.3(2)
O1-C5-N1	108.8(2)
O1-C6-C7	105.1(3)
O1-C6-C8	108.7(3)
C7-C6-C8	114.3(3)
C10-C9-C4	120.0(3)
C9-C10-C1	121.0(3)
C12-C11-C20	121.4(4)
C12-C11-Cl2	119.1(3)
C20-C11-Cl2	119.5(3)
C11-C12-C13	119.1(3)
C12-C13-C18	120.0(3)
C12-C13-N2	123.9(2)
C18-C13-N2	116.1(3)
O4-C14-O3	125.2(2)
O4-C14-N2	126.2(2)
O3-C14-N2	108.6(2)
O3-C15-C17	110.7(3)
O3-C15-C16	104.5(3)
C17-C15-C16	113.4(3)
C19-C18-C13	119.5(4)
C20-C19-C18	121.3(4)
C19-C20-C11	118.7(4)
C30-C21-C22	122.1(3)
C30-C21-Cl3	118.4(3)
C22-C21-Cl3	119.5(2)
C21-C22-C23	119.6(3)
C22-C23-C28	119.5(3)
C22-C23-N3	116.9(2)
C28-C23-N3	123.7(3)
O6-C24-O5	123.9(3)
O6-C24-N3	126.2(3)
O5-C24-N3	109.8(2)
O5-C25-C26	108.8(3)
O5-C25-C27	105.6(3)
C26-C25-C27	114.0(4)
C23-C28-C29	118.4(3)
C30-C29-C28	122.7(3)
C29-C30-C21	117.7(3)

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

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
Cl1	133(1)	110(1)	53(1)	15(1)	22(1)	11(1)
Cl2	81(1)	173(1)	130(1)	-63(1)	17(1)	13(1)
Cl3	65(1)	170(1)	91(1)	6(1)	-13(1)	-21(1)
O1	90(1)	68(1)	52(1)	12(1)	21(1)	16(1)
O2	81(1)	76(1)	51(1)	16(1)	10(1)	18(1)
O3	62(1)	78(1)	54(1)	4(1)	3(1)	10(1)
O4	60(1)	77(1)	50(1)	16(1)	0(1)	8(1)
O5	62(1)	88(1)	57(1)	-14(1)	12(1)	-13(1)
O6	87(1)	67(1)	49(1)	-0(1)	14(1)	7(1)
N1	83(2)	74(2)	47(1)	13(1)	9(1)	22(1)
N2	59(1)	66(1)	51(1)	14(1)	-4(1)	2(1)
N3	62(1)	64(1)	40(1)	-4(1)	1(1)	-3(1)
C1	71(2)	71(2)	68(2)	-17(2)	18(2)	-11(2)
C2	71(2)	68(2)	49(2)	-4(1)	8(1)	-11(2)
C3	63(2)	66(2)	48(1)	-0(1)	4(1)	4(1)
C4	56(2)	58(1)	47(1)	-2(1)	1(1)	-0(1)
C5	63(2)	60(2)	43(1)	6(1)	4(1)	-0(1)
C6	92(2)	57(2)	65(2)	10(1)	28(2)	9(2)
C7	140(3)	80(2)	68(2)	-5(2)	38(2)	5(2)
C8	90(3)	100(3)	99(3)	21(2)	17(2)	2(2)
C9	64(2)	66(2)	62(2)	1(1)	1(1)	4(1)
C10	67(2)	68(2)	82(2)	-10(2)	12(2)	5(2)
C11	57(2)	70(2)	114(3)	-24(2)	-9(2)	-0(2)
C12	58(2)	56(2)	73(2)	-9(1)	-11(1)	1(1)
C13	53(2)	49(1)	71(2)	7(1)	-12(1)	-8(1)
C14	51(1)	50(1)	52(1)	4(1)	-4(1)	-3(1)
C15	54(2)	66(2)	73(2)	-2(1)	-4(1)	7(1)
C16	70(2)	128(3)	112(3)	5(3)	18(2)	11(2)
C17	89(2)	67(2)	134(3)	4(2)	-4(2)	12(2)
C18	67(2)	82(2)	94(2)	28(2)	-25(2)	-4(2)
C19	73(2)	96(3)	150(4)	40(3)	-38(3)	2(2)
C20	56(2)	83(2)	168(5)	-2(3)	-19(3)	10(2)
C21	66(2)	73(2)	64(2)	8(1)	-15(1)	-3(2)
C22	66(2)	62(2)	45(1)	2(1)	-10(1)	-1(1)
C23	70(2)	47(1)	46(1)	2(1)	-9(1)	6(1)
C24	72(2)	47(1)	46(1)	1(1)	5(1)	2(1)
C25	64(2)	105(3)	82(2)	-27(2)	28(2)	-14(2)
C26	120(3)	131(4)	117(3)	3(3)	30(3)	-55(3)
C27	63(2)	155(4)	111(3)	-27(3)	4(2)	-2(2)
C28	86(2)	85(2)	50(2)	-12(1)	-9(2)	10(2)
C29	108(3)	95(2)	58(2)	-20(2)	-30(2)	9(2)
C30	84(2)	85(2)	77(2)	-4(2)	-34(2)	2(2)

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

	x	y	z	U(eq)
H1	1885	3937	-1698	81
H2	2027	6460	-484	70
H3	2521	4838	-3424	66
H1A	737	4158	497	84
H3A	2025	2624	-394	71
H6	3166	1891	-2133	86
H7A	2655	2173	-3042	144
H7B	3388	2016	-3141	144
H7C	3105	3033	-3154	144
H8A	3846	3561	-2373	145
H8B	4154	2581	-2242	145
H8C	3803	3128	-1734	145
H9	1128	4762	-1204	76
H10	555	5041	-355	87
H12	1278	6503	900	75
H15	3387	5405	593	77
H16A	3790	4912	-561	155
H16B	4240	4911	-4	155
H16C	3960	5858	-244	155
H17A	2747	4061	561	145
H17B	3470	3782	537	145
H17C	3059	3773	-45	145
H18	1122	7127	-835	97
H19	158	7829	-654	128
H20	-255	7894	293	123
H22	3590	5141	-3508	69
H25	709	4878	-2725	100
H26A	918	3019	-3105	184
H26B	330	3315	-2718	184
H26C	1022	3387	-2457	184
H27A	481	5260	-3706	164
H27B	-24	4533	-3480	164
H27C	536	4204	-3892	164
H28	2698	5610	-1951	88
H29	3651	6165	-1572	105
H30	4565	6204	-2132	98