Electron diffraction, X-ray powder diffraction and pair-distribution-function analyses to determine the crystal structures of Pigment Yellow 213, C₂₃H₂₁N₅O₉

The crystal structure of the nanocrystalline α phase of Pigment Yellow 213 (P.Y. 213) was solved by a combination of single-crystal electron diffraction and X-ray powder diffraction, despite the poor crystallinity of the material. The molecules form an efficient dense packing, which explains the observed insolubility and weather fastness of the pigment. The pair-distribution function (PDF) of the α phase is consistent with the determined crystal structure. The β phase of P.Y. 213 shows even lower crystal quality, so extracting any structural information directly from the diffraction data is not possible. PDF analysis indicates the β phase to have a columnar structure with a similar local structure as the α phase and a domain size in column direction of approximately 4 nm.

Computing details

Data collection: STOE WINXPOW (STOE & CIE GmbH, 2004); cell refinement: TOPAS (A.A.Coelho, 2007); data reduction: DASH (W.I.F.David et al., 2006); program(s) used to solve structure: DASH (W.I.F.David et al., 2006); program(s) used to refine structure: TOPAS (A.A.Coelho, 2007); molecular graphics: Mercury (C.F. Macrae et al., 2008); software used to prepare material for publication: DASH, TOPAS, Mercury.

Figures

(PY213)

Crystal data

C23H21N5O9	Z = 2
Mr = 511.45	F(000) = 532
Triclinic, P1	Dx = 1.513 Mg m^−3
a = 6.9006 (3) Å	Synchrotron radiation, λ = 0.40007 Å
b = 11.8347 (6) Å	µ = 0.03 mm^−1
c = 14.0592 (7) Å	T = 293 K
α = 81.811 (4)°	Particle morphology: no specific habit
β = 81.032 (9)°	yellow
γ = 87.541 (10)°	cylinder, 10 × 0.5 mm
V = 1122.31 (10) Å^3	Specimen preparation: Prepared at 293 K and 0.00 kPa

Data collection

High resolution diffractometer (ID31, ESRF)	Scan method: continuous
Double crystal Si 111 monochromator	2θmin = 1.300°, 2θmax = 18.750°, 2θstep = 0.005°
Data collection mode: transmission

Refinement

Refinement on Inet	1375 parameters
Least-squares matrix: full with fixed elements per cycle	159 restraints
Rp = 0.261	0 constraints
Rwp = 0.175	H-atom parameters not refined
Rexp = 0.130	Weighting scheme based on measured s.u.'s w = 1/σ[Yobs]^2
χ^2 = 1.346
5356 data points	Background function: Chebyshev polynomial with 25 terms
Profile function: modified Thompson-Cox-Hastings pseudo-Voigt (Young, 1993)	Preferred orientation correction: none

Special details

Experimental. specimen was rotated in its plane

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Biso*/Beq
C1	0.6787 (17)	0.6583 (4)	0.9909 (3)	4.5
C2	0.7340 (17)	0.5427 (4)	1.0186 (4)	4.5
C3	0.6212 (17)	0.7362 (4)	1.0593 (4)	4.5
N4	0.706 (3)	0.7056 (5)	0.8965 (4)	4.5
O5	0.798 (4)	0.4785 (8)	0.9554 (6)	4.5
N6	0.705 (2)	0.4938 (4)	1.1119 (3)	4.5
C7	0.5520 (8)	0.8567 (4)	1.0365 (3)	4.5
O8	0.577 (3)	0.6993 (10)	1.1475 (5)	4.5
N9	0.744 (2)	0.6544 (4)	0.8201 (3)	4.5
C10	0.747 (2)	0.3872 (4)	1.1535 (4)	4.5
H11	0.679 (4)	0.5485 (16)	1.1572 (12)	5.4
H12	0.398 (3)	0.8643 (17)	1.0669 (14)	5.4
H13	0.634 (3)	0.913 (2)	1.0690 (15)	5.4
H14	0.567 (4)	0.8874 (16)	0.9592 (14)	5.4
H15	0.750 (5)	0.5719 (17)	0.8303 (13)	5.4
C16	0.766 (2)	0.7065 (4)	0.7267 (3)	4.5
C17	0.8114 (19)	0.2954 (4)	1.1017 (4)	4.5
C18	0.700 (2)	0.3659 (4)	1.2555 (4)	4.5
C19	0.815 (2)	0.6412 (4)	0.6488 (3)	4.5
C20	0.7335 (19)	0.8254 (4)	0.7061 (3)	4.5
C21	0.8401 (18)	0.1854 (4)	1.1509 (3)	4.5
H22	0.837 (4)	0.3078 (16)	1.0279 (15)	5.4
C23	0.7358 (18)	0.2568 (4)	1.3049 (4)	4.5
O24	0.6400 (14)	0.4559 (6)	1.3033 (4)	4.5
C25	0.837 (2)	0.6999 (4)	0.5529 (3)	4.5
C26	0.8430 (19)	0.5215 (4)	0.6615 (3)	4.5
C27	0.755 (2)	0.8834 (4)	0.6104 (3)	4.5
H28	0.699 (4)	0.8716 (17)	0.7625 (12)	5.4
C29	0.8052 (17)	0.1670 (4)	1.2532 (3)	4.5
N30	0.9011 (18)	0.0952 (4)	1.1029 (3)	4.5
H31	0.715 (4)	0.2430 (17)	1.3790 (12)	5.4
C32	0.6596 (8)	0.4738 (4)	1.3998 (4)	4.5
C33	0.8074 (19)	0.8177 (4)	0.5342 (3)	4.5
H34	0.875 (6)	0.6570 (15)	0.4946 (16)	5.4
O35	0.831 (4)	0.4625 (8)	0.5953 (6)	4.5
O36	0.8788 (16)	0.4648 (5)	0.7482 (5)	4.5
C37	0.7094 (18)	1.0008 (4)	0.5907 (4)	4.5
N38	0.8397 (17)	0.0616 (4)	1.3000 (3)	4.5
C39	0.941 (2)	−0.0097 (4)	1.1500 (4)	4.5
H40	0.925 (4)	0.1060 (15)	1.0323 (15)	5.4
H41	0.582 (4)	0.4083 (16)	1.4529 (14)	5.4
H42	0.596 (4)	0.558 (2)	1.4118 (14)	5.4
H43	0.815 (4)	0.4719 (19)	1.4077 (13)	5.4
H44	0.824 (4)	0.8550 (15)	0.4635 (14)	5.4
C45	0.9248 (8)	0.3454 (4)	0.7683 (4)	4.5
O46	0.730 (4)	1.0514 (10)	0.5059 (6)	4.5
O47	0.6300 (15)	1.0623 (5)	0.6617 (5)	4.5
C48	0.9061 (18)	−0.0274 (4)	1.2524 (3)	4.5
H49	0.817 (4)	0.0489 (17)	1.3700 (13)	5.4
O50	0.996 (5)	−0.0883 (7)	1.1008 (6)	4.5
H51	1.080 (4)	0.3328 (17)	0.7741 (13)	5.4
H52	0.839 (4)	0.3105 (15)	0.8371 (12)	5.4
H53	0.891 (4)	0.301 (2)	0.7105 (14)	5.4
C54	0.5988 (8)	1.1843 (4)	0.6474 (4)	4.5
O55	0.918 (4)	−0.1248 (7)	1.3010 (7)	4.5
H56	0.445 (3)	1.2059 (15)	0.6697 (13)	5.4
H57	0.643 (5)	1.2184 (15)	0.5710 (12)	5.4
H58	0.688 (4)	1.2232 (17)	0.6909 (14)	5.4

Geometric parameters (Å, º)

C1—C2	1.420 (8)	C23—H31	1.02 (2)
C1—C3	1.425 (8)	O24—C32	1.429 (8)
C1—N4	1.353 (7)	C25—C33	1.394 (7)
C2—O5	1.27 (1)	C25—H34	1.02 (2)
C2—N6	1.344 (6)	C26—O35	1.25 (1)
C3—C7	1.491 (7)	C26—O36	1.357 (9)
C3—O8	1.250 (9)	C27—C33	1.406 (7)
N4—N9	1.294 (8)	C27—C37	1.409 (8)
N6—C10	1.351 (8)	C29—N38	1.354 (7)
N6—H11	0.96 (2)	N30—C39	1.359 (9)
C7—H12	1.09 (2)	N30—H40	0.97 (2)
C7—H13	1.09 (2)	C32—H41	1.09 (2)
C7—H14	1.09 (2)	C32—H42	1.10 (2)
N9—H15	0.97 (2)	C32—H43	1.09 (3)
N9—C16	1.357 (6)	C33—H44	1.02 (2)
C10—C17	1.412 (8)	O36—C45	1.433 (7)
C10—C18	1.409 (7)	C37—O46	1.246 (9)
C16—C19	1.418 (7)	C37—O47	1.352 (9)
C16—C20	1.411 (7)	N38—C48	1.354 (8)
C17—C21	1.406 (7)	N38—H49	0.96 (2)
C17—H22	1.01 (2)	C39—C48	1.408 (7)
C18—C23	1.407 (7)	C39—O50	1.25 (1)
C18—O24	1.356 (9)	C45—H51	1.09 (2)
C19—C25	1.414 (6)	C45—H52	1.09 (2)
C19—C26	1.412 (7)	C45—H53	1.09 (2)
C20—C27	1.409 (6)	O47—C54	1.440 (7)
C20—H28	1.02 (2)	C48—O55	1.26 (1)
C21—C29	1.408 (6)	C54—H56	1.09 (2)
C21—N30	1.361 (8)	C54—H57	1.09 (2)
C23—C29	1.398 (8)	C54—H58	1.09 (2)
C2—C1—C3	123.0 (4)	C33—C25—H34	117 (1)
C2—C1—N4	121.0 (6)	C19—C26—O35	122.2 (7)
C3—C1—N4	115.3 (5)	C19—C26—O36	120.6 (5)
C1—C2—O5	121.1 (6)	O35—C26—O36	117.1 (7)
C1—C2—N6	121.8 (6)	C20—C27—C33	117.4 (4)
O5—C2—N6	116.8 (6)	C20—C27—C37	121.8 (5)
C1—C3—C7	126.2 (5)	C33—C27—C37	120.6 (5)
C1—C3—O8	119.9 (7)	C21—C29—C23	119.9 (5)
C7—C3—O8	111.6 (8)	C21—C29—N38	119.0 (5)
C1—N4—N9	128.1 (5)	C23—C29—N38	121.0 (4)
C2—N6—C10	131.4 (6)	C21—N30—C39	122.4 (5)
C2—N6—H11	113 (1)	C21—N30—H40	120 (1)
C10—N6—H11	114 (1)	C39—N30—H40	118 (1)
C3—C7—H12	109 (1)	O24—C32—H41	110 (1)
C3—C7—H13	110 (1)	O24—C32—H42	108 (1)
C3—C7—H14	114 (1)	O24—C32—H43	110 (1)
H12—C7—H13	108 (1)	H41—C32—H42	109 (2)
H12—C7—H14	108 (2)	H41—C32—H43	110 (2)
H13—C7—H14	107 (2)	H42—C32—H43	109 (2)
N4—N9—H15	117 (1)	C25—C33—C27	121.0 (4)
N4—N9—C16	125.5 (5)	C25—C33—H44	118 (1)
H15—N9—C16	117 (1)	C27—C33—H44	121 (1)
N6—C10—C17	124.6 (5)	C26—O36—C45	126.0 (6)
N6—C10—C18	116.1 (6)	C27—C37—O46	121.2 (7)
C17—C10—C18	118.9 (4)	C27—C37—O47	121.9 (5)
N9—C16—C19	120.2 (4)	O46—C37—O47	116.7 (8)
N9—C16—C20	120.3 (5)	C29—N38—C48	122.6 (4)
C19—C16—C20	119.4 (4)	C29—N38—H49	119 (1)
C10—C17—C21	120.9 (4)	C48—N38—H49	118 (1)
C10—C17—H22	120 (1)	N30—C39—C48	118.8 (6)
C21—C17—H22	119 (1)	N30—C39—O50	118.6 (6)
C10—C18—C23	120.0 (5)	C48—C39—O50	122.5 (6)
C10—C18—O24	117.6 (5)	O36—C45—H51	110 (1)
C23—C18—O24	122.1 (5)	O36—C45—H52	109 (1)
C16—C19—C25	117.9 (5)	O36—C45—H53	110 (1)
C16—C19—C26	123.8 (4)	H51—C45—H52	109 (2)
C25—C19—C26	118.2 (4)	H51—C45—H53	109 (2)
C16—C20—C27	122.4 (4)	H52—C45—H53	109 (2)
C16—C20—H28	119 (1)	C37—O47—C54	124.2 (5)
C27—C20—H28	119 (1)	N38—C48—C39	118.6 (5)
C17—C21—C29	119.4 (5)	N38—C48—O55	118.6 (7)
C17—C21—N30	122.2 (4)	C39—C48—O55	122.5 (6)
C29—C21—N30	118.3 (4)	O47—C54—H56	110 (1)
C18—C23—C29	120.5 (4)	O47—C54—H57	110 (1)
C18—C23—H31	120 (1)	O47—C54—H58	109 (1)
C29—C23—H31	119 (1)	H56—C54—H57	109 (2)
C18—O24—C32	129.6 (6)	H56—C54—H58	109 (1)
C19—C25—C33	121.8 (5)	H57—C54—H58	108 (2)
C19—C25—H34	121 (1)