Packing-dependent photochromism: the case of photoinduced intramolecular proton transfer in 6-(2′,4′-dinitrobenzyl)-2,2′-bipyridine

Naumov, P.; Ohashi, Y.

doi:10.1107/S0108768104005506

Packing-dependent photochromism: the case of photoinduced intramolecular proton transfer in 6-(2′,4′-dinitrobenzyl)-2,2′-bipyridine

A new photoactive monoclinic polymorph (γ-form) of 6-(2′,4′-dinitrobenzyl)-2,2′-bipyridine was obtained from an acetone–methanol solution. The crystal structure was compared with those of two polymorphs reported previously (photoactive orthorhombic α-form and photoinactive monoclinic β-form) and with structures of related nitrobenzylpyridines to explain the relation between the structure and photochromism. The comparison of the reaction cavities around the reactive pyridyl–benzyl–nitro fragment among the polymorphs and related nitrobenzylpyridines revealed that a crucial factor for photochromic activity is the rotational freedom of the ortho-nitro group in their crystals and its accessibility from the proton–donor and proton–acceptor sites. This is because the ortho-nitro group should rotate around the N—C bond to transfer a proton from the methylene group to the N atom of the pyridine ring.

Keywords: photochromism; polymorphism; proton transfer; nitrobenzylpyridine; reaction cavity.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768104005506/og0001sup1.cif Contains datablocks alpha, gamma, global
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768104005506/og0001alphasup2.hkl Contains datablock alpha
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768104005506/og0001gammasup3.hkl Contains datablock gamma

CCDC references: 241471; 241472

Computing details top

For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SMART (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-II (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

(alpha) alpha form of 6-(2',4'-dinitrobenzyl)-2,2'-bipyridine top

Crystal data top

C₁₇H₁₂N₄O₄	F(000) = 1392
M_r = 336.31	D_x = 1.478 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
a = 14.0059 (1) Å	µ = 0.11 mm⁻¹
b = 5.1399 (1) Å	T = 78 K
c = 41.9853 (6) Å	Block, colorless
V = 3022.48 (8) Å³	0.35 × 0.10 × 0.05 mm
Z = 8

Data collection top

Siemens CCD diffractometer	6678 independent reflections
Radiation source: fine-focus sealed tube	4589 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.080
ω–scan	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: empirical SADABS (Sheldrick, 1996)	h = −15→18
T_min = 0.674, T_max = 1.000	k = −6→6
19857 measured reflections	l = −47→54

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.064	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.179	(Δ/σ)_max = 0.026
S = 1.03	Δρ_max = 1.13 e Å⁻³
6678 reflections	Δρ_min = −0.27 e Å⁻³
452 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0104 (11)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: −1.0 (19)

Crystal data top

C₁₇H₁₂N₄O₄	V = 3022.48 (8) Å³
M_r = 336.31	Z = 8
Orthorhombic, Pna2₁	Mo Kα radiation
a = 14.0059 (1) Å	µ = 0.11 mm⁻¹
b = 5.1399 (1) Å	T = 78 K
c = 41.9853 (6) Å	0.35 × 0.10 × 0.05 mm

Data collection top

Siemens CCD diffractometer	6678 independent reflections
Absorption correction: empirical SADABS (Sheldrick, 1996)	4589 reflections with I > 2σ(I)
T_min = 0.674, T_max = 1.000	R_int = 0.080
19857 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.179	Δρ_max = 1.13 e Å⁻³
S = 1.03	Δρ_min = −0.27 e Å⁻³
6678 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
452 parameters	Absolute structure parameter: −1.0 (19)
1 restraint

Special details top

Experimental. alpha form of 6-(2',4'-dinitrobenzyl)-2,2'-bipyridine

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.3904 (3)	0.4697 (7)	0.76327 (8)	0.0286 (8)
O2	0.4525 (2)	0.0817 (7)	0.75954 (9)	0.0335 (9)
O3	0.3690 (3)	−0.5085 (7)	0.84278 (9)	0.0370 (9)
O4	0.2391 (3)	−0.4489 (8)	0.87018 (8)	0.0400 (10)
O5	0.3681 (2)	0.9674 (7)	0.96382 (8)	0.0257 (7)
O6	0.3048 (2)	0.5852 (7)	0.96808 (9)	0.0316 (9)
O7	0.3880 (3)	−0.0107 (7)	0.88457 (8)	0.0313 (9)
O8	0.5188 (3)	0.0523 (7)	0.85709 (9)	0.0386 (9)
N1	0.2448 (3)	0.1759 (9)	0.71644 (9)	0.0175 (8)
N2	0.3891 (4)	0.2329 (8)	0.76866 (15)	0.0235 (13)
N3	0.2933 (3)	−0.3954 (8)	0.84807 (10)	0.0289 (10)
N4	0.3339 (3)	−0.0839 (7)	0.64269 (9)	0.0218 (8)
N5	0.5117 (3)	0.6786 (9)	1.01057 (9)	0.0179 (8)
N6	0.3683 (4)	0.7339 (8)	0.95974 (13)	0.0182 (12)
N7	0.4645 (3)	0.1024 (7)	0.87945 (10)	0.0262 (9)
N8	0.4164 (3)	0.4221 (7)	1.08432 (9)	0.0205 (8)
C1	0.2465 (3)	0.1251 (8)	0.68501 (10)	0.0169 (9)
C2	0.1879 (4)	0.2471 (8)	0.66291 (16)	0.0159 (15)
H2	0.1919	0.2081	0.6408	0.019*
C3	0.1224 (3)	0.4303 (8)	0.67458 (11)	0.0204 (9)
H3	0.0795	0.5147	0.6604	0.025*
C4	0.1206 (3)	0.4877 (8)	0.70673 (11)	0.0201 (9)
H4	0.0775	0.6144	0.7148	0.024*
C5	0.1821 (3)	0.3584 (9)	0.72688 (10)	0.0177 (9)
C6	0.1849 (3)	0.4290 (9)	0.76193 (11)	0.0225 (10)
H6A	0.1202	0.4869	0.7683	0.027*
H6B	0.2284	0.5792	0.7646	0.027*
C7	0.2166 (4)	0.2147 (10)	0.78485 (14)	0.0189 (12)
C8	0.3100 (3)	0.1193 (8)	0.78638 (10)	0.0161 (9)
C9	0.3353 (3)	−0.0801 (8)	0.80682 (11)	0.0207 (9)
H9	0.3991	−0.1423	0.8076	0.025*
C10	0.2661 (4)	−0.1861 (11)	0.82598 (12)	0.0234 (10)
C11	0.1725 (4)	−0.1019 (10)	0.82508 (11)	0.0266 (11)
H11	0.1254	−0.1773	0.8385	0.032*
C12	0.1491 (3)	0.0973 (9)	0.80387 (11)	0.0248 (10)
H12	0.0846	0.1537	0.8025	0.030*
C13	0.3176 (3)	−0.0769 (8)	0.67411 (10)	0.0168 (9)
C14	0.3624 (4)	−0.2407 (8)	0.69483 (15)	0.0165 (15)
H14	0.3495	−0.2263	0.7170	0.020*
C15	0.4258 (3)	−0.4260 (9)	0.68438 (11)	0.0195 (9)
H15	0.4562	−0.5413	0.6989	0.023*
C16	0.4436 (3)	−0.4385 (9)	0.65218 (11)	0.0193 (9)
H16	0.4861	−0.5645	0.6437	0.023*
C17	0.3977 (4)	−0.2628 (9)	0.63272 (16)	0.0197 (15)
H17	0.4122	−0.2679	0.6106	0.024*
C18	0.5055 (3)	0.6290 (8)	1.04231 (10)	0.0158 (9)
C19	0.5641 (5)	0.7588 (9)	1.06391 (18)	0.0238 (17)
H19	0.5596	0.7201	1.0860	0.029*
C20	0.6286 (3)	0.9427 (9)	1.05353 (11)	0.0228 (10)
H20	0.6685	1.0321	1.0682	0.027*
C21	0.6338 (3)	0.9946 (9)	1.02094 (10)	0.0191 (9)
H21	0.6776	1.1190	1.0128	0.023*
C22	0.5722 (3)	0.8570 (8)	1.00065 (10)	0.0168 (9)
C23	0.5727 (3)	0.9305 (9)	0.96536 (10)	0.0199 (9)
H23A	0.5299	1.0816	0.9622	0.024*
H23B	0.6380	0.9849	0.9593	0.024*
C24	0.5419 (4)	0.7169 (10)	0.94392 (15)	0.0182 (12)
C25	0.4484 (3)	0.6180 (9)	0.94088 (10)	0.0180 (9)
C26	0.4212 (3)	0.4185 (9)	0.92063 (10)	0.0196 (9)
H26	0.3573	0.3566	0.9200	0.023*
C27	0.4917 (4)	0.3127 (11)	0.90115 (11)	0.0204 (10)
C28	0.5863 (4)	0.3984 (10)	0.90207 (11)	0.0259 (10)
H28	0.6333	0.3259	0.8884	0.031*
C29	0.6093 (3)	0.5941 (9)	0.92376 (10)	0.0216 (10)
H29	0.6740	0.6482	0.9251	0.026*
C30	0.4359 (3)	0.4318 (8)	1.05291 (9)	0.0145 (9)
C31	0.3939 (4)	0.2593 (8)	1.02999 (17)	0.0200 (15)
H31	0.4084	0.2709	1.0079	0.024*
C32	0.3298 (3)	0.0713 (9)	1.04196 (11)	0.0214 (10)
H32	0.3001	−0.0492	1.0279	0.026*
C33	0.3101 (3)	0.0636 (9)	1.07481 (12)	0.0224 (10)
H33	0.2670	−0.0612	1.0832	0.027*
C34	0.3552 (4)	0.2427 (9)	1.09487 (18)	0.0233 (17)
H34	0.3417	0.2363	1.1170	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.036 (2)	0.0223 (19)	0.0270 (18)	−0.0014 (16)	0.0015 (15)	0.0025 (15)
O2	0.0202 (18)	0.037 (2)	0.043 (2)	0.0075 (15)	0.0023 (16)	−0.0013 (17)
O3	0.057 (3)	0.025 (2)	0.0285 (19)	0.0065 (19)	−0.0099 (18)	−0.0057 (15)
O4	0.047 (2)	0.045 (2)	0.028 (2)	−0.0183 (19)	−0.0095 (17)	0.0155 (17)
O5	0.0271 (18)	0.0256 (19)	0.0242 (18)	0.0038 (15)	0.0016 (14)	−0.0019 (14)
O6	0.0203 (18)	0.037 (2)	0.038 (2)	−0.0060 (16)	0.0059 (16)	0.0030 (17)
O7	0.050 (2)	0.0214 (19)	0.0228 (18)	−0.0073 (17)	−0.0091 (16)	0.0000 (14)
O8	0.045 (2)	0.040 (2)	0.031 (2)	0.0119 (18)	−0.0044 (17)	−0.0118 (18)
N1	0.0139 (19)	0.0194 (18)	0.019 (2)	0.0037 (18)	0.0001 (15)	−0.0020 (19)
N2	0.020 (2)	0.026 (3)	0.025 (3)	0.0025 (16)	0.000 (2)	0.0022 (16)
N3	0.035 (2)	0.026 (2)	0.025 (2)	−0.004 (2)	−0.008 (2)	0.0003 (18)
N4	0.021 (2)	0.024 (2)	0.020 (2)	0.0008 (17)	−0.0016 (16)	−0.0018 (16)
N5	0.020 (2)	0.0154 (18)	0.018 (2)	0.0031 (18)	−0.0033 (16)	−0.0012 (19)
N6	0.019 (2)	0.023 (3)	0.013 (2)	0.0026 (15)	−0.0063 (19)	0.0050 (14)
N7	0.040 (3)	0.019 (2)	0.020 (2)	0.0074 (19)	−0.0108 (19)	0.0002 (17)
N8	0.0188 (19)	0.020 (2)	0.023 (2)	0.0033 (16)	−0.0033 (16)	0.0013 (15)
C1	0.012 (2)	0.017 (2)	0.021 (2)	−0.0008 (17)	0.0024 (16)	0.0012 (17)
C2	0.020 (3)	0.019 (4)	0.009 (3)	0.0025 (16)	0.001 (2)	0.0014 (14)
C3	0.018 (2)	0.024 (2)	0.019 (2)	0.0010 (19)	−0.0046 (18)	0.0055 (18)
C4	0.018 (2)	0.019 (2)	0.024 (2)	0.0014 (18)	0.0000 (18)	−0.0004 (18)
C5	0.016 (2)	0.022 (3)	0.016 (2)	0.0023 (19)	0.0026 (17)	−0.0025 (18)
C6	0.019 (2)	0.020 (2)	0.028 (3)	0.0042 (18)	−0.0029 (19)	−0.0001 (19)
C7	0.024 (3)	0.024 (2)	0.008 (2)	0.007 (2)	−0.0089 (19)	0.0012 (19)
C8	0.013 (2)	0.018 (2)	0.017 (2)	−0.0003 (17)	−0.0005 (16)	−0.0047 (17)
C9	0.021 (2)	0.014 (2)	0.027 (2)	−0.0019 (19)	−0.0050 (19)	−0.0026 (18)
C10	0.033 (3)	0.019 (2)	0.018 (3)	−0.006 (2)	−0.009 (2)	−0.003 (2)
C11	0.024 (2)	0.033 (3)	0.023 (3)	−0.013 (2)	0.0003 (19)	−0.0021 (19)
C12	0.019 (2)	0.037 (3)	0.019 (2)	0.002 (2)	−0.0008 (18)	−0.005 (2)
C13	0.013 (2)	0.017 (2)	0.020 (2)	0.0008 (17)	0.0009 (17)	−0.0028 (17)
C14	0.015 (3)	0.022 (4)	0.013 (3)	−0.0030 (16)	0.001 (2)	0.0031 (15)
C15	0.020 (2)	0.015 (2)	0.023 (2)	−0.0030 (19)	−0.0049 (18)	0.0042 (17)
C16	0.017 (2)	0.016 (2)	0.024 (2)	−0.0013 (17)	0.0029 (18)	−0.0067 (18)
C17	0.021 (3)	0.027 (4)	0.012 (3)	0.0040 (18)	0.007 (2)	−0.0020 (16)
C18	0.0127 (19)	0.019 (2)	0.016 (2)	0.0043 (17)	−0.0023 (16)	−0.0012 (17)
C19	0.024 (3)	0.028 (5)	0.020 (4)	0.0004 (19)	−0.003 (3)	0.0018 (18)
C20	0.018 (2)	0.026 (2)	0.025 (2)	−0.002 (2)	−0.0066 (19)	−0.0011 (19)
C21	0.012 (2)	0.022 (2)	0.023 (2)	−0.0043 (17)	−0.0002 (17)	−0.0015 (18)
C22	0.010 (2)	0.018 (2)	0.022 (2)	0.0029 (17)	−0.0028 (17)	−0.0036 (18)
C23	0.021 (2)	0.025 (2)	0.013 (2)	−0.0080 (19)	0.0000 (17)	0.0031 (18)
C24	0.012 (2)	0.025 (3)	0.018 (3)	−0.0011 (19)	0.0013 (19)	0.012 (2)
C25	0.018 (2)	0.022 (2)	0.015 (2)	0.0000 (18)	−0.0016 (17)	0.0011 (17)
C26	0.021 (2)	0.022 (2)	0.016 (2)	−0.0034 (19)	−0.0056 (18)	0.0046 (18)
C27	0.031 (3)	0.015 (2)	0.015 (2)	0.003 (2)	−0.003 (2)	0.000 (2)
C28	0.029 (3)	0.028 (3)	0.021 (3)	0.003 (2)	0.001 (2)	0.0004 (18)
C29	0.018 (2)	0.030 (3)	0.017 (2)	0.002 (2)	−0.0009 (17)	0.0018 (19)
C30	0.017 (2)	0.017 (2)	0.010 (2)	0.0059 (17)	−0.0036 (16)	−0.0028 (16)
C31	0.021 (3)	0.017 (4)	0.022 (3)	0.0039 (17)	0.000 (2)	0.0015 (16)
C32	0.018 (2)	0.021 (2)	0.026 (2)	0.0015 (19)	0.0028 (19)	−0.0002 (19)
C33	0.021 (2)	0.018 (2)	0.028 (2)	−0.0011 (19)	0.0030 (19)	0.0067 (19)
C34	0.020 (3)	0.026 (4)	0.025 (4)	0.0069 (18)	−0.007 (3)	0.0032 (17)

Geometric parameters (Å, º) top

O1—N2	1.238 (5)	C9—H9	0.9500
O1—C6	2.887 (6)	C10—C11	1.382 (7)
O1—N1	3.210 (5)	C11—C12	1.396 (7)
O2—N2	1.241 (6)	C11—H11	0.9500
O3—N3	1.230 (5)	C12—H12	0.9500
O4—N3	1.230 (6)	C13—C14	1.364 (7)
O5—N6	1.212 (5)	C14—C15	1.374 (7)
O5—C23	2.873 (6)	C14—H14	0.9500
O5—N5	3.178 (5)	C15—C16	1.376 (7)
O6—N6	1.224 (6)	C15—H15	0.9500
O7—N7	1.238 (5)	C16—C17	1.377 (8)
O8—N7	1.235 (6)	C16—H16	0.9500
N1—C1	1.345 (6)	C17—H17	0.9500
N1—C5	1.358 (6)	C18—C19	1.393 (8)
N1—C6	2.459 (6)	C18—C30	1.475 (6)
N2—C8	1.456 (7)	C19—C20	1.378 (8)
N3—C10	1.470 (7)	C19—H19	0.9500
N4—C13	1.340 (6)	C20—C21	1.396 (7)
N4—C17	1.349 (6)	C20—H20	0.9500
N5—C22	1.316 (6)	C21—C22	1.403 (6)
N5—C18	1.360 (6)	C21—H21	0.9500
N5—C23	2.451 (6)	C22—C23	1.529 (6)
N6—C25	1.496 (7)	C23—C24	1.484 (7)
N7—C27	1.464 (7)	C23—H23A	0.9900
N8—C34	1.334 (7)	C23—H23B	0.9900
N8—C30	1.348 (5)	C24—C25	1.411 (7)
C1—C2	1.389 (7)	C24—C29	1.417 (7)
C1—C13	1.509 (6)	C25—C26	1.386 (6)
C2—C3	1.403 (7)	C26—C27	1.393 (7)
C2—H2	0.9500	C26—H26	0.9500
C3—C4	1.382 (6)	C27—C28	1.396 (7)
C3—H3	0.9500	C28—C29	1.395 (7)
C4—C5	1.378 (6)	C28—H28	0.9500
C4—H4	0.9500	C29—H29	0.9500
C5—C6	1.516 (6)	C30—C31	1.435 (7)
C6—C7	1.529 (7)	C31—C32	1.411 (7)
C6—H6A	0.9900	C31—H31	0.9500
C6—H6B	0.9900	C32—C33	1.407 (7)
C7—C12	1.377 (8)	C32—H32	0.9500
C7—C8	1.399 (7)	C33—C34	1.398 (8)
C8—C9	1.383 (6)	C33—H33	0.9500
C9—C10	1.372 (7)	C34—H34	0.9500

N2—O1—C6	85.3 (3)	C11—C12—H12	119.0
N2—O1—N1	68.9 (3)	N4—C13—C14	122.2 (4)
C6—O1—N1	47.20 (12)	N4—C13—C1	115.5 (4)
N6—O5—C23	86.3 (3)	C14—C13—C1	122.4 (4)
N6—O5—N5	67.9 (3)	C13—C14—C15	121.5 (6)
C23—O5—N5	47.46 (12)	C13—C14—H14	119.3
C1—N1—C5	117.5 (4)	C15—C14—H14	119.3
C1—N1—C6	150.5 (3)	C16—C15—C14	117.6 (5)
C5—N1—C6	33.2 (2)	C16—C15—H15	121.2
C1—N1—O1	132.9 (3)	C14—C15—H15	121.2
C5—N1—O1	83.6 (3)	C15—C16—C17	117.9 (4)
C6—N1—O1	59.49 (15)	C15—C16—H16	121.1
O1—N2—O2	123.3 (5)	C17—C16—H16	121.1
O1—N2—C8	119.9 (5)	N4—C17—C16	124.9 (6)
O2—N2—C8	116.8 (4)	N4—C17—H17	117.6
O4—N3—O3	124.2 (4)	C16—C17—H17	117.6
O4—N3—C10	118.7 (4)	N5—C18—C19	120.7 (5)
O3—N3—C10	117.1 (4)	N5—C18—C30	117.8 (4)
C13—N4—C17	115.9 (4)	C19—C18—C30	121.5 (4)
C22—N5—C18	118.8 (4)	C20—C19—C18	120.6 (6)
C22—N5—C23	33.2 (2)	C20—C19—H19	119.7
C18—N5—C23	151.7 (3)	C18—C19—H19	119.7
C22—N5—O5	83.5 (3)	C19—C20—C21	118.4 (5)
C18—N5—O5	130.7 (3)	C19—C20—H20	120.8
C23—N5—O5	59.72 (15)	C21—C20—H20	120.8
O5—N6—O6	125.1 (5)	C20—C21—C22	117.8 (4)
O5—N6—C25	118.1 (5)	C20—C21—H21	121.1
O6—N6—C25	116.6 (4)	C22—C21—H21	121.1
O8—N7—O7	124.6 (4)	N5—C22—C21	123.7 (4)
O8—N7—C27	117.8 (4)	N5—C22—C23	118.8 (4)
O7—N7—C27	117.6 (4)	C21—C22—C23	117.5 (4)
C34—N8—C30	118.8 (5)	C24—C23—C22	113.8 (4)
N1—C1—C2	123.9 (4)	C24—C23—N5	88.7 (3)
N1—C1—C13	116.3 (4)	C22—C23—N5	28.1 (2)
C2—C1—C13	119.9 (4)	C24—C23—O5	75.2 (3)
C1—C2—C3	117.1 (5)	C22—C23—O5	92.0 (3)
C1—C2—H2	121.4	N5—C23—O5	72.82 (16)
C3—C2—H2	121.4	C24—C23—H23A	108.8
C4—C3—C2	119.8 (5)	C22—C23—H23A	108.8
C4—C3—H3	120.1	N5—C23—H23A	107.9
C2—C3—H3	120.1	O5—C23—H23A	48.8
C5—C4—C3	119.0 (4)	C24—C23—H23B	108.8
C5—C4—H4	120.5	C22—C23—H23B	108.8
C3—C4—H4	120.5	N5—C23—H23B	132.1
N1—C5—C4	122.7 (4)	O5—C23—H23B	153.9
N1—C5—C6	117.5 (4)	H23A—C23—H23B	107.7
C4—C5—C6	119.7 (4)	C25—C24—C29	113.8 (5)
C5—C6—C7	116.5 (4)	C25—C24—C23	126.3 (5)
C5—C6—N1	29.3 (2)	C29—C24—C23	119.9 (4)
C7—C6—N1	90.5 (3)	C26—C25—C24	125.3 (4)
C5—C6—O1	93.5 (3)	C26—C25—N6	114.4 (4)
C7—C6—O1	75.5 (3)	C24—C25—N6	120.3 (4)
N1—C6—O1	73.30 (16)	C25—C26—C27	117.0 (4)
C5—C6—H6A	108.2	C25—C26—H26	121.5
C7—C6—H6A	108.2	C27—C26—H26	121.5
N1—C6—H6A	133.0	C26—C27—C28	122.2 (5)
O1—C6—H6A	152.2	C26—C27—N7	118.0 (5)
C5—C6—H6B	108.2	C28—C27—N7	119.8 (4)
C7—C6—H6B	108.2	C29—C28—C27	117.7 (4)
N1—C6—H6B	106.9	C29—C28—H28	121.2
O1—C6—H6B	47.7	C27—C28—H28	121.2
H6A—C6—H6B	107.3	C28—C29—C24	123.9 (5)
C12—C7—C8	117.5 (5)	C28—C29—H29	118.1
C12—C7—C6	118.8 (4)	C24—C29—H29	118.1
C8—C7—C6	123.6 (5)	N8—C30—C31	123.3 (4)
C9—C8—C7	121.8 (4)	N8—C30—C18	117.1 (4)
C9—C8—N2	114.8 (4)	C31—C30—C18	119.6 (4)
C7—C8—N2	123.2 (5)	C32—C31—C30	116.5 (6)
C10—C9—C8	118.5 (4)	C32—C31—H31	121.8
C10—C9—H9	120.7	C30—C31—H31	121.8
C8—C9—H9	120.7	C33—C32—C31	119.5 (5)
C9—C10—C11	122.0 (5)	C33—C32—H32	120.2
C9—C10—N3	118.5 (5)	C31—C32—H32	120.2
C11—C10—N3	119.4 (5)	C34—C33—C32	118.9 (5)
C10—C11—C12	118.0 (5)	C34—C33—H33	120.5
C10—C11—H11	121.0	C32—C33—H33	120.5
C12—C11—H11	121.0	N8—C34—C33	123.0 (6)
C7—C12—C11	122.0 (4)	N8—C34—H34	118.5
C7—C12—H12	119.0	C33—C34—H34	118.5

(gamma) gamma form of 6-(2',4'-dinitrobenzyl)-2,2'-bipyridine top

Crystal data top

C₁₇H₁₂N₄O₄	Z = 4
M_r = 336.31	F(000) = 696
Monoclinic, P2₁/c	D_x = 1.489 Mg m⁻³
a = 20.8360 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.2746 (1) Å	µ = 0.11 mm⁻¹
c = 14.0971 (2) Å	T = 78 K
β = 104.457 (1)°	Plate, colorless
V = 1500.23 (4) Å³	0.40 × 0.25 × 0.05 mm

Data collection top

Siemens CCD diffractometer	3445 independent reflections
Radiation source: fine-focus sealed tube	2934 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω–scan	θ_max = 27.6°, θ_min = 1.0°
Absorption correction: empirical SADABS (Sheldrick, 1996)	h = −27→20
T_min = 0.975, T_max = 1.000	k = −6→6
10094 measured reflections	l = −15→18

Refinement top

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
3445 reflections	(Δ/σ)_max = 0.001
228 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

C₁₇H₁₂N₄O₄	V = 1500.23 (4) Å³
M_r = 336.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 20.8360 (3) Å	µ = 0.11 mm⁻¹
b = 5.2746 (1) Å	T = 78 K
c = 14.0971 (2) Å	0.40 × 0.25 × 0.05 mm
β = 104.457 (1)°

Data collection top

Siemens CCD diffractometer	3445 independent reflections
Absorption correction: empirical SADABS (Sheldrick, 1996)	2934 reflections with I > 2σ(I)
T_min = 0.975, T_max = 1.000	R_int = 0.048
10094 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.40 e Å⁻³
3445 reflections	Δρ_min = −0.52 e Å⁻³
228 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.81007 (5)	1.6028 (2)	0.22845 (8)	0.0218 (3)
O2	0.81247 (5)	1.9763 (2)	0.29337 (8)	0.0234 (3)
O3	0.96491 (6)	2.5705 (2)	0.20348 (10)	0.0318 (3)
O4	1.01989 (6)	2.4242 (3)	0.10337 (10)	0.0408 (4)
N1	0.69744 (6)	1.8705 (2)	0.08211 (8)	0.0146 (3)
N2	0.82012 (6)	1.8321 (2)	0.22873 (8)	0.0161 (3)
N3	0.97264 (7)	2.4211 (3)	0.14122 (10)	0.0254 (3)
N4	0.56525 (6)	2.1212 (2)	0.17702 (9)	0.0187 (3)
C1	0.63491 (7)	1.9080 (3)	0.08969 (10)	0.0143 (3)
C2	0.58149 (7)	1.7649 (3)	0.03705 (10)	0.0176 (3)
H2	0.5378	1.7983	0.0426	0.021*
C3	0.59349 (7)	1.5736 (3)	−0.02329 (11)	0.0196 (3)
H3	0.5580	1.4724	−0.0595	0.023*
C4	0.65760 (7)	1.5307 (3)	−0.03051 (10)	0.0178 (3)
H4	0.6670	1.3999	−0.0714	0.021*
C5	0.70826 (7)	1.6842 (3)	0.02375 (10)	0.0148 (3)
C6	0.77891 (7)	1.6300 (3)	0.01972 (11)	0.0179 (3)
C7	0.82868 (7)	1.8387 (3)	0.05481 (10)	0.0161 (3)
C8	0.84580 (6)	1.9399 (3)	0.14952 (10)	0.0142 (3)
C9	0.89044 (7)	2.1354 (3)	0.17801 (10)	0.0153 (3)
H9	0.8986	2.2071	0.2417	0.018*
C10	0.92269 (7)	2.2221 (3)	0.11014 (11)	0.0189 (3)
C11	0.90986 (8)	2.1284 (3)	0.01600 (11)	0.0255 (4)
H11	0.9334	2.1893	−0.0290	0.031*
C12	0.86145 (7)	1.9421 (3)	−0.01124 (11)	0.0225 (3)
H12	0.8503	1.8834	−0.0770	0.027*
C13	0.62558 (7)	2.1097 (3)	0.15857 (10)	0.0146 (3)
C14	0.67691 (7)	2.2751 (3)	0.20159 (10)	0.0165 (3)
H14	0.7189	2.2621	0.1869	0.020*
C15	0.66582 (7)	2.4580 (3)	0.26585 (11)	0.0185 (3)
H15	0.6999	2.5732	0.2958	0.022*
C16	0.60399 (7)	2.4704 (3)	0.28583 (11)	0.0197 (3)
H16	0.5949	2.5933	0.3300	0.024*
C17	0.55597 (7)	2.2994 (3)	0.23989 (11)	0.0205 (3)
H17	0.5137	2.3090	0.2538	0.025*
H61	0.7935	1.4749	0.0555	0.028 (5)*
H62	0.7788	1.5799	−0.0468	0.042 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0242 (6)	0.0199 (5)	0.0247 (6)	−0.0020 (4)	0.0126 (4)	0.0049 (4)
O2	0.0306 (6)	0.0296 (6)	0.0143 (5)	0.0049 (4)	0.0138 (4)	−0.0018 (4)
O3	0.0247 (6)	0.0194 (6)	0.0464 (8)	0.0002 (4)	−0.0002 (5)	−0.0049 (5)
O4	0.0328 (7)	0.0639 (9)	0.0285 (7)	−0.0261 (6)	0.0128 (5)	0.0033 (6)
N1	0.0163 (6)	0.0164 (5)	0.0139 (6)	−0.0007 (4)	0.0091 (4)	0.0006 (4)
N2	0.0158 (6)	0.0220 (6)	0.0130 (6)	0.0018 (4)	0.0086 (4)	0.0021 (4)
N3	0.0225 (7)	0.0266 (7)	0.0247 (7)	−0.0065 (5)	0.0017 (5)	0.0076 (5)
N4	0.0175 (6)	0.0199 (6)	0.0229 (6)	0.0010 (4)	0.0129 (5)	0.0003 (5)
C1	0.0156 (6)	0.0156 (6)	0.0143 (6)	−0.0001 (5)	0.0085 (5)	0.0034 (5)
C2	0.0157 (6)	0.0210 (7)	0.0180 (7)	−0.0020 (5)	0.0081 (5)	0.0027 (5)
C3	0.0191 (7)	0.0222 (7)	0.0177 (7)	−0.0051 (5)	0.0052 (5)	−0.0006 (5)
C4	0.0221 (7)	0.0180 (7)	0.0152 (7)	−0.0028 (5)	0.0083 (5)	−0.0011 (5)
C5	0.0176 (6)	0.0167 (6)	0.0128 (6)	−0.0010 (5)	0.0089 (5)	0.0009 (5)
C6	0.0188 (7)	0.0201 (7)	0.0183 (7)	−0.0015 (5)	0.0110 (5)	−0.0063 (5)
C7	0.0153 (6)	0.0198 (7)	0.0162 (7)	−0.0001 (5)	0.0097 (5)	−0.0027 (5)
C8	0.0158 (6)	0.0178 (6)	0.0124 (6)	0.0024 (5)	0.0100 (5)	0.0023 (5)
C9	0.0165 (6)	0.0159 (6)	0.0143 (6)	0.0021 (5)	0.0054 (5)	0.0002 (5)
C10	0.0167 (7)	0.0201 (7)	0.0202 (7)	−0.0035 (5)	0.0052 (5)	0.0026 (5)
C11	0.0232 (8)	0.0381 (9)	0.0190 (7)	−0.0085 (6)	0.0124 (6)	0.0027 (6)
C12	0.0220 (7)	0.0354 (8)	0.0139 (7)	−0.0057 (6)	0.0117 (5)	−0.0042 (6)
C13	0.0160 (6)	0.0155 (6)	0.0152 (6)	0.0009 (5)	0.0093 (5)	0.0039 (5)
C14	0.0173 (6)	0.0181 (7)	0.0171 (7)	−0.0001 (5)	0.0100 (5)	0.0027 (5)
C15	0.0194 (7)	0.0192 (7)	0.0192 (7)	−0.0004 (5)	0.0089 (5)	0.0007 (5)
C16	0.0245 (7)	0.0196 (7)	0.0188 (7)	0.0038 (5)	0.0125 (5)	−0.0003 (5)
C17	0.0193 (7)	0.0220 (7)	0.0252 (8)	0.0024 (5)	0.0151 (5)	0.0013 (6)

Geometric parameters (Å, º) top

O1—N2	1.2275 (16)	C6—H61	0.9691
O2—N2	1.2276 (16)	C6—H62	0.9736
O3—N3	1.2197 (19)	C7—C12	1.3956 (19)
O4—N3	1.231 (2)	C7—C8	1.3989 (19)
N1—C5	1.3363 (17)	C8—C9	1.3793 (19)
N1—C1	1.3482 (17)	C9—C10	1.3775 (19)
N2—C8	1.4680 (16)	C9—H9	0.9500
N3—C10	1.4660 (18)	C10—C11	1.378 (2)
N4—C17	1.3386 (19)	C11—C12	1.392 (2)
N4—C13	1.3471 (18)	C11—H11	0.9500
C1—C2	1.3953 (19)	C12—H12	0.9500
C1—C13	1.485 (2)	C13—C14	1.3962 (19)
C2—C3	1.382 (2)	C14—C15	1.3819 (19)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.383 (2)	C15—C16	1.387 (2)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.3971 (18)	C16—C17	1.382 (2)
C4—H4	0.9500	C16—H16	0.9500
C5—C6	1.5145 (19)	C17—H17	0.9500
C6—C7	1.5086 (19)

C5—N1—C1	118.13 (12)	C8—C7—C6	125.59 (13)
O1—N2—O2	124.01 (12)	C9—C8—C7	123.77 (13)
O1—N2—C8	118.27 (11)	C9—C8—N2	114.54 (12)
O2—N2—C8	117.66 (12)	C7—C8—N2	121.58 (12)
O3—N3—O4	124.52 (14)	C10—C9—C8	117.15 (12)
O3—N3—C10	117.78 (14)	C10—C9—H9	121.4
O4—N3—C10	117.70 (14)	C8—C9—H9	121.4
C17—N4—C13	117.11 (12)	C9—C10—C11	122.59 (13)
N1—C1—C2	122.48 (13)	C9—C10—N3	117.60 (13)
N1—C1—C13	116.34 (12)	C11—C10—N3	119.81 (13)
C2—C1—C13	121.18 (13)	C10—C11—C12	118.15 (14)
C3—C2—C1	118.65 (13)	C10—C11—H11	120.9
C3—C2—H2	120.7	C12—C11—H11	120.9
C1—C2—H2	120.7	C11—C12—C7	122.24 (13)
C2—C3—C4	119.40 (13)	C11—C12—H12	118.9
C2—C3—H3	120.3	C7—C12—H12	118.9
C4—C3—H3	120.3	N4—C13—C14	122.57 (13)
C3—C4—C5	118.45 (13)	N4—C13—C1	116.07 (12)
C3—C4—H4	120.8	C14—C13—C1	121.36 (12)
C5—C4—H4	120.8	C15—C14—C13	119.06 (13)
N1—C5—C4	122.87 (13)	C15—C14—H14	120.5
N1—C5—C6	118.47 (12)	C13—C14—H14	120.5
C4—C5—C6	118.60 (12)	C14—C15—C16	118.80 (13)
C7—C6—C5	116.42 (11)	C14—C15—H15	120.6
C7—C6—H61	110.2	C16—C15—H15	120.6
C5—C6—H61	108.7	C17—C16—C15	118.33 (13)
C7—C6—H62	110.5	C17—C16—H16	120.8
C5—C6—H62	108.5	C15—C16—H16	120.8
H61—C6—H62	101.4	N4—C17—C16	124.12 (13)
C12—C7—C8	115.90 (13)	N4—C17—H17	117.9
C12—C7—C6	118.51 (12)	C16—C17—H17	117.9

Experimental details

	(alpha)	(gamma)
Crystal data
Chemical formula	C₁₇H₁₂N₄O₄	C₁₇H₁₂N₄O₄
M_r	336.31	336.31
Crystal system, space group	Orthorhombic, Pna2₁	Monoclinic, P2₁/c
Temperature (K)	78	78
a, b, c (Å)	14.0059 (1), 5.1399 (1), 41.9853 (6)	20.8360 (3), 5.2746 (1), 14.0971 (2)
α, β, γ (°)	90, 90, 90	90, 104.457 (1), 90
V (Å³)	3022.48 (8)	1500.23 (4)
Z	8	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.11	0.11
Crystal size (mm)	0.35 × 0.10 × 0.05	0.40 × 0.25 × 0.05

Data collection
Diffractometer	Siemens CCD diffractometer	Siemens CCD diffractometer
Absorption correction	Empirical SADABS (Sheldrick, 1996)	Empirical SADABS (Sheldrick, 1996)
T_min, T_max	0.674, 1.000	0.975, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	19857, 6678, 4589	10094, 3445, 2934
R_int	0.080	0.048
(sin θ/λ)_max (Å⁻¹)	0.649	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.179, 1.03	0.049, 0.153, 1.11
No. of reflections	6678	3445
No. of parameters	452	228
No. of restraints	1	0
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.13, −0.27	0.40, −0.52
Absolute structure	Flack H D (1983), Acta Cryst. A39, 876-881	?
Absolute structure parameter	−1.0 (19)	?

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-II (Johnson, 1976).

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