Salts of maleic and fumaric acids with organic polyamines: comparison of isomeric acids as building blocks in supramolecular chemistry

Maleic acid and fumaric acid both readily form adducts with organic diamines: maleic acid usually forms 2:1 adducts with bases, while fumaric acid usually forms 1:1 adducts, and the supramolecular stuctures within the two series are not simply related. The 1:2 adducts formed by 1,2-bis(4-pyridyl)ethane and by 4,4′-bipyridyl, respectively, with maleic acid, compounds (1) and (2), are salts [{(diamine)H₂}²⁺]·[(C₄H₃O₄)⁻]₂ in which the cations lie across a centre of inversion and a twofold rotation axis, respectively. The ions are linked by N—H...O hydrogen bonds into three-ion aggregates, which are further linked by C—H...O hydrogen bonds into two- and three-dimensional arrays, respectively. In the fumarate salts formed by 2,2′-dipyridyl­amine (1:1) and 1,4-diazabi­cyclo[2.2.2]octane (1:2), compounds (3) and (4), the ionic components are linked into molecular ladders. The 1:1 adduct of 4,4′-bipyridyl and fumaric acid, compound (5), contains two neutral components, both of which lie across centres of inversion; these components are linked into chains by a single O—H...N hydrogen bond and thence into sheets by C—H...O hydrogen bonds. The corresponding adduct formed by 1,4-diazabicyclo[2.2.2]­octane, compound (6), is a salt that again contains chains linked into sheets by C—H...O hydrogen bonds. In the 1:1 adducts, compounds (7), (8) and (10), that are formed between 1,2-bis(4-pyridyl)ethane, 4,4′-trimethylenedipyridine and hexamethylene­tetramine, respectively, with fumaric acid, and in the 1:2 adduct, compound (9), of 2,2′-dipyridylamine and maleic acid, the chains that are generated by the hard hydrogen bonds are linked by C—H...O hydrogen bonds to form, in each case, a single three-dimensional framework. In the 1:1 adduct, compound (11), of 2,2′-bipyridyl and fumaric acid the hydrogen bonds generate two interwoven three-dimensional frameworks.

Computing details

For all compounds, data collection: Kappa-CCD server software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997a) and PRPKAPPA (Ferguson, 1999).

(I) 1,2-Bis(4-pyridyl)ethane–maleic acid (1/2)

Crystal data

C12H14N2·2(C4H3O4)	Z = 1
Mr = 416.38	F(000) = 218
Triclinic, P1	Dx = 1.411 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7958 (3) Å	Cell parameters from 2236 reflections
b = 9.4489 (6) Å	θ = 3.1–27.6°
c = 9.6031 (7) Å	µ = 0.11 mm^−1
α = 86.787 (3)°	T = 150 K
β = 73.010 (3)°	Plate, colourless
γ = 76.986 (3)°	0.28 × 0.26 × 0.06 mm
V = 490.01 (5) Å^3

Data collection

Kappa-CCD diffractometer	2236 independent reflections
Radiation source: fine-focus sealed X-ray tube	1676 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
φ scans, and ω scans with κ offsets	θmax = 27.6°, θmin = 3.1°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −7→7
Tmin = 0.968, Tmax = 0.991	k = −12→12
5489 measured reflections	l = −11→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0493P)^2 + 0.1138P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
2236 reflections	Δρmax = 0.23 e Å^−3
137 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.061 (15)

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

	x	y	z	Uiso*/Ueq
N11	1.1352 (2)	0.10358 (13)	0.38056 (13)	0.0275 (3)
C12	1.1105 (3)	0.17890 (16)	0.49995 (16)	0.0294 (3)
C13	0.9007 (3)	0.28411 (16)	0.55604 (17)	0.0304 (4)
C14	0.7132 (3)	0.31199 (16)	0.48884 (17)	0.0295 (3)
C15	0.7440 (3)	0.22991 (17)	0.36647 (17)	0.0314 (4)
C16	0.9573 (3)	0.12584 (16)	0.31364 (17)	0.0299 (3)
C17	0.4877 (3)	0.43109 (17)	0.54376 (19)	0.0369 (4)
O1	1.5634 (2)	−0.07837 (12)	0.27416 (12)	0.0358 (3)
O2	1.3666 (2)	−0.13642 (14)	0.12722 (13)	0.0426 (3)
O3	1.4601 (2)	−0.30049 (16)	−0.08059 (14)	0.0519 (4)
O4	1.7916 (3)	−0.44128 (15)	−0.22358 (14)	0.0532 (4)
C1	1.5605 (3)	−0.14619 (17)	0.16573 (16)	0.0299 (3)
C2	1.8005 (3)	−0.23971 (18)	0.08343 (17)	0.0316 (4)
C3	1.8548 (3)	−0.32622 (17)	−0.03199 (17)	0.0324 (4)
C4	1.6967 (3)	−0.36002 (19)	−0.11790 (18)	0.0371 (4)
H11	1.2718	0.0377	0.3451	0.033*
H12	1.2386	0.1596	0.5461	0.035*
H13	0.8841	0.3376	0.6406	0.036*
H15	0.6177	0.2457	0.3192	0.038*
H16	0.9783	0.0699	0.2299	0.036*
H17A	0.4644	0.4515	0.6476	0.044*
H17B	0.3401	0.3992	0.5365	0.044*
H3	1.4250	−0.2454	−0.0082	0.078*
H2	1.9364	−0.2373	0.1189	0.038*
H3A	2.0237	−0.3748	−0.0653	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0260 (6)	0.0258 (6)	0.0295 (7)	−0.0027 (5)	−0.0076 (5)	−0.0040 (5)
C12	0.0308 (8)	0.0297 (8)	0.0304 (8)	−0.0070 (6)	−0.0124 (6)	−0.0014 (6)
C13	0.0346 (8)	0.0281 (8)	0.0290 (8)	−0.0073 (6)	−0.0086 (6)	−0.0055 (6)
C14	0.0281 (8)	0.0250 (7)	0.0329 (8)	−0.0056 (6)	−0.0052 (6)	0.0012 (6)
C15	0.0298 (8)	0.0337 (8)	0.0333 (8)	−0.0065 (6)	−0.0131 (6)	0.0008 (7)
C16	0.0334 (8)	0.0305 (8)	0.0275 (8)	−0.0074 (6)	−0.0109 (6)	−0.0022 (6)
C17	0.0290 (8)	0.0316 (8)	0.0421 (9)	−0.0023 (6)	−0.0012 (7)	0.0001 (7)
O1	0.0331 (6)	0.0406 (6)	0.0340 (6)	−0.0014 (5)	−0.0129 (5)	−0.0118 (5)
O2	0.0271 (6)	0.0614 (8)	0.0390 (7)	0.0010 (5)	−0.0135 (5)	−0.0173 (6)
O3	0.0418 (7)	0.0754 (10)	0.0431 (8)	−0.0071 (7)	−0.0190 (6)	−0.0237 (7)
O4	0.0643 (9)	0.0530 (8)	0.0419 (7)	−0.0125 (7)	−0.0108 (6)	−0.0218 (6)
C1	0.0280 (7)	0.0337 (8)	0.0278 (8)	−0.0041 (6)	−0.0089 (6)	−0.0034 (6)
C2	0.0267 (7)	0.0380 (8)	0.0300 (8)	−0.0028 (6)	−0.0105 (6)	−0.0041 (7)
C3	0.0331 (8)	0.0327 (8)	0.0293 (8)	−0.0032 (6)	−0.0083 (6)	−0.0030 (6)
C4	0.0456 (10)	0.0370 (9)	0.0295 (8)	−0.0102 (7)	−0.0102 (7)	−0.0050 (7)

Geometric parameters (Å, º)

N11—C12	1.3384 (18)	C17—H17A	0.99
N11—C16	1.3397 (19)	C17—H17B	0.99
N11—H11	0.88	O1—C1	1.2589 (18)
C12—C13	1.375 (2)	O2—C1	1.2650 (18)
C12—H12	0.95	O3—C4	1.309 (2)
C13—C14	1.389 (2)	O3—H3	0.84
C13—H13	0.95	O4—C4	1.222 (2)
C14—C15	1.390 (2)	C1—C2	1.491 (2)
C14—C17	1.501 (2)	C2—C3	1.333 (2)
C15—C16	1.376 (2)	C2—H2	0.95
C15—H15	0.95	C3—C4	1.492 (2)
C16—H16	0.95	C3—H3A	0.95
C17—C17^i	1.521 (3)
C12—N11—C16	121.71 (13)	C14—C17—H17A	109.4
C12—N11—H11	119.1	C17^i—C17—H17A	109.4
C16—N11—H11	119.1	C14—C17—H17B	109.4
N11—C12—C13	120.27 (13)	C17^i—C17—H17B	109.4
N11—C12—H12	119.9	H17A—C17—H17B	108.0
C13—C12—H12	119.9	C4—O3—H3	109.5
C12—C13—C14	119.87 (14)	O1—C1—O2	122.60 (15)
C12—C13—H13	120.1	O1—C1—C2	116.22 (13)
C14—C13—H13	120.1	O2—C1—C2	121.18 (14)
C13—C14—C15	118.13 (14)	C3—C2—C1	130.29 (14)
C13—C14—C17	120.87 (14)	C3—C2—H2	114.9
C15—C14—C17	120.96 (14)	C1—C2—H2	114.9
C16—C15—C14	120.14 (14)	C2—C3—C4	131.27 (15)
C16—C15—H15	119.9	C2—C3—H3A	114.4
C14—C15—H15	119.9	C4—C3—H3A	114.4
N11—C16—C15	119.87 (14)	O4—C4—O3	121.09 (15)
N11—C16—H16	120.1	O4—C4—C3	119.25 (16)
C15—C16—H16	120.1	O3—C4—C3	119.65 (14)
C14—C17—C17^i	110.95 (16)
C16—N11—C12—C13	−1.1 (2)	C13—C14—C17—C17^i	97.2 (2)
N11—C12—C13—C14	0.2 (2)	C15—C14—C17—C17^i	−80.6 (2)
C12—C13—C14—C15	0.8 (2)	O1—C1—C2—C3	178.12 (16)
C12—C13—C14—C17	−177.07 (14)	O2—C1—C2—C3	−2.0 (3)
C13—C14—C15—C16	−0.9 (2)	C1—C2—C3—C4	−0.3 (3)
C17—C14—C15—C16	176.90 (14)	C2—C3—C4—O4	178.01 (17)
C12—N11—C16—C15	0.9 (2)	C2—C3—C4—O3	−0.8 (3)
C14—C15—C16—N11	0.1 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.84	1.61	2.453 (2)	178
N11—H11···O1	0.88	1.76	2.637 (2)	173
C12—H12···O1^ii	0.95	2.34	3.246 (2)	158
C13—H13···O4^iii	0.95	2.40	3.272 (2)	153
C15—H15···O3^iv	0.95	2.47	3.274 (2)	143

Symmetry codes: (ii) −x+3, −y, −z+1; (iii) x−1, y+1, z+1; (iv) −x+2, −y, −z.

(II) 4,4'-Bipyridyl–maleic acid (1/2)

Crystal data

C10H10N2·2(C4H3O4)	F(000) = 808
Mr = 388.33	Dx = 1.548 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1888 reflections
a = 24.0370 (16) Å	θ = 3.5–27.5°
b = 6.7434 (6) Å	µ = 0.12 mm^−1
c = 11.4388 (10) Å	T = 150 K
β = 115.996 (4)°	Plate, colourless
V = 1666.5 (2) Å^3	0.40 × 0.30 × 0.07 mm
Z = 4

Data collection

Kappa-CCD diffractometer	1888 independent reflections
Radiation source: fine-focus sealed X-ray tube	1421 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.072
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.5°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −30→30
Tmin = 0.877, Tmax = 0.995	k = −8→8
6178 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0462P)^2 + 1.0798P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1888 reflections	Δρmax = 0.24 e Å^−3
129 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.016 (3)

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

	x	y	z	Uiso*/Ueq
N11	0.44588 (6)	0.2678 (2)	0.48738 (13)	0.0246 (4)
C12	0.40590 (8)	0.3044 (3)	0.36396 (16)	0.0257 (4)
C13	0.42605 (8)	0.3131 (3)	0.26812 (17)	0.0248 (4)
C14	0.48857 (7)	0.2796 (3)	0.30091 (15)	0.0218 (4)
C15	0.52904 (8)	0.2441 (3)	0.43110 (16)	0.0239 (4)
C16	0.50642 (8)	0.2395 (3)	0.52289 (16)	0.0247 (4)
O1	0.40810 (5)	0.2096 (2)	0.66811 (11)	0.0303 (4)
O2	0.32715 (6)	0.1011 (2)	0.49363 (11)	0.0316 (4)
O3	0.22399 (5)	−0.0399 (2)	0.43713 (11)	0.0282 (3)
O4	0.16824 (5)	−0.1073 (2)	0.54247 (12)	0.0318 (4)
C1	0.35393 (8)	0.1391 (3)	0.61348 (16)	0.0243 (4)
C2	0.32241 (8)	0.1016 (3)	0.69871 (16)	0.0269 (4)
C3	0.26661 (8)	0.0247 (3)	0.66884 (16)	0.0271 (4)
C4	0.21652 (8)	−0.0464 (3)	0.54370 (16)	0.0246 (4)
H2	0.3455	0.1379	0.7873	0.032*
H3	0.2585	0.0110	0.4533	0.042*
H3A	0.2571	0.0132	0.7409	0.033*
H11	0.4321	0.2621	0.5470	0.030*
H12	0.3634	0.3245	0.3421	0.031*
H13	0.3977	0.3414	0.1808	0.030*
H15	0.5719	0.2231	0.4562	0.029*
H16	0.5338	0.2162	0.6116	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0259 (7)	0.0279 (9)	0.0250 (7)	−0.0033 (6)	0.0158 (6)	−0.0023 (6)
C12	0.0223 (8)	0.0302 (10)	0.0266 (9)	−0.0002 (7)	0.0127 (7)	−0.0033 (7)
C13	0.0205 (8)	0.0307 (10)	0.0236 (8)	0.0006 (7)	0.0101 (7)	−0.0007 (7)
C14	0.0217 (8)	0.0227 (9)	0.0226 (8)	−0.0014 (6)	0.0113 (7)	−0.0006 (7)
C15	0.0221 (8)	0.0265 (10)	0.0240 (8)	−0.0018 (7)	0.0110 (7)	−0.0008 (7)
C16	0.0248 (8)	0.0270 (10)	0.0221 (8)	−0.0031 (7)	0.0101 (7)	0.0008 (7)
O1	0.0223 (6)	0.0444 (9)	0.0256 (6)	−0.0067 (5)	0.0118 (5)	−0.0028 (6)
O2	0.0305 (7)	0.0463 (9)	0.0216 (6)	−0.0096 (6)	0.0146 (5)	−0.0052 (6)
O3	0.0252 (6)	0.0388 (8)	0.0216 (6)	−0.0065 (6)	0.0111 (5)	−0.0024 (5)
O4	0.0242 (6)	0.0413 (9)	0.0315 (7)	−0.0056 (6)	0.0137 (5)	−0.0016 (6)
C1	0.0237 (8)	0.0267 (10)	0.0239 (8)	−0.0001 (7)	0.0117 (7)	0.0010 (7)
C2	0.0253 (8)	0.0369 (11)	0.0196 (8)	−0.0010 (7)	0.0109 (7)	−0.0026 (7)
C3	0.0260 (9)	0.0374 (11)	0.0214 (8)	−0.0006 (7)	0.0136 (7)	0.0013 (8)
C4	0.0230 (8)	0.0258 (10)	0.0258 (8)	0.0003 (7)	0.0115 (7)	0.0011 (7)

Geometric parameters (Å, º)

N11—C12	1.337 (2)	C16—H16	0.95
N11—C16	1.342 (2)	O1—C1	1.264 (2)
N11—H11	0.88	O2—C1	1.259 (2)
C12—C13	1.380 (2)	O3—C4	1.309 (2)
C12—H12	0.95	O3—H3	0.84
C13—C14	1.398 (2)	O4—C4	1.225 (2)
C13—H13	0.95	C1—C2	1.495 (2)
C14—C15	1.397 (2)	C2—C3	1.335 (2)
C14—C14^i	1.490 (3)	C2—H2	0.95
C15—C16	1.378 (2)	C3—C4	1.489 (2)
C15—H15	0.95	C3—H3A	0.95
C12—N11—C16	121.86 (14)	N11—C16—H16	119.9
C12—N11—H11	119.1	C15—C16—H16	119.9
C16—N11—H11	119.1	C4—O3—H3	109.5
N11—C12—C13	120.43 (15)	O2—C1—O1	122.61 (15)
N11—C12—H12	119.8	O2—C1—C2	120.80 (15)
C13—C12—H12	119.8	O1—C1—C2	116.58 (15)
C12—C13—C14	119.34 (16)	C3—C2—C1	129.64 (16)
C12—C13—H13	120.3	C3—C2—H2	115.2
C14—C13—H13	120.3	C1—C2—H2	115.2
C15—C14—C13	118.54 (14)	C2—C3—C4	132.01 (15)
C15—C14—C14^i	120.68 (17)	C2—C3—H3A	114.0
C13—C14—C14^i	120.77 (18)	C4—C3—H3A	114.0
C16—C15—C14	119.54 (15)	O4—C4—O3	121.09 (16)
C16—C15—H15	120.2	O4—C4—C3	118.79 (15)
C14—C15—H15	120.2	O3—C4—C3	120.10 (14)
N11—C16—C15	120.25 (16)
C16—N11—C12—C13	0.4 (3)	C14—C15—C16—N11	0.4 (3)
N11—C12—C13—C14	1.1 (3)	O2—C1—C2—C3	1.7 (3)
C12—C13—C14—C15	−1.8 (3)	O1—C1—C2—C3	−178.2 (2)
C12—C13—C14—C14^i	177.47 (13)	C1—C2—C3—C4	−1.2 (4)
C13—C14—C15—C16	1.1 (3)	C2—C3—C4—O4	−178.3 (2)
C14^i—C14—C15—C16	−178.24 (13)	C2—C3—C4—O3	0.5 (3)
C12—N11—C16—C15	−1.2 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O1	0.88	1.75	2.627 (2)	171
O3—H3···O2	0.84	1.62	2.463 (2)	176
C13—H13···O4^ii	0.95	2.37	3.315 (2)	175
C15—H15···O4^iii	0.95	2.38	3.176 (2)	142
C16—H16···O1^iv	0.95	2.28	3.223 (2)	170

Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1/2, y+1/2, z; (iv) −x+1, y, −z+3/2.

(III) 2,2'-Dipyridylamine–fumaric acid (1/1)

Crystal data

C10H10N3·C4H3O4	Z = 2
Mr = 287.27	F(000) = 300
Triclinic, P1	Dx = 1.442 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0021 (4) Å	Cell parameters from 3020 reflections
b = 8.7178 (4) Å	θ = 2.7–27.4°
c = 10.8497 (4) Å	µ = 0.11 mm^−1
α = 106.257 (3)°	T = 150 K
β = 109.127 (3)°	Plate, colourless
γ = 98.662 (2)°	0.30 × 0.14 × 0.08 mm
V = 661.55 (6) Å^3

Data collection

Kappa-CCD diffractometer	3020 independent reflections
Radiation source: fine-focus sealed X-ray tube	2028 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
φ scans, and ω scans with κ offsets	θmax = 27.4°, θmin = 2.7°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −10→10
Tmin = 0.889, Tmax = 0.989	k = −11→11
9473 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0572P)^2 + 0.037P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3020 reflections	Δρmax = 0.31 e Å^−3
192 parameters	Δρmin = −0.28 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (5)

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

	x	y	z	Uiso*/Ueq
N1	0.2045 (2)	0.04419 (19)	0.38397 (14)	0.0258 (4)
N11	0.2293 (2)	0.11496 (18)	0.61610 (14)	0.0248 (4)
C12	0.1994 (2)	0.1525 (2)	0.49968 (17)	0.0231 (4)
C13	0.1608 (2)	0.3044 (2)	0.50035 (18)	0.0273 (4)
C14	0.1550 (2)	0.4093 (2)	0.61770 (18)	0.0292 (4)
C15	0.1845 (3)	0.3661 (2)	0.73693 (18)	0.0299 (4)
C16	0.2209 (2)	0.2181 (2)	0.73292 (17)	0.0281 (4)
N21	0.3048 (2)	−0.15076 (19)	0.47897 (14)	0.0271 (4)
C22	0.2474 (2)	−0.1072 (2)	0.36691 (17)	0.0238 (4)
C23	0.2272 (3)	−0.2054 (2)	0.23362 (18)	0.0291 (4)
C24	0.2714 (3)	−0.3534 (2)	0.21863 (19)	0.0337 (5)
C25	0.3338 (3)	−0.4009 (2)	0.33454 (19)	0.0345 (5)
C26	0.3465 (3)	−0.2971 (2)	0.46046 (19)	0.0312 (4)
O11	0.82663 (17)	0.23026 (17)	0.09227 (12)	0.0298 (3)
O12	0.77187 (17)	0.11595 (17)	0.24051 (12)	0.0301 (3)
O21	0.12720 (16)	0.16171 (16)	0.16684 (12)	0.0266 (3)
O22	0.18362 (17)	0.25878 (17)	0.01065 (12)	0.0295 (3)
C1	0.7239 (2)	0.1800 (2)	0.15265 (16)	0.0217 (4)
C2	0.5398 (2)	0.2119 (2)	0.10509 (16)	0.0230 (4)
C3	0.4115 (2)	0.1612 (2)	0.14658 (16)	0.0229 (4)
C4	0.2273 (2)	0.1972 (2)	0.10124 (16)	0.0220 (4)
H1	0.1770	0.0738	0.3101	0.031*
H11A	0.2552	0.0205	0.6166	0.030*
H13	0.1390	0.3339	0.4197	0.033*
H14	0.1307	0.5129	0.6188	0.035*
H15	0.1790	0.4386	0.8183	0.036*
H16	0.2408	0.1861	0.8123	0.034*
H23	0.1842	−0.1704	0.1562	0.035*
H24	0.2596	−0.4233	0.1299	0.040*
H25	0.3666	−0.5025	0.3266	0.041*
H26	0.3871	−0.3305	0.5390	0.037*
H11	0.9287	0.2101	0.1222	0.045*
H2	0.5143	0.2710	0.0427	0.028*
H3	0.4359	0.0997	0.2072	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0305 (8)	0.0307 (9)	0.0218 (7)	0.0115 (7)	0.0127 (6)	0.0129 (6)
N11	0.0282 (8)	0.0252 (8)	0.0233 (7)	0.0078 (6)	0.0109 (6)	0.0107 (6)
C12	0.0204 (8)	0.0262 (10)	0.0233 (8)	0.0045 (7)	0.0092 (7)	0.0095 (7)
C13	0.0281 (9)	0.0294 (10)	0.0277 (9)	0.0090 (8)	0.0114 (7)	0.0136 (8)
C14	0.0274 (10)	0.0270 (10)	0.0333 (9)	0.0089 (8)	0.0109 (8)	0.0108 (8)
C15	0.0305 (10)	0.0302 (10)	0.0272 (9)	0.0076 (8)	0.0131 (8)	0.0055 (8)
C16	0.0296 (10)	0.0322 (10)	0.0230 (8)	0.0064 (8)	0.0120 (7)	0.0095 (8)
N21	0.0305 (8)	0.0264 (8)	0.0261 (7)	0.0082 (7)	0.0104 (6)	0.0122 (6)
C22	0.0206 (8)	0.0248 (9)	0.0261 (9)	0.0050 (7)	0.0095 (7)	0.0094 (7)
C23	0.0297 (10)	0.0339 (11)	0.0238 (9)	0.0070 (8)	0.0110 (8)	0.0105 (8)
C24	0.0377 (11)	0.0321 (11)	0.0306 (10)	0.0100 (9)	0.0158 (8)	0.0066 (8)
C25	0.0377 (11)	0.0276 (10)	0.0398 (11)	0.0120 (9)	0.0159 (9)	0.0115 (8)
C26	0.0349 (11)	0.0290 (10)	0.0321 (9)	0.0095 (8)	0.0118 (8)	0.0151 (8)
O11	0.0236 (7)	0.0442 (8)	0.0349 (7)	0.0160 (6)	0.0162 (6)	0.0241 (6)
O12	0.0283 (7)	0.0414 (8)	0.0317 (7)	0.0154 (6)	0.0151 (6)	0.0220 (6)
O21	0.0254 (7)	0.0370 (8)	0.0284 (6)	0.0137 (6)	0.0163 (5)	0.0177 (6)
O22	0.0282 (7)	0.0433 (8)	0.0269 (6)	0.0159 (6)	0.0138 (5)	0.0197 (6)
C1	0.0227 (9)	0.0230 (9)	0.0212 (8)	0.0063 (7)	0.0103 (7)	0.0079 (7)
C2	0.0240 (9)	0.0258 (9)	0.0226 (8)	0.0093 (7)	0.0102 (7)	0.0105 (7)
C3	0.0232 (9)	0.0275 (9)	0.0220 (8)	0.0105 (7)	0.0105 (7)	0.0104 (7)
C4	0.0221 (9)	0.0236 (9)	0.0204 (8)	0.0063 (7)	0.0094 (7)	0.0063 (7)

Geometric parameters (Å, º)

N1—C12	1.360 (2)	C23—C24	1.369 (3)
N1—C22	1.391 (2)	C23—H23	0.95
N1—H1	0.88	C24—C25	1.395 (3)
N11—C12	1.348 (2)	C24—H24	0.95
N11—C16	1.362 (2)	C25—C26	1.373 (3)
N11—H11A	0.88	C25—H25	0.95
C12—C13	1.403 (2)	C26—H26	0.95
C13—C14	1.364 (3)	O11—C1	1.305 (2)
C13—H13	0.95	O11—H11	0.84
C14—C15	1.404 (3)	O12—C1	1.2206 (19)
C14—H14	0.95	O21—C4	1.291 (2)
C15—C16	1.357 (3)	O22—C4	1.226 (2)
C15—H15	0.95	C1—C2	1.490 (2)
C16—H16	0.95	C2—C3	1.316 (3)
N21—C22	1.334 (2)	C2—H2	0.95
N21—C26	1.345 (2)	C3—C4	1.505 (2)
C22—C23	1.401 (2)	C3—H3	0.95
C12—N1—C22	128.59 (15)	C24—C23—C22	117.82 (17)
C12—N1—H1	115.7	C24—C23—H23	121.1
C22—N1—H1	115.7	C22—C23—H23	121.1
C12—N11—C16	122.32 (16)	C23—C24—C25	119.57 (18)
C12—N11—H11A	118.8	C23—C24—H24	120.2
C16—N11—H11A	118.8	C25—C24—H24	120.2
N11—C12—N1	120.49 (16)	C26—C25—C24	118.24 (18)
N11—C12—C13	118.47 (16)	C26—C25—H25	120.9
N1—C12—C13	121.03 (15)	C24—C25—H25	120.9
C14—C13—C12	119.49 (16)	N21—C26—C25	123.74 (17)
C14—C13—H13	120.3	N21—C26—H26	118.1
C12—C13—H13	120.3	C25—C26—H26	118.1
C13—C14—C15	120.82 (18)	C1—O11—H11	109.5
C13—C14—H14	119.6	O12—C1—O11	124.58 (15)
C15—C14—H14	119.6	O12—C1—C2	122.71 (15)
C16—C15—C14	118.30 (17)	O11—C1—C2	112.70 (14)
C16—C15—H15	120.8	C3—C2—C1	122.27 (16)
C14—C15—H15	120.8	C3—C2—H2	118.9
C15—C16—N11	120.58 (16)	C1—C2—H2	118.9
C15—C16—H16	119.7	C2—C3—C4	122.20 (16)
N11—C16—H16	119.7	C2—C3—H3	118.9
C22—N21—C26	116.90 (15)	C4—C3—H3	118.9
N21—C22—N1	117.81 (15)	O22—C4—O21	124.94 (15)
N21—C22—C23	123.72 (17)	O22—C4—C3	120.35 (15)
N1—C22—C23	118.47 (15)	O21—C4—C3	114.69 (14)
C16—N11—C12—N1	−178.33 (16)	C12—N1—C22—C23	174.19 (17)
C16—N11—C12—C13	0.9 (3)	N21—C22—C23—C24	−0.9 (3)
C22—N1—C12—N11	−3.7 (3)	N1—C22—C23—C24	179.46 (17)
C22—N1—C12—C13	177.14 (16)	C22—C23—C24—C25	0.1 (3)
N11—C12—C13—C14	0.1 (3)	C23—C24—C25—C26	0.8 (3)
N1—C12—C13—C14	179.35 (17)	C22—N21—C26—C25	0.3 (3)
C12—C13—C14—C15	−0.9 (3)	C24—C25—C26—N21	−1.0 (3)
C13—C14—C15—C16	0.7 (3)	O12—C1—C2—C3	−5.6 (3)
C14—C15—C16—N11	0.3 (3)	O11—C1—C2—C3	175.57 (17)
C12—N11—C16—C15	−1.1 (3)	C1—C2—C3—C4	178.45 (14)
C26—N21—C22—N1	−179.64 (16)	C2—C3—C4—O22	8.7 (3)
C26—N21—C22—C23	0.7 (3)	C2—C3—C4—O21	−169.92 (17)
C12—N1—C22—N21	−5.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O21^i	0.84	1.66	2.495 (2)	175
N1—H1···O21	0.88	1.87	2.751 (2)	174
N11—H11A···N21	0.88	1.98	2.651 (2)	132
N11—H11A···O12^ii	0.88	2.24	2.869 (2)	128
C16—H16···O22^iii	0.95	2.28	3.052 (2)	138
C16—H16···O12^ii	0.95	2.51	3.013 (2)	113

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z+1; (iii) x, y, z+1.

(IV) 1,4-Diazabicyclo[2.2.2]octane–fumaric acid (1/2)

Crystal data

C6H14N2·2(C4H3O4)	F(000) = 728
Mr = 344.32	Dx = 1.546 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3025 reflections
a = 20.1118 (9) Å	θ = 3.3–27.5°
b = 6.4737 (4) Å	µ = 0.13 mm^−1
c = 12.5409 (7) Å	T = 150 K
β = 115.070 (2)°	Needle, colourless
V = 1478.97 (14) Å^3	0.30 × 0.10 × 0.08 mm
Z = 4

Data collection

Kappa-CCD diffractometer	1691 independent reflections
Radiation source: fine-focus sealed X-ray tube	1182 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.10
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −26→25
Tmin = 0.956, Tmax = 0.995	k = −6→8
5858 measured reflections	l = −16→16

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.156	w = 1/[σ^2(Fo^2) + (0.0784P)^2 + 0.3794P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1691 reflections	Δρmax = 0.30 e Å^−3
119 parameters	Δρmin = −0.41 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.006 (2)

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

	x	y	z	Uiso*/Ueq
O1	0.14661 (8)	0.5421 (3)	0.01355 (11)	0.0270 (4)
O2	0.08393 (7)	0.5825 (3)	0.12067 (12)	0.0300 (4)
O3	0.34575 (7)	0.5197 (2)	0.43342 (11)	0.0258 (4)
O4	0.27761 (7)	0.5042 (2)	0.53483 (11)	0.0261 (4)
C1	0.14224 (10)	0.5559 (3)	0.11558 (16)	0.0215 (5)
C2	0.21349 (10)	0.5365 (3)	0.22280 (16)	0.0207 (5)
C3	0.21624 (10)	0.5492 (3)	0.32972 (16)	0.0200 (5)
C4	0.28518 (10)	0.5237 (3)	0.44005 (16)	0.0202 (5)
N1	0.44903 (8)	0.4534 (3)	0.64853 (13)	0.0212 (4)
C5	0.42802 (11)	0.3234 (4)	0.72790 (16)	0.0322 (6)
C6	0.46413 (12)	0.6685 (4)	0.69444 (17)	0.0336 (6)
C7	0.51633 (11)	0.3668 (4)	0.64430 (17)	0.0300 (6)
H1	0.1907	0.5264	0.0255	0.041*
H2	0.2575	0.5146	0.2137	0.028 (6)*
H3	0.1719	0.5761	0.3370	0.027 (6)*
H1A	0.4110	0.4539	0.5732	0.025*
H5A	0.3794	0.3561	0.7183	0.037 (7)*
H5B	0.4294	0.1804	0.7097	0.033 (7)*
H6A	0.4674	0.7589	0.6362	0.039 (7)*
H6B	0.4251	0.7159	0.7130	0.034 (6)*
H7A	0.5048	0.2418	0.5995	0.032 (6)*
H7B	0.5367	0.4625	0.6082	0.040 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0217 (7)	0.0451 (10)	0.0129 (7)	−0.0005 (6)	0.0059 (5)	−0.0011 (6)
O2	0.0175 (7)	0.0502 (11)	0.0213 (7)	0.0006 (6)	0.0074 (6)	0.0036 (7)
O3	0.0161 (7)	0.0440 (10)	0.0159 (7)	−0.0002 (6)	0.0054 (5)	0.0022 (6)
O4	0.0214 (7)	0.0439 (10)	0.0127 (7)	0.0012 (6)	0.0069 (5)	0.0012 (6)
C1	0.0194 (9)	0.0289 (12)	0.0149 (9)	−0.0031 (8)	0.0060 (7)	0.0007 (8)
C2	0.0152 (9)	0.0289 (12)	0.0172 (9)	0.0006 (7)	0.0061 (7)	0.0004 (8)
C3	0.0152 (9)	0.0274 (12)	0.0161 (9)	0.0011 (7)	0.0053 (7)	−0.0001 (8)
C4	0.0186 (9)	0.0261 (11)	0.0144 (9)	0.0007 (8)	0.0055 (7)	−0.0011 (8)
N1	0.0146 (8)	0.0338 (11)	0.0127 (8)	0.0000 (7)	0.0032 (6)	0.0008 (7)
C5	0.0234 (10)	0.0510 (17)	0.0182 (10)	−0.0116 (10)	0.0051 (8)	0.0051 (10)
C6	0.0358 (13)	0.0331 (14)	0.0226 (11)	0.0065 (10)	0.0036 (9)	0.0018 (9)
C7	0.0207 (10)	0.0510 (16)	0.0158 (9)	0.0079 (9)	0.0052 (8)	−0.0047 (10)

Geometric parameters (Å, º)

O1—C1	1.322 (2)	N1—C5	1.495 (3)
O1—H1	0.84	N1—H1A	0.93
O2—C1	1.213 (2)	C5—C7^i	1.543 (3)
O3—C4	1.256 (2)	C5—H5A	0.96
O4—C4	1.267 (2)	C5—H5B	0.96
C1—C2	1.498 (2)	C6—C6^i	1.523 (4)
C2—C3	1.321 (3)	C6—H6A	0.96
C2—H2	0.95	C6—H6B	0.96
C3—C4	1.496 (2)	C7—C5^i	1.543 (3)
C3—H3	0.95	C7—H7A	0.96
N1—C7	1.487 (2)	C7—H7B	0.96
N1—C6	1.488 (3)
C1—O1—H1	109.5	N1—C5—C7^i	107.68 (16)
O2—C1—O1	121.49 (17)	N1—C5—H5A	110.7
O2—C1—C2	122.88 (17)	C7^i—C5—H5A	110.1
O1—C1—C2	115.63 (16)	N1—C5—H5B	109.9
C3—C2—C1	121.24 (17)	C7^i—C5—H5B	110.1
C3—C2—H2	119.4	H5A—C5—H5B	108.4
C1—C2—H2	119.4	N1—C6—C6^i	108.24 (10)
C2—C3—C4	123.75 (17)	N1—C6—H6A	110.2
C2—C3—H3	118.1	C6^i—C6—H6A	110.6
C4—C3—H3	118.1	N1—C6—H6B	109.9
O3—C4—O4	124.44 (17)	C6^i—C6—H6B	109.4
O3—C4—C3	119.07 (17)	H6A—C6—H6B	108.4
O4—C4—C3	116.48 (17)	N1—C7—C5^i	107.60 (15)
C7—N1—C6	109.10 (16)	N1—C7—H7A	110.0
C7—N1—C5	109.24 (17)	C5^i—C7—H7A	110.2
C6—N1—C5	109.78 (17)	N1—C7—H7B	110.6
C7—N1—H1A	109.6	C5^i—C7—H7B	110.0
C6—N1—H1A	109.6	H7A—C7—H7B	108.5
C5—N1—H1A	109.6
O2—C1—C2—C3	−0.5 (3)	C7—N1—C6—C6^i	−48.6 (3)
O1—C1—C2—C3	179.5 (2)	C5—N1—C6—C6^i	71.1 (3)
C1—C2—C3—C4	177.76 (19)	C6—N1—C7—C5^i	72.6 (2)
C2—C3—C4—O3	10.8 (3)	C5—N1—C7—C5^i	−47.4 (2)
C2—C3—C4—O4	−168.1 (2)	N1—C6—C6^i—N1^i	−19.7 (2)
C7—N1—C5—C7^i	72.9 (2)	N1—C5—C7^i—N1^i	−21.2 (3)
C6—N1—C5—C7^i	−46.7 (2)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4^ii	0.84	1.71	2.551 (2)	174
N1—H1A···O3	0.93	1.74	2.651 (2)	166

Symmetry code: (ii) x, −y+1, z−1/2.

(V) 4,4'-Bipyridyl–fumaric acid (1/1)

Crystal data

C10H8N2·C4H4O4	Z = 1
Mr = 272.26	F(000) = 142
Triclinic, P1	Dx = 1.475 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.8040 (2) Å	Cell parameters from 1376 reflections
b = 8.8743 (5) Å	θ = 2.7–27.5°
c = 9.8764 (6) Å	µ = 0.11 mm^−1
α = 109.757 (2)°	T = 150 K
β = 97.246 (3)°	Block, colourless
γ = 96.813 (3)°	0.30 × 0.28 × 0.25 mm
V = 306.59 (3) Å^3

Data collection

Kappa-CCD diffractometer	1376 independent reflections
Radiation source: fine-focus sealed X-ray tube	1105 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −4→4
Tmin = 0.945, Tmax = 0.978	k = −11→10
3277 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0681P)^2 + 0.0475P] where P = (Fo^2 + 2Fc^2)/3
1376 reflections	(Δ/σ)max < 0.001
92 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.0669 (3)	0.65709 (14)	0.24935 (12)	0.0256 (3)
C12	0.0527 (4)	0.49682 (18)	0.21575 (15)	0.0278 (4)
C13	0.2181 (4)	0.43131 (18)	0.31066 (15)	0.0270 (3)
C14	0.4094 (3)	0.53270 (16)	0.44697 (14)	0.0219 (3)
C15	0.4234 (4)	0.69908 (18)	0.48087 (16)	0.0281 (3)
C16	0.2489 (4)	0.75511 (18)	0.38030 (17)	0.0301 (4)
O1	−0.2741 (3)	0.78815 (12)	0.08487 (11)	0.0299 (3)
O2	−0.0576 (3)	1.02003 (12)	0.27466 (11)	0.0351 (3)
C1	−0.2323 (4)	0.94605 (17)	0.15273 (15)	0.0243 (3)
C2	−0.4145 (3)	1.03429 (16)	0.06782 (15)	0.0245 (3)
H12	−0.0760	0.4251	0.1230	0.033*
H13	0.2006	0.3168	0.2825	0.032*
H15	0.5520	0.7738	0.5724	0.034*
H16	0.2594	0.8690	0.4059	0.036*
H1	−0.1607	0.7471	0.1382	0.045*
H2	−0.4063	1.1477	0.1150	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0279 (6)	0.0246 (7)	0.0265 (7)	0.0058 (5)	0.0014 (5)	0.0128 (5)
C12	0.0321 (8)	0.0264 (8)	0.0240 (8)	0.0072 (6)	0.0003 (6)	0.0087 (6)
C13	0.0329 (7)	0.0213 (7)	0.0255 (8)	0.0064 (6)	0.0000 (6)	0.0081 (6)
C14	0.0207 (6)	0.0240 (7)	0.0233 (7)	0.0058 (5)	0.0033 (5)	0.0111 (6)
C15	0.0334 (7)	0.0234 (7)	0.0246 (7)	0.0035 (6)	−0.0045 (6)	0.0091 (6)
C16	0.0356 (8)	0.0213 (7)	0.0325 (8)	0.0041 (6)	−0.0028 (6)	0.0119 (6)
O1	0.0395 (6)	0.0209 (6)	0.0271 (6)	0.0064 (4)	−0.0057 (4)	0.0096 (4)
O2	0.0469 (7)	0.0254 (6)	0.0275 (6)	0.0062 (5)	−0.0102 (5)	0.0085 (5)
C1	0.0274 (7)	0.0229 (7)	0.0226 (7)	0.0044 (5)	0.0008 (5)	0.0095 (6)
C2	0.0276 (7)	0.0196 (7)	0.0273 (7)	0.0053 (5)	0.0011 (5)	0.0106 (6)

Geometric parameters (Å, º)

N11—C16	1.3339 (19)	C15—H15	0.95
N11—C12	1.3395 (18)	C16—H16	0.95
C12—C13	1.385 (2)	O1—C1	1.3127 (17)
C12—H12	0.95	O1—H1	0.84
C13—C14	1.389 (2)	O2—C1	1.2177 (17)
C13—H13	0.95	C1—C2	1.4910 (19)
C14—C15	1.392 (2)	C2—C2^ii	1.313 (3)
C14—C14^i	1.494 (3)	C2—H2	0.95
C15—C16	1.386 (2)
C16—N11—C12	117.46 (12)	C14—C15—H15	120.2
N11—C12—C13	122.70 (13)	N11—C16—C15	123.29 (13)
N11—C12—H12	118.6	N11—C16—H16	118.4
C13—C12—H12	118.6	C15—C16—H16	118.4
C12—C13—C14	120.14 (13)	C1—O1—H1	109.5
C12—C13—H13	119.9	O2—C1—O1	124.72 (13)
C14—C13—H13	119.9	O2—C1—C2	120.49 (12)
C13—C14—C15	116.78 (12)	O1—C1—C2	114.79 (12)
C13—C14—C14^i	121.95 (15)	C2^ii—C2—C1	124.35 (16)
C15—C14—C14^i	121.27 (15)	C2^ii—C2—H2	117.8
C16—C15—C14	119.62 (13)	C1—C2—H2	117.8
C16—C15—H15	120.2
C16—N11—C12—C13	−0.1 (2)	C14^i—C14—C15—C16	−179.33 (14)
N11—C12—C13—C14	−0.2 (2)	C12—N11—C16—C15	0.5 (2)
C12—C13—C14—C15	0.0 (2)	C14—C15—C16—N11	−0.7 (2)
C12—C13—C14—C14^i	179.74 (14)	O2—C1—C2—C2^ii	174.8 (2)
C13—C14—C15—C16	0.4 (2)	O1—C1—C2—C2^ii	−4.4 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x−1, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N11	0.84	1.76	2.603 (2)	179
C15—H15···O2^iii	0.95	2.43	3.301 (2)	153

Symmetry code: (iii) −x+1, −y+2, −z+1.

(VI) 1,4-Diazabicyclo[2.2.2]octane–fumaric acid (1/1)

Crystal data

C6H13.57N2·C4H2.43O4	F(000) = 488
Mr = 228.25	Dx = 1.422 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8844 reflections
a = 9.6845 (2) Å	θ = 2.8–27.5°
b = 8.8805 (2) Å	µ = 0.11 mm^−1
c = 12.5886 (2) Å	T = 150 K
β = 100.0697 (15)°	Needle, colourless
V = 1065.98 (4) Å^3	0.32 × 0.20 × 0.16 mm
Z = 4

Data collection

Kappa-CCD diffractometer	2430 independent reflections
Radiation source: fine-focus sealed X-ray tube	2007 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −12→12
Tmin = 0.966, Tmax = 0.982	k = −10→11
9143 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: geomk
wR(F^2) = 0.124	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0622P)^2 + 0.2854P] where P = (Fo^2 + 2Fc^2)/3
2430 reflections	(Δ/σ)max < 0.001
147 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.46107 (10)	0.40974 (12)	0.37492 (8)	0.0272 (3)
O2	0.53991 (10)	0.20226 (12)	0.46644 (8)	0.0250 (3)
O3	0.07440 (11)	0.28810 (12)	0.58980 (9)	0.0303 (3)
O4	0.12888 (11)	0.04816 (13)	0.62980 (9)	0.0360 (3)
C1	0.45090 (13)	0.30099 (15)	0.44140 (10)	0.0198 (3)
C2	0.31756 (14)	0.30010 (15)	0.48718 (10)	0.0213 (3)
C3	0.28669 (13)	0.18717 (16)	0.54742 (10)	0.0213 (3)
C4	0.15360 (14)	0.17223 (16)	0.59276 (10)	0.0219 (3)
N1	0.67499 (11)	0.35705 (12)	0.28672 (8)	0.0193 (3)
N2	0.87017 (11)	0.28625 (13)	0.18768 (9)	0.0199 (3)
C11	0.80881 (14)	0.34589 (17)	0.36487 (10)	0.0241 (3)
C12	0.68855 (14)	0.47423 (16)	0.20498 (11)	0.0248 (3)
C13	0.64355 (14)	0.20880 (15)	0.23268 (11)	0.0218 (3)
C21	0.92824 (14)	0.30622 (17)	0.30466 (11)	0.0252 (3)
C22	0.80454 (14)	0.42896 (15)	0.14247 (11)	0.0230 (3)
C23	0.76288 (13)	0.16425 (15)	0.17339 (10)	0.0215 (3)
H1A	0.5308	0.3950	0.3448	0.041*	0.43 (3)
H2A	0.2542	0.3822	0.4726	0.026*
H3	0.3541	0.1091	0.5634	0.026*
H1	0.6028	0.3830	0.3232	0.023*	0.57 (3)
H2	0.9424	0.2604	0.1512	0.024*
H11A	0.8006	0.2673	0.4192	0.029*
H11B	0.8290	0.4430	0.4030	0.029*
H12A	0.7118	0.5723	0.2411	0.030*
H12B	0.5985	0.4851	0.1545	0.030*
H13A	0.5544	0.2152	0.1806	0.026*
H13B	0.6328	0.1312	0.2871	0.026*
H21A	0.9990	0.3878	0.3141	0.030*
H21B	0.9746	0.2121	0.3343	0.030*
H22A	0.7643	0.4152	0.0652	0.028*
H22B	0.8762	0.5094	0.1484	0.028*
H23A	0.8058	0.0685	0.2030	0.026*
H23B	0.7258	0.1495	0.0957	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0278 (5)	0.0252 (6)	0.0333 (5)	0.0058 (4)	0.0180 (4)	0.0082 (4)
O2	0.0213 (5)	0.0276 (6)	0.0275 (5)	0.0047 (4)	0.0080 (4)	0.0049 (4)
O3	0.0279 (5)	0.0238 (6)	0.0443 (6)	0.0014 (4)	0.0207 (5)	0.0038 (4)
O4	0.0291 (6)	0.0307 (6)	0.0520 (7)	0.0035 (5)	0.0178 (5)	0.0180 (5)
C1	0.0195 (6)	0.0217 (7)	0.0193 (6)	−0.0014 (5)	0.0063 (5)	−0.0019 (5)
C2	0.0189 (6)	0.0220 (7)	0.0243 (6)	0.0005 (5)	0.0077 (5)	−0.0010 (5)
C3	0.0178 (6)	0.0241 (7)	0.0227 (6)	−0.0009 (5)	0.0056 (5)	−0.0015 (5)
C4	0.0192 (6)	0.0255 (7)	0.0219 (6)	−0.0021 (5)	0.0065 (5)	0.0018 (5)
N1	0.0191 (5)	0.0189 (6)	0.0215 (5)	0.0005 (4)	0.0078 (4)	0.0005 (4)
N2	0.0195 (5)	0.0195 (6)	0.0226 (5)	0.0006 (4)	0.0087 (4)	0.0005 (4)
C11	0.0227 (7)	0.0299 (8)	0.0203 (6)	−0.0021 (6)	0.0058 (5)	−0.0025 (5)
C12	0.0262 (7)	0.0205 (7)	0.0306 (7)	0.0057 (5)	0.0130 (5)	0.0064 (5)
C13	0.0209 (6)	0.0214 (7)	0.0243 (6)	−0.0040 (5)	0.0075 (5)	−0.0035 (5)
C21	0.0192 (6)	0.0319 (8)	0.0242 (7)	0.0020 (5)	0.0029 (5)	−0.0018 (5)
C22	0.0257 (7)	0.0191 (7)	0.0270 (6)	0.0015 (5)	0.0122 (5)	0.0045 (5)
C23	0.0228 (6)	0.0185 (7)	0.0250 (6)	−0.0013 (5)	0.0091 (5)	−0.0017 (5)

Geometric parameters (Å, º)

O1—C1	1.2929 (16)	N2—H2	0.93
O1—H1A	0.84	C11—C21	1.5307 (18)
O2—C1	1.2313 (16)	C11—H11A	0.99
O3—C4	1.2800 (17)	C11—H11B	0.99
O4—C4	1.2360 (17)	C12—C22	1.5336 (17)
C1—C2	1.5033 (17)	C12—H12A	0.99
C2—C3	1.3226 (19)	C12—H12B	0.99
C2—H2A	0.95	C13—C23	1.5332 (17)
C3—C4	1.5039 (17)	C13—H13A	0.99
C3—H3	0.95	C13—H13B	0.99
N1—C12	1.4853 (17)	C21—H21A	0.99
N1—C11	1.4870 (17)	C21—H21B	0.99
N1—C13	1.4887 (17)	C22—H22A	0.99
N1—H1	0.93	C22—H22B	0.99
N2—C22	1.4858 (17)	C23—H23A	0.99
N2—C23	1.4901 (17)	C23—H23B	0.99
N2—C21	1.4923 (16)
C1—O1—H1A	109.5	N1—C12—C22	109.47 (11)
O2—C1—O1	124.64 (12)	N1—C12—H12A	109.8
O2—C1—C2	120.53 (12)	C22—C12—H12A	109.8
O1—C1—C2	114.82 (11)	N1—C12—H12B	109.8
C3—C2—C1	121.28 (12)	C22—C12—H12B	109.8
C3—C2—H2A	119.4	H12A—C12—H12B	108.2
C1—C2—H2A	119.4	N1—C13—C23	109.84 (10)
C2—C3—C4	125.39 (12)	N1—C13—H13A	109.7
C2—C3—H3	117.3	C23—C13—H13A	109.7
C4—C3—H3	117.3	N1—C13—H13B	109.7
O4—C4—O3	124.95 (12)	C23—C13—H13B	109.7
O4—C4—C3	117.21 (12)	H13A—C13—H13B	108.2
O3—C4—C3	117.84 (12)	N2—C21—C11	109.20 (10)
C12—N1—C11	109.43 (10)	N2—C21—H21A	109.8
C12—N1—C13	109.80 (10)	C11—C21—H21A	109.8
C11—N1—C13	109.17 (10)	N2—C21—H21B	109.8
C12—N1—H1	109.5	C11—C21—H21B	109.8
C11—N1—H1	109.5	H21A—C21—H21B	108.3
C13—N1—H1	109.5	N2—C22—C12	109.25 (10)
C22—N2—C23	109.35 (10)	N2—C22—H22A	109.8
C22—N2—C21	109.81 (11)	C12—C22—H22A	109.8
C23—N2—C21	109.88 (10)	N2—C22—H22B	109.8
C22—N2—H2	109.3	C12—C22—H22B	109.8
C23—N2—H2	109.3	H22A—C22—H22B	108.3
C21—N2—H2	109.3	N2—C23—C13	108.82 (10)
N1—C11—C21	109.54 (10)	N2—C23—H23A	109.9
N1—C11—H11A	109.8	C13—C23—H23A	109.9
C21—C11—H11A	109.8	N2—C23—H23B	109.9
N1—C11—H11B	109.8	C13—C23—H23B	109.9
C21—C11—H11B	109.8	H23A—C23—H23B	108.3
H11A—C11—H11B	108.2
N1—C11—C21—N2	−2.1 (2)	O2—C1—C2—C3	−6.1 (2)
N1—C12—C22—N2	−2.7 (2)	O3—C4—C3—C2	−13.1 (2)
N1—C13—C23—N2	−1.1 (2)	O4—C4—C3—C2	166.7 (2)
O1—C1—C2—C3	173.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.93	1.64	2.559 (2)	171
O1—H1A···N1	0.84	1.72	2.559 (2)	177
N2—H2···O3^i	0.93	1.66	2.592 (2)	178
C23—H23A···O4^ii	0.99	2.33	3.144 (2)	139

Symmetry codes: (i) x+1, −y+1/2, z−1/2; (ii) −x+1, −y, −z+1.

(VII) 1,2-Bis(4-pyridyl)ethane–fumaric acid (1/1)

Crystal data

C12H12N2·C4H4O4	F(000) = 632
Mr = 300.31	Dx = 1.362 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1653 reflections
a = 21.0296 (14) Å	θ = 2.8–27.5°
b = 4.7456 (3) Å	µ = 0.10 mm^−1
c = 16.6875 (11) Å	T = 150 K
β = 118.394 (3)°	Needle, colourless
V = 1465.03 (17) Å^3	0.28 × 0.16 × 0.12 mm
Z = 4

Data collection

Kappa-CCD diffractometer	1653 independent reflections
Radiation source: fine-focus sealed X-ray tube	1247 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
φ scans, and ω scans with κ offsets	θmax = 27.4°, θmin = 2.8°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −26→26
Tmin = 0.963, Tmax = 0.987	k = −4→6
4699 measured reflections	l = −20→21

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.3635P] where P = (Fo^2 + 2Fc^2)/3
1653 reflections	(Δ/σ)max < 0.001
101 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.35423 (6)	−0.0264 (3)	0.24699 (8)	0.0255 (3)
C12	0.41433 (8)	0.0954 (3)	0.25494 (10)	0.0290 (4)
C13	0.45224 (8)	0.2946 (3)	0.32133 (10)	0.0302 (4)
C14	0.42827 (7)	0.3712 (3)	0.38275 (9)	0.0253 (3)
C15	0.36608 (8)	0.2428 (3)	0.37441 (10)	0.0284 (3)
C16	0.33076 (8)	0.0469 (3)	0.30593 (10)	0.0282 (4)
C17	0.47056 (8)	0.5768 (3)	0.45852 (9)	0.0289 (4)
O1	0.28603 (5)	−0.3937 (2)	0.12220 (7)	0.0300 (3)
O2	0.37848 (5)	−0.3841 (2)	0.09086 (7)	0.0341 (3)
C1	0.32025 (7)	−0.4766 (3)	0.07838 (9)	0.0251 (3)
C2	0.28176 (7)	−0.7003 (3)	0.00932 (10)	0.0267 (3)
H12	0.4315	0.0436	0.2137	0.035*
H13	0.4945	0.3786	0.3249	0.036*
H15	0.3480	0.2889	0.4152	0.034*
H16	0.2881	−0.0392	0.3005	0.034*
H17A	0.4375	0.6746	0.4761	0.035*
H17B	0.4931	0.7204	0.4370	0.035*
H1	0.3114	−0.2751	0.1620	0.045*
H2	0.3048	−0.7751	−0.0231	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0244 (6)	0.0274 (7)	0.0241 (6)	−0.0024 (5)	0.0110 (5)	−0.0044 (5)
C12	0.0299 (8)	0.0329 (9)	0.0270 (7)	−0.0041 (6)	0.0160 (7)	−0.0040 (6)
C13	0.0280 (7)	0.0318 (9)	0.0321 (8)	−0.0052 (6)	0.0153 (7)	−0.0026 (6)
C14	0.0247 (7)	0.0230 (8)	0.0232 (7)	0.0012 (6)	0.0074 (6)	0.0006 (5)
C15	0.0278 (7)	0.0311 (8)	0.0272 (7)	0.0010 (6)	0.0137 (6)	−0.0019 (6)
C16	0.0248 (7)	0.0311 (9)	0.0293 (7)	−0.0025 (6)	0.0133 (6)	−0.0026 (6)
C17	0.0293 (8)	0.0246 (8)	0.0278 (7)	−0.0004 (6)	0.0096 (7)	−0.0022 (6)
O1	0.0281 (6)	0.0342 (7)	0.0313 (6)	−0.0082 (5)	0.0171 (5)	−0.0143 (4)
O2	0.0271 (6)	0.0410 (7)	0.0376 (6)	−0.0082 (5)	0.0181 (5)	−0.0105 (5)
C1	0.0244 (7)	0.0274 (8)	0.0239 (7)	−0.0005 (6)	0.0118 (6)	−0.0010 (6)
C2	0.0284 (7)	0.0274 (8)	0.0272 (7)	−0.0011 (6)	0.0156 (6)	−0.0046 (6)

Geometric parameters (Å, º)

N11—C12	1.3379 (19)	C16—H16	0.95
N11—C16	1.3393 (18)	C17—C17^i	1.533 (3)
C12—C13	1.384 (2)	C17—H17A	0.99
C12—H12	0.95	C17—H17B	0.99
C13—C14	1.388 (2)	O1—C1	1.3068 (16)
C13—H13	0.95	O1—H1	0.84
C14—C15	1.388 (2)	O2—C1	1.2218 (17)
C14—C17	1.508 (2)	C1—C2	1.491 (2)
C15—C16	1.384 (2)	C2—C2^ii	1.307 (3)
C15—H15	0.95	C2—H2	0.95
C12—N11—C16	118.40 (12)	C15—C16—H16	118.6
N11—C12—C13	122.13 (13)	C14—C17—C17^i	110.51 (16)
N11—C12—H12	118.9	C14—C17—H17A	109.5
C13—C12—H12	118.9	C17^i—C17—H17A	109.5
C12—C13—C14	119.75 (13)	C14—C17—H17B	109.5
C12—C13—H13	120.1	C17^i—C17—H17B	109.5
C14—C13—H13	120.1	H17A—C17—H17B	108.1
C15—C14—C13	117.81 (13)	C1—O1—H1	109.5
C15—C14—C17	121.33 (13)	O2—C1—O1	124.78 (13)
C13—C14—C17	120.80 (13)	O2—C1—C2	121.28 (13)
C16—C15—C14	119.19 (13)	O1—C1—C2	113.94 (12)
C16—C15—H15	120.4	C2^ii—C2—C1	123.97 (17)
C14—C15—H15	120.4	C2^ii—C2—H2	118.0
N11—C16—C15	122.70 (13)	C1—C2—H2	118.0
N11—C16—H16	118.6
C16—N11—C12—C13	−0.5 (2)	C12—N11—C16—C15	0.0 (2)
N11—C12—C13—C14	0.6 (2)	C14—C15—C16—N11	0.3 (2)
C12—C13—C14—C15	−0.2 (2)	C15—C14—C17—C17^i	91.2 (2)
C12—C13—C14—C17	176.97 (14)	C13—C14—C17—C17^i	−85.9 (2)
C13—C14—C15—C16	−0.2 (2)	O2—C1—C2—C2^ii	−177.37 (18)
C17—C14—C15—C16	−177.39 (14)	O1—C1—C2—C2^ii	2.6 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, −y−3/2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N11	0.84	1.73	2.567 (2)	172
C16—H16···O1^iii	0.95	2.55	3.217 (2)	128

Symmetry code: (iii) −x+1/2, y+1/2, −z+1/2.

(VIII) 4,4'-trimethylenedipyridine–fumaric acid (1/1)

Crystal data

C13H14N2·C4H4O4	F(000) = 664
Mr = 314.33	Dx = 1.319 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4202 reflections
a = 22.4349 (15) Å	θ = 3.7–27.5°
b = 4.6045 (3) Å	µ = 0.10 mm^−1
c = 17.1156 (12) Å	T = 150 K
β = 116.465 (3)°	Needle, colourless
V = 1582.79 (18) Å^3	0.10 × 0.06 × 0.04 mm
Z = 4

Data collection

Kappa-CCD diffractometer	1240 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.140
Graphite monochromator	θmax = 27.5°, θmin = 3.7°
φ scans, and ω scans with κ offsets	h = −28→26
5661 measured reflections	k = −5→5
1782 independent reflections	l = −22→22

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.069	H-atom parameters constrained
wR(F^2) = 0.193	w = 1/[σ^2(Fo^2) + (0.1093P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1782 reflections	Δρmax = 0.27 e Å^−3
106 parameters	Δρmin = −0.31 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (6)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N11	0.65217 (8)	0.9724 (4)	0.63119 (10)	0.0387 (5)
C12	0.59343 (10)	1.0831 (5)	0.57492 (13)	0.0432 (6)
C13	0.55721 (10)	1.2687 (5)	0.60078 (13)	0.0426 (6)
C14	0.58139 (9)	1.3500 (4)	0.68759 (13)	0.0352 (5)
C15	0.64227 (9)	1.2342 (4)	0.74545 (12)	0.0368 (5)
C16	0.67581 (9)	1.0466 (4)	0.71558 (12)	0.0376 (5)
C17	0.54165 (10)	1.5389 (5)	0.71876 (14)	0.0415 (6)
C18	0.5000	1.3549 (6)	0.7500	0.0350 (6)
O1	0.71653 (7)	0.6051 (3)	0.58206 (8)	0.0424 (5)
O2	0.62761 (8)	0.5954 (4)	0.45135 (10)	0.0536 (5)
C1	0.68302 (10)	0.5130 (5)	0.50161 (12)	0.0383 (5)
C2	0.71944 (10)	0.2940 (5)	0.47476 (12)	0.0390 (5)
H12	0.5760	1.0321	0.5150	0.052*
H13	0.5155	1.3411	0.5589	0.051*
H15	0.6609	1.2836	0.8056	0.044*
H16	0.7171	0.9674	0.7563	0.045*
H17A	0.5120	1.6668	0.6706	0.050*
H17B	0.5722	1.6636	0.7672	0.050*
H18A	0.5299	1.2283	0.7984	0.042*	0.50
H18B	0.4701	1.2283	0.7016	0.042*	0.50
H1	0.6936	0.7274	0.5932	0.064*
H2	0.6972	0.2134	0.4178	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0392 (9)	0.0432 (10)	0.0337 (9)	−0.0076 (7)	0.0164 (7)	−0.0042 (7)
C12	0.0441 (11)	0.0505 (13)	0.0288 (9)	−0.0066 (10)	0.0105 (8)	0.0023 (8)
C13	0.0369 (10)	0.0452 (12)	0.0367 (10)	−0.0001 (9)	0.0084 (8)	0.0100 (9)
C14	0.0339 (10)	0.0308 (10)	0.0410 (10)	−0.0039 (8)	0.0167 (8)	0.0060 (8)
C15	0.0373 (10)	0.0405 (11)	0.0303 (9)	−0.0019 (8)	0.0129 (8)	−0.0016 (8)
C16	0.0329 (10)	0.0427 (11)	0.0328 (9)	−0.0011 (8)	0.0105 (8)	−0.0022 (8)
C17	0.0383 (11)	0.0338 (11)	0.0529 (12)	−0.0004 (8)	0.0207 (9)	0.0036 (9)
C18	0.0322 (13)	0.0313 (14)	0.0383 (13)	0.000	0.0128 (11)	0.000
O1	0.0423 (8)	0.0495 (9)	0.0299 (7)	0.0019 (7)	0.0111 (6)	−0.0047 (6)
O2	0.0452 (9)	0.0681 (11)	0.0354 (8)	0.0095 (8)	0.0073 (7)	−0.0046 (7)
C1	0.0399 (11)	0.0423 (12)	0.0287 (9)	−0.0064 (9)	0.0117 (8)	−0.0008 (9)
C2	0.0427 (10)	0.0447 (12)	0.0259 (9)	−0.0044 (9)	0.0121 (8)	−0.0014 (8)

Geometric parameters (Å, º)

N11—C12	1.339 (3)	C17—H17A	0.99
N11—C16	1.342 (2)	C17—H17B	0.99
C12—C13	1.381 (3)	C18—C17^i	1.524 (3)
C12—H12	0.95	C18—H18A	0.99
C13—C14	1.387 (3)	C18—H18B	0.99
C13—H13	0.95	O1—C1	1.311 (2)
C14—C15	1.388 (3)	O1—H1	0.84
C14—C17	1.503 (3)	O2—C1	1.215 (2)
C15—C16	1.384 (3)	C1—C2	1.494 (3)
C15—H15	0.95	C2—C2^ii	1.317 (4)
C16—H16	0.95	C2—H2	0.95
C17—C18	1.524 (3)
C12—N11—C16	117.86 (18)	C18—C17—H17A	109.5
N11—C12—C13	122.43 (18)	C14—C17—H17B	109.5
N11—C12—H12	118.8	C18—C17—H17B	109.5
C13—C12—H12	118.8	H17A—C17—H17B	108.1
C12—C13—C14	120.35 (18)	C17—C18—C17^i	112.4 (2)
C12—C13—H13	119.8	C17—C18—H18A	109.1
C14—C13—H13	119.8	C17^i—C18—H18A	109.1
C13—C14—C15	116.83 (19)	C17—C18—H18B	109.1
C13—C14—C17	121.72 (19)	C17^i—C18—H18B	109.1
C15—C14—C17	121.33 (18)	H18A—C18—H18B	107.8
C16—C15—C14	120.03 (17)	C1—O1—H1	109.5
C16—C15—H15	120.0	O2—C1—O1	124.7 (2)
C14—C15—H15	120.0	O2—C1—C2	121.36 (17)
N11—C16—C15	122.49 (18)	O1—C1—C2	113.91 (17)
N11—C16—H16	118.8	C2^ii—C2—C1	123.9 (2)
C15—C16—H16	118.8	C2^ii—C2—H2	118.0
C14—C17—C18	110.87 (17)	C1—C2—H2	118.0
C14—C17—H17A	109.5
C16—N11—C12—C13	0.2 (3)	C14—C15—C16—N11	0.9 (3)
N11—C12—C13—C14	0.6 (3)	C13—C14—C17—C18	92.2 (2)
C12—C13—C14—C15	−0.6 (3)	C15—C14—C17—C18	−83.7 (2)
C12—C13—C14—C17	−176.72 (18)	C14—C17—C18—C17^i	−179.37 (19)
C13—C14—C15—C16	−0.1 (3)	O2—C1—C2—C2^ii	177.1 (3)
C17—C14—C15—C16	176.02 (18)	O1—C1—C2—C2^ii	−2.3 (4)
C12—N11—C16—C15	−0.9 (3)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+3/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N11	0.84	1.76	2.595 (2)	172
C16—H16···O1^iii	0.95	2.57	3.232 (2)	127

Symmetry code: (iii) −x+3/2, y+1/2, −z+3/2.

(IX) 2,2'-Dipyridylamine–maleic acid (1/2)

Crystal data

C10H10N3·C8H7O8	F(000) = 420
Mr = 403.35	Dx = 1.504 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2003 reflections
a = 11.566 (2) Å	θ = 2.9–27.4°
b = 5.4392 (11) Å	µ = 0.12 mm^−1
c = 14.334 (3) Å	T = 150 K
β = 99.03 (3)°	Block, colourless
V = 890.6 (3) Å^3	0.15 × 0.10 × 0.05 mm
Z = 2

Data collection

Kappa-CCD diffractometer	2003 independent reflections
Radiation source: fine-focus sealed X-ray tube	1476 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
φ scans, and ω scans with κ offsets	θmax = 27.4°, θmin = 2.9°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −14→14
Tmin = 0.980, Tmax = 0.994	k = −6→7
5891 measured reflections	l = −18→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.069	H-atom parameters constrained
wR(F^2) = 0.162	w = 1/[σ^2(Fo^2)P)^2 + 1.1216P] where P = (Fo^2 + 2Fc^2)/3
S = 1.21	(Δ/σ)max < 0.001
2003 reflections	Δρmax = 0.27 e Å^−3
139 parameters	Δρmin = −0.30 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.024 (4)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.3313 (2)	1.0183 (5)	0.5989 (2)	0.0579 (8)
O2	0.25063 (19)	1.2594 (4)	0.48242 (16)	0.0413 (6)
O3	0.12571 (17)	1.6316 (4)	0.46755 (14)	0.0337 (5)
O4	0.04532 (19)	1.8707 (4)	0.56569 (16)	0.0401 (6)
C1	0.2675 (3)	1.1915 (6)	0.5713 (2)	0.0378 (7)
C2	0.2084 (3)	1.3259 (6)	0.6405 (2)	0.0373 (7)
C3	0.1424 (3)	1.5262 (6)	0.6318 (2)	0.0335 (7)
C4	0.1037 (2)	1.6832 (5)	0.5477 (2)	0.0287 (6)
N1	0.4532 (4)	0.6736 (9)	0.5226 (3)	0.0299 (11)	0.50
C11	0.5094 (2)	0.5506 (5)	0.5992 (2)	0.0355 (7)	0.50
C12	0.5665 (2)	0.3488 (6)	0.57323 (19)	0.0354 (7)	0.50
C13	0.6305 (3)	0.2009 (6)	0.6388 (2)	0.0352 (7)
C14	0.6384 (3)	0.2555 (6)	0.7328 (2)	0.0385 (7)
C15	0.5815 (3)	0.4638 (6)	0.7603 (2)	0.0370 (7)
C16	0.5175 (2)	0.6078 (6)	0.6929 (2)	0.0344 (7)
N11	0.5094 (2)	0.5506 (5)	0.5992 (2)	0.0355 (7)	0.50
N12	0.5665 (2)	0.3488 (6)	0.57323 (19)	0.0354 (7)	0.50
H2	0.2116	1.3903	0.4765	0.062*
H4	0.0140	1.9359	0.5148	0.060*	0.50
H2A	0.2198	1.2558	0.7020	0.045*
H3A	0.1157	1.5778	0.6881	0.040*
H1	0.4195	0.8072	0.5403	0.036*	0.50
H13	0.6694	0.0606	0.6193	0.042*
H14	0.6822	0.1527	0.7790	0.046*
H15	0.5873	0.5050	0.8252	0.044*
H16	0.4782	0.7488	0.7114	0.041*
H11	0.4677	0.6448	0.5551	0.050*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0380 (13)	0.0335 (14)	0.100 (2)	0.0102 (11)	0.0027 (13)	0.0089 (14)
O2	0.0430 (13)	0.0297 (12)	0.0538 (14)	0.0078 (10)	0.0151 (10)	−0.0047 (11)
O3	0.0400 (11)	0.0310 (12)	0.0305 (11)	0.0056 (9)	0.0072 (8)	0.0008 (9)
O4	0.0403 (12)	0.0305 (12)	0.0511 (14)	0.0081 (10)	0.0122 (10)	−0.0029 (10)
C1	0.0274 (15)	0.0271 (17)	0.057 (2)	−0.0019 (12)	0.0011 (13)	0.0052 (15)
C2	0.0338 (16)	0.0360 (18)	0.0403 (17)	−0.0013 (13)	0.0000 (12)	0.0069 (14)
C3	0.0364 (15)	0.0328 (17)	0.0314 (15)	−0.0023 (13)	0.0057 (12)	−0.0005 (13)
C4	0.0265 (14)	0.0237 (15)	0.0360 (15)	−0.0022 (11)	0.0051 (11)	−0.0024 (12)
N1	0.032 (2)	0.025 (3)	0.033 (3)	0.007 (2)	0.009 (2)	−0.005 (2)
C11	0.0348 (14)	0.0336 (16)	0.0369 (15)	−0.0026 (12)	0.0022 (11)	0.0047 (12)
C12	0.0358 (14)	0.0399 (17)	0.0320 (14)	−0.0108 (12)	0.0095 (11)	−0.0011 (12)
C13	0.0336 (16)	0.0328 (17)	0.0400 (17)	0.0017 (13)	0.0080 (13)	0.0007 (13)
C14	0.0411 (17)	0.0401 (18)	0.0345 (16)	0.0031 (14)	0.0067 (13)	0.0055 (14)
C15	0.0356 (16)	0.047 (2)	0.0301 (15)	−0.0018 (14)	0.0099 (12)	−0.0004 (14)
C16	0.0324 (15)	0.0353 (17)	0.0369 (16)	−0.0004 (13)	0.0103 (12)	−0.0058 (13)
N11	0.0348 (14)	0.0336 (16)	0.0369 (15)	−0.0026 (12)	0.0022 (11)	0.0047 (12)
N12	0.0358 (14)	0.0399 (17)	0.0320 (14)	−0.0108 (12)	0.0095 (11)	−0.0011 (12)

Geometric parameters (Å, º)

O1—C1	1.223 (4)	N1—H1	0.88
O2—C1	1.311 (4)	N1—H11	0.4945
O2—H2	0.84	C11—C12	1.362 (4)
O3—C4	1.247 (3)	C11—C16	1.368 (4)
O4—C4	1.271 (3)	C11—H11	0.8934
O4—H4	0.84	C12—N1^i	1.363 (5)
C1—C2	1.483 (5)	C13—C14	1.369 (4)
C2—C3	1.325 (4)	C13—H13	0.95
C2—H2A	0.95	C14—C15	1.397 (4)
C3—C4	1.488 (4)	C14—H14	0.95
C3—H3A	0.95	C15—C16	1.367 (4)
N1—C11	1.360 (5)	C15—H15	0.95
N1—C12^i	1.363 (5)	C16—H16	0.95
C1—O2—H2	109.5	C12^i—N1—H11	154.0
C4—O4—H4	109.5	N1—C11—C12	111.5 (3)
O1—C1—O2	121.4 (3)	N1—C11—C16	129.1 (3)
O1—C1—C2	118.8 (3)	C12—C11—C16	119.3 (3)
O2—C1—C2	119.8 (3)	C12—C11—H11	120.0
C3—C2—C1	131.4 (3)	C16—C11—H11	120.7
C3—C2—H2A	114.3	C11—C12—N1^i	109.6 (3)
C1—C2—H2A	114.3	C14—C13—H13	120.1
C2—C3—C4	130.1 (3)	C13—C14—C15	119.4 (3)
C2—C3—H3A	115.0	C13—C14—H14	120.3
C4—C3—H3A	115.0	C15—C14—H14	120.3
O3—C4—O4	124.0 (3)	C16—C15—C14	119.5 (3)
O3—C4—C3	122.6 (3)	C16—C15—H15	120.3
O4—C4—C3	113.4 (3)	C14—C15—H15	120.3
C11—N1—C12^i	138.8 (4)	C15—C16—C11	120.6 (3)
C11—N1—H1	110.6	C15—C16—H16	119.7
C12^i—N1—H1	110.6	C11—C16—H16	119.7
O1—C1—C2—C3	174.7 (3)	C16—C11—C12—N1^i	−180.0 (3)
O2—C1—C2—C3	−5.3 (5)	C13—C14—C15—C16	0.9 (5)
C1—C2—C3—C4	1.1 (6)	C14—C15—C16—C11	−0.5 (5)
C2—C3—C4—O3	4.3 (5)	N1—C11—C16—C15	−178.0 (4)
C2—C3—C4—O4	−176.6 (3)	C12—C11—C16—C15	−0.4 (4)
C12^i—N1—C11—C12	2.7 (7)	N12—C11—N1—C12^i	2.8 (7)
C12^i—N1—C11—C16	−179.5 (4)	N11—C12—N1^i—C11^i	2.7 (7)
N1—C11—C12—N1^i	−1.9 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.84	1.64	2.477 (3)	175
O4—H4···O4^ii	0.84	1.63	2.451 (4)	164
N1—H1···O1	0.88	1.83	2.679 (5)	163
N11—H11···N12^i	0.89	1.82	2.548 (4)	137
N11—H11···O1	0.89	2.70	3.272 (4)	123
C13—H13···O2^i	0.95	2.54	3.454 (4)	162
C15—H15···O4^iii	0.95	2.47	3.128 (4)	127

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+4, −z+1; (iii) −x+1/2, y−3/2, −z+3/2.

(X) Hexamethylenetetramine–fumaric acid–succinic acid (1/0.726/0.224)

Crystal data

C6H12N4·0.726(C4H4O4)·0.274(C4H6O4)	F(000) = 544
Mr = 256.82	Dx = 1.504 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2583 reflections
a = 6.2877 (2) Å	θ = 2.6–27.5°
b = 15.9241 (6) Å	µ = 0.12 mm^−1
c = 11.3315 (5) Å	T = 150 K
β = 93.8556 (13)°	Plate, colourless
V = 1132.01 (7) Å^3	0.36 × 0.34 × 0.05 mm
Z = 4

Data collection

Kappa-CCD diffractometer	2583 independent reflections
Radiation source: fine-focus sealed X-ray tube	1686 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.101
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −8→8
Tmin = 0.913, Tmax = 0.996	k = −20→20
16012 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.164	w = 1/[σ^2(Fo^2) + (0.0644P)^2 + 0.4931P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2583 reflections	Δρmax = 0.28 e Å^−3
199 parameters	Δρmin = −0.25 e Å^−3
17 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.046 (7)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	1.1046 (3)	0.75081 (11)	0.44142 (19)	0.0454 (5)
N2	1.0221 (3)	0.89714 (11)	0.46895 (18)	0.0426 (5)
N3	1.3899 (3)	0.84863 (12)	0.48974 (18)	0.0432 (5)
N4	1.1445 (3)	0.81029 (11)	0.63792 (18)	0.0442 (5)
C12	0.9598 (4)	0.82280 (14)	0.4018 (2)	0.0486 (6)
C13	1.3322 (4)	0.77431 (15)	0.4221 (2)	0.0482 (6)
C14	1.0838 (4)	0.73576 (14)	0.5721 (2)	0.0482 (6)
C23	1.2449 (4)	0.91727 (14)	0.4512 (2)	0.0457 (6)
C24	1.0048 (4)	0.88023 (14)	0.5952 (2)	0.0471 (6)
C34	1.3645 (4)	0.83218 (15)	0.6154 (2)	0.0450 (6)
O1	1.0103 (5)	0.5804 (2)	0.3746 (4)	0.0472 (8)	0.726 (4)
O2	0.7165 (4)	0.65559 (13)	0.3731 (3)	0.0526 (9)	0.726 (4)
O3	0.4395 (4)	0.36126 (17)	0.3243 (3)	0.0465 (7)	0.726 (4)
O4	0.1437 (4)	0.43369 (17)	0.3477 (4)	0.0471 (8)	0.726 (4)
C1	0.8109 (5)	0.58825 (18)	0.3700 (4)	0.0441 (9)	0.726 (4)
C2	0.6861 (5)	0.50901 (19)	0.3568 (3)	0.0449 (9)	0.726 (4)
C3	0.4750 (5)	0.50755 (19)	0.3549 (3)	0.0435 (8)	0.726 (4)
C4	0.3500 (6)	0.4287 (3)	0.3409 (4)	0.0333 (11)	0.726 (4)
O41	0.9764 (14)	0.5729 (7)	0.4062 (9)	0.042 (3)*	0.274 (4)
O42	0.6893 (11)	0.6483 (4)	0.4511 (7)	0.0519 (19)*	0.274 (4)
O43	0.4369 (16)	0.3864 (6)	0.2853 (9)	0.060 (3)*	0.274 (4)
O44	0.1265 (12)	0.4450 (6)	0.2998 (7)	0.040 (2)*	0.274 (4)
C41	0.7759 (10)	0.5802 (4)	0.4338 (8)	0.0255 (17)*	0.274 (4)
C42	0.6502 (8)	0.5017 (3)	0.4553 (6)	0.0176 (15)*	0.274 (4)
C43	0.4145 (10)	0.5051 (4)	0.4171 (7)	0.0212 (15)*	0.274 (4)
C44	0.3255 (17)	0.4420 (8)	0.3290 (13)	0.062 (7)*	0.274 (4)
H1	1.0666	0.7026	0.3987	0.054*
H12A	0.9709	0.8335	0.3164	0.058*
H12B	0.8100	0.8083	0.4146	0.058*
H13A	1.4284	0.7275	0.4472	0.058*
H13B	1.3473	0.7850	0.3370	0.058*
H14A	0.9346	0.7209	0.5859	0.058*
H14B	1.1764	0.6884	0.5993	0.058*
H23A	1.2858	0.9688	0.4961	0.055*
H23B	1.2599	0.9288	0.3663	0.055*
H24A	0.8551	0.8662	0.6090	0.057*
H24B	1.0438	0.9315	0.6410	0.057*
H34A	1.4601	0.7856	0.6422	0.054*
H34B	1.4077	0.8827	0.6619	0.054*
H4	0.1088	0.4841	0.3562	0.071*	0.726 (4)
H2	0.7604	0.4575	0.3494	0.054*	0.726 (4)
H3	0.4008	0.5590	0.3627	0.052*	0.726 (4)
H44	0.0726	0.4865	0.3327	0.059*	0.274 (4)
H42A	0.6652	0.4889	0.5410	0.021*	0.274 (4)
H42B	0.7148	0.4546	0.4134	0.021*	0.274 (4)
H43A	0.3344	0.4998	0.4890	0.025*	0.274 (4)
H43B	0.3837	0.5617	0.3839	0.025*	0.274 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0464 (11)	0.0302 (9)	0.0585 (13)	0.0033 (8)	−0.0043 (9)	−0.0092 (9)
N2	0.0416 (11)	0.0310 (9)	0.0548 (13)	0.0033 (7)	0.0007 (8)	−0.0026 (8)
N3	0.0400 (10)	0.0368 (10)	0.0534 (12)	0.0000 (8)	0.0062 (9)	−0.0018 (9)
N4	0.0447 (11)	0.0369 (10)	0.0515 (12)	−0.0006 (8)	0.0064 (9)	0.0008 (9)
C12	0.0480 (14)	0.0338 (11)	0.0621 (17)	0.0071 (10)	−0.0105 (11)	−0.0036 (11)
C13	0.0473 (14)	0.0417 (13)	0.0561 (16)	0.0080 (10)	0.0067 (11)	−0.0084 (11)
C14	0.0464 (13)	0.0339 (12)	0.0645 (17)	−0.0011 (9)	0.0038 (11)	0.0062 (11)
C23	0.0494 (14)	0.0341 (11)	0.0541 (15)	−0.0011 (10)	0.0062 (11)	0.0001 (10)
C24	0.0453 (13)	0.0388 (12)	0.0584 (16)	0.0052 (10)	0.0126 (11)	−0.0026 (11)
C34	0.0418 (12)	0.0417 (12)	0.0508 (15)	−0.0028 (9)	−0.0022 (10)	−0.0011 (11)
O1	0.0499 (18)	0.0359 (15)	0.056 (2)	0.0009 (12)	0.0030 (16)	−0.0050 (15)
O2	0.0436 (13)	0.0292 (11)	0.083 (2)	0.0059 (9)	−0.0075 (12)	−0.0094 (12)
O3	0.0407 (14)	0.0314 (13)	0.068 (2)	0.0039 (10)	0.0044 (12)	−0.0052 (14)
O4	0.0414 (15)	0.0320 (13)	0.069 (2)	−0.0011 (10)	0.0111 (14)	−0.0035 (15)
C1	0.048 (2)	0.0341 (16)	0.050 (2)	0.0007 (13)	−0.0009 (16)	−0.0030 (14)
C2	0.0471 (19)	0.0352 (16)	0.053 (2)	0.0016 (13)	0.0050 (14)	−0.0014 (14)
C3	0.0464 (19)	0.0329 (16)	0.050 (2)	0.0020 (13)	−0.0033 (16)	−0.0001 (14)
C4	0.0299 (18)	0.0290 (16)	0.041 (2)	0.0010 (14)	0.0052 (13)	−0.0021 (16)

Geometric parameters (Å, º)

N1—C13	1.509 (3)	C34—H34B	0.99
N1—C12	1.513 (3)	O1—C1	1.257 (4)
N1—C14	1.515 (3)	O2—C1	1.227 (3)
N1—H1	0.93	O3—C4	1.233 (5)
N2—C12	1.447 (3)	O4—C4	1.307 (4)
N2—C23	1.464 (3)	O4—H4	0.84
N2—C24	1.467 (3)	C1—C2	1.488 (4)
N3—C13	1.443 (3)	C2—C3	1.326 (5)
N3—C34	1.467 (3)	C2—H2	0.95
N3—C23	1.471 (3)	C3—C4	1.484 (4)
N4—C14	1.439 (3)	C3—H3	0.95
N4—C34	1.465 (3)	O41—C41	1.324 (8)
N4—C24	1.480 (3)	O42—C41	1.234 (7)
C12—H12A	0.99	O43—C44	1.251 (9)
C12—H12B	0.99	O44—C44	1.274 (9)
C13—H13A	0.99	O44—H44	0.84
C13—H13B	0.99	C41—C42	1.507 (7)
C14—H14A	0.99	C42—C43	1.517 (7)
C14—H14B	0.99	C42—H42A	0.99
C23—H23A	0.99	C42—H42B	0.99
C23—H23B	0.99	C43—C44	1.498 (9)
C24—H24A	0.99	C43—H43A	0.99
C24—H24B	0.99	C43—H43B	0.99
C34—H34A	0.99
C13—N1—C12	109.06 (18)	N4—C24—H24A	109.2
C13—N1—C14	109.05 (18)	N2—C24—H24B	109.2
C12—N1—C14	108.66 (18)	N4—C24—H24B	109.2
C13—N1—H1	110.0	H24A—C24—H24B	107.9
C12—N1—H1	110.0	N4—C34—N3	112.19 (19)
C14—N1—H1	110.0	N4—C34—H34A	109.2
C12—N2—C23	109.53 (18)	N3—C34—H34A	109.2
C12—N2—C24	109.12 (19)	N4—C34—H34B	109.2
C23—N2—C24	107.96 (19)	N3—C34—H34B	109.2
C13—N3—C34	109.22 (19)	H34A—C34—H34B	107.9
C13—N3—C23	108.83 (19)	O2—C1—O1	124.7 (3)
C34—N3—C23	108.37 (18)	O2—C1—C2	119.4 (3)
C14—N4—C34	109.07 (19)	O1—C1—C2	115.9 (3)
C14—N4—C24	108.66 (19)	C3—C2—C1	122.5 (3)
C34—N4—C24	108.08 (18)	C3—C2—H2	118.8
N2—C12—N1	109.14 (18)	C1—C2—H2	118.8
N2—C12—H12A	109.9	C2—C3—C4	122.6 (3)
N1—C12—H12A	109.9	C2—C3—H3	118.7
N2—C12—H12B	109.9	C4—C3—H3	118.7
N1—C12—H12B	109.9	O3—C4—O4	121.8 (3)
H12A—C12—H12B	108.3	O3—C4—C3	120.6 (3)
N3—C13—N1	109.47 (18)	O4—C4—C3	117.5 (4)
N3—C13—H13A	109.8	C44—O44—H44	109.5
N1—C13—H13A	109.8	O42—C41—O41	123.5 (8)
N3—C13—H13B	109.8	O42—C41—C42	117.4 (6)
N1—C13—H13B	109.8	O41—C41—C42	118.9 (7)
H13A—C13—H13B	108.2	C41—C42—C43	115.9 (5)
N4—C14—N1	109.78 (18)	C41—C42—H42A	108.3
N4—C14—H14A	109.7	C43—C42—H42A	108.3
N1—C14—H14A	109.7	C41—C42—H42B	108.3
N4—C14—H14B	109.7	C43—C42—H42B	108.3
N1—C14—H14B	109.7	H42A—C42—H42B	107.4
H14A—C14—H14B	108.2	C44—C43—C42	118.7 (6)
N2—C23—N3	112.10 (18)	C44—C43—H43A	107.6
N2—C23—H23A	109.2	C42—C43—H43A	107.6
N3—C23—H23A	109.2	C44—C43—H43B	107.6
N2—C23—H23B	109.2	C42—C43—H43B	107.6
N3—C23—H23B	109.2	H43A—C43—H43B	107.1
H23A—C23—H23B	107.9	O43—C44—O44	119.4 (10)
N2—C24—N4	112.10 (18)	O43—C44—C43	123.0 (9)
N2—C24—H24A	109.2	O44—C44—C43	117.6 (9)
C23—N2—C12—N1	58.5 (3)	C23—N2—C24—N4	−58.6 (2)
C24—N2—C12—N1	−59.5 (2)	C14—N4—C24—N2	−59.9 (2)
C13—N1—C12—N2	−59.1 (3)	C34—N4—C24—N2	58.3 (2)
C14—N1—C12—N2	59.7 (2)	C14—N4—C34—N3	60.1 (2)
C34—N3—C13—N1	58.8 (2)	C24—N4—C34—N3	−57.9 (2)
C23—N3—C13—N1	−59.3 (2)	C13—N3—C34—N4	−60.3 (2)
C12—N1—C13—N3	59.8 (3)	C23—N3—C34—N4	58.1 (2)
C14—N1—C13—N3	−58.7 (2)	O2—C1—C2—C3	−3.9 (6)
C34—N4—C14—N1	−58.6 (2)	O1—C1—C2—C3	177.6 (4)
C24—N4—C14—N1	59.0 (2)	C1—C2—C3—C4	179.6 (4)
C13—N1—C14—N4	58.8 (2)	C2—C3—C4—O3	−3.8 (7)
C12—N1—C14—N4	−60.0 (2)	C2—C3—C4—O4	175.8 (4)
C12—N2—C23—N3	−59.9 (3)	O42—C41—C42—C43	39.0 (10)
C24—N2—C23—N3	58.8 (2)	O41—C41—C42—C43	−145.9 (8)
C13—N3—C23—N2	60.1 (3)	C41—C42—C43—C44	121.7 (10)
C34—N3—C23—N2	−58.5 (2)	C42—C43—C44—O43	−0.1 (19)
C12—N2—C24—N4	60.3 (2)	C42—C43—C44—O44	178.8 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1^i	0.84	1.67	2.507 (4)	173
O44—H44···O1^i	0.84	1.62	2.446 (11)	165
O4—H4···O41^i	0.84	1.75	2.560 (11)	160
O44—H44···O41^i	0.84	1.74	2.578 (14)	176
N1—H1···O1	0.93	1.99	2.868 (4)	156
N1—H1···O41	0.93	2.15	2.965 (11)	146
C12—H12A···O4^ii	0.99	2.52	3.360 (5)	143
C34—H34A···O3^iii	0.99	2.45	3.371 (4)	155

Symmetry codes: (i) x−1, y, z; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+2, −y+1, −z+1.

(XI) 2,2'-Bipyridyl–fumaric acid (1/1)

Crystal data

C10H8N2·C4H4O4	F(000) = 568
Mr = 272.26	Dx = 1.359 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 8494 reflections
a = 23.9702 (6) Å	θ = 3.2–27.5°
b = 3.7416 (1) Å	µ = 0.10 mm^−1
c = 14.8372 (4) Å	T = 150 K
V = 1330.70 (6) Å^3	Needle, colourless
Z = 4	0.26 × 0.20 × 0.20 mm

Data collection

Kappa-CCD diffractometer	1573 independent reflections
Radiation source: fine-focus sealed X-ray tube	1408 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
φ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −30→31
Tmin = 0.901, Tmax = 0.981	k = −4→4
8494 measured reflections	l = −16→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0458P)^2 + 0.1414P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1573 reflections	Δρmax = 0.18 e Å^−3
182 parameters	Δρmin = −0.15 e Å^−3
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (4)

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

	x	y	z	Uiso*/Ueq
N11	0.20316 (7)	0.4107 (4)	0.51434 (11)	0.0252 (4)
C12	0.15078 (8)	0.3235 (5)	0.48808 (14)	0.0227 (4)
C13	0.10838 (8)	0.2650 (6)	0.54988 (14)	0.0265 (4)
C14	0.11961 (9)	0.2952 (6)	0.64138 (15)	0.0324 (5)
C15	0.17319 (9)	0.3843 (6)	0.66830 (15)	0.0319 (5)
C16	0.21312 (9)	0.4401 (6)	0.60308 (14)	0.0289 (5)
N21	0.09205 (6)	0.3954 (4)	0.35691 (10)	0.0237 (4)
C22	0.14176 (8)	0.2874 (5)	0.38946 (14)	0.0220 (4)
C23	0.18240 (8)	0.1399 (5)	0.33414 (14)	0.0258 (4)
C24	0.17176 (8)	0.1042 (6)	0.24286 (15)	0.0291 (5)
C25	0.12116 (9)	0.2206 (6)	0.20877 (15)	0.0316 (5)
C26	0.08247 (9)	0.3625 (6)	0.26827 (14)	0.0287 (5)
O1	0.29010 (5)	0.5975 (4)	0.40953 (9)	0.0297 (4)
O2	0.33028 (6)	0.7445 (5)	0.54022 (11)	0.0430 (5)
O3	0.50957 (5)	1.2833 (4)	0.44452 (10)	0.0293 (3)
O4	0.47262 (6)	1.1552 (4)	0.30928 (10)	0.0352 (4)
C1	0.33097 (8)	0.7320 (5)	0.45894 (14)	0.0255 (4)
C2	0.37799 (8)	0.8686 (5)	0.40401 (13)	0.0256 (4)
C3	0.42352 (8)	0.9954 (5)	0.44275 (14)	0.0270 (4)
C4	0.47073 (7)	1.1503 (5)	0.39077 (14)	0.0248 (4)
H13	0.0719	0.2047	0.5298	0.032*
H14	0.0911	0.2555	0.6847	0.039*
H15	0.1822	0.4064	0.7304	0.038*
H16	0.2497	0.5028	0.6219	0.035*
H23	0.2171	0.0644	0.3586	0.031*
H24	0.1989	0.0010	0.2041	0.035*
H25	0.1132	0.2036	0.1462	0.038*
H26	0.0476	0.4401	0.2452	0.034*
H1	0.2646	0.5227	0.4435	0.045*
H3	0.5356	1.3692	0.4133	0.044*
H2	0.3754	0.8649	0.3401	0.031*
H3A	0.4262	0.9874	0.5066	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0234 (8)	0.0252 (9)	0.0272 (9)	−0.0007 (6)	−0.0006 (7)	0.0000 (7)
C12	0.0212 (9)	0.0209 (9)	0.0260 (10)	0.0000 (7)	0.0000 (8)	0.0006 (8)
C13	0.0226 (9)	0.0292 (10)	0.0278 (11)	−0.0009 (8)	0.0016 (8)	0.0016 (8)
C14	0.0327 (11)	0.0365 (13)	0.0281 (11)	0.0014 (9)	0.0053 (9)	0.0048 (9)
C15	0.0375 (12)	0.0339 (12)	0.0241 (10)	−0.0003 (9)	−0.0022 (9)	0.0004 (9)
C16	0.0275 (10)	0.0298 (11)	0.0294 (11)	−0.0022 (8)	−0.0045 (8)	−0.0005 (9)
N21	0.0210 (7)	0.0260 (8)	0.0242 (9)	−0.0006 (6)	−0.0008 (7)	−0.0008 (7)
C22	0.0197 (9)	0.0203 (10)	0.0261 (9)	−0.0027 (7)	0.0027 (8)	0.0009 (8)
C23	0.0231 (9)	0.0240 (10)	0.0301 (11)	−0.0014 (7)	0.0029 (8)	−0.0018 (8)
C24	0.0298 (10)	0.0262 (11)	0.0311 (11)	−0.0022 (8)	0.0089 (9)	−0.0058 (9)
C25	0.0367 (11)	0.0342 (12)	0.0239 (10)	−0.0029 (9)	0.0010 (9)	−0.0050 (9)
C26	0.0263 (10)	0.0328 (12)	0.0269 (11)	−0.0008 (9)	−0.0028 (8)	0.0000 (9)
O1	0.0225 (7)	0.0378 (9)	0.0287 (8)	−0.0070 (6)	−0.0020 (6)	0.0003 (6)
O2	0.0340 (9)	0.0662 (12)	0.0289 (9)	−0.0210 (8)	0.0013 (7)	−0.0060 (7)
O3	0.0205 (6)	0.0389 (8)	0.0285 (8)	−0.0071 (6)	0.0000 (6)	0.0000 (7)
O4	0.0282 (8)	0.0495 (10)	0.0280 (9)	−0.0086 (7)	−0.0028 (6)	0.0029 (7)
C1	0.0218 (9)	0.0251 (11)	0.0296 (11)	−0.0012 (8)	−0.0025 (8)	−0.0013 (8)
C2	0.0234 (10)	0.0262 (11)	0.0271 (11)	−0.0006 (8)	−0.0004 (8)	0.0001 (7)
C3	0.0238 (9)	0.0302 (10)	0.0271 (10)	−0.0014 (8)	0.0007 (8)	−0.0015 (9)
C4	0.0196 (9)	0.0264 (10)	0.0284 (11)	0.0013 (7)	−0.0004 (8)	0.0006 (8)

Geometric parameters (Å, º)

N11—C16	1.343 (3)	C24—C25	1.385 (3)
N11—C12	1.355 (2)	C24—H24	0.95
C12—C13	1.386 (3)	C25—C26	1.386 (3)
C12—C22	1.485 (3)	C25—H25	0.95
C13—C14	1.389 (3)	C26—H26	0.95
C13—H13	0.95	O1—C1	1.323 (2)
C14—C15	1.386 (3)	O1—H1	0.84
C14—H14	0.95	O2—C1	1.207 (2)
C15—C16	1.377 (3)	O3—C4	1.323 (2)
C15—H15	0.95	O3—H3	0.84
C16—H16	0.95	O4—C4	1.210 (3)
N21—C26	1.341 (3)	C1—C2	1.482 (3)
N21—C22	1.348 (2)	C2—C3	1.321 (3)
C22—C23	1.388 (3)	C2—H2	0.95
C23—C24	1.385 (3)	C3—C4	1.487 (3)
C23—H23	0.95	C3—H3A	0.95
C16—N11—C12	117.81 (17)	C23—C24—C25	119.23 (19)
N11—C12—C13	121.83 (18)	C23—C24—H24	120.4
N11—C12—C22	116.12 (17)	C25—C24—H24	120.4
C13—C12—C22	122.04 (18)	C24—C25—C26	118.3 (2)
C12—C13—C14	119.45 (19)	C24—C25—H25	120.9
C12—C13—H13	120.3	C26—C25—H25	120.9
C14—C13—H13	120.3	N21—C26—C25	123.1 (2)
C15—C14—C13	118.8 (2)	N21—C26—H26	118.5
C15—C14—H14	120.6	C25—C26—H26	118.5
C13—C14—H14	120.6	C1—O1—H1	109.5
C16—C15—C14	118.6 (2)	C4—O3—H3	109.5
C16—C15—H15	120.7	O2—C1—O1	123.95 (19)
C14—C15—H15	120.7	O2—C1—C2	123.12 (18)
N11—C16—C15	123.59 (19)	O1—C1—C2	112.93 (17)
N11—C16—H16	118.2	C3—C2—C1	120.85 (18)
C15—C16—H16	118.2	C3—C2—H2	119.6
C26—N21—C22	118.38 (16)	C1—C2—H2	119.6
N21—C22—C23	121.85 (19)	C2—C3—C4	122.88 (19)
N21—C22—C12	117.03 (17)	C2—C3—H3A	118.6
C23—C22—C12	121.09 (19)	C4—C3—H3A	118.6
C24—C23—C22	119.18 (19)	O4—C4—O3	124.77 (18)
C24—C23—H23	120.4	O4—C4—C3	123.54 (18)
C22—C23—H23	120.4	O3—C4—C3	111.68 (17)
C16—N11—C12—C13	−0.1 (3)	C13—C12—C22—C23	−141.6 (2)
C16—N11—C12—C22	−178.96 (18)	N21—C22—C23—C24	0.4 (3)
N11—C12—C13—C14	−0.2 (3)	C12—C22—C23—C24	178.60 (19)
C22—C12—C13—C14	178.6 (2)	C22—C23—C24—C25	0.8 (3)
C12—C13—C14—C15	0.1 (3)	C23—C24—C25—C26	−1.3 (3)
C13—C14—C15—C16	0.1 (3)	C22—N21—C26—C25	0.5 (3)
C12—N11—C16—C15	0.4 (3)	C24—C25—C26—N21	0.7 (3)
C14—C15—C16—N11	−0.4 (3)	O2—C1—C2—C3	3.7 (3)
C26—N21—C22—C23	−1.0 (3)	O1—C1—C2—C3	−176.56 (19)
C26—N21—C22—C12	−179.30 (18)	C1—C2—C3—C4	−177.20 (18)
N11—C12—C22—N21	−144.41 (17)	C2—C3—C4—O4	−4.1 (3)
C13—C12—C22—N21	36.7 (3)	C2—C3—C4—O3	175.26 (19)
N11—C12—C22—C23	37.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N11	0.84	1.86	2.692 (2)	173
O3—H3···N21^i	0.84	1.82	2.654 (2)	172
C14—H14···O4^ii	0.95	2.43	3.372 (3)	173
C16—H16···O2	0.95	2.45	3.171 (3)	132

Symmetry codes: (i) x+1/2, −y+2, z; (ii) −x+1/2, y−1, z+1/2.