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2,4-Dioxo-1,3-diazetidine-1,3-bis(methyl-m-phenylene) diisocyanate (dimerized toluene-2,4-diisocyanate, TDI) is one of the most widely used aromatic diisocyanates in the polymer industry, and it crystallizes in at least two polymorphic forms (form A and form B) depending on reaction conditions. The crystal structures of the two forms were determined from high-resolution laboratory X-ray powder diffraction data using simulated annealing and Rietveld refinement. In spite of a marked structural similarity between them, significant discrepancies in the physical properties of the two forms prompted analysis of their partitioned energy terms in an effort to better our understanding of the driving force behind such differences in behaviour.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768112008592/kd5060sup1.cif
Contains datablocks global, TDIC01, TDIC02

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768112008592/kd5060TDIC01sup2.hkl
Contains datablock TDIC01

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768112008592/kd5060TDIC02sup3.hkl
Contains datablock TDIC02

CCDC references: 879425; 879426

Computing details top

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
(TDIC01) toluene-2,4-diisocyanate top
Crystal data top
C18H12N4O4β = 81.6029 (15)°
Mr = 348γ = 81.2337 (13)°
Triclinic, P1V = 391.75 (1) Å3
a = 4.53125 (8) ÅZ = 1
b = 5.99235 (8) ÅCu Kα radiation, λ = 1.54059 Å
c = 14.7567 (3) ÅT = 298 K
α = 88.2562 (12)°?, ? × ? × ? mm
Data collection top
Bruker D8 ADVANCE
diffractometer
Scan method: step
Specimen mounting: Capillary2θmin = 5.0°, 2θmax = 68.3°, 2θstep = 0.009°
Data collection mode: transmission
Refinement top
Refinement on F2Profile function: Calculated from fundamental parameters
Rp = 0.03663 parameters
Rwp = 0.05047 restraints
Rexp = 0.015
χ2 = NOT FOUNDBackground function: Chebychev polynomial
7362 data points
Crystal data top
C18H12N4O4β = 81.6029 (15)°
Mr = 348γ = 81.2337 (13)°
Triclinic, P1V = 391.75 (1) Å3
a = 4.53125 (8) ÅZ = 1
b = 5.99235 (8) ÅCu Kα radiation, λ = 1.54059 Å
c = 14.7567 (3) ÅT = 298 K
α = 88.2562 (12)°?, ? × ? × ? mm
Data collection top
Bruker D8 ADVANCE
diffractometer
Scan method: step
Specimen mounting: Capillary2θmin = 5.0°, 2θmax = 68.3°, 2θstep = 0.009°
Data collection mode: transmission
Refinement top
Rp = 0.0367362 data points
Rwp = 0.05063 parameters
Rexp = 0.01547 restraints
χ2 = NOT FOUND
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3493 (11)0.1024 (10)1.0115 (4)0.04245
N20.5466 (4)0.0707 (5)0.9318 (2)0.04245
O30.1186 (8)0.2393 (6)1.0302 (3)0.04245
C50.6337 (3)0.2109 (3)0.8649 (1)0.04245
C80.5141 (3)0.4354 (3)0.8508 (1)0.04245
C90.8690 (3)0.1268 (4)0.8017 (1)0.04245
C130.6320 (3)0.5599 (4)0.7764 (1)0.04245
H140.3337 (16)0.5084 (12)0.8974 (5)0.05094
C151.0001 (2)0.2467 (4)0.7238 (1)0.04245
H160.9282 (17)0.0406 (10)0.8224 (5)0.05094
C210.8758 (3)0.4810 (4)0.7085 (1)0.04245
H220.5375 (17)0.7325 (11)0.7670 (4)0.05094
N231.2526 (4)0.1486 (5)0.6586 (2)0.04245
C270.9887 (5)0.6274 (5)0.6288 (2)0.04245
C281.4796 (14)0.2074 (12)0.6035 (3)0.04245
H311.1710 (14)0.7320 (15)0.6186 (2)0.05094
H320.987 (5)0.530 (3)0.5644 (6)0.05094
H330.773 (2)0.731 (2)0.6171 (18)0.05094
O341.5660 (11)0.2222 (8)0.5312 (3)0.04245
Geometric parameters (Å, º) top
O3—C11.229 (7)C13—C211.412 (2)
O34—C281.087 (6)C21—C271.521 (3)
N2—C51.332 (3)C8—H141.038 (7)
N23—C281.301 (6)C13—H221.071 (7)
C5—C81.393 (2)C27—H321.132 (11)
C5—C91.355 (2)C27—H331.108 (11)
C8—C131.396 (2)
N2—C5—C8128.46 (17)C5—C8—H14118.1 (4)
N2—C5—C9116.62 (19)C13—C8—H14120.6 (4)
C8—C5—C9114.92 (16)C8—C13—H22120.2 (4)
C5—C8—C13121.35 (15)C21—C13—H22113.7 (4)
C8—C13—C21126.1 (2)C21—C27—H32106.2 (7)
C13—C21—C27122.9 (2)C21—C27—H33100.0 (11)
O34—C28—N23142.1 (6)H32—C27—H3389.3 (16)
(TDIC02) toluene-2,4-diisocyanate top
Crystal data top
C18H12N4O4β = 99.7115 (6)°
Mr = 348γ = 114.0050 (6)°
Triclinic, P1V = 770.56 (1) Å3
a = 9.09477 (8) ÅZ = 2
b = 7.45366 (5) ÅCu Kα radiation, λ = 1.54059 Å
c = 12.75989 (16) ÅT = 298 K
α = 93.5753 (8)°?, ? × ? × ? mm
Data collection top
Bruker D8 ADVANCE
diffractometer
Scan method: step
Specimen mounting: Capillary2θmin = 5.0°, 2θmax = 67.4°, 2θstep = 0.009°
Data collection mode: transmission
Refinement top
Refinement on F2Profile function: Calculated from fundamental parameters
Rp = 0.019150 parameters
Rwp = 0.025104 restraints
Rexp = 0.012
χ2 = NOT FOUNDBackground function: Chebychev polynomial
7268 data points
Crystal data top
C18H12N4O4β = 99.7115 (6)°
Mr = 348γ = 114.0050 (6)°
Triclinic, P1V = 770.56 (1) Å3
a = 9.09477 (8) ÅZ = 2
b = 7.45366 (5) ÅCu Kα radiation, λ = 1.54059 Å
c = 12.75989 (16) ÅT = 298 K
α = 93.5753 (8)°?, ? × ? × ? mm
Data collection top
Bruker D8 ADVANCE
diffractometer
Scan method: step
Specimen mounting: Capillary2θmin = 5.0°, 2θmax = 67.4°, 2θstep = 0.009°
Data collection mode: transmission
Refinement top
Rp = 0.0197268 data points
Rwp = 0.025150 parameters
Rexp = 0.012104 restraints
χ2 = NOT FOUND
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.0703 (4)0.7858 (7)0.3017 (3)0.04011
N20.2307 (4)0.8069 (5)0.3074 (3)0.04011
O30.0331 (4)0.7936 (5)0.2318 (3)0.04011
N40.0699 (4)0.7589 (5)0.4111 (3)0.04011
C50.3247 (4)0.8023 (3)0.2331 (3)0.04011
C60.2320 (4)0.7805 (7)0.4170 (3)0.04011
C70.0349 (4)0.7428 (4)0.4810 (3)0.04011
C80.4932 (4)0.8636 (3)0.2670 (3)0.04011
C90.2510 (4)0.7340 (3)0.1275 (3)0.04011
O100.3391 (4)0.7768 (5)0.4910 (3)0.04011
C110.1903 (4)0.7282 (4)0.4456 (3)0.04011
C120.0211 (4)0.7419 (3)0.5860 (3)0.04011
C130.5879 (4)0.8557 (3)0.1948 (3)0.04011
H140.5511 (14)0.9174 (18)0.3498 (11)0.04813
C150.3499 (4)0.7301 (4)0.0555 (3)0.04011
H160.1171 (15)0.6822 (18)0.0999 (13)0.04813
C170.2898 (4)0.7111 (3)0.5161 (3)0.04011
H180.2344 (15)0.7314 (18)0.3619 (12)0.04813
C190.0797 (4)0.7254 (4)0.6611 (3)0.04011
H200.1474 (15)0.7576 (18)0.6119 (13)0.04813
C210.5195 (4)0.7890 (3)0.0876 (3)0.04011
H220.7204 (14)0.9077 (18)0.2248 (11)0.04813
N230.2597 (4)0.6579 (5)0.0496 (3)0.04011
C240.2407 (4)0.7089 (4)0.6270 (3)0.04011
H250.4075 (17)0.6980 (18)0.4848 (14)0.04813
N260.0092 (5)0.7234 (5)0.7693 (3)0.04011
C270.6218 (4)0.7851 (4)0.0097 (3)0.04011
C280.2965 (5)0.6435 (7)0.1378 (3)0.04011
C290.3540 (4)0.6866 (4)0.7065 (3)0.04011
C300.0409 (5)0.7544 (7)0.8574 (3)0.04011
H310.5585 (17)0.6578 (17)0.0518 (13)0.04813
H320.6552 (14)0.9230 (16)0.0237 (12)0.04813
H330.7292 (14)0.7817 (19)0.0511 (14)0.04813
O340.3068 (4)0.6249 (5)0.2279 (3)0.04011
H350.3927 (16)0.5402 (18)0.7350 (11)0.04813
H360.2883 (14)0.808 (2)0.7742 (11)0.04813
H370.4597 (15)0.6999 (18)0.6664 (12)0.04813
O380.0507 (5)0.7736 (5)0.9447 (3)0.04011
Geometric parameters (Å, º) top
C1—N21.391 (5)C13—C211.372 (5)
C1—O31.205 (6)C13—H221.093 (14)
C1—N41.423 (5)C15—C211.398 (5)
N2—C51.387 (5)C15—N231.393 (5)
N2—C61.423 (5)C17—C241.413 (5)
N4—C61.405 (6)C17—H251.040 (17)
N4—C71.388 (5)C19—C241.407 (5)
C5—C81.388 (5)C19—N261.425 (5)
C5—C91.362 (5)C21—C271.478 (5)
C6—O101.247 (6)N23—C281.238 (6)
C7—C111.366 (5)C24—C291.534 (5)
C7—C121.352 (5)N26—C301.238 (6)
C8—C131.377 (5)C27—H311.076 (15)
C8—H141.069 (14)C27—H321.084 (12)
C9—C151.397 (5)C27—H331.040 (16)
C9—H161.101 (15)C28—O341.173 (5)
C11—C171.356 (5)C29—H351.108 (13)
C11—H181.081 (15)C29—H361.100 (14)
C12—C191.412 (5)C29—H371.055 (15)
C12—H201.096 (16)C30—O381.137 (5)
C1—N2—C5135.3 (4)C11—C17—C24123.2 (4)
C1—N2—C685.6 (3)N26—C19—C12116.1 (3)
C5—N2—C6137.2 (3)N26—C19—C24123.8 (3)
C1—N4—C685.1 (3)C12—C19—C24120.1 (3)
C1—N4—C7136.9 (4)C13—C21—C15116.9 (3)
C6—N4—C7137.7 (4)C13—C21—C27121.3 (3)
C15—N23—C28134.3 (4)C15—C21—C27121.8 (3)
C19—N26—C30134.2 (4)C17—C24—C19115.7 (3)
O3—C1—N2133.9 (4)C17—C24—C29123.2 (3)
O3—C1—N4131.0 (4)C19—C24—C29121.1 (3)
N2—C1—N495.0 (3)O34—C28—N23169.6 (5)
N2—C5—C8119.8 (3)O38—C30—N26168.9 (5)
N2—C5—C9120.0 (3)C5—C8—H14120.2 (8)
C8—C5—C9120.2 (4)C13—C8—H14119.1 (8)
O10—C6—N2132.4 (4)C5—C9—H16120.9 (9)
O10—C6—N4133.2 (4)C15—C9—H16121.0 (9)
N2—C6—N494.4 (3)C7—C11—H18120.6 (9)
N4—C7—C11121.4 (3)C17—C11—H18119.6 (9)
N4—C7—C12118.0 (4)C7—C12—H20118.6 (9)
C11—C7—C12120.5 (4)C19—C12—H20120.7 (9)
C5—C8—C13120.7 (3)C8—C13—H22118.2 (8)
C5—C9—C15118.1 (3)C21—C13—H22120.5 (8)
C7—C11—C17119.8 (3)C11—C17—H25116.7 (10)
C7—C12—C19120.8 (4)C24—C17—H25120.1 (10)
C8—C13—C21121.3 (3)C21—C27—H31111.8 (9)
N23—C15—C9112.4 (3)C21—C27—H32107.1 (8)
N23—C15—C21124.8 (4)C21—C27—H33108.4 (10)
C9—C15—C21122.9 (3)H31—C27—H32111.8 (11)
H31—C27—H33109.4 (12)C24—C29—H37107.8 (9)
H32—C27—H33108.2 (11)H35—C29—H36111.0 (10)
C24—C29—H35111.7 (8)H35—C29—H37108.8 (11)
C24—C29—H36108.3 (8)H36—C29—H37109.2 (11)

Experimental details

(TDIC01)(TDIC02)
Crystal data
Chemical formulaC18H12N4O4C18H12N4O4
Mr348348
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)298298
a, b, c (Å)4.53125 (8), 5.99235 (8), 14.7567 (3)9.09477 (8), 7.45366 (5), 12.75989 (16)
α, β, γ (°)88.2562 (12), 81.6029 (15), 81.2337 (13)93.5753 (8), 99.7115 (6), 114.0050 (6)
V3)391.75 (1)770.56 (1)
Z12
Radiation typeCu Kα, λ = 1.54059 ÅCu Kα, λ = 1.54059 Å
µ (mm1)??
Specimen shape, size (mm)?, ? × ? × ??, ? × ? × ?
Data collection
DiffractometerBruker D8 ADVANCE
diffractometer
Bruker D8 ADVANCE
diffractometer
Specimen mountingCapillaryCapillary
Data collection modeTransmissionTransmission
Scan methodStepStep
2θ values (°)2θmin = 5.0 2θmax = 68.3 2θstep = 0.0092θmin = 5.0 2θmax = 67.4 2θstep = 0.009
Refinement
R factors and goodness of fitRp = 0.036, Rwp = 0.050, Rexp = 0.015, χ2 = NOT FOUNDRp = 0.019, Rwp = 0.025, Rexp = 0.012, χ2 = NOT FOUND
No. of data points73627268
No. of parameters63150
No. of restraints47104

 

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