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The third polymorph (denoted MH3) of maleic hydrazide (3,6-dihydroxypyridazine in the monolactim form, 6-hydroxy-3-pyridazinone, C4H4N2O2) has been studied by X-ray diffraction and shown to be monoclinic, space group P21/n. Polymorph MH3 was found as the prevailing form along with the rare triclinic polymorph MH1, space group P\bar 1, but they were obtained separately from monoclinic MH2, space group P21/c. The structure of MH1, previously studied by photographic methods, has been redetermined. Polymorph MH3 exhibits the same scheme of molecular association into hydrogen-bonded ribbons as in MH1 and MH2, but the arrangements of the aggregates and details of their supramolecular conformations are different. The accommodation of the supramolecular conformations to the requirements of close packing of the aggregates in crystal lattices, as well as the symmetries of the polymorphs, are analyzed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010876810101151X/bm0045sup1.cif
Contains datablocks mh3, mhc300

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010876810101151X/bm0045mh3sup2.hkl
Contains datablock mh3

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010876810101151X/bm0045mhc300sup3.hkl
Contains datablock mhc300

CCDC references: 174977; 174978

Computing details top

For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1]
[Figure 3]
[Figure 4]
[Figure 5]
(mh3) 1,2-dihydroxypyridazine; 6-hydroxy-3-pyridazinone polymorph 3 top
Crystal data top
C4H4N2O2V = 466.68 (17) Å3
Mr = 112.09Z = 4
?, P21/nF(000) = 232
a = 6.6070 (15) ÅDx = 1.595 Mg m3
b = 6.9070 (7) ÅCu Kα radiation, λ = 1.54178 Å
c = 10.539 (3) ŵ = 1.13 mm1
α = 90°T = 293 K
β = 104.00 (4)°, colourless
γ = 90°0.4 × 0.4 × 0.2 mm
Data collection top
Kuma KM-4
diffractometer
Rint = 0.027
Radiation source: fine-focus sealed tubeθmax = 62.0°, θmin = 7.2°
Graphite monochromatorh = 06
737 measured reflectionsk = 07
671 independent reflectionsl = 1211
580 reflections with I > 2σ(I)
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0983P)2 + 0.0404P]
where P = (Fo2 + 2Fc2)/3
671 reflections(Δ/σ)max < 0.001
89 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C4H4N2O2γ = 90°
Mr = 112.09V = 466.68 (17) Å3
?, P21/nZ = 4
a = 6.6070 (15) ÅCu Kα radiation
b = 6.9070 (7) ŵ = 1.13 mm1
c = 10.539 (3) ÅT = 293 K
α = 90°0.4 × 0.4 × 0.2 mm
β = 104.00 (4)°
Data collection top
Kuma KM-4
diffractometer
580 reflections with I > 2σ(I)
737 measured reflectionsRint = 0.027
671 independent reflectionsθmax = 62.0°
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.26 e Å3
671 reflectionsΔρmin = 0.20 e Å3
89 parameters
Special details top

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
xyzUiso*/Ueq
N10.0135 (3)0.5992 (3)0.34924 (17)0.0443 (6)
H20.007 (3)0.813 (3)0.469 (3)0.041 (6)*
N20.0101 (3)0.7895 (3)0.38456 (16)0.0440 (6)
C30.0021 (3)0.9454 (3)0.3073 (2)0.0421 (6)
O30.0011 (3)1.1127 (2)0.35400 (16)0.0545 (6)
C40.0167 (4)0.9031 (4)0.1720 (2)0.0495 (7)
H40.025 (4)1.004 (3)0.120 (3)0.055 (7)*
C50.0125 (4)0.7194 (3)0.13221 (19)0.0482 (7)
H50.017 (4)0.685 (4)0.043 (3)0.053 (7)*
C60.0037 (3)0.5689 (3)0.2268 (2)0.0427 (6)
O60.0045 (3)0.3867 (2)0.18410 (15)0.0546 (6)
H60.002 (4)0.294 (4)0.251 (3)0.083 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0686 (13)0.0342 (11)0.0315 (9)0.0019 (8)0.0150 (7)0.0005 (7)
N20.0720 (13)0.0350 (9)0.0271 (9)0.0004 (8)0.0158 (7)0.0033 (7)
C30.0580 (14)0.0335 (12)0.0359 (11)0.0006 (9)0.0139 (8)0.0021 (9)
O30.0940 (13)0.0355 (10)0.0380 (9)0.0015 (7)0.0237 (7)0.0054 (7)
C40.0799 (18)0.0386 (13)0.0318 (11)0.0009 (10)0.0173 (10)0.0045 (9)
C50.0774 (16)0.0415 (12)0.0270 (10)0.0004 (10)0.0152 (9)0.0011 (9)
C60.0596 (14)0.0367 (12)0.0326 (11)0.0000 (10)0.0127 (9)0.0031 (9)
O60.0947 (14)0.0356 (10)0.0356 (9)0.0001 (7)0.0196 (8)0.0045 (6)
Geometric parameters (Å, º) top
N1—C61.293 (3)C4—C51.339 (3)
N1—N21.368 (2)C4—H40.88 (3)
N2—C31.341 (3)C5—C61.426 (3)
N2—H20.91 (3)C5—H50.97 (3)
C3—O31.254 (2)C6—O61.337 (2)
C3—C41.436 (3)O6—H60.95 (3)
C6—N1—N2115.27 (19)C3—C4—H4116.0 (16)
C3—N2—N1127.52 (17)C4—C5—C6118.37 (19)
C3—N2—H2115.8 (15)C4—C5—H5122.8 (16)
N1—N2—H2116.5 (15)C6—C5—H5118.8 (16)
O3—C3—N2120.58 (18)N1—C6—O6119.02 (18)
O3—C3—C4124.6 (2)N1—C6—C5123.8 (2)
N2—C3—C4114.8 (2)O6—C6—C5117.12 (18)
C5—C4—C3120.2 (2)C6—O6—H6112.1 (16)
C5—C4—H4123.8 (16)
C6—N1—N2—C30.0 (3)C3—C4—C5—C60.9 (4)
N1—N2—C3—O3178.36 (19)N2—N1—C6—O6179.48 (18)
N1—N2—C3—C41.2 (3)N2—N1—C6—C50.8 (3)
O3—C3—C4—C5177.9 (2)C4—C5—C6—N10.4 (4)
N2—C3—C4—C51.6 (3)C4—C5—C6—O6179.1 (2)
(mhc300) 1,2-dihydropyridazine-3,6-dione; 6-hydroxy-3-pyridazinone top
Crystal data top
C4H4N2O2V = 229.74 (6) Å3
Mr = 112.09Z = 2
?, P1F(000) = 116
a = 5.8181 (10) ÅDx = 1.620 Mg m3
b = 5.800 (1) ÅMo Kα radiation, λ = 0.71073 Å
c = 7.309 (1) ŵ = 0.13 mm1
α = 78.80 (3)°T = 300 K
β = 99.36 (3)°, colourless
γ = 107.13 (3)°0.5 × 0.3 × 0.15 mm
Data collection top
KUMA KM-4 CCD
diffractometer
Rint = 0.045
Radiation source: fine-focus sealed tubeθmax = 29.7°, θmin = 3.7°
Graphite monochromatorh = 77
2196 measured reflectionsk = 78
1153 independent reflectionsl = 99
808 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.088 w = 1/[σ2(Fo2) + (0.010P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
1153 reflectionsΔρmax = 0.30 e Å3
90 parametersΔρmin = 0.22 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.035 (13)
Crystal data top
C4H4N2O2γ = 107.13 (3)°
Mr = 112.09V = 229.74 (6) Å3
?, P1Z = 2
a = 5.8181 (10) ÅMo Kα radiation
b = 5.800 (1) ŵ = 0.13 mm1
c = 7.309 (1) ÅT = 300 K
α = 78.80 (3)°0.5 × 0.3 × 0.15 mm
β = 99.36 (3)°
Data collection top
KUMA KM-4 CCD
diffractometer
808 reflections with I > 2σ(I)
2196 measured reflectionsRint = 0.045
1153 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.088H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.30 e Å3
1153 reflectionsΔρmin = 0.22 e Å3
90 parameters
Special details top

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
xyzUiso*/Ueq
N10.4544 (3)0.7461 (3)0.3306 (3)0.0395 (5)
N20.6793 (3)0.9000 (3)0.3692 (2)0.0376 (5)
C30.7526 (4)1.1405 (4)0.3096 (3)0.0346 (6)
O30.9663 (3)1.2616 (3)0.3553 (2)0.0487 (5)
C40.5716 (4)1.2444 (4)0.1938 (3)0.0378 (6)
C50.3483 (4)1.1015 (4)0.1529 (3)0.0368 (6)
C60.2966 (4)0.8486 (4)0.2248 (3)0.0338 (6)
O60.0736 (3)0.7090 (3)0.1823 (2)0.0518 (5)
H40.628 (4)1.433 (5)0.150 (4)0.074 (8)*
H50.208 (4)1.165 (4)0.072 (3)0.053 (6)*
H20.805 (5)0.820 (5)0.455 (4)0.082 (8)*
H60.040 (5)0.530 (5)0.248 (4)0.099 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0318 (11)0.0324 (10)0.0458 (11)0.0076 (8)0.0098 (9)0.0008 (8)
N20.0273 (10)0.0332 (10)0.0463 (12)0.0108 (8)0.0062 (9)0.0032 (8)
C30.0289 (12)0.0332 (12)0.0370 (12)0.0081 (10)0.0028 (10)0.0002 (9)
O30.0324 (10)0.0377 (10)0.0607 (11)0.0041 (7)0.0119 (8)0.0060 (8)
C40.0339 (13)0.0315 (12)0.0434 (13)0.0108 (10)0.0031 (10)0.0018 (10)
C50.0333 (13)0.0325 (12)0.0404 (13)0.0125 (10)0.0051 (10)0.0023 (9)
C60.0305 (12)0.0296 (12)0.0337 (12)0.0051 (9)0.0048 (10)0.0015 (9)
O60.0332 (10)0.0405 (11)0.0630 (11)0.0027 (7)0.0151 (8)0.0076 (8)
Geometric parameters (Å, º) top
N1—C61.306 (2)C4—C51.342 (3)
N1—N21.370 (2)C4—H41.05 (3)
N2—C31.339 (3)C5—C61.418 (3)
N2—H21.04 (3)C5—H51.04 (2)
C3—O31.262 (2)C6—O61.335 (2)
C3—C41.440 (3)O6—H61.03 (3)
C6—N1—N2115.52 (18)C3—C4—H4115.1 (13)
C3—N2—N1127.02 (17)C4—C5—C6118.6 (2)
C3—N2—H2117.0 (14)C4—C5—H5124.0 (12)
N1—N2—H2116.0 (14)C6—C5—H5117.4 (12)
O3—C3—N2120.65 (19)N1—C6—O6118.56 (19)
O3—C3—C4124.1 (2)N1—C6—C5123.60 (19)
N2—C3—C4115.21 (18)O6—C6—C5117.84 (18)
C5—C4—C3120.0 (2)C6—O6—H6114.9 (14)
C5—C4—H4124.9 (13)
C6—N1—N2—C30.3 (3)C3—C4—C5—C60.4 (3)
N1—N2—C3—O3179.9 (2)N2—N1—C6—O6179.8 (2)
N1—N2—C3—C40.4 (3)N2—N1—C6—C50.3 (3)
O3—C3—C4—C5179.8 (2)C4—C5—C6—N10.6 (3)
N2—C3—C4—C50.0 (3)C4—C5—C6—O6179.8 (2)

Experimental details

(mh3)(mhc300)
Crystal data
Chemical formulaC4H4N2O2C4H4N2O2
Mr112.09112.09
Crystal system, space group?, P21/n?, P1
Temperature (K)293300
a, b, c (Å)6.6070 (15), 6.9070 (7), 10.539 (3)5.8181 (10), 5.800 (1), 7.309 (1)
α, β, γ (°)90, 104.00 (4), 9078.80 (3), 99.36 (3), 107.13 (3)
V3)466.68 (17)229.74 (6)
Z42
Radiation typeCu KαMo Kα
µ (mm1)1.130.13
Crystal size (mm)0.4 × 0.4 × 0.20.5 × 0.3 × 0.15
Data collection
DiffractometerKuma KM-4
diffractometer
KUMA KM-4 CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
737, 671, 580 2196, 1153, 808
Rint0.0270.045
θmax (°)62.029.7
(sin θ/λ)max1)0.5730.697
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.104, 1.09 0.054, 0.088, 1.01
No. of reflections6711153
No. of parameters8990
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.26, 0.200.30, 0.22

Computer programs: SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).

 

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