The third polymorph (denoted MH3) of maleic hydrazide (3,6-dihydroxypyridazine in the monolactim form, 6-hydroxy-3-pyridazinone, C
4H
4N
2O
2) has been studied by X-ray diffraction and shown to be monoclinic, space group
P2
1/
n. Polymorph MH3 was found as the prevailing form along with the rare triclinic polymorph MH1, space group
P, but they were obtained separately from monoclinic MH2, space group
P2
1/
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
CCDC references: 174977; 174978
For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
(mh3) 1,2-dihydroxypyridazine; 6-hydroxy-3-pyridazinone polymorph 3
top
Crystal data top
C4H4N2O2 | V = 466.68 (17) Å3 |
Mr = 112.09 | Z = 4 |
?, P21/n | F(000) = 232 |
a = 6.6070 (15) Å | Dx = 1.595 Mg m−3 |
b = 6.9070 (7) Å | Cu Kα radiation, λ = 1.54178 Å |
c = 10.539 (3) Å | µ = 1.13 mm−1 |
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 tube | θmax = 62.0°, θmin = 7.2° |
Graphite monochromator | h = 0→6 |
737 measured reflections | k = 0→7 |
671 independent reflections | l = −12→11 |
580 reflections with I > 2σ(I) | |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H 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 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C4H4N2O2 | γ = 90° |
Mr = 112.09 | V = 466.68 (17) Å3 |
?, P21/n | Z = 4 |
a = 6.6070 (15) Å | Cu Kα radiation |
b = 6.9070 (7) Å | µ = 1.13 mm−1 |
c = 10.539 (3) Å | T = 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 reflections | Rint = 0.027 |
671 independent reflections | θmax = 62.0° |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.26 e Å−3 |
671 reflections | Δρmin = −0.20 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
N1 | 0.0135 (3) | 0.5992 (3) | 0.34924 (17) | 0.0443 (6) | |
H2 | 0.007 (3) | 0.813 (3) | 0.469 (3) | 0.041 (6)* | |
N2 | 0.0101 (3) | 0.7895 (3) | 0.38456 (16) | 0.0440 (6) | |
C3 | −0.0021 (3) | 0.9454 (3) | 0.3073 (2) | 0.0421 (6) | |
O3 | 0.0011 (3) | 1.1127 (2) | 0.35400 (16) | 0.0545 (6) | |
C4 | −0.0167 (4) | 0.9031 (4) | 0.1720 (2) | 0.0495 (7) | |
H4 | −0.025 (4) | 1.004 (3) | 0.120 (3) | 0.055 (7)* | |
C5 | −0.0125 (4) | 0.7194 (3) | 0.13221 (19) | 0.0482 (7) | |
H5 | −0.017 (4) | 0.685 (4) | 0.043 (3) | 0.053 (7)* | |
C6 | 0.0037 (3) | 0.5689 (3) | 0.2268 (2) | 0.0427 (6) | |
O6 | 0.0045 (3) | 0.3867 (2) | 0.18410 (15) | 0.0546 (6) | |
H6 | 0.002 (4) | 0.294 (4) | 0.251 (3) | 0.083 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0686 (13) | 0.0342 (11) | 0.0315 (9) | 0.0019 (8) | 0.0150 (7) | −0.0005 (7) |
N2 | 0.0720 (13) | 0.0350 (9) | 0.0271 (9) | 0.0004 (8) | 0.0158 (7) | −0.0033 (7) |
C3 | 0.0580 (14) | 0.0335 (12) | 0.0359 (11) | 0.0006 (9) | 0.0139 (8) | −0.0021 (9) |
O3 | 0.0940 (13) | 0.0355 (10) | 0.0380 (9) | −0.0015 (7) | 0.0237 (7) | −0.0054 (7) |
C4 | 0.0799 (18) | 0.0386 (13) | 0.0318 (11) | 0.0009 (10) | 0.0173 (10) | 0.0045 (9) |
C5 | 0.0774 (16) | 0.0415 (12) | 0.0270 (10) | −0.0004 (10) | 0.0152 (9) | −0.0011 (9) |
C6 | 0.0596 (14) | 0.0367 (12) | 0.0326 (11) | 0.0000 (10) | 0.0127 (9) | −0.0031 (9) |
O6 | 0.0947 (14) | 0.0356 (10) | 0.0356 (9) | −0.0001 (7) | 0.0196 (8) | −0.0045 (6) |
Geometric parameters (Å, º) top
N1—C6 | 1.293 (3) | C4—C5 | 1.339 (3) |
N1—N2 | 1.368 (2) | C4—H4 | 0.88 (3) |
N2—C3 | 1.341 (3) | C5—C6 | 1.426 (3) |
N2—H2 | 0.91 (3) | C5—H5 | 0.97 (3) |
C3—O3 | 1.254 (2) | C6—O6 | 1.337 (2) |
C3—C4 | 1.436 (3) | O6—H6 | 0.95 (3) |
| | | |
C6—N1—N2 | 115.27 (19) | C3—C4—H4 | 116.0 (16) |
C3—N2—N1 | 127.52 (17) | C4—C5—C6 | 118.37 (19) |
C3—N2—H2 | 115.8 (15) | C4—C5—H5 | 122.8 (16) |
N1—N2—H2 | 116.5 (15) | C6—C5—H5 | 118.8 (16) |
O3—C3—N2 | 120.58 (18) | N1—C6—O6 | 119.02 (18) |
O3—C3—C4 | 124.6 (2) | N1—C6—C5 | 123.8 (2) |
N2—C3—C4 | 114.8 (2) | O6—C6—C5 | 117.12 (18) |
C5—C4—C3 | 120.2 (2) | C6—O6—H6 | 112.1 (16) |
C5—C4—H4 | 123.8 (16) | | |
| | | |
C6—N1—N2—C3 | 0.0 (3) | C3—C4—C5—C6 | 0.9 (4) |
N1—N2—C3—O3 | −178.36 (19) | N2—N1—C6—O6 | −179.48 (18) |
N1—N2—C3—C4 | 1.2 (3) | N2—N1—C6—C5 | −0.8 (3) |
O3—C3—C4—C5 | 177.9 (2) | C4—C5—C6—N1 | 0.4 (4) |
N2—C3—C4—C5 | −1.6 (3) | C4—C5—C6—O6 | 179.1 (2) |
(mhc300) 1,2-dihydropyridazine-3,6-dione; 6-hydroxy-3-pyridazinone
top
Crystal data top
C4H4N2O2 | V = 229.74 (6) Å3 |
Mr = 112.09 | Z = 2 |
?, P1 | F(000) = 116 |
a = 5.8181 (10) Å | Dx = 1.620 Mg m−3 |
b = 5.800 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
c = 7.309 (1) Å | µ = 0.13 mm−1 |
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 tube | θmax = 29.7°, θmin = 3.7° |
Graphite monochromator | h = −7→7 |
2196 measured reflections | k = −7→8 |
1153 independent reflections | l = −9→9 |
808 reflections with I > 2σ(I) | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.054 | H 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 reflections | Δρmax = 0.30 e Å−3 |
90 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.035 (13) |
Crystal data top
C4H4N2O2 | γ = 107.13 (3)° |
Mr = 112.09 | V = 229.74 (6) Å3 |
?, P1 | Z = 2 |
a = 5.8181 (10) Å | Mo Kα radiation |
b = 5.800 (1) Å | µ = 0.13 mm−1 |
c = 7.309 (1) Å | T = 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 reflections | Rint = 0.045 |
1153 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.30 e Å−3 |
1153 reflections | Δρmin = −0.22 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
N1 | 0.4544 (3) | 0.7461 (3) | 0.3306 (3) | 0.0395 (5) | |
N2 | 0.6793 (3) | 0.9000 (3) | 0.3692 (2) | 0.0376 (5) | |
C3 | 0.7526 (4) | 1.1405 (4) | 0.3096 (3) | 0.0346 (6) | |
O3 | 0.9663 (3) | 1.2616 (3) | 0.3553 (2) | 0.0487 (5) | |
C4 | 0.5716 (4) | 1.2444 (4) | 0.1938 (3) | 0.0378 (6) | |
C5 | 0.3483 (4) | 1.1015 (4) | 0.1529 (3) | 0.0368 (6) | |
C6 | 0.2966 (4) | 0.8486 (4) | 0.2248 (3) | 0.0338 (6) | |
O6 | 0.0736 (3) | 0.7090 (3) | 0.1823 (2) | 0.0518 (5) | |
H4 | 0.628 (4) | 1.433 (5) | 0.150 (4) | 0.074 (8)* | |
H5 | 0.208 (4) | 1.165 (4) | 0.072 (3) | 0.053 (6)* | |
H2 | 0.805 (5) | 0.820 (5) | 0.455 (4) | 0.082 (8)* | |
H6 | 0.040 (5) | 0.530 (5) | 0.248 (4) | 0.099 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0318 (11) | 0.0324 (10) | 0.0458 (11) | 0.0076 (8) | −0.0098 (9) | 0.0008 (8) |
N2 | 0.0273 (10) | 0.0332 (10) | 0.0463 (12) | 0.0108 (8) | −0.0062 (9) | 0.0032 (8) |
C3 | 0.0289 (12) | 0.0332 (12) | 0.0370 (12) | 0.0081 (10) | −0.0028 (10) | −0.0002 (9) |
O3 | 0.0324 (10) | 0.0377 (10) | 0.0607 (11) | 0.0041 (7) | −0.0119 (8) | 0.0060 (8) |
C4 | 0.0339 (13) | 0.0315 (12) | 0.0434 (13) | 0.0108 (10) | −0.0031 (10) | 0.0018 (10) |
C5 | 0.0333 (13) | 0.0325 (12) | 0.0404 (13) | 0.0125 (10) | −0.0051 (10) | 0.0023 (9) |
C6 | 0.0305 (12) | 0.0296 (12) | 0.0337 (12) | 0.0051 (9) | −0.0048 (10) | 0.0015 (9) |
O6 | 0.0332 (10) | 0.0405 (11) | 0.0630 (11) | 0.0027 (7) | −0.0151 (8) | 0.0076 (8) |
Geometric parameters (Å, º) top
N1—C6 | 1.306 (2) | C4—C5 | 1.342 (3) |
N1—N2 | 1.370 (2) | C4—H4 | 1.05 (3) |
N2—C3 | 1.339 (3) | C5—C6 | 1.418 (3) |
N2—H2 | 1.04 (3) | C5—H5 | 1.04 (2) |
C3—O3 | 1.262 (2) | C6—O6 | 1.335 (2) |
C3—C4 | 1.440 (3) | O6—H6 | 1.03 (3) |
| | | |
C6—N1—N2 | 115.52 (18) | C3—C4—H4 | 115.1 (13) |
C3—N2—N1 | 127.02 (17) | C4—C5—C6 | 118.6 (2) |
C3—N2—H2 | 117.0 (14) | C4—C5—H5 | 124.0 (12) |
N1—N2—H2 | 116.0 (14) | C6—C5—H5 | 117.4 (12) |
O3—C3—N2 | 120.65 (19) | N1—C6—O6 | 118.56 (19) |
O3—C3—C4 | 124.1 (2) | N1—C6—C5 | 123.60 (19) |
N2—C3—C4 | 115.21 (18) | O6—C6—C5 | 117.84 (18) |
C5—C4—C3 | 120.0 (2) | C6—O6—H6 | 114.9 (14) |
C5—C4—H4 | 124.9 (13) | | |
| | | |
C6—N1—N2—C3 | −0.3 (3) | C3—C4—C5—C6 | −0.4 (3) |
N1—N2—C3—O3 | −179.9 (2) | N2—N1—C6—O6 | −179.8 (2) |
N1—N2—C3—C4 | 0.4 (3) | N2—N1—C6—C5 | −0.3 (3) |
O3—C3—C4—C5 | −179.8 (2) | C4—C5—C6—N1 | 0.6 (3) |
N2—C3—C4—C5 | 0.0 (3) | C4—C5—C6—O6 | −179.8 (2) |
Experimental details
| (mh3) | (mhc300) |
Crystal data |
Chemical formula | C4H4N2O2 | C4H4N2O2 |
Mr | 112.09 | 112.09 |
Crystal system, space group | ?, P21/n | ?, P1 |
Temperature (K) | 293 | 300 |
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), 90 | 78.80 (3), 99.36 (3), 107.13 (3) |
V (Å3) | 466.68 (17) | 229.74 (6) |
Z | 4 | 2 |
Radiation type | Cu Kα | Mo Kα |
µ (mm−1) | 1.13 | 0.13 |
Crystal size (mm) | 0.4 × 0.4 × 0.2 | 0.5 × 0.3 × 0.15 |
|
Data collection |
Diffractometer | Kuma 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 |
Rint | 0.027 | 0.045 |
θmax (°) | 62.0 | 29.7 |
(sin θ/λ)max (Å−1) | 0.573 | 0.697 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.104, 1.09 | 0.054, 0.088, 1.01 |
No. of reflections | 671 | 1153 |
No. of parameters | 89 | 90 |
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 |
Δρmax, Δρmin (e Å−3) | 0.26, −0.20 | 0.30, −0.22 |