organic papers
Acta Cryst.(2006). E62, o831–o832 doi:10.1107/S1600536806002923 Shiet al. C
11H10N4O2
o831
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
2-Amino-3-(4-hydroxybenzylideneamino)-butenedinitrile monohydrate
Jing-Min Shi,* Xia Zhang, Hai-Yan Xu and Lian-Dong Liu
Department of Chemistry, Shandong Normal University, Jinan 250014, People’s Republic of China
Correspondence e-mail: shijingmin@beelink.com
Key indicators
Single-crystal X-ray study T= 298 K
Mean(C–C) = 0.002 A˚ Rfactor = 0.050 wRfactor = 0.137
Data-to-parameter ratio = 15.1
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 3 January 2006 Accepted 24 January 2006
#2006 International Union of Crystallography
All rights reserved
In the crystal structure of the title compound, C11H8N4OH2O,
the molecules are held together by O—H O, O—H N and N—H N hydrogen bonds. The compound exhibits strong fluorescent emission in the solid state.
Comment
2-Amino-3-(4-hydroxybenzylidene)aminobutenedinitrile, (I), is a useful compound in the dye and medicine synthesis fields (Begland et al., 1974; Begland & Del, 1975), but its crystal structure is unknown to date. The crystal structures of the related compounds 2-amino-3-(2-hydroxybenzylideneamino)-2,3-butenedinitrile and 2-amino-3-[4-(diethylamino)-2-hydroxybenzylideneamino]-2,3-butenedinitrile have been reported by MacLachlanet al.(1996) and Costeset al.(2005), respectively. As part of an investigation of its physical prop-erties, we report the molecular structure of the title compound, (I) (Fig. 1).
The butenedinitrile molecule is approximately planar, with a dihedral angle of 7.73 (3) between the planes of the
hydroxylbenzylidene and diaminomaleonitrile groups. The bond lengths imply that all non-H atoms of the molecule are involved in a conjugated system. Hydrogen bonds (Table 1) connect the water molecule and the hydroxy group, the water molecule and the cyano group, and the amino and cyano groups. The title compound exhibits a strong fluorescence spectrum with a maximum emission peak at 564 nm when the excitation wavelength is selected at 320 nm.
Experimental
Crystal data
C11H10N4O2
Mr= 230.23
Monoclinic,P21=n
a= 9.848 (2) A˚
b= 7.0388 (15) A˚
c= 16.473 (3) A˚
= 90.604 (3)
V= 1141.9 (4) A˚3
Z= 4
Dx= 1.339 Mg m 3
MoKradiation Cell parameters from 2655
reflections
= 2.4–27.6
= 0.10 mm1
T= 298 (2) K Prism, yellow 0.230.210.19 mm
Data collection
Bruker SMART APEX CCD diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.978,Tmax= 0.982
6301 measured reflections
2358 independent reflections 1943 reflections withI> 2(I)
Rint= 0.039
max= 26.5
h=11!12
k=8!8
l=20!19
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.050
wR(F2) = 0.137
S= 1.03 2358 reflections 156 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0884P)2
+ 0.0552P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.004 max= 0.22 e A˚
3
min=0.30 e A˚
3
Extinction correction:SHELXL97
Extinction coefficient: 0.024 (4)
Table 1
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
O1—H4 O2i
0.82 1.87 2.6848 (16) 169 O2—H7 O1ii
0.88 2.04 2.8283 (15) 148 O2—H8 N2iii
0.89 2.26 3.115 (2) 161 N4—H4A N2iii 0.86 2.42 3.1691 (19) 146 N4—H4B N3iv
0.86 2.15 3.0053 (18) 171
Symmetry codes: (i)x1 2;yþ
1 2;z
1 2; (ii)xþ
1 2;y
1 2;zþ
1
2; (iii)x;yþ1;z; (iv)
xþ1 2;yþ
1 2;zþ
3 2.
The H atoms of the water molecule were located in a difference Fourier map and refined as riding, with O—H = 0.88 and 0.89 A˚ and
Uiso(H) = 1.5Ueq(O). Other H atoms were placed in calculated positions, with C—H = 0.93 A˚ , O—H = 0.82 A˚ and N—H = 0.93 A˚, and were refined as riding, withUiso(H) = 1.2Ueq(C,N) and 1.5Ueq(O). Data collection:SMART(Bruker, 1997); cell refinement:SAINT
(Bruker, 1997); data reduction:SAINT; program(s) used to solve
structure: SHELXTL (Bruker, 2001); program(s) used to refine
structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.
The authors thank the Natural Science Foundation of China (grant No. 20271043).
References
Begland, R. W. & Del, W. (1975). US Patent No. 3 912 724.
Begland, R. W., Hartter, D. R., Jones, F. N., Sam, D. J., Sheppard, W. A., Webste, O. W. & Weigert, F. J. (1974).J. Org. Chem.39, 2341–2350. Bruker (1997).SMART(Version 5.6) andSAINT(Version 5. A06). Bruker
AXS Inc., Madison, Wisconsin, USA.
Bruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.
Costes, J. P., Lame`re, J. F., Lepetit, C., Lacroix, P. G., Dahan, F & Nakatani, K. (2005).Inorg. Chem.44, 1973–1982.
MacLachlan, M. J., Park, M. K. & Thompson, L. K. (1996).Inorg. Chem.35, 5492–5499.
[image:2.610.312.566.71.202.2]Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany.
Figure 1
supporting information
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Acta Cryst. (2006). E62, o831–o832
supporting information
Acta Cryst. (2006). E62, o831–o832 [https://doi.org/10.1107/S1600536806002923]
2-Amino-3-(4-hydroxybenzylideneamino)butenedinitrile monohydrate
Jing-Min Shi, Xia Zhang, Hai-Yan Xu and Lian-Dong Liu
2-Amino-3-(4-hydroxybenzylideneamino)butenedinitrile monohydrate
Crystal data
C11H10N4O2
Mr = 230.23 Monoclinic, P21/n Hall symbol: -P 2yn a = 9.848 (2) Å b = 7.0388 (15) Å c = 16.473 (3) Å β = 90.604 (3)° V = 1141.9 (4) Å3
Z = 4
F(000) = 480 Dx = 1.339 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2655 reflections θ = 2.4–27.6°
µ = 0.10 mm−1
T = 298 K Prism, yellow
0.23 × 0.21 × 0.19 mm
Data collection
Bruker SMART APEX CCD diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.978, Tmax = 0.982
6301 measured reflections 2358 independent reflections 1943 reflections with I > 2σ(I) Rint = 0.039
θmax = 26.5°, θmin = 2.4°
h = −11→12 k = −8→8 l = −20→19
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.050
wR(F2) = 0.137
S = 1.03 2358 reflections 156 parameters 3 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.0884P)2 + 0.0552P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.004 Δρmax = 0.22 e Å−3 Δρmin = −0.30 e Å−3
Special details
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)
x y z Uiso*/Ueq
N1 0.15384 (11) 0.02846 (15) 0.45425 (6) 0.0334 (3)
O1 0.01828 (11) 0.41676 (15) 0.11294 (6) 0.0508 (3)
H4 −0.0076 0.3519 0.0744 0.076*
C8 0.18530 (13) −0.08908 (19) 0.51945 (7) 0.0328 (3)
C7 0.13287 (13) −0.03927 (19) 0.38325 (7) 0.0342 (3)
H6 0.1379 −0.1700 0.3758 0.041*
C5 0.10147 (12) 0.08086 (19) 0.31369 (7) 0.0331 (3)
C4 0.10162 (15) 0.2776 (2) 0.31899 (8) 0.0422 (4)
H5 0.1207 0.3359 0.3685 0.051*
C6 0.07016 (16) −0.0016 (2) 0.23923 (8) 0.0425 (4)
H1 0.0692 −0.1333 0.2347 0.051*
C11 0.24004 (14) −0.1223 (2) 0.66272 (8) 0.0399 (4)
C2 0.04374 (13) 0.3024 (2) 0.17805 (8) 0.0370 (3)
C10 0.20193 (13) −0.00669 (19) 0.59391 (7) 0.0332 (3)
C9 0.20000 (15) −0.2904 (2) 0.51078 (8) 0.0406 (4)
N3 0.27179 (15) −0.2099 (2) 0.71749 (8) 0.0571 (4)
N4 0.18443 (13) 0.17866 (17) 0.60808 (7) 0.0450 (3)
H4A 0.1613 0.2534 0.5690 0.054*
H4B 0.1963 0.2231 0.6563 0.054*
C1 0.04046 (15) 0.1075 (2) 0.17185 (8) 0.0425 (4)
H2 0.0184 0.0499 0.1226 0.051*
C3 0.07373 (16) 0.3871 (2) 0.25154 (8) 0.0466 (4)
H3 0.0751 0.5189 0.2556 0.056*
N2 0.21026 (18) −0.4505 (2) 0.50026 (8) 0.0640 (4)
O2 0.44395 (12) 0.25802 (15) 0.47460 (6) 0.0527 (3)
H8 0.3651 0.3197 0.4772 0.079*
H7 0.4335 0.1756 0.4345 0.079*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
N1 0.0427 (6) 0.0296 (6) 0.0278 (6) 0.0011 (4) −0.0059 (4) 0.0035 (4)
O1 0.0699 (7) 0.0446 (7) 0.0376 (6) −0.0057 (5) −0.0138 (5) 0.0148 (5)
supporting information
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Acta Cryst. (2006). E62, o831–o832
C4 0.0595 (9) 0.0348 (8) 0.0319 (7) −0.0053 (6) −0.0140 (6) −0.0012 (5)
C6 0.0653 (9) 0.0292 (7) 0.0328 (7) 0.0045 (6) −0.0064 (6) −0.0013 (5)
C11 0.0483 (8) 0.0411 (8) 0.0303 (7) −0.0008 (6) −0.0044 (6) 0.0028 (6)
C2 0.0402 (7) 0.0399 (8) 0.0308 (7) −0.0018 (6) −0.0047 (5) 0.0093 (5)
C10 0.0391 (7) 0.0331 (7) 0.0273 (6) −0.0017 (5) −0.0051 (5) 0.0044 (5)
C9 0.0552 (8) 0.0348 (8) 0.0317 (7) 0.0019 (6) −0.0092 (6) 0.0036 (5)
N3 0.0724 (9) 0.0609 (9) 0.0378 (7) 0.0062 (7) −0.0092 (6) 0.0165 (6)
N4 0.0724 (8) 0.0348 (7) 0.0277 (6) 0.0026 (6) −0.0079 (5) −0.0011 (5)
C1 0.0624 (9) 0.0392 (8) 0.0257 (6) 0.0048 (7) −0.0056 (6) −0.0028 (5)
C3 0.0671 (10) 0.0290 (8) 0.0433 (8) −0.0075 (7) −0.0157 (7) 0.0050 (6)
N2 0.1055 (12) 0.0331 (8) 0.0532 (8) 0.0077 (7) −0.0173 (7) 0.0000 (6)
O2 0.0683 (7) 0.0451 (7) 0.0445 (6) 0.0015 (5) −0.0045 (5) −0.0032 (4)
Geometric parameters (Å, º)
N1—C7 1.2778 (16) C6—H1 0.9300
N1—C8 1.3883 (15) C11—N3 1.1341 (18)
O1—C2 1.3623 (15) C11—C10 1.4417 (17)
O1—H4 0.8200 C2—C1 1.376 (2)
C8—C10 1.3651 (17) C2—C3 1.3787 (19)
C8—C9 1.432 (2) C10—N4 1.3368 (18)
C7—C5 1.4548 (17) C9—N2 1.145 (2)
C7—H6 0.9300 N4—H4A 0.8600
C5—C4 1.387 (2) N4—H4B 0.8600
C5—C6 1.3887 (17) C1—H2 0.9300
C4—C3 1.3779 (19) C3—H3 0.9300
C4—H5 0.9300 O2—H8 0.8914
C6—C1 1.3786 (18) O2—H7 0.8848
C7—N1—C8 121.23 (11) O1—C2—C1 121.79 (12)
C2—O1—H4 109.5 O1—C2—C3 118.13 (13)
C10—C8—N1 117.76 (12) C1—C2—C3 120.07 (12)
C10—C8—C9 119.92 (11) N4—C10—C8 123.85 (11)
N1—C8—C9 122.32 (11) N4—C10—C11 116.52 (11)
N1—C7—C5 122.35 (12) C8—C10—C11 119.63 (12)
N1—C7—H6 118.8 N2—C9—C8 176.94 (14)
C5—C7—H6 118.8 C10—N4—H4A 120.0
C4—C5—C6 118.22 (12) C10—N4—H4B 120.0
C4—C5—C7 122.03 (11) H4A—N4—H4B 120.0
C6—C5—C7 119.74 (12) C2—C1—C6 119.40 (12)
C3—C4—C5 120.50 (12) C2—C1—H2 120.3
C3—C4—H5 119.7 C6—C1—H2 120.3
C5—C4—H5 119.7 C4—C3—C2 120.34 (14)
C1—C6—C5 121.44 (13) C4—C3—H3 119.8
C1—C6—H1 119.3 C2—C3—H3 119.8
C5—C6—H1 119.3 H8—O2—H7 105.1
C7—N1—C8—C10 −177.91 (12) C9—C8—C10—N4 −177.04 (13)
C7—N1—C8—C9 1.88 (19) N1—C8—C10—C11 −177.51 (11)
C8—N1—C7—C5 −179.19 (11) C9—C8—C10—C11 2.69 (19)
N1—C7—C5—C4 4.6 (2) O1—C2—C1—C6 178.49 (13)
N1—C7—C5—C6 −175.42 (13) C3—C2—C1—C6 −1.3 (2)
C6—C5—C4—C3 −1.1 (2) C5—C6—C1—C2 0.9 (2)
C7—C5—C4—C3 178.85 (13) C5—C4—C3—C2 0.8 (2)
C4—C5—C6—C1 0.3 (2) O1—C2—C3—C4 −179.33 (13)
C7—C5—C6—C1 −179.70 (13) C1—C2—C3—C4 0.5 (2)
N1—C8—C10—N4 2.76 (19)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O1—H4···O2i 0.82 1.87 2.6848 (16) 169
O2—H7···O1ii 0.88 2.04 2.8283 (15) 148
O2—H8···N2iii 0.89 2.26 3.115 (2) 161
N4—H4A···N2iii 0.86 2.42 3.1691 (19) 146
N4—H4B···N3iv 0.86 2.15 3.0053 (18) 171
