Z. Kristallogr. NCS 223 (2008) 345-346 / DOI 10.1524/ncrs.2008.0150
345
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Crystal structure of N,N,N',N'-tetramethylchloroformamidinium chloride, [C5H12N2Cl]Cl Ioannis TiritirisI and Willi Kantlehner*,II I II
Universität Stuttgart, Institut für Organische Chemie, Pfaffenwaldring 55, 70569 Stuttgart, Germany Hochschule Aalen, Fakultät Chemie/Organische Chemie, Beethovenstr. 1, 73430 Aalen, Germany
Received February 26, 2008, accepted and available on-line September 25, 2008; CCDC no. 1267/2315
gous investigations on salts of type similiar to the title compound are missing. The crystal structure contains isolated N,N,N',N'-tetramethylchloroformamidinium cations and chloride anions. The C1—Cl2 bond in the cation is characterized by the distance of 1.730(1) Å, the N1—C1 and the N2—C1 bond lenghts are clearly shorter, falling in a small range between 1.313(2) Å to 1.320(2) Å. The N1−C1−N2 angle with 125.1(1)° also the N2−C1−Cl2 and N1− C1−Cl2 angles in a range from 117.16(9)° to 117.67(9)° are indicating a strong deviation of the cation from an ideal trigonal planar geometry. Table 1. Data collection and handling. Crystal: Wavelength: m: Diffractometer, scan mode: 2qmax: N(hkl)measured, N(hkl)unique: Criterion for Iobs, N(hkl)gt: N(param)refined: Programs:
Abstract C5H12Cl2N2, monoclinic, P21/n (no. 14), a = 9.3586(2) Å, b = 9.0716(2) Å, c = 9.5704(2) Å, b = 90.140(3)°, V = 812.5 Å3, Z = 4, Rgt(F) = 0.029, wRref(F2) = 0.078, T = 100 K. Source of material N,N,N',N'-Tetramethylchloroformamidinium chloride represents an iminium salt which can be derived from carbonic acid. The strongly hygroscopic and moisture sensitive compound is accessible by the action of phosgene on N,N,N',N'-tetramethylurea [13]. Colourless single crystals of the title compound were obtained by crystallization from acetonitrile solution at 0 °C. From the title compound ortho carbonic acid derivatives [4,5] and N,N,N',N'hexa-substituted guanidinium salts [6,7] can be prepared, which can serve as ionic liquids. Discussion The crystal structures of serveral N,N,N',N',N'',N''-hexamethylguanidinium salts have been elucidated [8-11] whereas analo-
colourless lath-shaped, size 0.2 × 0.2 × 0.3 mm Mo Ka radiation (0.71073 Å) 7.19 cm−1 Bruker-Nonius Kappa CCD, w 55.04° 14480, 1861 Iobs > 4 s(Iobs), 1725 131 SHELXS-97 [12], SHELXL-97 [13], SHELXTL-plus [14]
Table 2. Atomic coordinates and displacement parameters (in Å2). Atom
Site
H(2A) H(2B) H(2C) H(3A) H(3B) H(3C) H(4A) H(4B) H(4C) H(5A) H(5B) H(5C)
4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e
x
y
−0.200(2) −0.070(2) −0.064(2) −0.196(2) −0.050(2) −0.103(2) 0.352(2) 0.211(2) 0.258(2) 0.173(2) 0.183(2) 0.312(2)
0.375(2) 0.346(2) 0.484(2) 0.168(2) 0.100(2) 0.100(2) 0.495(2) 0.534(2) 0.633(2) 0.390(2) 0.554(2) 0.455(2)
z
Uiso
0.314(2) 0.422(2) 0.326(2) 0.161(2) 0.123(2) 0.283(2) 0.080(2) −0.004(2) 0.126(2) 0.387(2) 0.361(2) 0.330(2)
0.021(4) 0.033(4) 0.022(4) 0.029(4) 0.028(4) 0.027(4) 0.029(4) 0.026(4) 0.039(5) 0.025(4) 0.035(5) 0.032(4)
U13
U23
Table 3. Atomic coordinates and displacement parameters (in Å2). Atom
Site
x
y
Cl(1) Cl(2)
4e 4e
0.03521(3) 0.07938(3)
0.21611(3) 0.28908(3)
z −0.34734(3) −0.03139(3)
U11
U22
U33
0.0189(2) 0.0190(2)
0.0159(2) 0.0283(2)
0.0180(2) 0.0152(2)
_____________
* Correspondence author (e-mail:
[email protected])
U12 −0.00113(9) 0.0056(1)
−0.0009(1) 0.0011(1)
−0.00144(9) −0.0046(1)
346
[C5H12N2Cl]Cl
Table 3. Continued. Atom
Site
N(1) N(2) C(1) C(2) C(3) C(4) C(5)
4e 4e 4e 4e 4e 4e 4e
x −0.0306(1) 0.1690(1) 0.0732(1) −0.0972(1) −0.1006(1) 0.2549(1) 0.2102(1)
y
z
U11
U22
U33
0.2957(1) 0.4451(1) 0.3483(1) 0.3835(1) 0.1533(1) 0.5345(2) 0.4636(2)
0.2190(1) 0.1809(1) 0.1403(1) 0.3309(1) 0.1935(2) 0.0842(2) 0.3281(1)
0.0145(5) 0.0130(5) 0.0149(5) 0.0187(6) 0.0178(6) 0.0166(6) 0.0180(6)
0.0125(5) 0.0152(5) 0.0138(5) 0.0197(6) 0.0139(6) 0.0225(6) 0.0216(6)
0.0181(5) 0.0194(5) 0.0147(5) 0.0174(6) 0.0351(7) 0.0322(7) 0.0215(6)
U12 −0.0002(3) −0.0001(4) 0.0049(4) 0.0015(4) −0.0033(4) −0.0010(5) −0.0008(5)
U13 0.0007(4) 0.0014(4) 0.0005(4) 0.0053(4) 0.0001(5) 0.0037(5) −0.0029(5)
U23 −0.0004(4) 0.0021(4) 0.0001(4) −0.0003(5) −0.0013(5) 0.0099(5) −0.0047(5)
Acknowledgments. We are indebted to Dr. Falk Lissner, Institute of Inorganic Chemistry, University of Stuttgart, for the measurement of the low temperature crystal data and Dr. Wolfgang Frey, Institute of Organic Chemistry, University of Stuttgart, for preparation of the publication files.
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