organic compounds
Cyclobutylamine hemihydrate
aSchool of Chemistry, The University of Edinburgh, King's Buildings, West Mains Road, Edinburgh EH9 3JJ, Scotland
*Correspondence e-mail: d.r.allan@ed.ac.uk
The 4H9N·0.5H2O, consists of two cyclobutylamine molecules bridged by a water molecule via N⋯H—O hydrogen bonds. This molecular arrangement is further connected by significantly weaker N—H⋯O contacts to form columns parallel to the b axis.
of cyclobutylamine hemihydrate, CComment
The 4H7NH2·0.5H2O), (I), was determined at 205 K (just below the ∼210 K melting point) as part of our low-temperature and high-pressure structural studies of prototypical hydrogen-bonded molecular systems. It crystallizes in the monoclinic P21/n with two cyclobutylamine molecules and one water molecule in the (Fig. 1). Pairs of cyclobutylamine molecules are bridged by a single water molecule through N⋯H—O hydrogen bonds, which have N⋯O distances of 2.880 (3) and 2.895 (2) Å (Fig. 2 and Table 1). Significantly weaker N—H⋯O contacts link this molecular assembly to form columns parallel to the b axis, with N⋯O distances ranging in length from 3.176 (3) and 3.281 (3) Å to a more marginal distance of 3.604 (3) Å. As the N⋯O distances increase, there is a concomitant decrease in the N—H⋯O angles from 173.0 (19) to 160.1 (19)° as the interaction weakens. The remaining N—H⋯O interaction (N11—H111⋯O1) would appear to link the columns into slabs parallel to (01). However, as this interaction has a very long N⋯O contact distance of 3.833 (3) Å, and the N—H⋯O angle is 134.3 (15)°, it is unlikely to offer any significant contribution to the intermolecular bonding.
of cyclobutylamine hemihydrate (CExperimental
The sample of cyclobutylamine hemihydrate was prepared from anhydrous starting material (of 99% purity, as received from Aldrich) and placed in a sealed glass capillary tube with an internal diameter of ca 0.2 mm. The sample was cooled using an Oxford Cryosystems low-temperature device (Cosier & Glazer, 1986) until crystallization was observed. The temperature was then cycled, by successive translations of the capillary through the gas stream, so that the sample was partially remelted and the number of crystallites reduced, until a single crystal was obtained at 205 K.
Crystal data
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Refinement
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H atoms attached to C atoms were placed in idealized positions (C—H = 0.94–1.00 Å) and allowed to ride on their parent atoms. H atoms attached to N and O atoms were located in a difference map and restrained to idealized distances and angles [N—H = 0.90 (1) Å, O—H = 0.82 (1) Å and O—H—O = 104 (1)°]. All H atoms were constrained so that Uiso(H) was equal to 1.2Ueq of their respective parent atoms.
Data collection: SMART (Bruker, 2001); cell SAINT; data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS and PLATON (Spek, 2003).
Supporting information
https://doi.org/10.1107/S1600536806002327/jh2001sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock CRYSTALS_cif. DOI: https://doi.org/10.1107/S1600536806002327/jh2001Isup2.hkl
Data collection: SMART (Bruker, 2001); cell
SAINT; data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS and PLATON (Spek, 2003).C4H9N·0.5H2O | F(000) = 360 |
Mr = 80.13 | Dx = 1.012 Mg m−3 |
Monoclinic, P21/n | Synchrotron radiation, λ = 0.68130 Å |
Hall symbol: -P 2yn | Cell parameters from 2051 reflections |
a = 14.048 (6) Å | θ = 8–46° |
b = 5.209 (2) Å | µ = 0.07 mm−1 |
c = 14.489 (6) Å | T = 205 K |
β = 97.369 (4)° | Cylinder, colourless |
V = 1051.5 (7) Å3 | 0.20 × 0.20 × 0.20 × 0.20 (radius) mm |
Z = 8 |
Bruker SMART diffractometer | 1411 reflections with I > 2σ(I) |
Curved silicon monochromator | Rint = 0.071 |
ω/2θ scans | θmax = 27.5°, θmin = 4.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −18→19 |
Tmin = 0.55, Tmax = 0.99 | k = −6→6 |
8565 measured reflections | l = −19→18 |
2525 independent reflections |
Refinement on F | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.063 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.072 | w = [1-(Fo-Fc)2/36σ2(F)]2/[2.28To(x) + 0.243T1(x) + 1.74T2(x)] where Ti are the Chebychev polynomials and x = Fc/Fmax (Prince, 1982; Watkin, 1994) |
S = 1.14 | (Δ/σ)max = 0.000218 |
1411 reflections | Δρmax = 0.17 e Å−3 |
118 parameters | Δρmin = −0.18 e Å−3 |
7 restraints |
Refinement. ABSTM02_ALERT_3_B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75 T min and Tmax reported: 0.550 0.990 T min(prime) and Tmax expected: 0.987 0.987 RR(prime) = 0.556 SADABS was also used to correct for the decay of the synchrotron X-ray beam. The overall sample absorption, especially at the relatively short wavelength, is extremely low. PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C23 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C12 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C22 The data were collected very close to the sample melting temperature and, consequently, the temperature factors are relatively large. PLAT420_ALERT_2_C D—H Without Acceptor N11 - H111 ··· ? PLAT420_ALERT_2_C D—H Without Acceptor N21 - H211 ··· ? Although the relevant N—H···O angles suggest that the oxygen atom acts as an acceptor for both N11—H111 and N21—H211, the H···A distances are relatively long and suggest that these interactions are at best extremely weak. Details of the various distances are mentioned in the comments section. |
x | y | z | Uiso*/Ueq | ||
N11 | 0.66281 (12) | 0.6261 (3) | 0.22065 (10) | 0.0590 | |
C12 | 0.63480 (12) | 0.6188 (3) | 0.31320 (12) | 0.0524 | |
C13 | 0.52996 (14) | 0.5731 (4) | 0.32271 (17) | 0.0742 | |
C14 | 0.54031 (19) | 0.7577 (5) | 0.40528 (19) | 0.0882 | |
C15 | 0.62917 (17) | 0.8626 (4) | 0.37068 (15) | 0.0751 | |
O1 | 0.60087 (11) | 0.1702 (3) | 0.11547 (10) | 0.0705 | |
N21 | 0.40677 (12) | 0.2763 (3) | 0.03446 (11) | 0.0623 | |
C22 | 0.33839 (13) | 0.2419 (4) | 0.09937 (11) | 0.0534 | |
C25 | 0.34180 (17) | −0.0039 (5) | 0.15398 (16) | 0.0773 | |
C24 | 0.23267 (16) | 0.0020 (5) | 0.14836 (15) | 0.0752 | |
C23 | 0.23237 (15) | 0.1925 (6) | 0.06886 (15) | 0.0846 | |
H121 | 0.6732 | 0.4839 | 0.3504 | 0.0625* | |
H131 | 0.5138 | 0.3963 | 0.3372 | 0.0889* | |
H132 | 0.4884 | 0.6336 | 0.2675 | 0.0894* | |
H141 | 0.5514 | 0.6690 | 0.4633 | 0.1089* | |
H142 | 0.4882 | 0.8755 | 0.4054 | 0.1088* | |
H151 | 0.6820 | 0.8860 | 0.4183 | 0.0917* | |
H152 | 0.6191 | 1.0139 | 0.3349 | 0.0923* | |
H221 | 0.3435 | 0.3886 | 0.1421 | 0.0646* | |
H251 | 0.3778 | 0.0052 | 0.2178 | 0.0935* | |
H252 | 0.3650 | −0.1418 | 0.1190 | 0.0938* | |
H241 | 0.2105 | 0.0777 | 0.2026 | 0.0910* | |
H242 | 0.1995 | −0.1578 | 0.1341 | 0.0915* | |
H231 | 0.1894 | 0.3458 | 0.0706 | 0.1014* | |
H232 | 0.2216 | 0.1046 | 0.0084 | 0.1013* | |
H211 | 0.4070 (17) | 0.435 (2) | 0.0116 (15) | 0.0744* | |
H1 | 0.6198 (15) | 0.303 (3) | 0.1417 (16) | 0.1011* | |
H2 | 0.5447 (9) | 0.202 (5) | 0.0966 (18) | 0.1017* | |
H212 | 0.4029 (16) | 0.142 (3) | −0.0039 (13) | 0.0737* | |
H111 | 0.7268 (7) | 0.634 (4) | 0.2227 (14) | 0.0715* | |
H112 | 0.6347 (14) | 0.767 (3) | 0.1950 (14) | 0.0719* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N11 | 0.0650 (9) | 0.0589 (9) | 0.0525 (8) | −0.0002 (7) | 0.0051 (7) | −0.0081 (7) |
C12 | 0.0524 (9) | 0.0517 (9) | 0.0517 (9) | 0.0010 (7) | 0.0018 (7) | −0.0005 (7) |
C13 | 0.0556 (11) | 0.0703 (13) | 0.0975 (15) | −0.0014 (9) | 0.0131 (10) | −0.0004 (12) |
C14 | 0.0908 (16) | 0.0859 (16) | 0.0964 (16) | 0.0068 (13) | 0.0448 (13) | −0.0057 (14) |
C15 | 0.0918 (15) | 0.0652 (12) | 0.0728 (13) | −0.0111 (10) | 0.0278 (11) | −0.0215 (10) |
O1 | 0.0712 (9) | 0.0643 (9) | 0.0741 (9) | 0.0055 (7) | 0.0025 (7) | −0.0171 (7) |
N21 | 0.0700 (10) | 0.0620 (10) | 0.0558 (8) | −0.0048 (8) | 0.0120 (7) | 0.0000 (8) |
C22 | 0.0667 (10) | 0.0482 (9) | 0.0447 (8) | 0.0021 (8) | 0.0054 (7) | −0.0016 (7) |
C25 | 0.0811 (14) | 0.0738 (14) | 0.0764 (13) | 0.0088 (11) | 0.0073 (10) | 0.0255 (11) |
C24 | 0.0802 (14) | 0.0782 (15) | 0.0694 (13) | −0.0122 (11) | 0.0181 (10) | 0.0092 (11) |
C23 | 0.0596 (11) | 0.122 (2) | 0.0709 (12) | 0.0029 (12) | 0.0025 (9) | 0.0293 (13) |
N11—C12 | 1.446 (2) | O1—H2 | 0.819 (10) |
N11—H111 | 0.896 (9) | N21—C22 | 1.439 (2) |
N11—H112 | 0.892 (9) | N21—H211 | 0.892 (9) |
C12—C13 | 1.516 (3) | N21—H212 | 0.892 (9) |
C12—C15 | 1.526 (3) | C22—C25 | 1.502 (3) |
C12—H121 | 1.001 | C22—C23 | 1.520 (3) |
C13—C14 | 1.527 (4) | C22—H221 | 0.980 |
C13—H131 | 0.977 | C25—C24 | 1.525 (3) |
C13—H132 | 0.980 | C25—H251 | 0.996 |
C14—C15 | 1.506 (3) | C25—H252 | 0.960 |
C14—H141 | 0.955 | C24—C23 | 1.520 (3) |
C14—H142 | 0.955 | C24—H241 | 0.966 |
C15—H151 | 0.954 | C24—H242 | 0.963 |
C15—H152 | 0.944 | C23—H231 | 1.004 |
O1—H1 | 0.817 (10) | C23—H232 | 0.983 |
C12—N11—H111 | 111.2 (14) | C22—N21—H211 | 113.2 (15) |
C12—N11—H112 | 104.5 (14) | C22—N21—H212 | 108.5 (14) |
H111—N11—H112 | 111.5 (19) | H211—N21—H212 | 120 (2) |
N11—C12—C13 | 118.15 (16) | N21—C22—C25 | 118.13 (17) |
N11—C12—C15 | 121.58 (16) | N21—C22—C23 | 122.83 (15) |
C13—C12—C15 | 87.84 (15) | C25—C22—C23 | 88.44 (17) |
N11—C12—H121 | 109.1 | N21—C22—H221 | 108.3 |
C13—C12—H121 | 107.7 | C25—C22—H221 | 109.7 |
C15—C12—H121 | 110.6 | C23—C22—H221 | 107.8 |
C12—C13—C14 | 88.64 (17) | C22—C25—C24 | 89.49 (16) |
C12—C13—H131 | 115.0 | C22—C25—H251 | 115.2 |
C14—C13—H131 | 115.2 | C24—C25—H251 | 115.9 |
C12—C13—H132 | 111.1 | C22—C25—H252 | 110.5 |
C14—C13—H132 | 115.1 | C24—C25—H252 | 113.2 |
H131—C13—H132 | 110.4 | H251—C25—H252 | 111.0 |
C13—C14—C15 | 88.14 (16) | C25—C24—C23 | 87.61 (15) |
C13—C14—H141 | 111.9 | C25—C24—H241 | 113.1 |
C15—C14—H141 | 114.9 | C23—C24—H241 | 112.4 |
C13—C14—H142 | 114.2 | C25—C24—H242 | 116.7 |
C15—C14—H142 | 115.8 | C23—C24—H242 | 116.6 |
H141—C14—H142 | 110.3 | H241—C24—H242 | 109.2 |
C12—C15—C14 | 89.01 (17) | C22—C23—C24 | 89.02 (15) |
C12—C15—H151 | 114.3 | C22—C23—H231 | 115.4 |
C14—C15—H151 | 114.0 | C24—C23—H231 | 116.3 |
C12—C15—H152 | 114.2 | C22—C23—H232 | 111.8 |
C14—C15—H152 | 114.5 | C24—C23—H232 | 110.9 |
H151—C15—H152 | 109.8 | H231—C23—H232 | 111.6 |
H1—O1—H2 | 103 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N11 | 0.82 (1) | 2.08 (1) | 2.895 (2) | 174 (3) |
O1—H2···N21 | 0.82 (1) | 2.07 (1) | 2.880 (3) | 174 (3) |
Acknowledgements
We thank Dr T. Prior of Daresbury Laboratory for his help during the experiment on station 9.8 at SRS. We also thank the EPSRC for funding both this project and DRA's Advanced Research Fellowship.
References
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