Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807019344/hk2228sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807019344/hk2228Isup2.hkl |
CCDC reference: 647694
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.031
- wR factor = 0.090
- Data-to-parameter ratio = 14.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) . 500 Ang. PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.92 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for Si - C6 .. 5.10 su
Alert level G REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max 33.89 From the CIF: _reflns_number_total 2436 From the CIF: _diffrn_reflns_limit_ max hkl 13. 13. 15. From the CIF: _diffrn_reflns_limit_ min hkl -10. -12. -12. TEST1: Expected hkl limits for theta max Calculated maximum hkl 13. 16. 18. Calculated minimum hkl -13. -16. -18.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Jaska et al. (2003); Mountford et al. (2003); Chitsaz et al. (2002).
B2H6 (b.p. 181 K) was generated by the reaction of BF3(OEt2) (51.6 mmol, 6.53 ml) and NaBH4 (1.46 g, 38.7 mmol) in bis(2-methoxyethyl) ether (20 ml) under nitrogen prior to being condensed at 166 K (liquid nitrogen/iso-octane slurrey). The liquid B2H6 was reacted with a solution of N-(trimethylsilyl)pyrrolidine (17.2 mmol, 3.0 ml) in hexane. Colorless crystals of (I) were obtained after 5 d.
H atoms were located in difference syntheses and refined isotropically [C—H = 0.893 (15)–1.010 (12) Å, B—H = 1.104 (14)–1.121 (13) Å and Uiso(H) = 0.013 (3)–0.051 (5) Å2].
As part of a broader study aimed at using various borane derivatives as hydroborating agents for octenes, we have recently begun to explore the use of activated amine adducts of BH3. Our goal in this work was to prepare and structurally characterize a relatively stable silylated secondary amine adduct of BH3 as a potentially active hydroborating reagent for alkenes.
The molecular structure of (I), (Fig. 1), reflects sp3 hybridized geometries for boron and nitrogen, consistent with the formation of a regular dative covalent bond to boron. Viewing (I) down the N–Si bond vector shows that the B–N bond roughly bisects the C5–Si–C7 angle to give a staggered conformation around the Si–N bond [C7–Si–N–B = 69 (1)°]. The BH3 group therefore fits within the space generated by the closest two methyls of the SiMe3 group.
The B–N bond of (I) (Table 1) is significantly longer than that of B(C6F5)3.(pyrrolidine) [1.628 Å; Mountford et al., 2003], (pyrrolidine)2(BH2)2 [1.596 Å; Jaska et al., 2003] and BH3.(pyrrolidine) (1.591 Å; Chitsaz et al., 2002). The origin of this effect is unclear, since the present structure exhibits no repulsive (short) B···Si steric interactions that might favour marked elongation of the B–N bond. Indeed the B–N–Si bond angle [108.8 (1)°] is close to the ideal sp3 hybridized value of 109.5°.
It is possible that silylation of the pyrrolidine nitrogen in (I) reduces its σ-donor power, culminating in a weaker, longer N–B bond. Also relevant is the fact that the pyrrolidine ring of (I) adopts a slightly distorted envelope conformation, with N as the flap atom; N is displaced by 0.602 (3) Å from the mean plane of the other four atoms. The ring carbon atoms C2 and C3 tip towards the BH3 unit leading to a short intramolecular contact between H3B and B [3.02 (1) Å]. It has also a pseudo mirror plane passing through atom N and the mid-point of C2—C3 bond, as evidenced by the torsion angles (Table 1). This conformation is not observed for the pyrrolidine adduct of BH3 where the envelope conformation of the pyrrolidine ring is folded away from the BH3 group, presumably due to the absence of the bulky SiMe3 group.
There are no short intermolecular contacts between molecules of (I) in the crystal lattice and the 4-molecule unit cell (Fig. 2) shows the expected packing.
For related literature, see: Jaska et al. (2003); Mountford et al. (2003); Chitsaz et al. (2002).
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: WinGX.
C7H20BNSi | F(000) = 352 |
Mr = 157.14 | Dx = 1.04 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4177 reflections |
a = 8.613 (5) Å | θ = 3.8–33.9° |
b = 10.321 (5) Å | µ = 0.17 mm−1 |
c = 11.753 (5) Å | T = 100 K |
β = 106.080 (5)° | Block, colorless |
V = 1003.9 (9) Å3 | 0.4 × 0.3 × 0.2 mm |
Z = 4 |
Oxford Diffraction Xcalibur2 CCD diffractometer | 2436 independent reflections |
Radiation source: fine-focus sealed tube | 1970 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
Detector resolution: 8.4190 pixels mm-1 | θmax = 33.9°, θmin = 4.0° |
ω scans | h = −10→13 |
Absorption correction: multi-scan (Blessing, 1995) | k = −12→13 |
Tmin = 0.934, Tmax = 0.971 | l = −12→15 |
6834 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.0589P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.090 | (Δ/σ)max = 0.001 |
S = 1.06 | Δρmax = 0.39 e Å−3 |
2436 reflections | Δρmin = −0.21 e Å−3 |
171 parameters |
C7H20BNSi | V = 1003.9 (9) Å3 |
Mr = 157.14 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.613 (5) Å | µ = 0.17 mm−1 |
b = 10.321 (5) Å | T = 100 K |
c = 11.753 (5) Å | 0.4 × 0.3 × 0.2 mm |
β = 106.080 (5)° |
Oxford Diffraction Xcalibur2 CCD diffractometer | 2436 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 1970 reflections with I > 2σ(I) |
Tmin = 0.934, Tmax = 0.971 | Rint = 0.016 |
6834 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.090 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.39 e Å−3 |
2436 reflections | Δρmin = −0.21 e Å−3 |
171 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.85439 (13) | 0.12797 (11) | 0.34325 (10) | 0.0169 (2) | |
C2 | 0.68293 (13) | 0.15220 (11) | 0.35366 (10) | 0.0194 (3) | |
C3 | 0.66737 (13) | 0.30030 (12) | 0.36165 (10) | 0.0194 (3) | |
C4 | 0.82484 (12) | 0.35392 (11) | 0.34436 (10) | 0.0153 (2) | |
C5 | 1.24120 (13) | 0.41217 (11) | 0.40765 (11) | 0.0198 (3) | |
C6 | 1.06149 (15) | 0.29146 (14) | 0.17331 (11) | 0.0239 (3) | |
C7 | 1.24759 (15) | 0.11565 (12) | 0.36983 (13) | 0.0257 (3) | |
B | 1.00502 (16) | 0.24707 (13) | 0.53477 (12) | 0.0185 (3) | |
N | 0.94841 (11) | 0.24928 (8) | 0.38998 (8) | 0.0124 (2) | |
Si | 1.12767 (3) | 0.26715 (3) | 0.33653 (3) | 0.01435 (12) | |
H1A | 0.9113 (13) | 0.0563 (12) | 0.3895 (10) | 0.021 (3)* | |
H1B | 0.8533 (14) | 0.1164 (13) | 0.2613 (11) | 0.023 (3)* | |
H2A | 0.6659 (14) | 0.1066 (13) | 0.4225 (10) | 0.024 (3)* | |
H2B | 0.6058 (14) | 0.1173 (12) | 0.2842 (10) | 0.021 (3)* | |
H3A | 0.5724 (14) | 0.3351 (12) | 0.2980 (11) | 0.022 (3)* | |
H3B | 0.6545 (15) | 0.3236 (13) | 0.4371 (12) | 0.028 (3)* | |
H4A | 0.8639 (13) | 0.4323 (12) | 0.3881 (10) | 0.017 (3)* | |
H4B | 0.8130 (13) | 0.3645 (11) | 0.2611 (10) | 0.013 (3)* | |
H5A | 1.1743 (16) | 0.4884 (14) | 0.3951 (12) | 0.037 (4)* | |
H5B | 1.2849 (14) | 0.3980 (12) | 0.4911 (11) | 0.023 (3)* | |
H5C | 1.3241 (16) | 0.4273 (13) | 0.3727 (11) | 0.033 (4)* | |
H6A | 0.9977 (19) | 0.2279 (14) | 0.1352 (13) | 0.042 (5)* | |
H6B | 1.1574 (19) | 0.2906 (14) | 0.1439 (14) | 0.041 (4)* | |
H6C | 1.0107 (16) | 0.3754 (17) | 0.1528 (11) | 0.046 (4)* | |
H7A | 1.3255 (19) | 0.1171 (15) | 0.3272 (12) | 0.051 (4)* | |
H7B | 1.2976 (18) | 0.1068 (15) | 0.4542 (14) | 0.051 (5)* | |
H7C | 1.1859 (17) | 0.0430 (16) | 0.3421 (12) | 0.047 (4)* | |
H8A | 0.9040 (16) | 0.2120 (13) | 0.5674 (12) | 0.033 (4)* | |
H8B | 1.0372 (15) | 0.3472 (13) | 0.5678 (10) | 0.030 (4)* | |
H8C | 1.1110 (16) | 0.1800 (14) | 0.5637 (11) | 0.040 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0208 (5) | 0.0125 (5) | 0.0170 (6) | −0.0037 (4) | 0.0045 (4) | −0.0025 (5) |
C2 | 0.0176 (5) | 0.0210 (6) | 0.0194 (6) | −0.0059 (4) | 0.0047 (5) | −0.0015 (5) |
C3 | 0.0166 (5) | 0.0226 (6) | 0.0197 (6) | 0.0008 (4) | 0.0061 (5) | −0.0010 (5) |
C4 | 0.0167 (5) | 0.0131 (5) | 0.0161 (5) | 0.0031 (4) | 0.0046 (4) | 0.0012 (4) |
C5 | 0.0172 (5) | 0.0173 (6) | 0.0248 (6) | −0.0016 (4) | 0.0057 (5) | −0.0027 (5) |
C6 | 0.0239 (6) | 0.0307 (7) | 0.0183 (6) | −0.0053 (5) | 0.0080 (5) | −0.0028 (5) |
C7 | 0.0218 (6) | 0.0198 (6) | 0.0342 (7) | 0.0042 (5) | 0.0054 (6) | −0.0068 (6) |
B | 0.0217 (6) | 0.0198 (6) | 0.0128 (6) | −0.0014 (5) | 0.0027 (5) | 0.0012 (5) |
N | 0.0144 (4) | 0.0098 (4) | 0.0125 (4) | 0.0001 (3) | 0.0029 (4) | −0.0002 (3) |
Si | 0.01368 (16) | 0.01410 (18) | 0.01535 (19) | 0.00015 (10) | 0.00415 (12) | −0.00203 (12) |
C1—N | 1.5095 (14) | C5—H5B | 0.959 (12) |
C1—C2 | 1.5357 (17) | C5—H5C | 0.931 (14) |
C1—H1A | 0.967 (12) | C6—Si | 1.8606 (15) |
C1—H1B | 0.968 (12) | C6—H6A | 0.893 (15) |
C2—C3 | 1.5395 (18) | C6—H6B | 0.980 (16) |
C2—H2A | 0.982 (12) | C6—H6C | 0.971 (17) |
C2—H2B | 0.968 (12) | C7—Si | 1.8551 (14) |
C3—C4 | 1.5296 (16) | C7—H7A | 0.943 (16) |
C3—H3A | 1.010 (12) | C7—H7B | 0.969 (15) |
C3—H3B | 0.955 (13) | C7—H7C | 0.925 (16) |
C4—N | 1.5068 (14) | B—N | 1.6354 (17) |
C4—H4A | 0.967 (12) | B—H8A | 1.104 (14) |
C4—H4B | 0.961 (11) | B—H8B | 1.112 (13) |
C5—Si | 1.8553 (13) | B—H8C | 1.121 (13) |
C5—H5A | 0.962 (14) | N—Si | 1.8303 (13) |
N—C1—C2 | 105.47 (9) | Si—C6—H6A | 112.9 (10) |
N—C1—H1A | 107.0 (7) | Si—C6—H6B | 108.4 (9) |
C2—C1—H1A | 115.4 (7) | H6A—C6—H6B | 106.2 (12) |
N—C1—H1B | 108.7 (8) | Si—C6—H6C | 111.4 (8) |
C2—C1—H1B | 110.8 (7) | H6A—C6—H6C | 111.1 (12) |
H1A—C1—H1B | 109.2 (10) | H6B—C6—H6C | 106.7 (11) |
C1—C2—C3 | 105.57 (8) | Si—C7—H7A | 108.1 (10) |
C1—C2—H2A | 110.7 (7) | Si—C7—H7B | 111.0 (9) |
C3—C2—H2A | 113.0 (7) | H7A—C7—H7B | 111.4 (13) |
C1—C2—H2B | 108.8 (7) | Si—C7—H7C | 112.2 (9) |
C3—C2—H2B | 111.7 (8) | H7A—C7—H7C | 104.5 (12) |
H2A—C2—H2B | 107.0 (10) | H7B—C7—H7C | 109.5 (12) |
C4—C3—C2 | 104.82 (9) | N—B—H8A | 109.2 (7) |
C4—C3—H3A | 109.8 (7) | N—B—H8B | 108.9 (6) |
C2—C3—H3A | 112.0 (7) | H8A—B—H8B | 109.1 (9) |
C4—C3—H3B | 111.6 (8) | N—B—H8C | 107.9 (7) |
C2—C3—H3B | 110.0 (8) | H8A—B—H8C | 110.3 (10) |
H3A—C3—H3B | 108.7 (10) | H8B—B—H8C | 111.4 (9) |
N—C4—C3 | 104.97 (9) | C4—N—C1 | 102.14 (9) |
N—C4—H4A | 107.6 (7) | C4—N—B | 110.97 (8) |
C3—C4—H4A | 115.0 (7) | C1—N—B | 110.02 (8) |
N—C4—H4B | 108.0 (7) | C4—N—Si | 112.67 (7) |
C3—C4—H4B | 109.2 (7) | C1—N—Si | 112.16 (7) |
H4A—C4—H4B | 111.7 (9) | B—N—Si | 108.77 (7) |
Si—C5—H5A | 111.9 (8) | N—Si—C7 | 108.42 (6) |
Si—C5—H5B | 110.3 (8) | N—Si—C5 | 108.43 (5) |
H5A—C5—H5B | 109.2 (11) | C7—Si—C5 | 113.07 (7) |
Si—C5—H5C | 108.0 (8) | N—Si—C6 | 108.71 (6) |
H5A—C5—H5C | 107.2 (11) | C7—Si—C6 | 108.96 (6) |
H5B—C5—H5C | 110.2 (11) | C5—Si—C6 | 109.17 (6) |
N—C1—C2—C3 | 20.37 (11) | C4—N—Si—C7 | −167.46 (7) |
C1—C2—C3—C4 | 4.88 (11) | C1—N—Si—C7 | −52.87 (9) |
C2—C3—C4—N | −28.50 (11) | B—N—Si—C7 | 69.06 (8) |
C3—C4—N—C1 | 41.07 (11) | C4—N—Si—C5 | 69.43 (9) |
C3—C4—N—B | −76.15 (10) | C1—N—Si—C5 | −175.98 (7) |
C3—C4—N—Si | 161.60 (7) | B—N—Si—C5 | −54.05 (8) |
C2—C1—N—C4 | −37.80 (11) | C4—N—Si—C6 | −49.15 (9) |
C2—C1—N—B | 80.10 (10) | C1—N—Si—C6 | 65.44 (8) |
C2—C1—N—Si | −158.69 (7) | B—N—Si—C6 | −172.63 (7) |
Experimental details
Crystal data | |
Chemical formula | C7H20BNSi |
Mr | 157.14 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 8.613 (5), 10.321 (5), 11.753 (5) |
β (°) | 106.080 (5) |
V (Å3) | 1003.9 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur2 CCD |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.934, 0.971 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6834, 2436, 1970 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.785 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.090, 1.06 |
No. of reflections | 2436 |
No. of parameters | 171 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.39, −0.21 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), WinGX (Farrugia, 1999), WinGX.
C1—N | 1.5095 (14) | B—N | 1.6354 (17) |
C4—N | 1.5068 (14) | B—H8A | 1.104 (14) |
C5—Si | 1.8553 (13) | B—H8B | 1.112 (13) |
C6—Si | 1.8606 (15) | B—H8C | 1.121 (13) |
C7—Si | 1.8551 (14) | N—Si | 1.8303 (13) |
N—B—H8A | 109.2 (7) | C4—N—Si | 112.67 (7) |
N—B—H8B | 108.9 (6) | C1—N—Si | 112.16 (7) |
H8A—B—H8B | 109.1 (9) | B—N—Si | 108.77 (7) |
N—B—H8C | 107.9 (7) | N—Si—C7 | 108.42 (6) |
H8A—B—H8C | 110.3 (10) | N—Si—C5 | 108.43 (5) |
H8B—B—H8C | 111.4 (9) | C7—Si—C5 | 113.07 (7) |
C4—N—C1 | 102.14 (9) | N—Si—C6 | 108.71 (6) |
C4—N—B | 110.97 (8) | C7—Si—C6 | 108.96 (6) |
C1—N—B | 110.02 (8) | C5—Si—C6 | 109.17 (6) |
N—C1—C2—C3 | 20.37 (11) | C3—C4—N—C1 | 41.07 (11) |
C1—C2—C3—C4 | 4.88 (11) | C2—C1—N—C4 | −37.80 (11) |
C2—C3—C4—N | −28.50 (11) |
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As part of a broader study aimed at using various borane derivatives as hydroborating agents for octenes, we have recently begun to explore the use of activated amine adducts of BH3. Our goal in this work was to prepare and structurally characterize a relatively stable silylated secondary amine adduct of BH3 as a potentially active hydroborating reagent for alkenes.
The molecular structure of (I), (Fig. 1), reflects sp3 hybridized geometries for boron and nitrogen, consistent with the formation of a regular dative covalent bond to boron. Viewing (I) down the N–Si bond vector shows that the B–N bond roughly bisects the C5–Si–C7 angle to give a staggered conformation around the Si–N bond [C7–Si–N–B = 69 (1)°]. The BH3 group therefore fits within the space generated by the closest two methyls of the SiMe3 group.
The B–N bond of (I) (Table 1) is significantly longer than that of B(C6F5)3.(pyrrolidine) [1.628 Å; Mountford et al., 2003], (pyrrolidine)2(BH2)2 [1.596 Å; Jaska et al., 2003] and BH3.(pyrrolidine) (1.591 Å; Chitsaz et al., 2002). The origin of this effect is unclear, since the present structure exhibits no repulsive (short) B···Si steric interactions that might favour marked elongation of the B–N bond. Indeed the B–N–Si bond angle [108.8 (1)°] is close to the ideal sp3 hybridized value of 109.5°.
It is possible that silylation of the pyrrolidine nitrogen in (I) reduces its σ-donor power, culminating in a weaker, longer N–B bond. Also relevant is the fact that the pyrrolidine ring of (I) adopts a slightly distorted envelope conformation, with N as the flap atom; N is displaced by 0.602 (3) Å from the mean plane of the other four atoms. The ring carbon atoms C2 and C3 tip towards the BH3 unit leading to a short intramolecular contact between H3B and B [3.02 (1) Å]. It has also a pseudo mirror plane passing through atom N and the mid-point of C2—C3 bond, as evidenced by the torsion angles (Table 1). This conformation is not observed for the pyrrolidine adduct of BH3 where the envelope conformation of the pyrrolidine ring is folded away from the BH3 group, presumably due to the absence of the bulky SiMe3 group.
There are no short intermolecular contacts between molecules of (I) in the crystal lattice and the 4-molecule unit cell (Fig. 2) shows the expected packing.