2-[(1-{[3-(dimethylazaniumyl)propyl]methylamino}ethylidene)azaniumyl]­nona­hydro-closo-deca­borate dimethyl sulfoxide disolvate

The title compound, 2-B₁₀H₉NH=C(CH₃)N(CH₃)CH₂CH₂CH₂N(CH₃)₂H·2C₂H₆OS or C₈H₂₉B₁₀N₃·2C₂H₆OS, is zwitterionic with the negative charge localized on the deca­borate cage and the positive charge on the terminal ammonium group. Two mol­ecules of dimethyl sulfoxide (DMSO) and one mol­ecule of the title compound constitute the asymmetric unit. One DMSO mol­ecule is disordered [ratio 0.739 (3):0.261 (3)]. The bonds and angles within the deca­borate cage are within the normal ranges. The amidine fragment of the ligand, which is expected to be planar, is significantly distorted from planarity as exemplified by four torsion angles [B-N-C-C = 8.4 (3), H-N-C-N = 5(2), N-C-N-C = 7.3 (3) and C-C-N-C = 14.8 (3)°] found within this portion of the mol­ecule. The crystal packing consists of head-to-tail-arranged dimers of the title mol­ecule held together by four mol­ecules of DMSO which are attached via strong N-H...O and weak C-H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 564 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in solvent or counterion
• R factor = 0.045
• wR factor = 0.135
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT430_ALERT_2_A Short Inter D...A Contact  S21    ..  O212    ..       2.68 Ang.

Author Response: This molecule is at 26.1% occupancy and this close contact is due to the disorder.

Alert level B
PLAT413_ALERT_2_B Short Inter XH3 .. XHn     H7     ..  H225    ..       2.01 Ang.

Author Response: This involves an H atom attached to one of the B atoms in close proximity to one of the H atoms on the methyl group of the disordered DMSO ligand. This may be due to the H atom on the disordered group located at not an optimal calculated position.

Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of          S1
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H11D   ...          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H11D   ..  O111    ..       2.67 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.594          2

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          8
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT244_ALERT_4_G Low   'Solvent' Ueq as Compared to Neighbors of          S2
PLAT244_ALERT_4_G Low   'Solvent' Ueq as Compared to Neighbors of         S21
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................         50 Perc.
PLAT432_ALERT_2_G Short Inter X...Y Contact  S21    ..  C224    ..       3.19 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  O212   ..  C224    ..       2.71 Ang.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          52 Perc.

   1 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The title compound, 2-B₁₀H₉NH=C(CH₃)N(CH₃)CH₂CH₂CH₂N(CH₃)₂H, (I), is zwitterionic with the negative charge localized on the decaborate cage and the positive charge on the terminal ammonium group. Two molecules of DMSO and one molecule of I constitute the asymmetric unit. One DMSO molecule is disordered over two closely situated sites with a 0.739 (3):0.261 (3) occupancy ratio. The disordered DMSO molecules display inverted conformations relative to each other, and such an arrangement was noted previously in a structure containing DMSO with a 0.95:0.05 disordered ratio (Hulme & Tocher, 2004). Fig. 1 shows the asymmetric unit, with only the major orientation of the disordered DMSO molecule drawn. Molecule I crystallizes in the form of head to tail arranged dimers held together by four molecules of DMSO which are attached via strong and weak hydrogen bonds as illustrated in Fig. 2. Both disordered DMSO molecules are involved with strong H-bonds involving the O atoms and a hydrogen atom bonded to atom N9 of I. As expected (Geremia et al., 2000), this results in longer S—O bonds for S2—O211 = 1.509 (5) Å and S21—O212 = 1.53 (1) Å compared to the S1—O111 distance of 1.478 (2) Å where weaker interactions exist. The ordered DMSO molecule binds to two molecules of I via weak long range H-bonded interactions and close contacts, see Fig. 2. The H9···S1 interaction at 2.9Å is less than the sum of the van der Waals radii at 3.05Å and, given the hydridic nature of H9, is best thought of as a close contact between a hydridic hydrogen and the partially positively charged sulfur of a DMSO molecule. The "dimers" are further weakly linked to adjacent dimers via long range H-bonded interactions resulting in a three-dimensional linked unit.

The molecular structure of I defines a slightly distorted bicapped square antiprism with an amidine ligand coordinated to an equatorial boron atom (B2). The exo B—N distance, 1.541 (3) Å, in I is slightly longer than that found in [2-B₁₀H₉NCCH₃]^- (II), 1.515 (5) Å, (Dou et al., 1994) and [2-B₁₀H₉NCCH=CH₂]^- (III), 1.523 (4) Å (Siriwardane et al., 1989). The average apical-equatorial distance in I is B1—B_eq = 1.693 (5) Å, which compares favorably to the analogous distances of 1.682 (4) Å and 1.693 (5) Å in II and III, respectively, and B10—B_eq = 1.692 (11) Å, which compares favorably to the analogous distances of 1.689 (2)Å and 1.686 (5) Å in II and III, respectively. The average B—B distance between equatorial planes is 1.815 (9) Å. The average B_eq—B_eq distance defined by B2, B3, B4 and B5 is 1.835 (13) Å, and that defined by B6, B7, B8 and B9 is 1.826 (5) Å. Each of these distances is similar to those found in II and III.

The amidine ligand found in I is analogous to a protonated amidinium cation, wherein the boron hydride cage substitutes for a proton on the imino nitrogen. Amidines contain two different nitrogen atoms: a formally single-bonded amide like amino nitrogen (N_am) and a formally double-bonded imino nitrogen (N_im). The sp² characters of the atoms N1, C2, and N4 are supported by the sum of the bond angles about each of these atoms of 360°, 360.0° and 359.6°, respectively. The CN_im and CN_am bond lengths C2—N1, 1.318 (3) Å, and C2—N4, 1.335 (3) Å, respectively, as well as the difference between these bonds 0.016 Å, found in I are consistent with CN_im, CN_am bonds, and the difference(CN_am—CN_im) found within other reported amidine substituted polyhedral borane molecules (Froehner et al., 2006) as well as amidinium cations (Häfelinger & Kuske, 1991). The steric congestion within the amidine portion of I is illustrated by the nonplanarity of this portion of the molecule as exemplified by the following torsion angles: B2—N1—C2—C3 8.4 (3)°, H11D—N1—C2—N4 5(2)°, N1—C2—N4—C5 7.3 (3)°, and C3—C2—N4—C6 14.8 (3)°.

Related literature

For related structures of 2-substituted decaborate compounds, see: Dou et al. (1994); Siriwardane et al. (1989). For related structures of amidine-substituted polyhedral boranes, see: Froehner et al. (2006). For related structures involving DMSO as solvate, see: Geremia et al. (2000); Hulme & Tocher (2004). For structural parameters involving amidinium cations, see: Häfelinger & Kuske (1991). For related synthetic work, see: Froehner et al. (2006).

S2. Experimental

The title compound was prepared by the reaction of [2-B₁₀H₉NCCH₃]^- with N,N,N'-trimethyl-1,3-propanediamine (see special details section). The title compound spontaneously crystallized from DMSO solution after sitting undisturbed for a period of one week. High resolution TOF MS ES+ for ¹²C₈¹H₃₀¹⁴N₃¹¹B₁₀⁺: calcd, 278.3370, found, 278.3379.

S3. Refinement

H atoms were placed at calculated positions, with C—H = 0.97 Å (ethyl) or 0.97 Å (methyl) and refined using a riding model with U_iso(H) constrained to be 1.2 U_eq(C) for ethyl groups and 1.5 U_eq(C) for the methyl groups. The H atoms bonded to the N atoms were constrained and refined to 0.79 (3) and 0.84 (3) Å for N1—H11D and N9—H91A respectively. One DMSO molecule is disordered over two sites with a 0.739 (3):0.261 (3) ratio.

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. POV-RAY rendered drawing of an ORTEP-3 (Farrugia, 1997) illustration of the molecules constituting the asymmetric unit. The thermal ellipsoids are drawn at 50% probability and the H atoms are drawn as spheres of arbritary radii. Only the major orientation of the disordered DMSO molecule is shown.

Fig. 2. POV-RAY rendered drawing of a Mercury (Macrae et al., 2006) illustration of the H-bonded arrangement. The thermal ellipsoids are drawn at 50% probability and the H atoms are drawn as spheres of arbitrary radii. Hydrogen bonds and close contacts are shown as dashed lines and the minor orientation of the DMSO molecule is not shown. Labelled atoms are at x,y,z except for atoms S2 and O211 which were generated by symmetry code 1.5 - x,1/2 + y,1/2 - z.

2-[(1-{[3-(dimethylazaniumyl)propyl]methylamino}ethylidene)azaniumyl]nonahydro- closo-decaborate dimethyl sulfoxide disolvate

Crystal data

C8H29B10N3·2C2H6OS	F(000) = 928
Mr = 431.7	Dx = 1.14 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 9.503 (2) Å	θ = 10–15°
b = 15.123 (5) Å	µ = 0.23 mm^−1
c = 18.032 (5) Å	T = 564 K
β = 103.94 (2)°	Prism, colourless
V = 2515.1 (12) Å^3	0.54 × 0.42 × 0.25 mm
Z = 4

Data collection

Enraf–Nonius TurboCAD-4 diffractometer	3208 reflections with I > 2σ(I)
Radiation source: Enraf–Nonius FR590	Rint = 0.016
Graphite monochromator	θmax = 25.0°, θmin = 1.8°
non–profiled ω/2θ scans	h = 0→11
Absorption correction: ψ scan (North et al., 1968)	k = −1→17
Tmin = 0.989, Tmax = 1.000	l = −21→20
5016 measured reflections	3 standard reflections every 166 min
4412 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.069P)^2 + 1.0018P] where P = (Fo^2 + 2Fc^2)/3
4412 reflections	(Δ/σ)max < 0.001
316 parameters	Δρmax = 0.32 e Å^−3
3 restraints	Δρmin = −0.32 e Å^−3

Special details

Experimental. Synthesis: N,N,N'-trimethyl-1,3-propanediamnine, 0.337 g, 2.90 mmol, was added to a solution of NEt₃H[2-B₁₀H₉NCCH₃], 0.760 g, 2.92 mmol, in 15 ml of acetonitrile. The light yellow solution was stirred for 30 minutes, then taken to dryness on a rotary evaporator. The resulting solid was dissolved in 10 ml of 1.0 M sodium hydroxide. The basic solution was extracted with pentane, to remove the generated triethylamine. The resulting aqueous solution was acidified with 1.0 M HCl until a precipitate formed. The white precipitate was vacuum filtered and dried overnight at 50°C under dynamic vacuum. Yield of the title compound was 0.632 g, 79%. Characterization: Hi-Res TOF MS ES⁺: calcd, 278.3370, found, 278.3379, NMR spectroscopic assignments are made using the numbering in figure 1. ¹¹B NMR in p.p.m.: -0.482 (B10), -3.81 (B1), -13.66 (B2), -24.86 (B4,7,8), -28.22 (B3,5,6,9). ¹H NMR in p.p.m.: 9.24 (s,H91A), 5.85 (s, H11D), 3.35 (t, H8A,B), 3.00 (t, H6A,B), 2.96 (s, H3A,B,C), 2.75 (s, H10A,B,C,H11A,B,C), 2.38 (s, H5A,B,C), 1.83 (q, H7A,B). Protons attached to boron not resolved. ¹³C NMR in p.p.m.: 164.35 (C2), 53.85, 47.52, 42.23, 35.83, 21.89, 15.44 (remaining aliphatic carbons). MP: 193–195°C decomposition.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
B1	0.1680 (3)	−0.0714 (2)	0.23061 (16)	0.0550 (8)
H1	0.2248	−0.0404	0.1909	0.066*
B2	0.2214 (3)	−0.08614 (16)	0.32607 (14)	0.0360 (5)
B3	0.0548 (3)	−0.02616 (18)	0.28008 (16)	0.0473 (7)
H3	0.0314	0.045	0.2737	0.057*
B4	0.0015 (3)	−0.1179 (2)	0.21324 (16)	0.0512 (7)
H4	−0.0646	−0.1189	0.1541	0.061*
B5	0.1694 (3)	−0.1780 (2)	0.25976 (17)	0.0482 (7)
H5	0.2354	−0.2262	0.2374	0.058*
B6	0.0692 (3)	−0.07928 (17)	0.37162 (15)	0.0397 (6)
H6	0.0771	−0.039	0.4232	0.048*
B7	−0.0838 (3)	−0.10342 (18)	0.29181 (17)	0.0461 (7)
H7	−0.1977	−0.0822	0.2804	0.055*
B8	−0.0033 (3)	−0.21016 (17)	0.27737 (16)	0.0436 (6)
H8	−0.0527	−0.2734	0.2546	0.052*
B9	0.1497 (3)	−0.18587 (16)	0.35776 (15)	0.0387 (6)
H9	0.2211	−0.2297	0.399	0.046*
B10	−0.0246 (3)	−0.17579 (19)	0.36349 (16)	0.0442 (6)
H10	−0.0823	−0.2071	0.4026	0.053*
N1	0.3759 (2)	−0.06191 (13)	0.37114 (11)	0.0379 (4)
H11D	0.422 (3)	−0.1011 (18)	0.3941 (15)	0.057*
C2	0.4476 (2)	0.01325 (14)	0.37510 (12)	0.0349 (5)
C3	0.3696 (3)	0.09380 (16)	0.33963 (15)	0.0509 (6)
H3A	0.4242	0.1218	0.3078	0.076*
H3B	0.3587	0.1341	0.379	0.076*
H3C	0.2757	0.0775	0.3092	0.076*
N4	0.58795 (18)	0.01902 (11)	0.41023 (11)	0.0382 (4)
C5	0.6728 (3)	−0.05969 (16)	0.43804 (16)	0.0521 (6)
H5A	0.7738	−0.0446	0.4523	0.078*
H5B	0.6566	−0.1036	0.3985	0.078*
H5C	0.6437	−0.0827	0.4817	0.078*
C6	0.6612 (2)	0.10402 (15)	0.43152 (13)	0.0413 (5)
H6A	0.7104	0.1023	0.4853	0.05*
H6B	0.5886	0.1503	0.4247	0.05*
C7	0.7710 (2)	0.12761 (14)	0.38569 (13)	0.0395 (5)
H7A	0.852	0.0867	0.3972	0.047*
H7B	0.7263	0.1246	0.3314	0.047*
C8	0.8226 (2)	0.22097 (15)	0.40810 (15)	0.0442 (6)
H8A	0.7417	0.2612	0.3911	0.053*
H8B	0.8519	0.2244	0.4634	0.053*
N9	0.9463 (2)	0.25199 (13)	0.37648 (12)	0.0446 (5)
H91A	0.957 (3)	0.3051 (19)	0.3909 (16)	0.067*
C10	0.9142 (3)	0.2499 (2)	0.29185 (16)	0.0624 (7)
H10A	0.9909	0.2787	0.2749	0.094*
H10B	0.8243	0.28	0.2711	0.094*
H10C	0.9065	0.1896	0.2747	0.094*
C11	1.0845 (3)	0.20572 (19)	0.41085 (18)	0.0605 (7)
H11A	1.1038	0.2091	0.4655	0.091*
H11B	1.1623	0.2333	0.3939	0.091*
H11C	1.077	0.1448	0.3953	0.091*
S1	0.51507 (7)	0.32140 (4)	0.52668 (4)	0.0539 (2)
O111	0.4605 (2)	0.23024 (12)	0.51022 (13)	0.0745 (6)
C111	0.5090 (4)	0.3423 (3)	0.62190 (17)	0.0923 (12)
H112	0.583	0.3085	0.6558	0.138*
H113	0.4157	0.3256	0.6291	0.138*
H114	0.5249	0.4041	0.6328	0.138*
C121	0.3700 (4)	0.3916 (2)	0.48091 (19)	0.0803 (10)
H122	0.3593	0.3894	0.4266	0.12*
H123	0.3906	0.4512	0.4985	0.12*
H124	0.2819	0.3721	0.4928	0.12*
S2	0.51955 (11)	−0.00035 (6)	0.14776 (7)	0.0572 (4)	0.739 (3)
O211	0.5077 (9)	−0.0774 (4)	0.0934 (3)	0.0675 (15)	0.739 (3)
C211	0.3870 (7)	0.0760 (4)	0.1009 (4)	0.0696 (17)	0.739 (3)
H212	0.2921	0.0524	0.0983	0.104*	0.739 (3)
H213	0.3982	0.0865	0.0501	0.104*	0.739 (3)
H214	0.3985	0.1306	0.1288	0.104*	0.739 (3)
C221	0.6739 (5)	0.0601 (3)	0.1376 (3)	0.0789 (15)	0.739 (3)
H222	0.7597	0.0256	0.1571	0.118*	0.739 (3)
H223	0.68	0.1144	0.1657	0.118*	0.739 (3)
H224	0.6654	0.0729	0.0846	0.118*	0.739 (3)
S21	0.5500 (3)	0.01848 (17)	0.08259 (17)	0.0560 (11)	0.261 (3)
O212	0.500 (3)	−0.0766 (10)	0.0621 (7)	0.057 (4)	0.261 (3)
C223	0.591 (2)	0.0268 (12)	0.1855 (12)	0.142 (10)	0.261 (3)
H225	0.6873	0.0058	0.2067	0.213*	0.261 (3)
H226	0.5229	−0.0083	0.2045	0.213*	0.261 (3)
H227	0.5833	0.0874	0.1999	0.213*	0.261 (3)
C224	0.389 (2)	0.0806 (13)	0.0630 (8)	0.059 (4)	0.261 (3)
H228	0.3483	0.0823	0.0088	0.089*	0.261 (3)
H229	0.4092	0.1398	0.0819	0.089*	0.261 (3)
H230	0.3205	0.0537	0.0877	0.089*	0.261 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
B1	0.0530 (17)	0.070 (2)	0.0389 (15)	−0.0207 (15)	0.0048 (13)	0.0014 (14)
B2	0.0328 (13)	0.0324 (13)	0.0408 (14)	−0.0062 (10)	0.0051 (10)	−0.0027 (11)
B3	0.0460 (15)	0.0344 (14)	0.0517 (16)	−0.0045 (12)	−0.0073 (13)	0.0062 (12)
B4	0.0498 (16)	0.0574 (18)	0.0398 (15)	−0.0130 (14)	−0.0023 (12)	−0.0038 (13)
B5	0.0375 (14)	0.0510 (17)	0.0570 (17)	−0.0090 (12)	0.0131 (12)	−0.0212 (14)
B6	0.0360 (13)	0.0382 (14)	0.0420 (14)	0.0033 (11)	0.0037 (11)	−0.0047 (11)
B7	0.0315 (13)	0.0424 (15)	0.0584 (17)	−0.0011 (11)	−0.0011 (12)	−0.0048 (13)
B8	0.0319 (13)	0.0352 (13)	0.0599 (17)	−0.0058 (11)	0.0036 (12)	−0.0117 (12)
B9	0.0342 (13)	0.0286 (13)	0.0510 (15)	−0.0013 (10)	0.0057 (11)	0.0006 (11)
B10	0.0329 (13)	0.0478 (16)	0.0519 (16)	−0.0039 (12)	0.0101 (11)	0.0005 (13)
N1	0.0338 (10)	0.0338 (10)	0.0433 (11)	−0.0057 (8)	0.0038 (8)	0.0024 (8)
C2	0.0345 (11)	0.0347 (12)	0.0362 (11)	−0.0052 (9)	0.0100 (9)	−0.0008 (9)
C3	0.0403 (13)	0.0402 (13)	0.0673 (16)	−0.0060 (11)	0.0030 (11)	0.0072 (12)
N4	0.0308 (10)	0.0323 (10)	0.0494 (11)	−0.0070 (8)	0.0057 (8)	−0.0013 (8)
C5	0.0371 (13)	0.0416 (13)	0.0727 (17)	−0.0021 (10)	0.0035 (12)	0.0093 (12)
C6	0.0336 (11)	0.0398 (13)	0.0492 (13)	−0.0098 (10)	0.0076 (10)	−0.0075 (10)
C7	0.0374 (12)	0.0306 (11)	0.0503 (13)	−0.0045 (9)	0.0103 (10)	−0.0019 (10)
C8	0.0361 (12)	0.0332 (12)	0.0656 (15)	−0.0026 (10)	0.0163 (11)	−0.0038 (11)
N9	0.0352 (10)	0.0281 (10)	0.0702 (14)	−0.0050 (8)	0.0120 (9)	−0.0012 (9)
C10	0.0569 (16)	0.0615 (17)	0.0705 (19)	−0.0039 (13)	0.0187 (14)	0.0140 (14)
C11	0.0324 (13)	0.0577 (16)	0.087 (2)	−0.0005 (12)	0.0047 (13)	−0.0022 (15)
S1	0.0505 (4)	0.0492 (4)	0.0594 (4)	−0.0044 (3)	0.0084 (3)	0.0005 (3)
O111	0.0801 (14)	0.0471 (11)	0.0977 (16)	−0.0085 (10)	0.0241 (12)	−0.0160 (11)
C111	0.104 (3)	0.107 (3)	0.0568 (19)	0.036 (2)	0.0018 (18)	−0.0131 (18)
C121	0.078 (2)	0.073 (2)	0.080 (2)	0.0112 (17)	−0.0002 (17)	0.0143 (17)
S2	0.0522 (6)	0.0373 (5)	0.0858 (9)	0.0033 (4)	0.0238 (5)	0.0100 (5)
O211	0.077 (3)	0.0317 (17)	0.094 (4)	0.0092 (16)	0.020 (4)	0.003 (2)
C211	0.056 (3)	0.037 (2)	0.111 (5)	0.0094 (19)	0.010 (4)	0.001 (4)
C221	0.052 (2)	0.069 (3)	0.118 (4)	−0.008 (2)	0.023 (3)	0.016 (3)
S21	0.0507 (16)	0.0411 (15)	0.076 (2)	0.0038 (11)	0.0158 (13)	−0.0055 (12)
O212	0.074 (6)	0.032 (5)	0.054 (7)	0.012 (4)	−0.003 (8)	−0.007 (5)
C223	0.138 (18)	0.089 (13)	0.144 (17)	0.039 (12)	−0.076 (15)	−0.056 (12)
C224	0.079 (9)	0.040 (7)	0.054 (8)	0.024 (6)	0.006 (8)	0.004 (7)

Geometric parameters (Å, º)

B1—B2	1.688 (4)	C6—C7	1.521 (3)
B1—B4	1.690 (4)	C6—H6A	0.97
B1—B5	1.694 (4)	C6—H6B	0.97
B1—B3	1.698 (5)	C7—C8	1.517 (3)
B1—H1	1.1	C7—H7A	0.97
B2—N1	1.541 (3)	C7—H7B	0.97
B2—B9	1.804 (3)	C8—N9	1.499 (3)
B2—B5	1.822 (4)	C8—H8A	0.97
B2—B6	1.830 (4)	C8—H8B	0.97
B2—B3	1.840 (4)	N9—C10	1.483 (3)
B3—B7	1.810 (4)	N9—C11	1.486 (3)
B3—B6	1.811 (4)	N9—H91A	0.84 (3)
B3—B4	1.827 (4)	C10—H10A	0.96
B3—H3	1.1	C10—H10B	0.96
B4—B7	1.807 (4)	C10—H10C	0.96
B4—B8	1.820 (4)	C11—H11A	0.96
B4—B5	1.852 (4)	C11—H11B	0.96
B4—H4	1.1	C11—H11C	0.96
B5—B8	1.812 (4)	S1—O111	1.478 (2)
B5—B9	1.825 (4)	S1—C111	1.761 (3)
B5—H5	1.1	S1—C121	1.777 (3)
B6—B10	1.698 (4)	C111—H112	0.96
B6—B7	1.819 (4)	C111—H113	0.96
B6—B9	1.827 (4)	C111—H114	0.96
B6—H6	1.1	C121—H122	0.96
B7—B10	1.684 (4)	C121—H123	0.96
B7—B8	1.832 (4)	C121—H124	0.96
B7—H7	1.1	S2—O211	1.509 (5)
B8—B10	1.695 (4)	S2—C211	1.767 (6)
B8—B9	1.826 (4)	S2—C221	1.774 (4)
B8—H8	1.1	C211—H212	0.96
B9—B10	1.691 (3)	C211—H213	0.96
B9—H9	1.1	C211—H214	0.96
B10—H10	1.1	C221—H222	0.96
N1—C2	1.318 (3)	C221—H223	0.96
N1—H11D	0.79 (3)	C221—H224	0.96
C2—N4	1.335 (3)	S21—O212	1.530 (14)
C2—C3	1.488 (3)	S21—C224	1.760 (19)
C3—H3A	0.96	S21—C223	1.81 (2)
C3—H3B	0.96	C223—H225	0.96
C3—H3C	0.96	C223—H226	0.96
N4—C5	1.457 (3)	C223—H227	0.96
N4—C6	1.468 (3)	C224—H228	0.96
C5—H5A	0.96	C224—H229	0.96
C5—H5B	0.96	C224—H230	0.96
C5—H5C	0.96
B2—B1—B4	99.9 (2)	B10—B9—B2	113.22 (19)
B2—B1—B5	65.17 (17)	B10—B9—B5	112.57 (19)
B4—B1—B5	66.37 (18)	B2—B9—B5	60.26 (14)
B2—B1—B3	65.83 (17)	B10—B9—B8	57.48 (15)
B4—B1—B3	65.28 (18)	B2—B9—B8	101.90 (17)
B5—B1—B3	100.3 (2)	B5—B9—B8	59.50 (15)
B2—B1—H1	130.2	B10—B9—B6	57.56 (15)
B4—B1—H1	129.9	B2—B9—B6	60.54 (14)
B5—B1—H1	129.7	B5—B9—B6	102.63 (18)
B3—B1—H1	129.9	B8—B9—B6	90.37 (16)
N1—B2—B1	121.4 (2)	B10—B9—H9	117.8
N1—B2—B9	114.61 (18)	B2—B9—H9	120
B1—B2—B9	112.92 (18)	B5—B9—H9	120.3
N1—B2—B5	126.94 (19)	B8—B9—H9	131.3
B1—B2—B5	57.57 (17)	B6—B9—H9	130.5
B9—B2—B5	60.45 (15)	B7—B10—B9	99.36 (19)
N1—B2—B6	120.34 (18)	B7—B10—B8	65.64 (17)
B1—B2—B6	111.95 (19)	B9—B10—B8	65.26 (16)
B9—B2—B6	60.37 (14)	B7—B10—B6	65.10 (16)
B5—B2—B6	102.65 (16)	B9—B10—B6	65.24 (15)
N1—B2—B3	136.68 (19)	B8—B10—B6	99.59 (19)
B1—B2—B3	57.34 (17)	B7—B10—H10	130.3
B9—B2—B3	101.84 (16)	B9—B10—H10	130.4
B5—B2—B3	90.69 (17)	B8—B10—H10	130.1
B6—B2—B3	59.13 (14)	B6—B10—H10	130.3
B1—B3—B7	111.8 (2)	C2—N1—B2	130.38 (19)
B1—B3—B6	112.4 (2)	C2—N1—H11D	114 (2)
B7—B3—B6	60.32 (15)	B2—N1—H11D	116 (2)
B1—B3—B4	57.13 (17)	N1—C2—N4	121.8 (2)
B7—B3—B4	59.57 (15)	N1—C2—C3	119.04 (19)
B6—B3—B4	102.27 (18)	N4—C2—C3	119.19 (19)
B1—B3—B2	56.82 (15)	C2—C3—H3A	109.5
B7—B3—B2	101.56 (17)	C2—C3—H3B	109.5
B6—B3—B2	60.16 (14)	H3A—C3—H3B	109.5
B4—B3—B2	89.69 (18)	C2—C3—H3C	109.5
B1—B3—H3	118.5	H3A—C3—H3C	109.5
B7—B3—H3	120.7	H3B—C3—H3C	109.5
B6—B3—H3	119.9	C2—N4—C5	121.11 (18)
B4—B3—H3	131.1	C2—N4—C6	122.56 (18)
B2—B3—H3	131.3	C5—N4—C6	115.92 (17)
B1—B4—B7	112.4 (2)	N4—C5—H5A	109.5
B1—B4—B8	111.5 (2)	N4—C5—H5B	109.5
B7—B4—B8	60.66 (16)	H5A—C5—H5B	109.5
B1—B4—B3	57.58 (17)	N4—C5—H5C	109.5
B7—B4—B3	59.75 (16)	H5A—C5—H5C	109.5
B8—B4—B3	102.03 (19)	H5B—C5—H5C	109.5
B1—B4—B5	56.93 (17)	N4—C6—C7	114.05 (18)
B7—B4—B5	101.81 (19)	N4—C6—H6A	108.7
B8—B4—B5	59.12 (15)	C7—C6—H6A	108.7
B3—B4—B5	90.13 (17)	N4—C6—H6B	108.7
B1—B4—H4	118.4	C7—C6—H6B	108.7
B7—B4—H4	120.2	H6A—C6—H6B	107.6
B8—B4—H4	120.6	C8—C7—C6	107.10 (18)
B3—B4—H4	130.8	C8—C7—H7A	110.3
B5—B4—H4	131.4	C6—C7—H7A	110.3
B1—B5—B8	111.7 (2)	C8—C7—H7B	110.3
B1—B5—B2	57.26 (15)	C6—C7—H7B	110.3
B8—B5—B2	101.76 (18)	H7A—C7—H7B	108.6
B1—B5—B9	111.57 (19)	N9—C8—C7	115.02 (19)
B8—B5—B9	60.28 (15)	N9—C8—H8A	108.5
B2—B5—B9	59.29 (14)	C7—C8—H8A	108.5
B1—B5—B4	56.70 (16)	N9—C8—H8B	108.5
B8—B5—B4	59.55 (15)	C7—C8—H8B	108.5
B2—B5—B4	89.49 (17)	H8A—C8—H8B	107.5
B9—B5—B4	101.10 (18)	C10—N9—C11	111.2 (2)
B1—B5—H5	118.7	C10—N9—C8	113.50 (19)
B8—B5—H5	120.4	C11—N9—C8	112.9 (2)
B2—B5—H5	131.2	C10—N9—H91A	109 (2)
B9—B5—H5	120.8	C11—N9—H91A	107 (2)
B4—B5—H5	131.6	C8—N9—H91A	103 (2)
B10—B6—B3	112.32 (19)	N9—C10—H10A	109.5
B10—B6—B7	57.07 (15)	N9—C10—H10B	109.5
B3—B6—B7	59.83 (15)	H10A—C10—H10B	109.5
B10—B6—B9	57.20 (14)	N9—C10—H10C	109.5
B3—B6—B9	102.06 (18)	H10A—C10—H10C	109.5
B7—B6—B9	89.77 (17)	H10B—C10—H10C	109.5
B10—B6—B2	111.58 (18)	N9—C11—H11A	109.5
B3—B6—B2	60.71 (15)	N9—C11—H11B	109.5
B7—B6—B2	101.60 (18)	H11A—C11—H11B	109.5
B9—B6—B2	59.10 (13)	N9—C11—H11C	109.5
B10—B6—H6	118.5	H11A—C11—H11C	109.5
B3—B6—H6	120	H11B—C11—H11C	109.5
B7—B6—H6	131.2	O111—S1—C111	105.73 (18)
B9—B6—H6	131.3	O111—S1—C121	105.57 (15)
B2—B6—H6	120.7	C111—S1—C121	98.14 (17)
B10—B7—B4	113.1 (2)	S1—C111—H112	109.5
B10—B7—B3	113.03 (19)	S1—C111—H113	109.5
B4—B7—B3	60.68 (16)	H112—C111—H113	109.5
B10—B7—B6	57.83 (15)	S1—C111—H114	109.5
B4—B7—B6	102.73 (18)	H112—C111—H114	109.5
B3—B7—B6	59.85 (14)	H113—C111—H114	109.5
B10—B7—B8	57.48 (16)	S1—C121—H122	109.5
B4—B7—B8	60.01 (16)	S1—C121—H123	109.5
B3—B7—B8	102.22 (19)	H122—C121—H123	109.5
B6—B7—B8	90.44 (16)	S1—C121—H124	109.5
B10—B7—H7	117.7	H122—C121—H124	109.5
B4—B7—H7	119.8	H123—C121—H124	109.5
B3—B7—H7	120.1	O211—S2—C211	105.1 (4)
B6—B7—H7	130.7	O211—S2—C221	105.4 (4)
B8—B7—H7	131	C211—S2—C221	97.2 (3)
B10—B8—B5	113.03 (18)	O212—S21—C224	104.5 (12)
B10—B8—B4	111.9 (2)	O212—S21—C223	106.9 (9)
B5—B8—B4	61.33 (16)	C224—S21—C223	97.4 (7)
B10—B8—B9	57.26 (14)	S21—C223—H225	109.5
B5—B8—B9	60.22 (14)	S21—C223—H226	109.5
B4—B8—B9	102.30 (17)	H225—C223—H226	109.5
B10—B8—B7	56.87 (16)	S21—C223—H227	109.5
B5—B8—B7	102.42 (18)	H225—C223—H227	109.5
B4—B8—B7	59.32 (16)	H226—C223—H227	109.5
B9—B8—B7	89.42 (16)	S21—C224—H228	109.5
B10—B8—H8	118.3	S21—C224—H229	109.5
B5—B8—H8	119.4	H228—C224—H229	109.5
B4—B8—H8	120.2	S21—C224—H230	109.5
B9—B8—H8	131.1	H228—C224—H230	109.5
B7—B8—H8	131.6	H229—C224—H230	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H91A···O211^i	0.84 (3)	1.82 (3)	2.651 (6)	169 (3)
N9—H91A···O212^i	0.84 (3)	1.98 (3)	2.817 (15)	172 (3)
N1—H11D···O111^ii	0.79 (3)	2.67 (3)	3.446 (3)	168 (3)
C5—H5C···O111^ii	0.96	2.46	3.114 (3)	125
C6—H6B···O111	0.97	2.5	3.256 (3)	135

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+1, −y, −z+1.