The effect of hydrogen bonding on the conformations of 2-(1H-indol-3-yl)-2-oxoacetamide and 2-(1H-indol-3-yl)-N,N-dimethyl-2-oxoacetamide

In the title compounds, C₁₀H₈N₂O₂, (I), and C₁₂H₁₂N₂O₂, (II), the two carbonyl groups are oriented with torsion angles of -149.3 (3) and -88.55 (15)°, respectively. The single-bond distances linking the two carbonyl groups are 1.528 (4) and 1.5298 (17) Å, respectively. In (I), the mol­ecules are linked by an elaborate system of N-H...O hydrogen bonds, which form adjacent R²₂(8) and R⁴₂(8) ring motifs to generate a ladder-like construct. Adjacent ladders are further linked by N-H...O hydrogen bonds to build a three-dimensional network. The hydrogen bonding in (II) is far simpler, consisting of helical chains of N-H...O-linked mol­ecules that follow the 2₁ screw of the b axis. It is the presence of an elaborate hydrogen-bonding system in the crystal structure of (I) that leads to the different torsion angle for the orientation of the two adjacent carbonyl groups from that in (II).

S1. Comment

The title compounds, 2-(1H-indol-3-yl)-2-oxoacetamide, (I), and 2-(1H-indol-3-yl)- N,N-dimethyl-2-oxoacetamide, (II), are synthetic intermediates in the preparation of tryptamine and N,N-dimethyltryptamine, and are prepared by treating indole with oxalyl chloride followed by quenching with aqueous ammonia or dimethylamine, respectively. The products were characterized by spectroscopic analysis and their X-ray crystal structure determinations were carried out to ascertain the conformations of these molecules, especially the orientations of the carbonyl groups, as 1,2-diones have been shown to be potent inhibitors of carboxylesterases (Hyatt et al., 2007). The inhibitory properties of ethane-1,2-diones toward carboxylesterases are such that, when the carbonyl O atoms are cis-coplanar, the compounds demonstrate specificity for human liver carboxylesterase. Conversely, when the dione O atoms are not planar (or are trans-coplanar), the compounds are more potent at human intestinal carboxylesterase inhibition (Hyatt et al., 2007). Thus, the title compounds and their analogs were screened for their inhibition of human carboxylesterases and it was planned to determine their conformations to compare with the observation reported for ethane-1,2-diones.

X-ray crystallography confirmed the molecular structures and atom connectivities of (I) and (II), and selected geometric parameters are listed in Tables 1 and 3. The two carbonyl groups are in a trans orientation, with torsion angle O1—C9—C10—O2 = 149.3 (3)° and O1—C10—C11—O2 = 88.55 (15)°. The deviation from 180° may be due to repulsive interactions between non-bonded electron pairs on atoms O1 and O2. However, in (I) the extensive hydrogen bonding introduces rigidity into the molecule. Since the C9═O1 and C10═O1 groups are coplanar with the indole nucleus, there is extended conjugation from atom O1 through to the indole ring. This is evident from the shortening of the C8—C9 [1.421 (4) Å] and C1—C10 [1.4380 (17) Å] bond lengths compared with the standard value for a single bond connecting a C_ar atom to a Csp² atom [1.470 (15) Å; Allen et al., 1987]. Possibly due to repulsive interactions between non-bonded electron pairs, the C9—C10 and C10—C11 bonds are stretched, resulting in bond lengths of 1.528 (4) and 1.5298 (17) Å, respectively. These are longer than expected, the characteristic value for a Csp²—Csp² bond being 1.50 Å (Zukerman-Schpector et al., 1994). The C10—N2 [1.323 (4) Å] and C11—N12 [1.3287 (16) Å] bond lengths, and the bond angles around atoms N2 and N12, suggest that the lone pairs of electrons on N2 and N12 undergo delocalization, bestowing double-bond character on the C10—N2 and C11—N12 bonds.

The packing of compounds (I) and (II), as viewed down the c axis [b axis for (II)?], are illustrated in Figs. 2 and 4, respectively. Amides undergo extensive hydrogen bonding, but in (I), in addition to primary amide functionality, there is a hydrogen-bond accepting carbonyl group and a variable glyoxylamide torsion angle. In (I), the molecules are linked by an elaborate system of N—H···O hydrogen bonds [N1—H1···O1ⁱ and N2—H2A···O2ⁱⁱ; symmetry codes: (i) x - 1, -y + 3/2, z + 1/2; (ii) -x + 1, -y + 1, -z + 1] which include adjacent R²₂(8) and R⁴₂(8) ring motifs (Bernstein et al., 1995) to form a ladder-like construct. Adjacent ladders are further linked by N—H···O hydrogen bonds [N2—H2B···O2ⁱⁱⁱ; symmetry code: (iii) x + 1, y, z] to build a three-dimensional network. The hydrogen bonding in (II) is far simpler, consisting of helical chains of N—H···O [N3—H3···O2ⁱ; symmetry code: (i) -x + 1, y - 1/2, -z + 1/2] linked molecules that follow the 2₁ screw of the b axis.

Related literature

For related literature, see: Allen et al. (1987); Bernstein et al. (1995); Da Settimo, Primofiore, Da Settimo, Marini, Novellino, Greco, Martini, Giannaccini & Lucacchini (1996); Hyatt et al. (2007); Zukerman-Schpector, Pinto, DaC, Da Silva & Da Silva (1994).

S2. Experimental

The title compounds were prepared using a previously reported procedure (Da Settimo et al., 1996). Recrystallization from ethyl acetate afforded (I) and (II) as yellow [Both colourless in CIF data tables - please clarify] crystalline products which were suitable for X-ray analysis. Spectroscopic analysis for (I): ¹H NMR (300 MHz, DMSO-d₆, δ, p.p.m): 7.22–7.25 (m, 2H), 7.49–7.52 (m, 1H), 7.70 (sb, 1H), 8.06 (sb, 1H), 8.19–8.22 (m, 1H), 8.67 (d, 1H), 12.17 (sb, 1H); ¹³C NMR (75 MHz, DMSO-d₆, δ p.p.m.): 111.95, 112.41, 121.10, 122.32, 123.22, 125.98, 136.11, 138.10, 165.80, 182.72. Spectroscopic analysis for (II): ¹H NMR (300 MHz, DMSO-d₆, δ, p.p.m): 2.93 (s, 3H), 3.01 (s, 3H), 7.23–7.32 (m, 2H), 7.51–7.57 (m, 1H), 8.10 (dd, 1H), 8.14 (s, 1H), 12.17 (sb, 1H); ¹³C NMR (75 MHz, DMSO-d₆, δ, p.p.m.): 33.41, 36.81, 112.52, 112.83, 120.71, 122.38, 123.38, 124.75, 136.73, 136.83, 167.11, 186.44.

S3. Refinement

H atoms were found in difference Fourier maps and subsequently placed in idealized positions, with C—H = 0.95 (C_ArH), 0.98 (C_MeH) or 0.88 Å (NH₂), and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(methyl C).

Computing details

Data collection: APEX2 (Bruker, 2006) for (I); COLLECT (Nonius, 1999) for (II). Cell refinement: APEX2 (Bruker, 2006) for (I); SCALEPACK (Otwinowski & Minor, 1997) for (II). Data reduction: APEX2 (Bruker, 2006) for (I); DENZO-SMN (Otwinowski & Minor, 1997) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and local procedures.

Figures

	Fig. 1. A view of the molecule of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram for (I), viewed down the c axis. Dashed lines indicate hydrogen bonds. H atoms not involved in these interactions have been omitted for clarity. [Added text OK?]
	Fig. 3. A view of the molecule of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. A packing diagram for (II), viewed down the c axis [b axis?]. Dashed lines indicate hydrogen bonds. H atoms not involved in these interactions have been omitted for clarity. [Added text OK?]

(I) 2-(1H-indol-3-yl)-2-oxoacetamide

Crystal data

C10H8N2O2	F(000) = 392
Mr = 188.18	Dx = 1.479 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 8721 reflections
a = 5.1253 (4) Å	θ = 4.6–69.0°
b = 19.4363 (14) Å	µ = 0.88 mm^−1
c = 8.4953 (6) Å	T = 90 K
β = 93.251 (3)°	Needle, colourless
V = 844.91 (11) Å^3	0.30 × 0.08 × 0.06 mm
Z = 4

Data collection

Bruker X8 Proteum diffractometer	1518 independent reflections
Radiation source: fine-focus rotating anode	1481 reflections with I > 2σ(I)
Graded multilayer optics monochromator	Rint = 0.042
Detector resolution: 18 pixels mm^-1	θmax = 68.9°, θmin = 4.6°
ϕ and ω scans	h = −4→6
Absorption correction: multi-scan [SADABS (Bruker, 2006) and XABS2 (Parkin et al., 1995)]	k = −23→23
Tmin = 0.744, Tmax = 0.949	l = −10→10
10887 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.058	H-atom parameters constrained
wR(F^2) = 0.158	w = 1/[σ^2(Fo^2) + (0.037P)^2 + 1.8838P] where P = (Fo^2 + 2Fc^2)/3
S = 1.24	(Δ/σ)max < 0.001
1518 reflections	Δρmax = 0.33 e Å^−3
128 parameters	Δρmin = −0.33 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0033 (9)

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 > 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
N1	0.0782 (5)	0.77152 (13)	0.5558 (3)	0.0227 (6)
H1	−0.0529	0.7766	0.6173	0.027*
N2	0.7272 (5)	0.56011 (12)	0.4103 (3)	0.0219 (6)
H2A	0.7242	0.5163	0.4362	0.026*
H2B	0.8761	0.5800	0.3904	0.026*
O1	0.7253 (4)	0.68365 (10)	0.2684 (2)	0.0221 (5)
O2	0.2916 (4)	0.57240 (10)	0.4272 (3)	0.0231 (5)
C1	0.1826 (5)	0.71168 (15)	0.5181 (3)	0.0195 (6)
H1A	0.1282	0.6681	0.5546	0.023*
C2	0.2054 (6)	0.82452 (15)	0.4845 (3)	0.0207 (7)
C3	0.1592 (6)	0.89462 (16)	0.4918 (4)	0.0274 (7)
H3	0.0254	0.9129	0.5524	0.033*
C4	0.3164 (6)	0.93666 (16)	0.4069 (4)	0.0297 (8)
H4	0.2880	0.9850	0.4068	0.036*
C5	0.5163 (6)	0.90938 (16)	0.3211 (4)	0.0270 (7)
H5	0.6249	0.9396	0.2663	0.032*
C6	0.5597 (6)	0.83963 (15)	0.3143 (4)	0.0225 (7)
H6	0.6958	0.8218	0.2548	0.027*
C7	0.4006 (5)	0.79562 (15)	0.3960 (3)	0.0186 (6)
C8	0.3834 (5)	0.72223 (15)	0.4173 (3)	0.0183 (6)
C9	0.5462 (5)	0.67120 (15)	0.3542 (3)	0.0185 (6)
C10	0.5078 (5)	0.59616 (15)	0.4013 (3)	0.0192 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0145 (12)	0.0325 (14)	0.0213 (13)	0.0038 (10)	0.0036 (10)	−0.0025 (10)
N2	0.0094 (11)	0.0211 (13)	0.0356 (15)	−0.0008 (9)	0.0044 (10)	0.0028 (10)
O1	0.0138 (10)	0.0286 (11)	0.0247 (11)	−0.0003 (8)	0.0072 (8)	0.0019 (8)
O2	0.0120 (10)	0.0239 (11)	0.0335 (12)	−0.0002 (8)	0.0037 (8)	0.0031 (9)
C1	0.0142 (14)	0.0269 (15)	0.0175 (14)	0.0009 (11)	0.0007 (11)	0.0001 (11)
C2	0.0155 (14)	0.0276 (16)	0.0186 (15)	0.0018 (11)	−0.0028 (11)	−0.0035 (11)
C3	0.0221 (16)	0.0295 (17)	0.0301 (18)	0.0043 (13)	−0.0037 (13)	−0.0079 (13)
C4	0.0274 (17)	0.0231 (16)	0.0375 (19)	0.0039 (13)	−0.0071 (14)	−0.0030 (13)
C5	0.0239 (16)	0.0261 (16)	0.0302 (18)	−0.0039 (12)	−0.0049 (13)	0.0023 (13)
C6	0.0167 (15)	0.0268 (16)	0.0237 (16)	−0.0012 (12)	−0.0016 (12)	0.0005 (12)
C7	0.0130 (13)	0.0253 (15)	0.0171 (14)	0.0009 (11)	−0.0024 (11)	−0.0001 (11)
C8	0.0124 (13)	0.0229 (14)	0.0195 (14)	0.0015 (11)	0.0011 (11)	−0.0003 (11)
C9	0.0118 (13)	0.0238 (15)	0.0200 (15)	−0.0011 (11)	0.0009 (11)	0.0007 (11)
C10	0.0128 (14)	0.0245 (15)	0.0206 (15)	−0.0003 (11)	0.0028 (11)	−0.0010 (11)

Geometric parameters (Å, º)

N1—C1	1.327 (4)	C3—C4	1.379 (5)
N1—C2	1.378 (4)	C3—H3	0.9500
N1—H1	0.8800	C4—C5	1.395 (5)
N2—C10	1.323 (4)	C4—H4	0.9500
N2—H2A	0.8800	C5—C6	1.376 (4)
N2—H2B	0.8800	C5—H5	0.9500
O1—C9	1.228 (3)	C6—C7	1.394 (4)
O2—C10	1.232 (3)	C6—H6	0.9500
C1—C8	1.391 (4)	C7—C8	1.441 (4)
C1—H1A	0.9500	C8—C9	1.421 (4)
C2—C3	1.385 (4)	C9—C10	1.528 (4)
C2—C7	1.403 (4)
C1—N1—C2	110.0 (2)	C6—C5—C4	121.5 (3)
C1—N1—H1	125.0	C6—C5—H5	119.3
C2—N1—H1	125.0	C4—C5—H5	119.3
C10—N2—H2A	120.0	C5—C6—C7	118.9 (3)
C10—N2—H2B	120.0	C5—C6—H6	120.6
H2A—N2—H2B	120.0	C7—C6—H6	120.6
N1—C1—C8	110.0 (3)	C6—C7—C2	118.5 (3)
N1—C1—H1A	125.0	C6—C7—C8	135.4 (3)
C8—C1—H1A	125.0	C2—C7—C8	106.2 (2)
N1—C2—C3	129.1 (3)	C1—C8—C9	126.9 (3)
N1—C2—C7	107.8 (3)	C1—C8—C7	106.0 (2)
C3—C2—C7	123.1 (3)	C9—C8—C7	127.0 (3)
C4—C3—C2	117.0 (3)	O1—C9—C8	124.1 (3)
C4—C3—H3	121.5	O1—C9—C10	117.1 (3)
C2—C3—H3	121.5	C8—C9—C10	118.7 (2)
C3—C4—C5	121.1 (3)	O2—C10—N2	124.1 (3)
C3—C4—H4	119.5	O2—C10—C9	122.3 (2)
C5—C4—H4	119.5	N2—C10—C9	113.5 (2)
C2—N1—C1—C8	−0.9 (3)	N1—C1—C8—C9	178.3 (3)
C1—N1—C2—C3	179.8 (3)	N1—C1—C8—C7	1.0 (3)
C1—N1—C2—C7	0.4 (3)	C6—C7—C8—C1	178.4 (3)
N1—C2—C3—C4	−179.5 (3)	C2—C7—C8—C1	−0.7 (3)
C7—C2—C3—C4	−0.2 (4)	C6—C7—C8—C9	1.0 (5)
C2—C3—C4—C5	−1.5 (5)	C2—C7—C8—C9	−178.1 (3)
C3—C4—C5—C6	1.9 (5)	C1—C8—C9—O1	−178.2 (3)
C4—C5—C6—C7	−0.4 (5)	C7—C8—C9—O1	−1.3 (5)
C5—C6—C7—C2	−1.2 (4)	C1—C8—C9—C10	−1.4 (4)
C5—C6—C7—C8	179.8 (3)	C7—C8—C9—C10	175.5 (3)
N1—C2—C7—C6	−179.0 (3)	O1—C9—C10—O2	−149.3 (3)
C3—C2—C7—C6	1.5 (4)	C8—C9—C10—O2	33.7 (4)
N1—C2—C7—C8	0.2 (3)	O1—C9—C10—N2	30.4 (4)
C3—C2—C7—C8	−179.2 (3)	C8—C9—C10—N2	−146.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.88	1.92	2.768 (3)	160
N2—H2A···O2^ii	0.88	2.08	2.926 (3)	161
N2—H2B···O2^iii	0.88	2.14	2.898 (3)	144

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

(II) 2-(1H-indol-3-yl)-N,N-dimethyl-2-oxoacetamide

Crystal data

C12H12N2O2	F(000) = 456
Mr = 216.24	Dx = 1.313 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2759 reflections
a = 10.1813 (2) Å	θ = 1.0–27.5°
b = 6.0048 (1) Å	µ = 0.09 mm^−1
c = 18.0625 (4) Å	T = 90 K
β = 97.7222 (8)°	Rod, colourless
V = 1094.27 (4) Å^3	0.65 × 0.25 × 0.15 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	2515 independent reflections
Radiation source: fine-focus sealed tube	2031 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 18 pixels mm^-1	θmax = 27.5°, θmin = 2.0°
ω scans at fixed χ = 55°	h = −13→13
Absorption correction: multi-scan SCALEPACK (Otwinowski & Minor, 1997)	k = −7→7
Tmin = 0.943, Tmax = 0.986	l = −23→23
4780 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0561P)^2 + 0.2642P] where P = (Fo^2 + 2Fc^2)/3
2515 reflections	(Δ/σ)max < 0.001
147 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

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

Refinement. Refinement of F² against all reflections. The weighted R-value wR and goodness of fit S are based on F². Conventional R-values 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-values based on F² are statistically about twice as large as those based on F, and R-values based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.46067 (12)	0.5029 (2)	0.30948 (7)	0.0250 (3)
H1	0.5263	0.4004	0.2983	0.030*
N1	0.32928 (10)	0.47893 (19)	0.28893 (6)	0.0262 (3)
H1A	0.2914	0.3676	0.2625	0.031*
N2	0.77326 (10)	0.48231 (18)	0.42133 (6)	0.0253 (3)
O1	0.63689 (9)	0.95880 (17)	0.41126 (6)	0.0341 (3)
O2	0.78438 (8)	0.65588 (16)	0.31061 (5)	0.0295 (2)
C2	0.26301 (12)	0.6570 (2)	0.31595 (6)	0.0229 (3)
C3	0.12758 (12)	0.6955 (2)	0.31215 (7)	0.0268 (3)
H3	0.0643	0.5964	0.2866	0.032*
C4	0.08930 (13)	0.8841 (3)	0.34723 (7)	0.0310 (3)
H4	−0.0024	0.9150	0.3463	0.037*
C5	0.18277 (13)	1.0309 (2)	0.38423 (8)	0.0317 (3)
H5	0.1530	1.1600	0.4074	0.038*
C6	0.31755 (12)	0.9925 (2)	0.38792 (7)	0.0264 (3)
H6	0.3802	1.0936	0.4130	0.032*
C7	0.35877 (11)	0.8014 (2)	0.35382 (6)	0.0217 (3)
C8	0.48596 (11)	0.6990 (2)	0.34928 (6)	0.0218 (3)
C9	0.61495 (11)	0.7791 (2)	0.37998 (7)	0.0229 (3)
C10	0.73240 (11)	0.6301 (2)	0.36848 (7)	0.0224 (3)
C11	0.70814 (13)	0.4489 (2)	0.48773 (7)	0.0294 (3)
H11A	0.6463	0.5716	0.4923	0.044*
H11B	0.7750	0.4449	0.5321	0.044*
H11C	0.6594	0.3077	0.4833	0.044*
C12	0.88222 (13)	0.3315 (2)	0.41201 (8)	0.0316 (3)
H12A	0.9080	0.3512	0.3621	0.047*
H12B	0.8538	0.1774	0.4179	0.047*
H12C	0.9581	0.3648	0.4498	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0232 (6)	0.0284 (7)	0.0245 (6)	−0.0007 (5)	0.0069 (5)	−0.0014 (5)
N1	0.0243 (5)	0.0296 (6)	0.0250 (5)	−0.0045 (4)	0.0048 (4)	−0.0056 (4)
N2	0.0231 (5)	0.0277 (6)	0.0260 (5)	0.0025 (4)	0.0068 (4)	0.0028 (4)
O1	0.0264 (5)	0.0303 (6)	0.0454 (6)	−0.0025 (4)	0.0043 (4)	−0.0106 (4)
O2	0.0247 (5)	0.0379 (6)	0.0275 (5)	0.0043 (4)	0.0092 (4)	0.0068 (4)
C2	0.0233 (6)	0.0271 (7)	0.0190 (5)	−0.0009 (5)	0.0048 (4)	0.0014 (5)
C3	0.0213 (6)	0.0344 (7)	0.0242 (6)	−0.0032 (5)	0.0019 (5)	0.0042 (5)
C4	0.0210 (6)	0.0391 (8)	0.0332 (7)	0.0037 (6)	0.0048 (5)	0.0050 (6)
C5	0.0270 (7)	0.0311 (8)	0.0377 (7)	0.0064 (6)	0.0073 (5)	−0.0012 (6)
C6	0.0245 (6)	0.0261 (7)	0.0289 (6)	0.0002 (5)	0.0048 (5)	−0.0009 (5)
C7	0.0206 (6)	0.0258 (6)	0.0193 (5)	−0.0001 (5)	0.0044 (4)	0.0033 (5)
C8	0.0200 (6)	0.0251 (6)	0.0211 (5)	0.0004 (5)	0.0058 (4)	0.0009 (5)
C9	0.0233 (6)	0.0244 (7)	0.0219 (5)	−0.0004 (5)	0.0059 (4)	0.0006 (5)
C10	0.0180 (5)	0.0249 (7)	0.0243 (6)	−0.0019 (5)	0.0031 (4)	−0.0005 (5)
C11	0.0345 (7)	0.0311 (7)	0.0241 (6)	0.0005 (6)	0.0088 (5)	0.0016 (5)
C12	0.0255 (7)	0.0323 (8)	0.0378 (7)	0.0062 (5)	0.0074 (5)	0.0059 (6)

Geometric parameters (Å, º)

C1—N1	1.3471 (16)	C4—H4	0.9500
C1—C8	1.3858 (18)	C5—C6	1.3842 (17)
C1—H1	0.9500	C5—H5	0.9500
N1—C2	1.3874 (16)	C6—C7	1.3936 (18)
N1—H1A	0.8800	C6—H6	0.9500
N2—C10	1.3287 (16)	C7—C8	1.4457 (16)
N2—C12	1.4591 (16)	C8—C9	1.4380 (17)
N2—C11	1.4602 (15)	C9—C10	1.5298 (17)
O1—C9	1.2244 (16)	C11—H11A	0.9800
O2—C10	1.2431 (15)	C11—H11B	0.9800
C2—C3	1.3906 (17)	C11—H11C	0.9800
C2—C7	1.4110 (17)	C12—H12A	0.9800
C3—C4	1.380 (2)	C12—H12B	0.9800
C3—H3	0.9500	C12—H12C	0.9800
C4—C5	1.399 (2)
N1—C1—C8	110.00 (11)	C6—C7—C2	119.39 (11)
N1—C1—H1	125.0	C6—C7—C8	134.46 (12)
C8—C1—H1	125.0	C2—C7—C8	106.09 (11)
C1—N1—C2	109.43 (10)	C1—C8—C9	125.50 (11)
C1—N1—H1A	125.3	C1—C8—C7	106.58 (10)
C2—N1—H1A	125.3	C9—C8—C7	127.92 (12)
C10—N2—C12	120.07 (10)	O1—C9—C8	124.97 (12)
C10—N2—C11	123.31 (11)	O1—C9—C10	118.72 (11)
C12—N2—C11	116.46 (10)	C8—C9—C10	116.23 (11)
N1—C2—C3	129.53 (12)	O2—C10—N2	124.03 (11)
N1—C2—C7	107.88 (10)	O2—C10—C9	118.05 (11)
C3—C2—C7	122.53 (12)	N2—C10—C9	117.91 (10)
C4—C3—C2	116.96 (12)	N2—C11—H11A	109.5
C4—C3—H3	121.5	N2—C11—H11B	109.5
C2—C3—H3	121.5	H11A—C11—H11B	109.5
C3—C4—C5	121.36 (12)	N2—C11—H11C	109.5
C3—C4—H4	119.3	H11A—C11—H11C	109.5
C5—C4—H4	119.3	H11B—C11—H11C	109.5
C6—C5—C4	121.63 (13)	N2—C12—H12A	109.5
C6—C5—H5	119.2	N2—C12—H12B	109.5
C4—C5—H5	119.2	H12A—C12—H12B	109.5
C5—C6—C7	118.12 (12)	N2—C12—H12C	109.5
C5—C6—H6	120.9	H12A—C12—H12C	109.5
C7—C6—H6	120.9	H12B—C12—H12C	109.5
C8—C1—N1—C2	−1.24 (14)	C6—C7—C8—C1	177.34 (13)
C1—N1—C2—C3	−175.89 (12)	C2—C7—C8—C1	0.23 (13)
C1—N1—C2—C7	1.37 (13)	C6—C7—C8—C9	−2.1 (2)
N1—C2—C3—C4	177.12 (12)	C2—C7—C8—C9	−179.18 (11)
C7—C2—C3—C4	0.20 (18)	C1—C8—C9—O1	175.49 (12)
C2—C3—C4—C5	0.64 (19)	C7—C8—C9—O1	−5.2 (2)
C3—C4—C5—C6	−0.6 (2)	C1—C8—C9—C10	−1.37 (17)
C4—C5—C6—C7	−0.3 (2)	C7—C8—C9—C10	177.94 (11)
C5—C6—C7—C2	1.11 (18)	C12—N2—C10—O2	−2.49 (19)
C5—C6—C7—C8	−175.71 (13)	C11—N2—C10—O2	−177.78 (12)
N1—C2—C7—C6	−178.59 (11)	C12—N2—C10—C9	178.11 (11)
C3—C2—C7—C6	−1.10 (18)	C11—N2—C10—C9	2.82 (18)
N1—C2—C7—C8	−0.96 (13)	O1—C9—C10—O2	−88.55 (15)
C3—C2—C7—C8	176.54 (11)	C8—C9—C10—O2	88.51 (14)
N1—C1—C8—C9	−179.96 (11)	O1—C9—C10—N2	90.89 (15)
N1—C1—C8—C7	0.61 (13)	C8—C9—C10—N2	−92.05 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^i	0.88	1.92	2.7885 (14)	170

Symmetry code: (i) −x+1, y−1/2, −z+1/2.