New 1:1 and 2:1 salts in the `DL-norvaline–maleic acid' system as an example of assembling various crystal structures from similar supramolecular building blocks

Mol­ecular salts and cocrystals of amino acids have potential applications as mol­ecular materials with nonlinear optical, ferroelectric, piezoelectric, and other various target physical properties. The wide choice of amino acids and coformers makes it possible to design various crystal structures. The amino acid–maleic acid system provides a perfect example of a rich variety of crystal structures with different stoichiometries, symmetries and packing motifs built from the mol­ecular building blocks, which are either exactly the same, or differ merely by protonation or as optical isomers. The present paper reports the crystal structures of two new salts of the DL-norvaline–maleic acid system with 1:1 and 2:1 stoichiometries, namely DL-norvalinium hydrogen maleate, C₅H₁₂NO₂⁺·C₄H₃O₄⁻, (I), and DL-norvalinium hydrogen maleate–DL-norvaline, C₅H₁₂NO₂⁺·C₄H₃O₄⁻·C₅H₁₁NO₂, (II). These are the first examples of mol­ecular salts of DL-norvaline with an organic anion. The crystal structure of (I) has the same C₂²(12) structure-forming motif which is common for hydrogen maleates of amino acids. The structure of (II) has dimeric cations. Of special inter­est is that the single crystals of (I) which are originally formed on crystallization from aqueous solution transform into single crystals of (II) if stored in the mother liquor for several hours.

Computing details

Data collection: CrysAlis PRO (Agilent, 2014) for (I); CrysAlis PRO (Rigaku OD, 2015) for 2dl_nv_mal. Cell refinement: CrysAlis PRO (Agilent, 2014) for (I); CrysAlis PRO (Rigaku OD, 2015) for 2dl_nv_mal. Data reduction: CrysAlis PRO (Agilent, 2014) for (I); CrysAlis PRO (Rigaku OD, 2015) for 2dl_nv_mal. For both compounds, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b). Molecular graphics: OLEX2 (Dolomanov et al., 2009) for (I); Mercury (Macrae et al., 2008) for 2dl_nv_mal. For both compounds, software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(I) DL-Norvalinium hydrogen maleate

Crystal data

C5H12NO2^+·C4H3O4^−	F(000) = 992
Mr = 233.22	Dx = 1.247 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.6385 (15) Å	Cell parameters from 3032 reflections
b = 5.62705 (18) Å	θ = 1.8–25.1°
c = 23.6867 (10) Å	µ = 0.11 mm^−1
β = 108.283 (6)°	T = 293 K
V = 2485.4 (2) Å^3	Block, clear light colourless
Z = 8	0.25 × 0.15 × 0.1 mm

Data collection

Agilent Xcalibur Ruby Gemini ultra diffractometer	2198 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1807 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 10.3457 pixels mm^-1	θmax = 25.0°, θmin = 1.8°
ω scans	h = −23→23
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −6→6
Tmin = 0.866, Tmax = 1.000	l = −28→28
13186 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.068	H-atom parameters constrained
wR(F^2) = 0.166	w = 1/[σ^2(Fo^2) + (0.0688P)^2 + 1.2674P] where P = (Fo^2 + 2Fc^2)/3
S = 1.23	(Δ/σ)max < 0.001
2198 reflections	Δρmax = 0.25 e Å^−3
169 parameters	Δρmin = −0.15 e Å^−3
12 restraints

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O2	0.30316 (12)	0.1684 (3)	0.75497 (7)	0.0587 (6)
O4	0.33415 (13)	0.3088 (3)	0.45870 (8)	0.0634 (6)
O6	0.34166 (13)	0.3563 (3)	0.56205 (8)	0.0653 (6)
H6	0.3388	0.3428	0.5269	0.098*
O5	0.33741 (12)	0.1258 (4)	0.63532 (8)	0.0640 (6)
O3	0.32140 (14)	0.0195 (3)	0.39432 (8)	0.0733 (7)
O1	0.35365 (15)	0.4538 (4)	0.71650 (9)	0.0797 (8)
H1	0.3461	0.3614	0.6884	0.120*
N1	0.29849 (14)	0.4474 (4)	0.84537 (9)	0.0530 (6)
H1A	0.2541	0.4754	0.8218	0.064*
H1B	0.3073	0.5355	0.8781	0.064*
H1C	0.3030	0.2943	0.8553	0.064*
C9	0.33889 (16)	0.1511 (4)	0.58407 (10)	0.0472 (7)
C1	0.33256 (16)	0.3576 (5)	0.75847 (11)	0.0493 (7)
C6	0.32998 (17)	0.0889 (5)	0.44513 (11)	0.0517 (7)
C2	0.35023 (16)	0.5090 (5)	0.81368 (11)	0.0513 (7)
H2	0.3446	0.6770	0.8022	0.062*
C8	0.33796 (19)	−0.0648 (5)	0.54893 (11)	0.0602 (9)
H8	0.3401	−0.2063	0.5697	0.072*
C7	0.33452 (19)	−0.0911 (5)	0.49233 (12)	0.0637 (9)
H7	0.3350	−0.2480	0.4802	0.076*
C3	0.4257 (2)	0.4676 (7)	0.85504 (15)	0.0804 (11)
H3AA	0.4303	0.5434	0.8928	0.097*	0.865 (8)
H3AB	0.4325	0.2983	0.8623	0.097*	0.865 (8)
H3BC	0.4217	0.3299	0.8784	0.097*	0.135 (8)
H3BD	0.4525	0.4145	0.8292	0.097*	0.135 (8)
C4A	0.4845 (3)	0.5576 (11)	0.8329 (2)	0.1011 (19)	0.865 (8)
H4AA	0.5301	0.5092	0.8608	0.121*	0.865 (8)
H4AB	0.4800	0.4808	0.7952	0.121*	0.865 (8)
C4B	0.473 (2)	0.624 (7)	0.8964 (16)	0.114 (9)	0.135 (8)
H4BA	0.4527	0.6638	0.9274	0.136*	0.135 (8)
H4BB	0.5181	0.5409	0.9150	0.136*	0.135 (8)
C5A	0.4863 (4)	0.8168 (15)	0.8244 (5)	0.143 (3)	0.865 (8)
H5AA	0.4440	0.8653	0.7934	0.214*	0.865 (8)
H5AB	0.5280	0.8578	0.8135	0.214*	0.865 (8)
H5AC	0.4881	0.8961	0.8607	0.214*	0.865 (8)
C5B	0.488 (4)	0.829 (11)	0.872 (3)	0.166 (18)	0.135 (8)
H5BA	0.4471	0.8746	0.8392	0.249*	0.135 (8)
H5BB	0.5285	0.8054	0.8581	0.249*	0.135 (8)
H5BC	0.4988	0.9530	0.9014	0.249*	0.135 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0956 (16)	0.0514 (12)	0.0351 (10)	−0.0135 (11)	0.0289 (9)	−0.0092 (8)
O4	0.1220 (19)	0.0344 (10)	0.0397 (10)	−0.0056 (10)	0.0336 (10)	0.0026 (7)
O6	0.1231 (19)	0.0385 (11)	0.0417 (11)	−0.0051 (11)	0.0364 (12)	−0.0074 (8)
O5	0.1054 (17)	0.0600 (12)	0.0355 (10)	0.0015 (11)	0.0350 (10)	−0.0014 (8)
O3	0.139 (2)	0.0517 (12)	0.0381 (11)	−0.0037 (12)	0.0405 (12)	−0.0057 (8)
O1	0.129 (2)	0.0787 (16)	0.0470 (12)	−0.0372 (14)	0.0501 (13)	−0.0171 (10)
N1	0.0863 (18)	0.0445 (13)	0.0319 (11)	0.0082 (11)	0.0240 (11)	−0.0036 (9)
C9	0.0698 (19)	0.0395 (14)	0.0354 (14)	0.0031 (12)	0.0208 (12)	0.0009 (10)
C1	0.0698 (19)	0.0502 (17)	0.0322 (13)	−0.0032 (14)	0.0221 (12)	−0.0026 (11)
C6	0.087 (2)	0.0372 (14)	0.0364 (14)	−0.0011 (13)	0.0279 (13)	−0.0007 (11)
C2	0.072 (2)	0.0471 (15)	0.0380 (14)	−0.0066 (13)	0.0210 (13)	−0.0077 (11)
C8	0.111 (3)	0.0333 (14)	0.0418 (15)	0.0039 (15)	0.0321 (15)	0.0065 (11)
C7	0.124 (3)	0.0296 (13)	0.0429 (15)	0.0042 (15)	0.0347 (16)	−0.0041 (11)
C3	0.082 (3)	0.088 (3)	0.065 (2)	0.002 (2)	0.0144 (19)	−0.0186 (18)
C4A	0.072 (3)	0.129 (5)	0.096 (3)	−0.002 (3)	0.019 (3)	−0.028 (3)
C4B	0.114 (16)	0.106 (16)	0.104 (16)	−0.005 (15)	0.012 (14)	−0.044 (14)
C5A	0.112 (5)	0.122 (6)	0.195 (9)	−0.031 (4)	0.050 (6)	−0.010 (6)
C5B	0.15 (3)	0.15 (3)	0.17 (3)	−0.03 (3)	0.01 (3)	−0.05 (3)

Geometric parameters (Å, º)

O2—C1	1.202 (3)	C7—H7	0.9300
O4—C6	1.274 (3)	C3—H3AA	0.9700
O6—H6	0.8200	C3—H3AB	0.9700
O6—C9	1.275 (3)	C3—H3BC	0.9700
O5—C9	1.231 (3)	C3—H3BD	0.9700
O3—C6	1.226 (3)	C3—C4A	1.498 (6)
O1—H1	0.8200	C3—C4B	1.43 (3)
O1—C1	1.308 (3)	C4A—H4AA	0.9700
N1—H1A	0.8900	C4A—H4AB	0.9700
N1—H1B	0.8900	C4A—C5A	1.474 (9)
N1—H1C	0.8900	C4B—H4BA	0.9700
N1—C2	1.482 (4)	C4B—H4BB	0.9700
C9—C8	1.469 (4)	C4B—C5B	1.36 (7)
C1—C2	1.507 (4)	C5A—H5AA	0.9600
C6—C7	1.490 (4)	C5A—H5AB	0.9600
C2—H2	0.9800	C5A—H5AC	0.9600
C2—C3	1.517 (5)	C5B—H5BA	0.9600
C8—H8	0.9300	C5B—H5BB	0.9600
C8—C7	1.329 (4)	C5B—H5BC	0.9600
C9—O6—H6	109.5	H3AA—C3—H3AB	107.5
C1—O1—H1	109.5	H3BC—C3—H3BD	105.7
H1A—N1—H1B	109.5	C4A—C3—C2	115.2 (3)
H1A—N1—H1C	109.5	C4A—C3—H3AA	108.5
H1B—N1—H1C	109.5	C4A—C3—H3AB	108.5
C2—N1—H1A	109.5	C4B—C3—C2	130.3 (16)
C2—N1—H1B	109.5	C4B—C3—H3BC	104.7
C2—N1—H1C	109.5	C4B—C3—H3BD	104.7
O6—C9—C8	120.8 (2)	C3—C4A—H4AA	108.3
O5—C9—O6	121.7 (2)	C3—C4A—H4AB	108.3
O5—C9—C8	117.6 (2)	H4AA—C4A—H4AB	107.4
O2—C1—O1	125.0 (2)	C5A—C4A—C3	115.9 (5)
O2—C1—C2	122.4 (2)	C5A—C4A—H4AA	108.3
O1—C1—C2	112.6 (2)	C5A—C4A—H4AB	108.3
O4—C6—C7	119.1 (2)	C3—C4B—H4BA	108.7
O3—C6—O4	122.4 (2)	C3—C4B—H4BB	108.7
O3—C6—C7	118.5 (2)	H4BA—C4B—H4BB	107.6
N1—C2—C1	107.4 (2)	C5B—C4B—C3	114 (3)
N1—C2—H2	109.3	C5B—C4B—H4BA	108.7
N1—C2—C3	108.9 (2)	C5B—C4B—H4BB	108.7
C1—C2—H2	109.3	C4A—C5A—H5AA	109.5
C1—C2—C3	112.7 (3)	C4A—C5A—H5AB	109.5
C3—C2—H2	109.3	C4A—C5A—H5AC	109.5
C9—C8—H8	114.7	H5AA—C5A—H5AB	109.5
C7—C8—C9	130.6 (2)	H5AA—C5A—H5AC	109.5
C7—C8—H8	114.7	H5AB—C5A—H5AC	109.5
C6—C7—H7	114.6	C4B—C5B—H5BA	109.5
C8—C7—C6	130.8 (2)	C4B—C5B—H5BB	109.5
C8—C7—H7	114.6	C4B—C5B—H5BC	109.5
C2—C3—H3AA	108.5	H5BA—C5B—H5BB	109.5
C2—C3—H3AB	108.5	H5BA—C5B—H5BC	109.5
C2—C3—H3BC	104.7	H5BB—C5B—H5BC	109.5
C2—C3—H3BD	104.7
O2—C1—C2—N1	−26.0 (4)	N1—C2—C3—C4A	−170.8 (3)
O2—C1—C2—C3	93.9 (4)	N1—C2—C3—C4B	−90 (2)
O4—C6—C7—C8	5.0 (6)	C9—C8—C7—C6	−0.4 (7)
O6—C9—C8—C7	−5.4 (6)	C1—C2—C3—C4A	70.1 (4)
O5—C9—C8—C7	175.1 (4)	C1—C2—C3—C4B	151 (2)
O3—C6—C7—C8	−174.1 (4)	C2—C3—C4A—C5A	63.3 (7)
O1—C1—C2—N1	154.9 (3)	C2—C3—C4B—C5B	−57 (5)
O1—C1—C2—C3	−85.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O4	0.82	1.60	2.421 (2)	178
O1—H1···O5	0.82	1.80	2.612 (3)	171
N1—H1A···O2^i	0.89	2.11	2.864 (3)	142
N1—H1B···O4^ii	0.89	2.01	2.898 (3)	172
N1—H1C···O3^iii	0.89	1.97	2.850 (3)	168

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

(2dl_nv_mal) DL-Norvalinium hydrogen maleate–DL-norvaline (1/1)

Crystal data

C5H12NO2^+·C4H3O4^−·C5H11NO2	Dx = 1.226 Mg m^−3
Mr = 350.37	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 6447 reflections
a = 8.8572 (4) Å	θ = 2.3–27.7°
b = 27.3614 (11) Å	µ = 0.10 mm^−1
c = 7.8306 (4) Å	T = 293 K
V = 1897.71 (15) Å^3	Block, clear light colourless
Z = 4	0.5 × 0.25 × 0.2 mm
F(000) = 752

Data collection

Agilent Xcalibur Ruby Gemini ultra diffractometer	1975 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1731 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 10.3457 pixels mm^-1	θmax = 26.4°, θmin = 3.0°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −34→34
Tmin = 0.948, Tmax = 1.000	l = −9→9
21923 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.079	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.146	w = 1/[σ^2(Fo^2) + 2.5627P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max < 0.001
1975 reflections	Δρmax = 0.15 e Å^−3
216 parameters	Δρmin = −0.20 e Å^−3
298 restraints

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.3996 (7)	0.5283 (3)	0.4353 (8)	0.0588 (14)	0.733 (5)
O2	0.2253 (12)	0.4842 (4)	0.5382 (11)	0.0673 (19)	0.733 (5)
N1	0.1895 (3)	0.58452 (10)	0.2864 (4)	0.0436 (9)	0.733 (5)
H1A	0.209236	0.566396	0.194754	0.052*	0.733 (5)
H1B	0.271973	0.601006	0.316357	0.052*	0.733 (5)
H1C	0.115546	0.605455	0.262507	0.052*	0.733 (5)
C1	0.2668 (10)	0.5162 (3)	0.486 (2)	0.053 (2)	0.733 (5)
C6	0.4597 (4)	0.69058 (10)	0.2591 (5)	0.0667 (9)
C3	0.0925 (9)	0.5831 (2)	0.5848 (10)	0.0563 (15)	0.733 (5)
H3A	0.015017	0.605821	0.547903	0.068*	0.733 (5)
H3B	0.047697	0.561615	0.669252	0.068*	0.733 (5)
C2	0.1420 (5)	0.55218 (16)	0.4302 (6)	0.0450 (10)	0.733 (5)
H2	0.054865	0.533011	0.392004	0.054*	0.733 (5)
O4	0.4852 (12)	0.70580 (16)	0.1052 (7)	0.082 (3)	0.532 (13)
C4	0.2156 (11)	0.6112 (4)	0.6672 (11)	0.078 (2)	0.733 (5)
H4A	0.258051	0.633807	0.584784	0.093*	0.733 (5)
H4B	0.295023	0.588785	0.701321	0.093*	0.733 (5)
C7	0.4209 (11)	0.7257 (3)	0.3969 (11)	0.055 (2)	0.532 (13)
H7	0.391943	0.711475	0.499571	0.066*	0.532 (13)
O4B	0.5932 (11)	0.70603 (18)	0.1975 (19)	0.112 (5)	0.468 (13)
N1B	0.0750 (11)	0.5607 (3)	0.3297 (13)	0.054 (3)	0.267 (5)
H1BA	0.116614	0.543114	0.246574	0.065*	0.267 (5)
H1BB	0.034246	0.587671	0.285670	0.065*	0.267 (5)
H1BC	0.003694	0.543223	0.381236	0.065*	0.267 (5)
O1B	0.425 (2)	0.5365 (8)	0.503 (2)	0.067 (5)	0.267 (5)
O2B	0.229 (4)	0.4803 (10)	0.593 (3)	0.066 (5)	0.267 (5)
C2B	0.1906 (15)	0.5742 (4)	0.4535 (19)	0.054 (3)	0.267 (5)
H2B	0.259337	0.597557	0.399015	0.064*	0.267 (5)
C7B	0.3551 (12)	0.7257 (3)	0.3272 (18)	0.068 (3)	0.468 (13)
H7B	0.271968	0.711838	0.381295	0.082*	0.468 (13)
C1B	0.271 (3)	0.5271 (8)	0.473 (7)	0.049 (4)	0.267 (5)
C3B	0.117 (4)	0.5995 (9)	0.605 (4)	0.086 (6)	0.267 (5)
H3BA	0.052294	0.625599	0.563819	0.103*	0.267 (5)
H3BB	0.053207	0.576156	0.664850	0.103*	0.267 (5)
C4B	0.223 (4)	0.6193 (12)	0.723 (4)	0.107 (7)	0.267 (5)
H4BA	0.240324	0.596531	0.815453	0.129*	0.267 (5)
H4BB	0.318602	0.625157	0.665381	0.129*	0.267 (5)
O3	0.453 (5)	0.6486 (10)	0.284 (6)	0.073 (7)	0.532 (13)
O3B	0.440 (5)	0.6447 (12)	0.290 (6)	0.063 (5)	0.468 (13)
C5	0.1602 (13)	0.6408 (3)	0.8296 (14)	0.096 (3)	0.733 (5)
H5A	0.089387	0.665441	0.794706	0.145*	0.733 (5)
H5B	0.245280	0.656078	0.883680	0.145*	0.733 (5)
H5C	0.112409	0.618901	0.908534	0.145*	0.733 (5)
C5B	0.170 (5)	0.6600 (9)	0.782 (5)	0.129 (11)	0.267 (5)
H5BA	0.103300	0.674308	0.698621	0.193*	0.267 (5)
H5BB	0.251346	0.682068	0.804935	0.193*	0.267 (5)
H5BC	0.114773	0.653731	0.885012	0.193*	0.267 (5)
H1	0.500000	0.500000	0.500000	0.193*
H4	0.483 (9)	0.750000	0.115 (11)	0.193*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.044 (3)	0.052 (3)	0.080 (4)	0.016 (2)	0.004 (2)	0.021 (3)
O2	0.058 (2)	0.061 (4)	0.083 (6)	0.005 (2)	0.002 (4)	0.030 (4)
N1	0.0397 (17)	0.0352 (15)	0.056 (2)	0.0090 (13)	−0.0013 (15)	0.0050 (14)
C1	0.045 (3)	0.051 (4)	0.061 (5)	0.023 (3)	0.001 (3)	0.019 (5)
C6	0.064 (2)	0.0354 (15)	0.101 (3)	0.0003 (13)	0.0253 (19)	−0.0043 (17)
C3	0.048 (3)	0.052 (3)	0.069 (4)	0.018 (2)	0.009 (3)	0.006 (3)
C2	0.040 (2)	0.034 (2)	0.061 (3)	0.0051 (18)	0.001 (2)	0.008 (2)
O4	0.115 (7)	0.047 (2)	0.084 (3)	0.000 (3)	0.028 (4)	−0.011 (2)
C4	0.072 (4)	0.080 (4)	0.081 (5)	0.010 (3)	0.014 (4)	−0.023 (4)
C7	0.066 (5)	0.035 (3)	0.065 (4)	−0.001 (3)	0.007 (4)	0.003 (3)
O4B	0.070 (5)	0.043 (3)	0.223 (12)	0.004 (3)	0.081 (7)	0.000 (4)
N1B	0.050 (6)	0.041 (5)	0.070 (6)	0.009 (4)	−0.002 (5)	0.010 (4)
O1B	0.044 (6)	0.057 (7)	0.101 (14)	0.013 (5)	0.003 (7)	0.017 (9)
O2B	0.074 (7)	0.059 (6)	0.064 (11)	0.029 (5)	0.017 (8)	0.050 (7)
C2B	0.050 (6)	0.029 (5)	0.083 (8)	0.012 (5)	−0.006 (6)	0.008 (5)
C7B	0.048 (5)	0.038 (3)	0.119 (9)	0.000 (4)	0.027 (5)	−0.002 (5)
C1B	0.053 (7)	0.035 (8)	0.059 (10)	0.006 (6)	0.014 (6)	0.026 (7)
C3B	0.084 (13)	0.090 (14)	0.083 (10)	0.037 (11)	−0.002 (9)	−0.005 (9)
C4B	0.127 (15)	0.103 (14)	0.092 (15)	0.041 (12)	−0.025 (13)	−0.013 (10)
O3	0.071 (14)	0.023 (4)	0.124 (11)	0.004 (5)	0.026 (9)	0.005 (5)
O3B	0.050 (6)	0.032 (6)	0.108 (12)	0.002 (6)	0.019 (7)	−0.007 (7)
C5	0.098 (5)	0.094 (7)	0.097 (6)	0.020 (5)	0.004 (4)	−0.023 (5)
C5B	0.20 (3)	0.071 (14)	0.12 (2)	0.029 (16)	0.020 (18)	0.002 (12)

Geometric parameters (Å, º)

O1—C1	1.286 (11)	N1B—H1BA	0.8900
O1—H1	1.284 (6)	N1B—H1BB	0.8900
O2—C1	1.034 (15)	N1B—H1BC	0.8900
N1—H1A	0.8900	N1B—C2B	1.457 (17)
N1—H1B	0.8900	O1B—C1B	1.41 (2)
N1—H1C	0.8900	O1B—H1	1.20 (2)
N1—C2	1.492 (6)	O2B—C1B	1.63 (4)
C1—C2	1.544 (7)	C2B—H2B	0.9800
C6—O4	1.295 (6)	C2B—C1B	1.481 (18)
C6—C7	1.486 (8)	C2B—C3B	1.52 (3)
C6—O4B	1.345 (6)	C7B—C7B^i	1.331 (17)
C6—C7B	1.437 (9)	C7B—H7B	0.9300
C6—O3	1.17 (3)	C3B—H3BA	0.9700
C6—O3B	1.29 (3)	C3B—H3BB	0.9700
C3—H3A	0.9700	C3B—C4B	1.42 (3)
C3—H3B	0.9700	C4B—H4BA	0.9700
C3—C2	1.541 (8)	C4B—H4BB	0.9700
C3—C4	1.481 (10)	C4B—C5B	1.29 (4)
C2—H2	0.9800	C5—H5A	0.9600
O4—H4	1.212 (7)	C5—H5B	0.9600
C4—H4A	0.9700	C5—H5C	0.9600
C4—H4B	0.9700	C5B—H5BA	0.9600
C4—C5	1.586 (12)	C5B—H5BB	0.9600
C7—C7^i	1.327 (14)	C5B—H5BC	0.9600
C7—H7	0.9300
C1—O1—H1	110.8 (7)	C2B—N1B—H1BA	109.5
H1A—N1—H1B	109.5	C2B—N1B—H1BB	109.5
H1A—N1—H1C	109.5	C2B—N1B—H1BC	109.5
H1B—N1—H1C	109.5	C1B—O1B—H1	112.4 (17)
C2—N1—H1A	109.5	N1B—C2B—H2B	108.1
C2—N1—H1B	109.5	N1B—C2B—C1B	100.8 (18)
C2—N1—H1C	109.5	N1B—C2B—C3B	109.4 (15)
O1—C1—C2	113.7 (8)	C1B—C2B—H2B	108.1
O2—C1—O1	131.8 (9)	C1B—C2B—C3B	121 (2)
O2—C1—C2	113.5 (9)	C3B—C2B—H2B	108.1
O4—C6—C7	120.5 (4)	C6—C7B—H7B	114.0
O4B—C6—C7B	119.3 (5)	C7B^i—C7B—C6	131.9 (4)
O3—C6—O4	119 (2)	C7B^i—C7B—H7B	114.0
O3—C6—C7	120 (2)	O1B—C1B—O2B	106 (2)
O3B—C6—O4B	120 (2)	O1B—C1B—C2B	109.0 (19)
O3B—C6—C7B	120 (2)	C2B—C1B—O2B	129 (3)
H3A—C3—H3B	107.6	C2B—C3B—H3BA	109.0
C2—C3—H3A	108.6	C2B—C3B—H3BB	109.0
C2—C3—H3B	108.6	H3BA—C3B—H3BB	107.8
C4—C3—H3A	108.6	C4B—C3B—C2B	113 (3)
C4—C3—H3B	108.6	C4B—C3B—H3BA	109.0
C4—C3—C2	114.7 (6)	C4B—C3B—H3BB	109.0
N1—C2—C1	113.0 (6)	C3B—C4B—H4BA	110.0
N1—C2—C3	110.3 (4)	C3B—C4B—H4BB	110.0
N1—C2—H2	108.0	H4BA—C4B—H4BB	108.4
C1—C2—H2	108.0	C5B—C4B—C3B	108 (3)
C3—C2—C1	109.3 (8)	C5B—C4B—H4BA	110.0
C3—C2—H2	108.0	C5B—C4B—H4BB	110.0
C6—O4—H4	105 (4)	C4—C5—H5A	109.5
C3—C4—H4A	109.0	C4—C5—H5B	109.5
C3—C4—H4B	109.0	C4—C5—H5C	109.5
C3—C4—C5	112.7 (8)	H5A—C5—H5B	109.5
H4A—C4—H4B	107.8	H5A—C5—H5C	109.5
C5—C4—H4A	109.0	H5B—C5—H5C	109.5
C5—C4—H4B	109.0	C4B—C5B—H5BA	109.5
C6—C7—H7	114.8	C4B—C5B—H5BB	109.5
C7^i—C7—C6	130.4 (3)	C4B—C5B—H5BC	109.5
C7^i—C7—H7	114.8	H5BA—C5B—H5BB	109.5
H1BA—N1B—H1BB	109.5	H5BA—C5B—H5BC	109.5
H1BA—N1B—H1BC	109.5	H5BB—C5B—H5BC	109.5
H1BB—N1B—H1BC	109.5
O1—C1—C2—N1	17.9 (14)	N1B—C2B—C1B—O1B	147 (3)
O1—C1—C2—C3	−105.4 (12)	N1B—C2B—C1B—O2B	−83 (4)
O2—C1—C2—N1	−151.9 (12)	N1B—C2B—C3B—C4B	−173 (2)
O2—C1—C2—C3	84.9 (15)	C2B—C3B—C4B—C5B	144 (3)
C2—C3—C4—C5	−177.9 (7)	C1B—C2B—C3B—C4B	71 (3)
O4—C6—C7—C7^i	−7.7 (7)	C3B—C2B—C1B—O1B	−92 (3)
C4—C3—C2—N1	−67.1 (8)	C3B—C2B—C1B—O2B	38 (4)
C4—C3—C2—C1	57.7 (9)	O3—C6—C7—C7^i	−180 (3)
O4B—C6—C7B—C7B^i	8.4 (9)	O3B—C6—C7B—C7B^i	174 (3)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^ii	0.89	1.94	2.807 (8)	165
N1—H1B···O3	0.89	2.08	2.92 (4)	157
N1—H1C···O3^iii	0.89	1.90	2.79 (4)	178
O1—H1···O1^iv	1.28 (1)	1.28 (1)	2.568 (13)	180 (1)
O4—H4···O4^i	1.21 (1)	1.21 (1)	2.418 (9)	173 (8)

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