Ethyl (E)-3-(2-hydroxy­phenyl)-2-(morpholino­carbonyl)­propenoate

The title compound, C₁₆H₁₉NO₅, crystallizes as a centrosymmetric dimer through strong O—H...O hydrogen-bonding interactions between the hydroxy­phenyl and morpholino­carbonyl groups. The morpholino­carbonyl group is almost perpendicular to the propenoate moiety. Electron delocalization in the N—C(=O) fragment leads to the formation of hydrogen-bonded S(5) ring motifs through C—H...O interactions.

S1. Comment

Lignin-related phenylpropanoids, such as cinnamic acid, are abundant in plant cells and are precursors not only of lignin, the second most abundant carbon compound on earth after cellulose, but also of anthocyanins, phytoalexins and flavonoids (Peng et al., 2003). Many phenylpropanoids are pharmacologically active and thus of pharmaceutical interest (Dixon et al., 1996). The biodegradation of phenylpropanoids is important for the global carbon cycle from an environmental point of view, since these compounds are released from plant wastes as breakdown products from lignin. In view of their importance, augmented further by the potential use of phenylpropanoids as feedstock for bioconversion into valuable molecules (Rosazza et al., 1995), we analyzed the crystal structure of the title compound, (I), which is reported here.

The molecular structure of (I) and the atom-numbering scheme are shown in Fig. 1. Selected bond lengths and angles are listed in Table 1. The observed bond lengths and angles in the hydroxyphenyl group are in agreement with the average values reported in the literature (Domenicano et al., 1975; Allen et al., 1987). The morpholine ring presents a chair conformation, and its bond lengths and angles are comparable to those reported for a related structure (Decken et al., 2003).

The cinammic derivative (I) has a C8—C9 bond length of 1.339 (3) Å, which confirms its double-bond character. The ester and 2-hydroxyphenyl groups are arranged in opposite positions around the double bond [C16—C8—C9—C10 = 177.9 (2)°], giving it an E configuration. The –OEt group points towards the double bond and is almost coplanar with it [C9—C8—C16—O17 = 14.5 (3)°]. These features support the formation of an S(5) ring motif (Bernstein et al., 1995) through the soft C9(sp²)—H9···O17 intramolecular hydrogen-bonding interaction [C9···O17 = 2.747 (2) Å] (Desiraju, 1995), in spite of the small angle observed for C9—H9···O17 (103°). In the same context, the N-carboxy moiety is almost coplanar with the neighbouring C6 atom of the morpholine ring [C6—N1—C7—O7 = 2.3 (3)°] and the C6—N1—C7 angle [121.59 (18)°] is slightly less open than the C2—N1—C7 angle [124.81 (18)°]. Another plausible soft S(5) hydrogen motif is formed through the C6(sp³)—H6A···O7 interaction [C6···O7 = 2.774 (3) Å and C6—H6A···O7 = 103°; Fig. 2]. The hydrogen-bonding geometry is listed in Table 2. This interaction appears as a consequence of the planarity imposed by electron delocalization in the amide N—C(=O) fragment, as indicated by the short N1—C7 distance of only 1.327 (3) Å; this is even shorter than the value found in N-benzylmorpholine (1.343 Å; Bennet et al., 1991).

The N-carboxymorpholine group is almost perpendicular to the propenoic ester group, with N1—C7—C8—C16 and O7—C7—C8—C16 torsion angles of −81.5 (2) and 97.2 (2)°, respectively. This orthogonal disposition of the two S(5) hydrogen-bonding motifs must be forced by the steric requirements of the morpholine ring, in addition to the restricted rotation of the amide N—C(O) bond (Bennet et al., 1991). The conformation exhibited by (I) in the solid state is similar to that found in solution, as supported by the ¹³C NMR spectrum, which shows four different signals, at 66.4 and 66.3 p.p.m., and 46.9 and 41.9 p.p.m., for the CH₂O and CH₂N morpholine ring C atoms, respectively.

Finally, the crystal packing is mediated by a strong (Steiner, 2002) O15—H15···O7ⁱ intermolecular interaction [H15···O7ⁱ = 1.88 Å, O15···O7ⁱ = 2.688 (2) Å and O15—H15···O7ⁱ = 168°; symmetry code: (i) 1 − x, 1 − y, 1 − z], leading to dimerization in the ac plane. As a result, a 16-membered ring is formed between molecules whose topological motif corresponds to the first-level graph-set descriptor R²₂(16) (Fig. 2). No other hydorgen-bonding interactions linking this centrosymmetric dimer are formed.

S2. Experimental

Compound (I) was synthesized starting from equimolar quantities of ethyl coumarin-3-carboxylate (2.12 mmol) and morpholine, refluxed in dry ethyl alcohol (20 ml) for 24 h. The product crystallized from the reaction mixture as a white solid (56% yield; m.p. 488–493 K). Crystals suitable for X-ray analysis were obtained after slow recrystallization from an ethyl alcohol solution. IR (KBr, cm⁻¹): 1764 (C=O), 1606(C=C); ¹H NMR (p.p.m., DMSO-d₆): 10.3 (b, 1H, OH), 7.94 (s, 1H, H-vinyl), 7.40 (d, 1H, H_o), 7.31 (dd, 1H, H_p), 6.98 (d, 1H, H_m), 6.80 (dd, 1H, H_m), 4.22 (q, 2H, CH₂), 3.57–3.41 (m, 4H, CH₂O), 3.22–3.11 (m, 4H, CH₂N), 1.24 (t, 3H, CH₃); ¹³C NMR (p.p.m., DMSO-d₆): 165.5 (COO), 164.9 (NCO), 157.4 (C—OH), 135.2 (C—Ar), 132.9 (C_p), 128.9 (C_o), 126.1 (C_i), 120.3 (CCO), 120.0 and 116.6 (C_m), 66.4 and 66.3 (CH₂O), 46.9 and 41.9 (CH₂N), 16.6 (CH₂), 14.8 (CH₃).

S3. Refinement

All H atoms were postioned geometrically and included in the refinement as riding atoms.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXL97 and WinGX2003 (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A view of the intra- and intermolecular hydrogen-bonding scheme in the crystal structure of (I). Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).

Ethyl (E)-3-(2-hydroxyphenyl)-2-(morpholinocarbonyl)propenoate

Crystal data

C16H19NO5	Z = 2
Mr = 305.32	F(000) = 324
Triclinic, P1	Dx = 1.332 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.790 (2) Å	Cell parameters from 600 reflections
b = 9.971 (2) Å	θ = 20–25°
c = 10.832 (2) Å	µ = 0.10 mm^−1
α = 72.59 (3)°	T = 293 K
β = 74.79 (3)°	Block, colourless
γ = 75.64 (3)°	0.40 × 0.30 × 0.30 mm
V = 761.5 (3) Å^3

Data collection

Bruker SMART area-detector diffractometer	Rint = 0.025
Graphite monochromator	θmax = 26.1°, θmin = 2.0°
ϕ and ω scans	h = −9→9
5151 measured reflections	k = −11→12
3003 independent reflections	l = −13→13
1669 reflections with I > 2σ(I)

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)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.0361P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3003 reflections	Δρmax = 0.22 e Å^−3
200 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.027 (3)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 > σ(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
O4	0.1046 (2)	−0.02996 (18)	0.29525 (16)	0.0754 (7)
O7	0.53751 (18)	0.22049 (14)	0.34063 (13)	0.0530 (5)
O15	0.31995 (18)	0.63836 (15)	0.54654 (13)	0.0566 (6)
O16	0.2882 (2)	0.41502 (16)	0.09461 (15)	0.0810 (7)
O17	0.2584 (2)	0.62165 (15)	0.14519 (13)	0.0619 (6)
N1	0.2753 (2)	0.15794 (17)	0.34815 (16)	0.0503 (6)
C2	0.0807 (3)	0.1906 (2)	0.3507 (2)	0.0632 (9)
C3	0.0394 (3)	0.1194 (3)	0.2627 (2)	0.0738 (10)
C5	0.2951 (3)	−0.0581 (3)	0.2839 (2)	0.0731 (10)
C6	0.3512 (3)	0.0049 (2)	0.3720 (2)	0.0609 (9)
C7	0.3745 (3)	0.2534 (2)	0.33642 (17)	0.0435 (7)
C8	0.2880 (3)	0.4097 (2)	0.31390 (18)	0.0444 (7)
C9	0.2424 (2)	0.4822 (2)	0.40727 (19)	0.0458 (7)
C10	0.2420 (2)	0.4244 (2)	0.54811 (18)	0.0432 (7)
C11	0.1995 (3)	0.2918 (2)	0.6204 (2)	0.0561 (8)
C12	0.2017 (3)	0.2416 (3)	0.7526 (2)	0.0675 (9)
C13	0.2456 (3)	0.3240 (3)	0.8171 (2)	0.0711 (10)
C14	0.2848 (3)	0.4563 (3)	0.7501 (2)	0.0596 (9)
C15	0.2826 (3)	0.5076 (2)	0.6168 (2)	0.0458 (7)
C16	0.2767 (3)	0.4807 (2)	0.1744 (2)	0.0530 (8)
C18	0.2461 (3)	0.6969 (3)	0.0102 (2)	0.0730 (10)
C19	0.2696 (4)	0.8439 (3)	−0.0106 (3)	0.1026 (13)
H2A	0.01527	0.15807	0.44028	0.0758*
H2B	0.04165	0.29326	0.32193	0.0758*
H3A	0.09407	0.16022	0.17185	0.0886*
H3B	−0.09056	0.13715	0.26955	0.0886*
H5A	0.33777	−0.16070	0.30558	0.0878*
H5B	0.35182	−0.01953	0.19310	0.0878*
H6A	0.48220	−0.00927	0.35519	0.0731*
H6B	0.30880	−0.04235	0.46360	0.0731*
H9	0.20681	0.58073	0.37915	0.0550*
H11	0.16884	0.23544	0.57780	0.0673*
H12	0.17349	0.15217	0.79847	0.0810*
H13	0.24876	0.28978	0.90649	0.0854*
H14	0.31304	0.51214	0.79442	0.0715*
H15	0.36256	0.67099	0.59053	0.0849*
H18A	0.33947	0.65029	−0.05048	0.0876*
H18B	0.12914	0.69694	−0.00556	0.0876*
H19A	0.26079	0.89627	−0.09951	0.1540*
H19B	0.17708	0.88888	0.05019	0.1540*
H19C	0.38637	0.84275	0.00400	0.1540*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.0778 (12)	0.0706 (12)	0.0942 (13)	−0.0290 (9)	−0.0244 (10)	−0.0260 (9)
O7	0.0464 (9)	0.0500 (9)	0.0696 (10)	−0.0040 (7)	−0.0224 (7)	−0.0200 (7)
O15	0.0642 (10)	0.0522 (10)	0.0615 (9)	−0.0131 (7)	−0.0213 (7)	−0.0167 (7)
O16	0.1293 (16)	0.0638 (11)	0.0574 (10)	−0.0062 (10)	−0.0356 (10)	−0.0213 (9)
O17	0.0898 (12)	0.0476 (10)	0.0463 (9)	−0.0058 (8)	−0.0254 (8)	−0.0046 (7)
N1	0.0461 (10)	0.0414 (11)	0.0699 (12)	−0.0054 (8)	−0.0220 (9)	−0.0166 (8)
C2	0.0518 (14)	0.0601 (15)	0.0805 (17)	−0.0073 (11)	−0.0193 (12)	−0.0193 (12)
C3	0.0680 (16)	0.084 (2)	0.0804 (18)	−0.0191 (14)	−0.0320 (14)	−0.0177 (14)
C5	0.0831 (19)	0.0606 (16)	0.0849 (18)	−0.0140 (13)	−0.0213 (15)	−0.0275 (13)
C6	0.0723 (16)	0.0417 (13)	0.0725 (16)	−0.0046 (11)	−0.0281 (12)	−0.0132 (11)
C7	0.0487 (13)	0.0453 (13)	0.0399 (12)	−0.0055 (10)	−0.0133 (10)	−0.0143 (9)
C8	0.0470 (12)	0.0411 (12)	0.0469 (12)	−0.0056 (9)	−0.0151 (10)	−0.0107 (10)
C9	0.0440 (12)	0.0397 (12)	0.0542 (13)	−0.0024 (9)	−0.0152 (10)	−0.0124 (10)
C10	0.0413 (12)	0.0423 (12)	0.0437 (12)	−0.0011 (9)	−0.0086 (9)	−0.0130 (10)
C11	0.0648 (15)	0.0492 (14)	0.0545 (15)	−0.0088 (11)	−0.0116 (12)	−0.0151 (11)
C12	0.0837 (18)	0.0550 (15)	0.0522 (15)	−0.0138 (13)	−0.0068 (13)	−0.0017 (12)
C13	0.0839 (18)	0.0798 (19)	0.0444 (14)	−0.0116 (15)	−0.0144 (13)	−0.0094 (13)
C14	0.0640 (15)	0.0700 (17)	0.0508 (14)	−0.0116 (12)	−0.0144 (11)	−0.0223 (12)
C15	0.0400 (12)	0.0457 (13)	0.0493 (13)	−0.0013 (9)	−0.0089 (10)	−0.0141 (10)
C16	0.0597 (14)	0.0486 (15)	0.0519 (14)	−0.0026 (11)	−0.0183 (11)	−0.0144 (11)
C18	0.0948 (19)	0.0692 (18)	0.0495 (15)	−0.0083 (14)	−0.0256 (13)	−0.0028 (12)
C19	0.180 (3)	0.0603 (19)	0.0676 (17)	−0.0293 (19)	−0.0411 (18)	0.0035 (13)

Geometric parameters (Å, º)

O4—C3	1.416 (3)	C13—C14	1.368 (4)
O4—C5	1.419 (3)	C14—C15	1.383 (3)
O7—C7	1.240 (3)	C18—C19	1.465 (4)
O15—C15	1.357 (3)	C2—H2A	0.9699
O16—C16	1.205 (3)	C2—H2B	0.9705
O17—C16	1.324 (3)	C3—H3A	0.9705
O17—C18	1.446 (3)	C3—H3B	0.9702
O15—H15	0.8200	C5—H5A	0.9699
N1—C2	1.464 (3)	C5—H5B	0.9697
N1—C7	1.327 (3)	C6—H6A	0.9700
N1—C6	1.463 (3)	C6—H6B	0.9701
C2—C3	1.482 (3)	C9—H9	0.9300
C5—C6	1.487 (3)	C11—H11	0.9302
C7—C8	1.510 (3)	C12—H12	0.9301
C8—C16	1.480 (3)	C13—H13	0.9302
C8—C9	1.339 (3)	C14—H14	0.9301
C9—C10	1.460 (3)	C18—H18A	0.9702
C10—C15	1.402 (3)	C18—H18B	0.9699
C10—C11	1.390 (3)	C19—H19A	0.9596
C11—C12	1.372 (3)	C19—H19B	0.9600
C12—C13	1.374 (4)	C19—H19C	0.9601
O4···N1	2.808 (3)	C8···H11	2.9133
O7···O15^i	2.688 (2)	C8···H15^i	3.0038
O15···C2^ii	3.250 (3)	C9···H15^i	3.0804
O15···O7^i	2.688 (2)	C15···H2B^ii	2.8609
O15···C15^i	3.356 (3)	C16···H2B	2.7882
O15···C10^i	3.252 (2)	C16···H18A^ix	3.0747
O16···N1	3.145 (2)	H2A···H11	2.5151
O16···C2	3.323 (3)	H2A···O4^iii	2.7764
O4···H2A^iii	2.7764	H2A···O15^ii	2.8824
O4···H19B^iv	2.8797	H2B···O16	2.8482
O7···H6A	2.3868	H2B···C8	2.4486
O7···H15^i	1.8810	H2B···C16	2.7882
O7···H3B^v	2.7742	H2B···O15^ii	2.8200
O7···H6B^vi	2.6662	H2B···C15^ii	2.8609
O15···H5A^vii	2.7685	H3A···H5B	2.3468
O15···H2B^ii	2.8200	H3B···O7^x	2.7742
O15···H9	2.4714	H5A···O15^iv	2.7685
O15···H2A^ii	2.8824	H5B···H3A	2.3468
O16···H2B	2.8482	H6A···O7	2.3868
O16···H13^viii	2.8014	H6B···O7^vi	2.6662
O16···H18A	2.4621	H9···O15	2.4714
O16···H18B	2.7869	H9···O17	2.3830
O16···H18A^ix	2.7545	H11···N1	2.6875
O17···H9	2.3830	H11···C2	2.9016
N1···O4	2.808 (3)	H11···C7	2.6644
N1···O16	3.145 (2)	H11···C8	2.9133
N1···C11	3.446 (3)	H11···H2A	2.5151
N1···H11	2.6875	H12···H19A^xi	2.4577
C2···O16	3.323 (3)	H13···O16^xii	2.8014
C2···C16	3.421 (3)	H14···H15	2.3017
C2···O15^ii	3.250 (3)	H14···H18A^xii	2.5435
C7···C11	3.117 (3)	H15···H14	2.3017
C9···C10^ii	3.593 (3)	H15···O7^i	1.8810
C10···O15^i	3.252 (2)	H15···C7^i	2.7136
C10···C9^ii	3.593 (3)	H15···C8^i	3.0038
C11···C7	3.117 (3)	H15···C9^i	3.0804
C11···N1	3.446 (3)	H18A···O16	2.4621
C15···O15^i	3.356 (3)	H18A···H14^viii	2.5435
C16···C2	3.421 (3)	H18A···O16^ix	2.7545
C2···H11	2.9016	H18A···C16^ix	3.0747
C7···H11	2.6644	H18B···O16	2.7869
C7···H15^i	2.7136	H19A···H12^xiii	2.4577
C8···H2B	2.4486	H19B···O4^vii	2.8797
C3—O4—C5	110.11 (19)	O4—C3—H3A	109.25
C16—O17—C18	116.27 (18)	O4—C3—H3B	109.28
C15—O15—H15	109.46	C2—C3—H3A	109.25
C2—N1—C7	124.81 (18)	C2—C3—H3B	109.26
C6—N1—C7	121.59 (18)	H3A—C3—H3B	107.88
C2—N1—C6	113.39 (17)	O4—C5—H5A	109.10
N1—C2—C3	110.20 (18)	O4—C5—H5B	109.12
O4—C3—C2	111.84 (19)	C6—C5—H5A	109.03
O4—C5—C6	112.6 (2)	C6—C5—H5B	109.05
N1—C6—C5	109.79 (19)	H5A—C5—H5B	107.86
O7—C7—C8	117.9 (2)	N1—C6—H6A	109.68
N1—C7—C8	119.2 (2)	N1—C6—H6B	109.68
O7—C7—N1	122.86 (19)	C5—C6—H6A	109.75
C7—C8—C16	113.61 (16)	C5—C6—H6B	109.74
C9—C8—C16	122.28 (18)	H6A—C6—H6B	108.19
C7—C8—C9	123.77 (18)	C8—C9—H9	116.24
C8—C9—C10	127.50 (19)	C10—C9—H9	116.26
C9—C10—C15	118.82 (18)	C10—C11—H11	119.01
C11—C10—C15	117.19 (18)	C12—C11—H11	119.06
C9—C10—C11	123.98 (18)	C11—C12—H12	120.15
C10—C11—C12	121.9 (2)	C13—C12—H12	120.10
C11—C12—C13	119.7 (2)	C12—C13—H13	119.98
C12—C13—C14	120.1 (2)	C14—C13—H13	119.89
C13—C14—C15	120.4 (2)	C13—C14—H14	119.82
O15—C15—C14	122.4 (2)	C15—C14—H14	119.79
C10—C15—C14	120.6 (2)	O17—C18—H18A	110.11
O15—C15—C10	117.03 (18)	O17—C18—H18B	110.14
O16—C16—O17	123.54 (19)	C19—C18—H18A	110.08
O17—C16—C8	113.81 (17)	C19—C18—H18B	110.09
O16—C16—C8	122.63 (19)	H18A—C18—H18B	108.42
O17—C18—C19	108.0 (2)	C18—C19—H19A	109.48
N1—C2—H2A	109.62	C18—C19—H19B	109.45
N1—C2—H2B	109.59	C18—C19—H19C	109.44
C3—C2—H2A	109.64	H19A—C19—H19B	109.51
C3—C2—H2B	109.64	H19A—C19—H19C	109.49
H2A—C2—H2B	108.11	H19B—C19—H19C	109.47
C5—O4—C3—C2	−59.8 (2)	C7—C8—C16—O16	19.1 (3)
C3—O4—C5—C6	59.4 (2)	C7—C8—C16—O17	−159.0 (2)
C18—O17—C16—C8	−179.82 (19)	C9—C8—C16—O16	−167.4 (2)
C16—O17—C18—C19	−166.9 (2)	C16—C8—C9—C10	177.9 (2)
C18—O17—C16—O16	2.1 (3)	C9—C8—C16—O17	14.5 (3)
C2—N1—C7—C8	−4.7 (3)	C7—C8—C9—C10	−9.3 (3)
C6—N1—C7—C8	−179.09 (16)	C8—C9—C10—C15	147.4 (2)
C6—N1—C7—O7	2.3 (3)	C8—C9—C10—C11	−34.1 (3)
C7—N1—C6—C5	−134.9 (2)	C11—C10—C15—O15	−178.52 (19)
C2—N1—C7—O7	176.66 (17)	C9—C10—C15—C14	−179.6 (2)
C6—N1—C2—C3	−51.1 (2)	C9—C10—C15—O15	0.1 (3)
C7—N1—C2—C3	134.1 (2)	C11—C10—C15—C14	1.8 (3)
C2—N1—C6—C5	50.2 (2)	C15—C10—C11—C12	−1.8 (3)
N1—C2—C3—O4	55.4 (2)	C9—C10—C11—C12	179.7 (2)
O4—C5—C6—N1	−54.2 (2)	C10—C11—C12—C13	0.5 (4)
O7—C7—C8—C16	97.2 (2)	C11—C12—C13—C14	0.8 (4)
O7—C7—C8—C9	−76.3 (3)	C12—C13—C14—C15	−0.7 (4)
N1—C7—C8—C9	105.1 (3)	C13—C14—C15—O15	179.8 (2)
N1—C7—C8—C16	−81.5 (2)	C13—C14—C15—C10	−0.6 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) −x, −y, −z+1; (iv) x, y−1, z; (v) x+1, y, z; (vi) −x+1, −y, −z+1; (vii) x, y+1, z; (viii) x, y, z−1; (ix) −x+1, −y+1, −z; (x) x−1, y, z; (xi) x, y−1, z+1; (xii) x, y, z+1; (xiii) x, y+1, z−1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O15—H15···O7^i	0.82	1.88	2.688 (2)	168
C6—H6A···O7	0.97	2.39	2.774 (3)	103
C9—H9···O17	0.93	2.38	2.747 (2)	103

Symmetry code: (i) −x+1, −y+1, −z+1.