[3-(5-Hy-droxy-5H-dibenzo[a,d]cyclo-hepten-5-yl)prop-yl]dimethyl-ammonium 3-carboxyprop-2-enoate.

In the cation of the title salt, C(20)H(24)NO(+)·C(4)H(3)O(4) (-), the N atom in the dimethyl-ammonium group is protonated. The dihedral angle between the mean planes of the two six-membered rings fused to the cyclo-hepten-5-yl ring is 54.4 (1)°. An intra-molecular O-H⋯O hydrogen bond occurs in the anion. The crystal packing is stabilized by inter-molecular O-H⋯O and N-H⋯(O,O) hydrogen bonds and weak C-H⋯O inter-actions, forming a two-dimensional network.

Related literature

The title compound is used in the preparation of cyclo­benzaprine (systematic name: 3-(5H-dibenzo[a,d]cyclo­hepten-5-yl­idene)-N,N-dimethyl-1-propanamine), a muscle relaxant used to relieve skeletal muscle spasms and associated pain in acute musculoskeletal conditions. For its structural relationships to first-generation tricyclic anti­depressants, see: Com­miss­iong et al. (1981 ▶); Katz & Dube (1988 ▶); Cimolai (2009 ▶). For related structures, see: Bindya et al. (2007 ▶); Jasinski, Pek et al. (2010 ▶); Jasinski, Butcher et al. (2010 ▶); Fun et al. (2011 ▶); Siddegowda et al. (2011 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C20H24NO+·C4H3O4 −

M = 409.47

Monoclinic,

a = 9.2115 (2) Å

b = 11.5840 (2) Å

c = 10.4640 (2) Å

β = 101.591 (2)°

V = 1093.80 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 173 K

0.40 × 0.22 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T min = 0.966, T max = 0.983

9674 measured reflections

2834 independent reflections

2683 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.093

S = 1.04

2834 reflections

282 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.26 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811036257/bt5634sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036257/bt5634Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811036257/bt5634Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C20H24NO+·C4H3O4−	F(000) = 436
Mr = 409.47	Dx = 1.243 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5270 reflections
a = 9.2115 (2) Å	θ = 3.2–32.2°
b = 11.5840 (2) Å	µ = 0.09 mm−1
c = 10.4640 (2) Å	T = 173 K
β = 101.591 (2)°	Block, colorless
V = 1093.80 (4) Å3	0.40 × 0.22 × 0.20 mm
Z = 2

Oxford Diffraction Xcalibur Eos Gemini diffractometer	2834 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2683 reflections with I > 2σ(I)
graphite	Rint = 0.016
ω scans	θmax = 28.3°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	h = −12→9
Tmin = 0.966, Tmax = 0.983	k = −15→15
9674 measured reflections	l = −13→13

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0573P)2 + 0.1521P] where P = (Fo2 + 2Fc2)/3
2834 reflections	(Δ/σ)max = 0.002
282 parameters	Δρmax = 0.33 e Å−3
4 restraints	Δρmin = −0.26 e Å−3

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-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.

	x	y	z	Uiso*/Ueq
O1	0.41330 (14)	0.34062 (11)	0.16548 (12)	0.0302 (3)
H1O	0.348 (2)	0.353 (2)	0.208 (2)	0.036*
O2	−0.0516 (2)	0.7602 (3)	0.6263 (2)	0.0758 (7)
H2O	0.037 (3)	0.759 (4)	0.606 (3)	0.091*
O3	−0.2140 (2)	0.8844 (3)	0.6744 (2)	0.0924 (10)
O4	0.18355 (17)	0.77043 (15)	0.55298 (16)	0.0460 (4)
O5	0.32094 (17)	0.90841 (13)	0.49397 (16)	0.0450 (3)
N1	0.46816 (15)	0.73787 (12)	0.40245 (12)	0.0244 (3)
H1N	0.412 (2)	0.7907 (18)	0.430 (2)	0.029*
C1	0.39082 (17)	0.42003 (14)	0.06008 (14)	0.0240 (3)
C2	0.53853 (18)	0.42751 (15)	0.01408 (16)	0.0277 (3)
C3	0.6595 (2)	0.36330 (18)	0.0782 (2)	0.0372 (4)
H3A	0.6485	0.3144	0.1485	0.045*
C4	0.7959 (2)	0.3695 (2)	0.0410 (3)	0.0502 (6)
H4A	0.8766	0.3244	0.0852	0.060*
C5	0.8143 (2)	0.4409 (2)	−0.0598 (3)	0.0527 (6)
H5A	0.9076	0.4455	−0.0850	0.063*
C6	0.6963 (3)	0.5059 (2)	−0.1237 (2)	0.0455 (5)
H6A	0.7101	0.5559	−0.1922	0.055*
C7	0.5557 (2)	0.49996 (16)	−0.09015 (18)	0.0328 (4)
C8	0.4376 (2)	0.56887 (17)	−0.16865 (17)	0.0366 (4)
H8A	0.4668	0.6404	−0.2000	0.044*
C9	0.2936 (2)	0.54318 (16)	−0.20162 (17)	0.0348 (4)
H9A	0.2312	0.5988	−0.2522	0.042*
C10	0.22200 (19)	0.43761 (15)	−0.16756 (16)	0.0284 (3)
C11	0.1030 (2)	0.39442 (19)	−0.26041 (17)	0.0369 (4)
H11A	0.0649	0.4393	−0.3357	0.044*
C12	0.0399 (2)	0.2891 (2)	−0.2456 (2)	0.0423 (5)
H12A	−0.0394	0.2610	−0.3106	0.051*
C13	0.0926 (2)	0.22432 (19)	−0.1354 (2)	0.0419 (4)
H13A	0.0516	0.1505	−0.1253	0.050*
C14	0.2057 (2)	0.26732 (17)	−0.03967 (18)	0.0336 (4)
H14A	0.2395	0.2229	0.0368	0.040*
C15	0.27125 (18)	0.37390 (14)	−0.05244 (15)	0.0253 (3)
C16	0.34051 (18)	0.53637 (14)	0.10869 (15)	0.0257 (3)
H16A	0.3252	0.5924	0.0357	0.031*
H16B	0.2442	0.5252	0.1352	0.031*
C17	0.45116 (19)	0.58700 (16)	0.22342 (16)	0.0293 (3)
H17A	0.4873	0.5258	0.2880	0.035*
H17B	0.5373	0.6196	0.1925	0.035*
C18	0.37420 (18)	0.68131 (15)	0.28617 (15)	0.0269 (3)
H18A	0.3389	0.7413	0.2198	0.032*
H18B	0.2860	0.6476	0.3127	0.032*
C19	0.5987 (2)	0.79753 (19)	0.3701 (2)	0.0382 (4)
H19A	0.6437	0.8475	0.4429	0.057*
H19B	0.5672	0.8444	0.2914	0.057*
H19C	0.6713	0.7401	0.3546	0.057*
C20	0.5116 (3)	0.65885 (18)	0.51531 (18)	0.0389 (4)
H20A	0.5644	0.7025	0.5907	0.058*
H20B	0.5763	0.5981	0.4931	0.058*
H20C	0.4226	0.6238	0.5367	0.058*
C21	−0.0942 (3)	0.8652 (3)	0.6456 (2)	0.0626 (8)
C22	0.0010 (3)	0.9628 (3)	0.6312 (3)	0.0649 (8)
H22A	−0.0342	1.0349	0.6559	0.078*
C23	0.1278 (2)	0.9692 (2)	0.5899 (3)	0.0547 (7)
H23A	0.1684	1.0446	0.5898	0.066*
C24	0.2169 (2)	0.87546 (18)	0.54356 (19)	0.0359 (4)

	U11	U22	U33	U12	U13	U23
O1	0.0362 (6)	0.0289 (6)	0.0263 (6)	0.0060 (5)	0.0077 (5)	0.0048 (5)
O2	0.0552 (11)	0.1038 (19)	0.0738 (13)	−0.0219 (13)	0.0254 (10)	0.0128 (14)
O3	0.0507 (10)	0.174 (3)	0.0613 (11)	−0.0215 (15)	0.0322 (9)	−0.0421 (16)
O4	0.0427 (8)	0.0403 (8)	0.0564 (9)	−0.0014 (6)	0.0132 (7)	0.0013 (7)
O5	0.0435 (7)	0.0345 (7)	0.0622 (9)	−0.0019 (6)	0.0230 (7)	−0.0127 (7)
N1	0.0313 (7)	0.0222 (6)	0.0213 (6)	0.0016 (5)	0.0087 (5)	−0.0019 (5)
C1	0.0290 (7)	0.0213 (7)	0.0223 (7)	0.0007 (6)	0.0066 (5)	−0.0008 (6)
C2	0.0313 (8)	0.0245 (7)	0.0292 (7)	−0.0030 (6)	0.0104 (6)	−0.0104 (6)
C3	0.0328 (9)	0.0362 (9)	0.0422 (10)	0.0017 (7)	0.0069 (7)	−0.0097 (8)
C4	0.0315 (9)	0.0550 (13)	0.0647 (14)	0.0034 (9)	0.0110 (9)	−0.0216 (11)
C5	0.0373 (10)	0.0592 (14)	0.0688 (15)	−0.0114 (10)	0.0283 (10)	−0.0299 (12)
C6	0.0548 (12)	0.0439 (11)	0.0461 (11)	−0.0196 (10)	0.0302 (10)	−0.0193 (9)
C7	0.0414 (9)	0.0294 (8)	0.0313 (8)	−0.0092 (7)	0.0165 (7)	−0.0126 (7)
C8	0.0594 (11)	0.0265 (8)	0.0287 (8)	−0.0071 (8)	0.0204 (8)	−0.0012 (6)
C9	0.0536 (11)	0.0287 (8)	0.0235 (7)	0.0044 (8)	0.0111 (7)	0.0042 (6)
C10	0.0332 (8)	0.0297 (8)	0.0239 (7)	0.0045 (7)	0.0091 (6)	−0.0015 (6)
C11	0.0353 (9)	0.0484 (11)	0.0266 (8)	0.0060 (8)	0.0051 (6)	−0.0022 (8)
C12	0.0317 (9)	0.0552 (13)	0.0382 (10)	−0.0044 (9)	0.0026 (7)	−0.0119 (9)
C13	0.0414 (10)	0.0364 (10)	0.0476 (11)	−0.0099 (8)	0.0083 (8)	−0.0076 (9)
C14	0.0370 (9)	0.0281 (8)	0.0349 (9)	−0.0015 (7)	0.0051 (7)	−0.0008 (7)
C15	0.0273 (7)	0.0253 (7)	0.0243 (7)	0.0024 (6)	0.0080 (5)	−0.0029 (6)
C16	0.0316 (8)	0.0253 (7)	0.0209 (7)	0.0045 (6)	0.0070 (6)	−0.0025 (6)
C17	0.0286 (7)	0.0315 (8)	0.0284 (8)	0.0035 (6)	0.0073 (6)	−0.0091 (6)
C18	0.0283 (7)	0.0278 (8)	0.0246 (7)	0.0028 (6)	0.0053 (6)	−0.0061 (6)
C19	0.0383 (9)	0.0371 (10)	0.0408 (10)	−0.0093 (8)	0.0113 (8)	−0.0027 (8)
C20	0.0598 (11)	0.0346 (9)	0.0230 (8)	0.0057 (9)	0.0101 (7)	0.0043 (7)
C21	0.0449 (12)	0.111 (3)	0.0342 (10)	−0.0096 (15)	0.0146 (9)	−0.0235 (13)
C22	0.0394 (11)	0.092 (2)	0.0651 (15)	0.0005 (12)	0.0148 (10)	−0.0473 (16)
C23	0.0382 (10)	0.0539 (14)	0.0739 (16)	−0.0045 (10)	0.0158 (10)	−0.0352 (12)
C24	0.0314 (8)	0.0394 (10)	0.0366 (9)	0.0002 (8)	0.0059 (7)	−0.0117 (8)

O1—C1	1.4191 (19)	C10—C11	1.403 (2)
O1—H1O	0.826 (16)	C10—C15	1.408 (2)
O2—C21	1.306 (5)	C11—C12	1.374 (3)
O2—H2O	0.885 (19)	C11—H11A	0.9500
O3—C21	1.221 (3)	C12—C13	1.379 (3)
O4—C24	1.264 (3)	C12—H12A	0.9500
O5—C24	1.238 (2)	C13—C14	1.385 (3)
N1—C19	1.484 (2)	C13—H13A	0.9500
N1—C20	1.484 (2)	C14—C15	1.392 (2)
N1—C18	1.495 (2)	C14—H14A	0.9500
N1—H1N	0.884 (16)	C16—C17	1.527 (2)
C1—C2	1.534 (2)	C16—H16A	0.9900
C1—C15	1.537 (2)	C16—H16B	0.9900
C1—C16	1.544 (2)	C17—C18	1.521 (2)
C2—C3	1.394 (3)	C17—H17A	0.9900
C2—C7	1.410 (3)	C17—H17B	0.9900
C3—C4	1.390 (3)	C18—H18A	0.9900
C3—H3A	0.9500	C18—H18B	0.9900
C4—C5	1.377 (4)	C19—H19A	0.9800
C4—H4A	0.9500	C19—H19B	0.9800
C5—C6	1.380 (4)	C19—H19C	0.9800
C5—H5A	0.9500	C20—H20A	0.9800
C6—C7	1.410 (3)	C20—H20B	0.9800
C6—H6A	0.9500	C20—H20C	0.9800
C7—C8	1.461 (3)	C21—C22	1.457 (5)
C8—C9	1.336 (3)	C22—C23	1.327 (3)
C8—H8A	0.9500	C22—H22A	0.9500
C9—C10	1.467 (3)	C23—C24	1.500 (3)
C9—H9A	0.9500	C23—H23A	0.9500
C1—O1—H1O	107.3 (17)	C14—C13—H13A	120.1
C21—O2—H2O	112 (3)	C13—C14—C15	121.80 (18)
C19—N1—C20	111.58 (15)	C13—C14—H14A	119.1
C19—N1—C18	112.43 (13)	C15—C14—H14A	119.1
C20—N1—C18	113.37 (14)	C14—C15—C10	118.40 (15)
C19—N1—H1N	107.7 (14)	C14—C15—C1	119.49 (14)
C20—N1—H1N	104.6 (15)	C10—C15—C1	122.08 (15)
C18—N1—H1N	106.5 (14)	C17—C16—C1	113.39 (13)
O1—C1—C2	106.28 (13)	C17—C16—H16A	108.9
O1—C1—C15	109.89 (13)	C1—C16—H16A	108.9
C2—C1—C15	108.87 (12)	C17—C16—H16B	108.9
O1—C1—C16	108.44 (12)	C1—C16—H16B	108.9
C2—C1—C16	113.44 (13)	H16A—C16—H16B	107.7
C15—C1—C16	109.84 (13)	C18—C17—C16	108.65 (13)
C3—C2—C7	119.14 (16)	C18—C17—H17A	110.0
C3—C2—C1	119.49 (16)	C16—C17—H17A	110.0
C7—C2—C1	121.36 (15)	C18—C17—H17B	110.0
C4—C3—C2	121.2 (2)	C16—C17—H17B	110.0
C4—C3—H3A	119.4	H17A—C17—H17B	108.3
C2—C3—H3A	119.4	N1—C18—C17	114.97 (13)
C5—C4—C3	120.2 (2)	N1—C18—H18A	108.5
C5—C4—H4A	119.9	C17—C18—H18A	108.5
C3—C4—H4A	119.9	N1—C18—H18B	108.5
C4—C5—C6	119.49 (19)	C17—C18—H18B	108.5
C4—C5—H5A	120.3	H18A—C18—H18B	107.5
C6—C5—H5A	120.3	N1—C19—H19A	109.5
C5—C6—C7	121.8 (2)	N1—C19—H19B	109.5
C5—C6—H6A	119.1	H19A—C19—H19B	109.5
C7—C6—H6A	119.1	N1—C19—H19C	109.5
C6—C7—C2	118.20 (19)	H19A—C19—H19C	109.5
C6—C7—C8	116.77 (18)	H19B—C19—H19C	109.5
C2—C7—C8	125.02 (16)	N1—C20—H20A	109.5
C9—C8—C7	127.72 (17)	N1—C20—H20B	109.5
C9—C8—H8A	116.1	H20A—C20—H20B	109.5
C7—C8—H8A	116.1	N1—C20—H20C	109.5
C8—C9—C10	126.48 (17)	H20A—C20—H20C	109.5
C8—C9—H9A	116.8	H20B—C20—H20C	109.5
C10—C9—H9A	116.8	O3—C21—O2	121.5 (3)
C11—C10—C15	118.57 (17)	O3—C21—C22	118.4 (4)
C11—C10—C9	117.12 (16)	O2—C21—C22	120.1 (2)
C15—C10—C9	124.18 (16)	C23—C22—C21	131.7 (3)
C12—C11—C10	121.86 (18)	C23—C22—H22A	114.2
C12—C11—H11A	119.1	C21—C22—H22A	114.2
C10—C11—H11A	119.1	C22—C23—C24	129.8 (3)
C11—C12—C13	119.46 (18)	C22—C23—H23A	115.1
C11—C12—H12A	120.3	C24—C23—H23A	115.1
C13—C12—H12A	120.3	O5—C24—O4	123.40 (18)
C12—C13—C14	119.77 (19)	O5—C24—C23	115.6 (2)
C12—C13—H13A	120.1	O4—C24—C23	120.98 (19)
O1—C1—C2—C3	−1.1 (2)	C12—C13—C14—C15	−1.6 (3)
C15—C1—C2—C3	−119.38 (16)	C13—C14—C15—C10	−1.3 (3)
C16—C1—C2—C3	118.00 (16)	C13—C14—C15—C1	176.88 (17)
O1—C1—C2—C7	−179.70 (14)	C11—C10—C15—C14	4.0 (2)
C15—C1—C2—C7	61.98 (19)	C9—C10—C15—C14	−171.64 (16)
C16—C1—C2—C7	−60.64 (19)	C11—C10—C15—C1	−174.11 (15)
C7—C2—C3—C4	−0.1 (3)	C9—C10—C15—C1	10.2 (2)
C1—C2—C3—C4	−178.74 (17)	O1—C1—C15—C14	−0.9 (2)
C2—C3—C4—C5	0.8 (3)	C2—C1—C15—C14	115.13 (16)
C3—C4—C5—C6	−0.2 (3)	C16—C1—C15—C14	−120.10 (16)
C4—C5—C6—C7	−1.0 (3)	O1—C1—C15—C10	177.21 (14)
C5—C6—C7—C2	1.7 (3)	C2—C1—C15—C10	−66.78 (19)
C5—C6—C7—C8	−177.35 (19)	C16—C1—C15—C10	57.99 (18)
C3—C2—C7—C6	−1.1 (2)	O1—C1—C16—C17	58.28 (17)
C1—C2—C7—C6	177.53 (15)	C2—C1—C16—C17	−59.54 (18)
C3—C2—C7—C8	177.82 (17)	C15—C1—C16—C17	178.38 (13)
C1—C2—C7—C8	−3.5 (3)	C1—C16—C17—C18	−164.67 (13)
C6—C7—C8—C9	145.99 (19)	C19—N1—C18—C17	61.9 (2)
C2—C7—C8—C9	−33.0 (3)	C20—N1—C18—C17	−65.79 (19)
C7—C8—C9—C10	−1.2 (3)	C16—C17—C18—N1	178.82 (13)
C8—C9—C10—C11	−144.80 (19)	O3—C21—C22—C23	−173.0 (3)
C8—C9—C10—C15	30.9 (3)	O2—C21—C22—C23	6.2 (5)
C15—C10—C11—C12	−4.1 (3)	C21—C22—C23—C24	−0.1 (5)
C9—C10—C11—C12	171.89 (17)	C22—C23—C24—O5	170.5 (3)
C10—C11—C12—C13	1.2 (3)	C22—C23—C24—O4	−8.0 (4)
C11—C12—C13—C14	1.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O3i	0.83 (2)	1.95 (2)	2.770 (2)	173 (2)
O2—H2O···O4	0.89 (2)	1.56 (2)	2.442 (2)	171 (4)
N1—H1N···O5	0.88 (2)	1.80 (2)	2.6797 (19)	172 (2)
N1—H1N···O4	0.88 (2)	2.69 (2)	3.340 (2)	131.(2)
C16—H16B···O3i	0.99	2.63	3.267 (3)	122.
C19—H19A···O3ii	0.98	2.55	3.452 (3)	154.
C20—H20A···O3ii	0.98	2.94	3.781 (4)	144.
C9—H9A···O4iii	0.95	2.82	3.675 (2)	151.
C12—H12A···O4iv	0.95	2.62	3.460 (3)	148.
C17—H17A···O5v	0.99	2.92	3.865 (2)	159.
C20—H20B···O5v	0.98	2.39	3.296 (3)	154.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O3i	0.83 (2)	1.95 (2)	2.770 (2)	173 (2)
O2—H2O⋯O4	0.89 (2)	1.56 (2)	2.442 (2)	171 (4)
N1—H1N⋯O5	0.88 (2)	1.80 (2)	2.6797 (19)	172 (2)
N1—H1N⋯O4	0.88 (2)	2.69 (2)	3.340 (2)	131 (2)
C16—H16B⋯O3i	0.99	2.63	3.267 (3)	122
C19—H19A⋯O3ii	0.98	2.55	3.452 (3)	154
C20—H20A⋯O3ii	0.98	2.94	3.781 (4)	144
C9—H9A⋯O4iii	0.95	2.82	3.675 (2)	151
C12—H12A⋯O4iv	0.95	2.62	3.460 (3)	148
C17—H17A⋯O5v	0.99	2.92	3.865 (2)	159
C20—H20B⋯O5v	0.98	2.39	3.296 (3)	154

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .