Crystal structures of bis­[(9S,13S,14S)-3-meth­oxy-17-methyl­morphinanium] tetra­chlorido­cobaltate and tetra­chlorido­cuprate

In the crystal structures of title compounds, two identical protonated dextromethorphan cations are connected to tetra­chlorido­cobaltate (or tetra­chlorido­cuprate) anions via strong N—H...Cl hydrogen bonds, forming neutral ion associates

Key indicators

Structure: a

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.034
• wR factor = 0.083
• Data-to-parameter ratio = 21.4

Structure: b

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.039
• wR factor = 0.100
• Data-to-parameter ratio = 20.3

checkCIF/PLATON results

No syntax errors found



Datablock: a


Alert level C
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00661 Ang.

Alert level G
PLAT791_ALERT_4_G The Model has Chirality at N1      (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C9      (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G The Model has Chirality at C13     (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G The Model has Chirality at C14     (Chiral SPGR)          S Verify
PLAT850_ALERT_4_G Check Flack Parameter Exact Value 0.00 and s.u.        0.01 Check
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          4 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          7 Note

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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




Datablock: b


Alert level C
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00661 Ang.

Alert level G
PLAT791_ALERT_4_G The Model has Chirality at N1      (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C9      (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G The Model has Chirality at C13     (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G The Model has Chirality at C14     (Chiral SPGR)          S Verify
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          4 Note

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

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

---

Computing details

For both compounds, data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013). Program(s) used to solve structure: SHELXT (Sheldrick, 2015) for a; SHELXS97 (Sheldrick, 2008) for b. For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(a) Bis[(9S,13S,14S)-3-methoxy-17-methylmorphinanium] tetrachloridocobaltate

Crystal data

(C18H26NO)2[CoCl4]	F(000) = 786
Mr = 745.52	Dx = 1.336 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 13.8447 (6) Å	Cell parameters from 9174 reflections
b = 9.2316 (4) Å	θ = 2.9–28.3°
c = 14.7018 (6) Å	µ = 0.79 mm^−1
β = 99.605 (2)°	T = 173 K
V = 1852.68 (14) Å^3	Plate, blue
Z = 2	0.48 × 0.26 × 0.14 mm

Data collection

Bruker PHOTON-100 CMOS diffractometer	4183 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.061
φ and ω scans	θmax = 28.8°, θmin = 2.8°
Absorption correction: multi-scan (SADABS, Bruker, 2015)	h = −18→18
Tmin = 0.761, Tmax = 0.979	k = −12→12
43153 measured reflections	l = −19→19
4803 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0494P)^2 + 0.4319P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.083	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.50 e Å^−3
4803 reflections	Δρmin = −0.26 e Å^−3
224 parameters	Absolute structure: Flack x determined using 1711 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.000 (7)

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
O1	0.16362 (18)	0.6052 (3)	0.55317 (15)	0.0489 (6)
N1	0.25197 (17)	0.4294 (2)	0.12297 (15)	0.0277 (5)
C3	0.1767 (2)	0.6210 (3)	0.4633 (2)	0.0363 (7)
C4	0.2614 (2)	0.5804 (3)	0.43052 (18)	0.0302 (5)
H4	0.316 (2)	0.5398 (15)	0.4727 (15)	0.036*
C12	0.26809 (18)	0.5975 (3)	0.33709 (17)	0.0257 (5)
C11	0.1890 (2)	0.6534 (3)	0.27670 (18)	0.0295 (6)
C1	0.1055 (2)	0.6958 (4)	0.3114 (2)	0.0429 (7)
H1A	0.055 (2)	0.7347 (18)	0.2728 (17)	0.051*
C2	0.0990 (2)	0.6796 (5)	0.4031 (2)	0.0467 (8)
H2	0.037 (3)	0.7107 (14)	0.4268 (10)	0.056*
C18	0.2367 (3)	0.5315 (4)	0.6139 (2)	0.0544 (10)
H18A	0.2440 (18)	0.436 (3)	0.5914 (14)	0.082*
H18B	0.2184 (13)	0.526 (3)	0.6733 (18)	0.082*
H18C	0.2970 (18)	0.582 (2)	0.6180 (18)	0.082*
C10	0.1886 (2)	0.6676 (3)	0.17396 (18)	0.0320 (6)
H10A	0.1270 (16)	0.6305 (10)	0.1415 (9)	0.038*
H10B	0.1917 (2)	0.770 (3)	0.1590 (4)	0.038*
C9	0.2708 (2)	0.5904 (3)	0.13877 (18)	0.0277 (5)
H9	0.2785 (4)	0.6312 (16)	0.084 (2)	0.033*
C14	0.3669 (2)	0.6068 (3)	0.20608 (18)	0.0291 (5)
H14	0.4161 (19)	0.554 (2)	0.1814 (9)	0.035*
C8	0.3998 (3)	0.7643 (4)	0.2153 (2)	0.0424 (7)
H8A	0.3525 (15)	0.8185 (17)	0.2353 (6)	0.051*
H8B	0.4083 (3)	0.7987 (12)	0.1591 (17)	0.051*
C7	0.4956 (3)	0.7790 (5)	0.2833 (2)	0.0519 (9)
H7A	0.5481 (18)	0.7293 (17)	0.2587 (9)	0.062*
H7B	0.5132 (7)	0.881 (3)	0.2911 (3)	0.062*
C6	0.4853 (2)	0.7140 (5)	0.3763 (2)	0.0458 (8)
H6A	0.4353 (13)	0.7693 (15)	0.4036 (8)	0.055*
H6B	0.5490 (17)	0.7216 (5)	0.4192 (12)	0.055*
C5	0.4548 (2)	0.5556 (4)	0.36542 (19)	0.0374 (7)
H5A	0.4490 (2)	0.5175 (12)	0.4233 (17)	0.045*
H5B	0.5036 (14)	0.5032 (16)	0.3426 (6)	0.045*
C13	0.35654 (19)	0.5369 (3)	0.29939 (17)	0.0267 (5)
C15	0.33688 (19)	0.3737 (4)	0.28147 (16)	0.0297 (5)
H15A	0.3903 (14)	0.3325 (11)	0.2615 (5)	0.036*
H15B	0.3292 (3)	0.3292 (12)	0.3359 (14)	0.036*
C16	0.2462 (2)	0.3475 (3)	0.20999 (18)	0.0302 (6)
H16A	0.2401 (3)	0.248 (3)	0.1968 (4)	0.036*
H16B	0.1903 (15)	0.3772 (8)	0.2337 (7)	0.036*
C17	0.1662 (2)	0.3993 (4)	0.0495 (2)	0.0412 (7)
H17A	0.1063 (15)	0.427 (3)	0.0712 (9)	0.062*
H17B	0.1640 (12)	0.296 (3)	0.0350 (13)	0.062*
H17C	0.1725 (10)	0.455 (3)	−0.0055 (16)	0.062*
Co1	0.5000	0.37707 (5)	0.0000	0.02972 (14)
Cl1	0.41931 (5)	0.22074 (7)	0.08249 (4)	0.03266 (16)
Cl2	0.61476 (7)	0.52069 (9)	0.08226 (7)	0.0570 (3)
H1	0.306 (3)	0.389 (5)	0.102 (2)	0.045 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0563 (15)	0.0602 (15)	0.0369 (11)	0.0015 (13)	0.0271 (10)	−0.0068 (11)
N1	0.0275 (11)	0.0271 (11)	0.0289 (11)	0.0014 (9)	0.0057 (9)	−0.0015 (8)
C3	0.0418 (16)	0.0377 (16)	0.0331 (14)	−0.0024 (13)	0.0173 (12)	−0.0085 (12)
C4	0.0307 (13)	0.0330 (14)	0.0279 (12)	0.0019 (12)	0.0083 (10)	−0.0013 (11)
C12	0.0254 (12)	0.0264 (12)	0.0267 (11)	0.0021 (11)	0.0079 (9)	−0.0019 (10)
C11	0.0274 (13)	0.0308 (14)	0.0306 (13)	0.0074 (11)	0.0054 (10)	−0.0041 (10)
C1	0.0319 (15)	0.0512 (19)	0.0450 (16)	0.0152 (14)	0.0048 (13)	−0.0101 (15)
C2	0.0362 (16)	0.060 (2)	0.0474 (17)	0.0076 (15)	0.0187 (14)	−0.0163 (16)
C18	0.083 (3)	0.049 (2)	0.0373 (17)	0.000 (2)	0.0278 (18)	0.0019 (15)
C10	0.0346 (14)	0.0312 (13)	0.0286 (12)	0.0069 (12)	0.0009 (11)	0.0000 (10)
C9	0.0344 (14)	0.0254 (12)	0.0236 (11)	−0.0031 (11)	0.0054 (10)	0.0037 (10)
C14	0.0279 (13)	0.0341 (14)	0.0271 (12)	−0.0018 (11)	0.0097 (10)	0.0007 (11)
C8	0.0501 (19)	0.0430 (18)	0.0353 (15)	−0.0152 (15)	0.0104 (13)	−0.0005 (13)
C7	0.0452 (19)	0.062 (2)	0.0488 (19)	−0.0242 (17)	0.0089 (15)	−0.0114 (17)
C6	0.0308 (15)	0.065 (2)	0.0392 (15)	−0.0089 (16)	−0.0003 (12)	−0.0110 (16)
C5	0.0239 (13)	0.057 (2)	0.0296 (13)	0.0048 (13)	0.0008 (11)	−0.0016 (13)
C13	0.0215 (12)	0.0371 (15)	0.0220 (11)	0.0024 (11)	0.0053 (9)	0.0004 (10)
C15	0.0332 (13)	0.0313 (13)	0.0259 (11)	0.0103 (13)	0.0089 (10)	0.0048 (12)
C16	0.0345 (14)	0.0242 (14)	0.0335 (13)	−0.0016 (11)	0.0108 (11)	0.0024 (10)
C17	0.0424 (16)	0.0376 (18)	0.0391 (15)	−0.0017 (14)	−0.0062 (12)	−0.0043 (13)
Co1	0.0263 (3)	0.0280 (3)	0.0351 (3)	0.000	0.0058 (2)	0.000
Cl1	0.0312 (3)	0.0354 (3)	0.0342 (3)	−0.0025 (3)	0.0137 (3)	−0.0038 (3)
Cl2	0.0577 (5)	0.0342 (4)	0.0711 (6)	−0.0164 (4)	−0.0130 (4)	0.0022 (4)

Geometric parameters (Å, º)

O1—C3	1.372 (3)	C14—C13	1.544 (4)
O1—C18	1.408 (5)	C8—H8A	0.91 (3)
N1—C9	1.520 (3)	C8—H8B	0.91 (3)
N1—C16	1.500 (3)	C8—C7	1.527 (5)
N1—C17	1.491 (3)	C7—H7A	0.98 (3)
N1—H1	0.93 (4)	C7—H7B	0.98 (3)
C3—C4	1.391 (4)	C7—C6	1.521 (5)
C3—C2	1.384 (5)	C6—H6A	1.00 (3)
C4—H4	0.97 (3)	C6—H6B	1.00 (3)
C4—C12	1.401 (3)	C6—C5	1.523 (6)
C12—C11	1.389 (4)	C5—H5A	0.94 (3)
C12—C13	1.532 (3)	C5—H5B	0.94 (3)
C11—C1	1.396 (4)	C5—C13	1.543 (4)
C11—C10	1.515 (4)	C13—C15	1.546 (4)
C1—H1A	0.90 (4)	C15—H15A	0.92 (2)
C1—C2	1.375 (5)	C15—H15B	0.92 (2)
C2—H2	1.02 (4)	C15—C16	1.516 (4)
C18—H18A	0.95 (3)	C16—H16A	0.94 (2)
C18—H18B	0.95 (3)	C16—H16B	0.94 (2)
C18—H18C	0.95 (3)	C17—H17A	0.97 (2)
C10—H10A	0.97 (2)	C17—H17B	0.97 (2)
C10—H10B	0.97 (2)	C17—H17C	0.97 (2)
C10—C9	1.506 (4)	Co1—Cl1^i	2.2920 (7)
C9—H9	0.91 (3)	Co1—Cl1	2.2921 (7)
C9—C14	1.527 (4)	Co1—Cl2^i	2.2592 (8)
C14—H14	0.96 (4)	Co1—Cl2	2.2591 (8)
C14—C8	1.523 (4)
C3—O1—C18	117.8 (3)	H8A—C8—H8B	108.0
C9—N1—H1	109 (3)	C7—C8—H8A	109.5
C16—N1—C9	113.3 (2)	C7—C8—H8B	109.5
C16—N1—H1	104 (2)	C8—C7—H7A	109.5
C17—N1—C9	112.9 (2)	C8—C7—H7B	109.5
C17—N1—C16	112.0 (2)	H7A—C7—H7B	108.1
C17—N1—H1	106 (2)	C6—C7—C8	110.6 (3)
O1—C3—C4	124.0 (3)	C6—C7—H7A	109.5
O1—C3—C2	116.3 (3)	C6—C7—H7B	109.5
C2—C3—C4	119.7 (3)	C7—C6—H6A	109.6
C3—C4—H4	119.8	C7—C6—H6B	109.6
C3—C4—C12	120.4 (3)	C7—C6—C5	110.5 (3)
C12—C4—H4	119.8	H6A—C6—H6B	108.1
C4—C12—C13	120.1 (2)	C5—C6—H6A	109.6
C11—C12—C4	119.6 (2)	C5—C6—H6B	109.6
C11—C12—C13	119.8 (2)	C6—C5—H5A	109.2
C12—C11—C1	118.9 (3)	C6—C5—H5B	109.2
C12—C11—C10	122.7 (2)	C6—C5—C13	111.9 (3)
C1—C11—C10	118.3 (3)	H5A—C5—H5B	107.9
C11—C1—H1A	119.3	C13—C5—H5A	109.2
C2—C1—C11	121.4 (3)	C13—C5—H5B	109.2
C2—C1—H1A	119.3	C12—C13—C14	111.5 (2)
C3—C2—H2	120.1	C12—C13—C5	113.9 (2)
C1—C2—C3	119.9 (3)	C12—C13—C15	106.8 (2)
C1—C2—H2	120.1	C14—C13—C15	107.2 (2)
O1—C18—H18A	109.5	C5—C13—C14	108.0 (2)
O1—C18—H18B	109.5	C5—C13—C15	109.1 (2)
O1—C18—H18C	109.5	C13—C15—H15A	109.2
H18A—C18—H18B	109.5	C13—C15—H15B	109.2
H18A—C18—H18C	109.5	H15A—C15—H15B	107.9
H18B—C18—H18C	109.5	C16—C15—C13	112.1 (2)
C11—C10—H10A	108.5	C16—C15—H15A	109.2
C11—C10—H10B	108.5	C16—C15—H15B	109.2
H10A—C10—H10B	107.5	N1—C16—C15	110.8 (2)
C9—C10—C11	115.1 (2)	N1—C16—H16A	109.5
C9—C10—H10A	108.5	N1—C16—H16B	109.5
C9—C10—H10B	108.5	C15—C16—H16A	109.5
N1—C9—H9	108.3	C15—C16—H16B	109.5
N1—C9—C14	107.7 (2)	H16A—C16—H16B	108.1
C10—C9—N1	113.3 (2)	N1—C17—H17A	109.5
C10—C9—H9	108.3	N1—C17—H17B	109.5
C10—C9—C14	110.9 (2)	N1—C17—H17C	109.5
C14—C9—H9	108.3	H17A—C17—H17B	109.5
C9—C14—H14	107.5	H17A—C17—H17C	109.5
C9—C14—C13	109.5 (2)	H17B—C17—H17C	109.5
C8—C14—C9	111.5 (2)	Cl1^i—Co1—Cl1	101.95 (4)
C8—C14—H14	107.5	Cl2^i—Co1—Cl1	106.94 (3)
C8—C14—C13	113.0 (2)	Cl2—Co1—Cl1^i	106.94 (3)
C13—C14—H14	107.5	Cl2—Co1—Cl1	116.59 (3)
C14—C8—H8A	109.5	Cl2^i—Co1—Cl1^i	116.59 (3)
C14—C8—H8B	109.5	Cl2—Co1—Cl2^i	108.13 (5)
C14—C8—C7	110.9 (3)
O1—C3—C4—C12	178.7 (3)	C10—C9—C14—C13	61.9 (3)
O1—C3—C2—C1	−178.5 (3)	C9—N1—C16—C15	−54.1 (3)
N1—C9—C14—C8	171.6 (2)	C9—C14—C8—C7	179.6 (2)
N1—C9—C14—C13	−62.6 (3)	C9—C14—C13—C12	−54.0 (3)
C3—C4—C12—C11	−1.0 (4)	C9—C14—C13—C5	−180.0 (2)
C3—C4—C12—C13	−173.0 (3)	C9—C14—C13—C15	62.5 (3)
C4—C3—C2—C1	0.7 (5)	C14—C8—C7—C6	−55.7 (4)
C4—C12—C11—C1	2.2 (4)	C14—C13—C15—C16	−57.8 (3)
C4—C12—C11—C10	−176.6 (3)	C8—C14—C13—C12	71.0 (3)
C4—C12—C13—C14	−162.0 (2)	C8—C14—C13—C5	−55.0 (3)
C4—C12—C13—C5	−39.4 (4)	C8—C14—C13—C15	−172.5 (2)
C4—C12—C13—C15	81.2 (3)	C8—C7—C6—C5	57.4 (4)
C12—C11—C1—C2	−1.9 (5)	C7—C6—C5—C13	−59.0 (4)
C12—C11—C10—C9	11.7 (4)	C6—C5—C13—C12	−68.1 (3)
C12—C13—C15—C16	61.8 (3)	C6—C5—C13—C14	56.4 (3)
C11—C12—C13—C14	26.0 (4)	C6—C5—C13—C15	172.6 (2)
C11—C12—C13—C5	148.6 (3)	C5—C13—C15—C16	−174.6 (2)
C11—C12—C13—C15	−90.8 (3)	C13—C12—C11—C1	174.2 (3)
C11—C1—C2—C3	0.4 (6)	C13—C12—C11—C10	−4.6 (4)
C11—C10—C9—N1	81.1 (3)	C13—C14—C8—C7	55.7 (3)
C11—C10—C9—C14	−40.1 (3)	C13—C15—C16—N1	53.7 (3)
C1—C11—C10—C9	−167.1 (3)	C16—N1—C9—C10	−64.7 (3)
C2—C3—C4—C12	−0.4 (5)	C16—N1—C9—C14	58.4 (3)
C18—O1—C3—C4	−6.0 (5)	C17—N1—C9—C10	63.9 (3)
C18—O1—C3—C2	173.2 (3)	C17—N1—C9—C14	−173.0 (2)
C10—C11—C1—C2	176.9 (3)	C17—N1—C16—C15	176.9 (2)
C10—C9—C14—C8	−63.9 (3)

Symmetry code: (i) −x+1, y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.93 (4)	2.26 (4)	3.145 (2)	158 (4)
C10—H10B···Cl2^ii	0.97 (3)	2.71 (2)	3.609 (3)	153 (1)
C17—H17B···Cl2^iii	0.98 (3)	2.75 (3)	3.615 (4)	148 (1)

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

(b) Bis[(9S,13S,14S)-3-methoxy-17-methylmorphinanium] tetrachloridocuprate

Crystal data

(C18H26NO)[CuCl4]	F(000) = 790
Mr = 750.13	Dx = 1.343 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 13.8066 (16) Å	Cell parameters from 1064 reflections
b = 9.2934 (12) Å	θ = 3.1–24.8°
c = 14.651 (3) Å	µ = 0.91 mm^−1
β = 99.318 (6)°	T = 173 K
V = 1855.1 (5) Å^3	Plate, yellow
Z = 2	0.45 × 0.3 × 0.15 mm

Data collection

Bruker PHOTON-100 CMOS diffractometer	3521 reflections with I > 2σ(I)
Radiation source: sealedtube	Rint = 0.047
φ and ω scans	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan (SADABS, Bruker, 2015)	h = −17→17
Tmin = 0.714, Tmax = 0.933	k = −12→12
31097 measured reflections	l = −19→19
4243 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0512P)^2 + 1.3109P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.100	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.51 e Å^−3
4243 reflections	Δρmin = −0.33 e Å^−3
209 parameters	Absolute structure: Flack x determined using 1463 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.005 (6)

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
O1	0.1671 (3)	0.6033 (4)	0.5575 (2)	0.0560 (9)
N1	0.2499 (3)	0.4329 (4)	0.1218 (2)	0.0329 (8)
H1	0.296 (4)	0.402 (6)	0.100 (4)	0.049*
C1	0.1031 (3)	0.6887 (6)	0.3155 (4)	0.0497 (12)
H1A	0.0477	0.7261	0.2756	0.060*
C2	0.0989 (4)	0.6737 (7)	0.4073 (4)	0.0535 (13)
H2	0.0413	0.7018	0.4304	0.064*
C3	0.1774 (3)	0.6181 (5)	0.4669 (3)	0.0400 (10)
C4	0.2621 (3)	0.5790 (5)	0.4319 (3)	0.0340 (9)
H4	0.3167	0.5404	0.4723	0.041*
C5	0.4546 (3)	0.5603 (6)	0.3624 (3)	0.0456 (12)
H5A	0.4499	0.5191	0.4239	0.055*
H5B	0.5064	0.5072	0.3369	0.055*
C6	0.4833 (4)	0.7196 (7)	0.3735 (3)	0.0562 (14)
H6A	0.4333	0.7725	0.4016	0.067*
H6B	0.5471	0.7288	0.4150	0.067*
C7	0.4911 (4)	0.7841 (7)	0.2798 (4)	0.0639 (16)
H7A	0.5438	0.7347	0.2535	0.077*
H7B	0.5085	0.8872	0.2873	0.077*
C8	0.3941 (4)	0.7686 (6)	0.2138 (3)	0.0506 (13)
H8A	0.3426	0.8246	0.2376	0.061*
H8B	0.4014	0.8078	0.1524	0.061*
C9	0.2665 (3)	0.5938 (4)	0.1385 (3)	0.0325 (9)
H9	0.2729	0.6402	0.0781	0.039*
C10	0.1834 (3)	0.6653 (5)	0.1759 (3)	0.0374 (9)
H10A	0.1834	0.7690	0.1604	0.045*
H10B	0.1208	0.6242	0.1441	0.045*
C11	0.1865 (3)	0.6506 (4)	0.2785 (3)	0.0335 (9)
C12	0.2669 (3)	0.5965 (4)	0.3383 (3)	0.0287 (8)
C13	0.3559 (3)	0.5401 (5)	0.2980 (3)	0.0313 (9)
C14	0.3634 (3)	0.6116 (5)	0.2038 (3)	0.0340 (9)
H14	0.4149	0.5590	0.1763	0.041*
C15	0.3388 (3)	0.3775 (5)	0.2790 (3)	0.0364 (9)
H15A	0.3966	0.3365	0.2562	0.044*
H15B	0.3322	0.3283	0.3376	0.044*
C16	0.2482 (3)	0.3492 (5)	0.2089 (3)	0.0349 (9)
H16A	0.2440	0.2451	0.1943	0.042*
H16B	0.1893	0.3761	0.2356	0.042*
C17	0.1634 (4)	0.4004 (5)	0.0501 (3)	0.0492 (12)
H17A	0.1031	0.4261	0.0736	0.074*
H17B	0.1625	0.2975	0.0355	0.074*
H17C	0.1676	0.4562	−0.0058	0.074*
C18	0.2410 (5)	0.5329 (7)	0.6180 (4)	0.0624 (16)
H18A	0.2501	0.4356	0.5950	0.094*
H18B	0.2222	0.5270	0.6796	0.094*
H18C	0.3026	0.5868	0.6218	0.094*
Cu1	0.5000	0.36997 (7)	0.0000	0.0369 (2)
Cl1	0.41472 (7)	0.21415 (11)	0.07511 (7)	0.0354 (2)
Cl2	0.62112 (11)	0.51975 (14)	0.05807 (10)	0.0632 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.068 (2)	0.066 (2)	0.043 (2)	0.0020 (19)	0.0321 (18)	−0.0075 (17)
N1	0.0336 (19)	0.0322 (17)	0.0332 (19)	0.0029 (15)	0.0062 (15)	−0.0022 (15)
C1	0.036 (2)	0.059 (3)	0.053 (3)	0.017 (2)	0.005 (2)	−0.014 (2)
C2	0.036 (2)	0.067 (3)	0.061 (3)	0.010 (2)	0.020 (2)	−0.016 (3)
C3	0.047 (3)	0.040 (2)	0.038 (2)	−0.003 (2)	0.020 (2)	−0.0082 (19)
C4	0.036 (2)	0.035 (2)	0.033 (2)	0.0031 (17)	0.0112 (17)	−0.0017 (17)
C5	0.027 (2)	0.073 (4)	0.036 (2)	0.004 (2)	−0.0010 (17)	−0.002 (2)
C6	0.036 (2)	0.087 (4)	0.044 (3)	−0.013 (3)	0.000 (2)	−0.011 (3)
C7	0.052 (3)	0.075 (4)	0.064 (4)	−0.034 (3)	0.011 (3)	−0.012 (3)
C8	0.059 (3)	0.055 (3)	0.038 (3)	−0.023 (2)	0.008 (2)	0.001 (2)
C9	0.039 (2)	0.031 (2)	0.027 (2)	−0.0030 (17)	0.0024 (16)	0.0040 (16)
C10	0.039 (2)	0.034 (2)	0.036 (2)	0.0091 (18)	−0.0027 (18)	−0.0012 (18)
C11	0.027 (2)	0.032 (2)	0.042 (2)	0.0062 (16)	0.0047 (17)	−0.0049 (18)
C12	0.0298 (19)	0.0282 (19)	0.030 (2)	0.0030 (16)	0.0097 (16)	−0.0006 (16)
C13	0.0249 (19)	0.043 (2)	0.027 (2)	0.0045 (17)	0.0049 (15)	0.0007 (18)
C14	0.033 (2)	0.041 (2)	0.029 (2)	−0.0017 (18)	0.0101 (17)	0.0025 (18)
C15	0.041 (2)	0.036 (2)	0.034 (2)	0.015 (2)	0.0109 (16)	0.004 (2)
C16	0.039 (2)	0.028 (2)	0.039 (2)	0.0003 (17)	0.0110 (17)	0.0042 (18)
C17	0.052 (3)	0.041 (3)	0.049 (3)	−0.002 (2)	−0.008 (2)	−0.008 (2)
C18	0.099 (5)	0.054 (3)	0.041 (3)	0.002 (3)	0.033 (3)	0.006 (3)
Cu1	0.0381 (4)	0.0337 (4)	0.0402 (4)	0.000	0.0105 (3)	0.000
Cl1	0.0329 (5)	0.0376 (5)	0.0381 (5)	−0.0018 (4)	0.0126 (4)	−0.0028 (4)
Cl2	0.0780 (10)	0.0484 (7)	0.0639 (8)	−0.0284 (7)	0.0131 (7)	−0.0041 (6)

Geometric parameters (Å, º)

O1—C3	1.366 (5)	C9—H9	1.0000
O1—C18	1.401 (7)	C9—C10	1.504 (6)
N1—H1	0.81 (5)	C9—C14	1.523 (6)
N1—C9	1.526 (5)	C10—H10A	0.9900
N1—C16	1.499 (5)	C10—H10B	0.9900
N1—C17	1.487 (6)	C10—C11	1.503 (6)
C1—H1A	0.9500	C11—C12	1.392 (6)
C1—C2	1.363 (7)	C12—C13	1.539 (5)
C1—C11	1.395 (6)	C13—C14	1.551 (6)
C2—H2	0.9500	C13—C15	1.548 (7)
C2—C3	1.377 (7)	C14—H14	1.0000
C3—C4	1.398 (6)	C15—H15A	0.9900
C4—H4	0.9500	C15—H15B	0.9900
C4—C12	1.394 (6)	C15—C16	1.507 (6)
C5—H5A	0.9900	C16—H16A	0.9900
C5—H5B	0.9900	C16—H16B	0.9900
C5—C6	1.535 (9)	C17—H17A	0.9800
C5—C13	1.538 (6)	C17—H17B	0.9800
C6—H6A	0.9900	C17—H17C	0.9800
C6—H6B	0.9900	C18—H18A	0.9800
C6—C7	1.517 (8)	C18—H18B	0.9800
C7—H7A	0.9900	C18—H18C	0.9800
C7—H7B	0.9900	Cu1—Cl1^i	2.2615 (11)
C7—C8	1.526 (7)	Cu1—Cl1	2.2614 (11)
C8—H8A	0.9900	Cu1—Cl2	2.2354 (13)
C8—H8B	0.9900	Cu1—Cl2^i	2.2354 (13)
C8—C14	1.519 (6)
C3—O1—C18	118.8 (4)	C11—C10—C9	115.1 (3)
C9—N1—H1	108 (4)	C11—C10—H10A	108.5
C16—N1—H1	106 (4)	C11—C10—H10B	108.5
C16—N1—C9	113.3 (3)	C1—C11—C10	118.2 (4)
C17—N1—H1	104 (4)	C12—C11—C1	118.1 (4)
C17—N1—C9	113.3 (3)	C12—C11—C10	123.6 (4)
C17—N1—C16	112.0 (3)	C4—C12—C13	120.4 (3)
C2—C1—H1A	119.1	C11—C12—C4	120.1 (4)
C2—C1—C11	121.8 (4)	C11—C12—C13	119.1 (4)
C11—C1—H1A	119.1	C5—C13—C12	114.0 (3)
C1—C2—H2	119.7	C5—C13—C14	108.3 (3)
C1—C2—C3	120.6 (4)	C5—C13—C15	108.9 (4)
C3—C2—H2	119.7	C12—C13—C14	111.6 (3)
O1—C3—C2	117.3 (4)	C12—C13—C15	107.0 (3)
O1—C3—C4	123.7 (4)	C15—C13—C14	106.8 (3)
C2—C3—C4	119.0 (4)	C8—C14—C9	111.6 (4)
C3—C4—H4	119.8	C8—C14—C13	112.5 (4)
C12—C4—C3	120.4 (4)	C8—C14—H14	107.7
C12—C4—H4	119.8	C9—C14—C13	109.5 (3)
H5A—C5—H5B	107.9	C9—C14—H14	107.7
C6—C5—H5A	109.3	C13—C14—H14	107.7
C6—C5—H5B	109.3	C13—C15—H15A	109.1
C6—C5—C13	111.7 (4)	C13—C15—H15B	109.1
C13—C5—H5A	109.3	H15A—C15—H15B	107.9
C13—C5—H5B	109.3	C16—C15—C13	112.3 (3)
C5—C6—H6A	109.7	C16—C15—H15A	109.1
C5—C6—H6B	109.7	C16—C15—H15B	109.1
H6A—C6—H6B	108.2	N1—C16—C15	111.4 (3)
C7—C6—C5	109.9 (4)	N1—C16—H16A	109.4
C7—C6—H6A	109.7	N1—C16—H16B	109.4
C7—C6—H6B	109.7	C15—C16—H16A	109.4
C6—C7—H7A	109.5	C15—C16—H16B	109.4
C6—C7—H7B	109.5	H16A—C16—H16B	108.0
C6—C7—C8	110.7 (4)	N1—C17—H17A	109.5
H7A—C7—H7B	108.1	N1—C17—H17B	109.5
C8—C7—H7A	109.5	N1—C17—H17C	109.5
C8—C7—H7B	109.5	H17A—C17—H17B	109.5
C7—C8—H8A	109.5	H17A—C17—H17C	109.5
C7—C8—H8B	109.5	H17B—C17—H17C	109.5
H8A—C8—H8B	108.1	O1—C18—H18A	109.5
C14—C8—C7	110.8 (5)	O1—C18—H18B	109.5
C14—C8—H8A	109.5	O1—C18—H18C	109.5
C14—C8—H8B	109.5	H18A—C18—H18B	109.5
N1—C9—H9	108.3	H18A—C18—H18C	109.5
C10—C9—N1	112.8 (3)	H18B—C18—H18C	109.5
C10—C9—H9	108.3	Cl1—Cu1—Cl1^i	100.36 (6)
C10—C9—C14	111.6 (3)	Cl2—Cu1—Cl1^i	99.65 (5)
C14—C9—N1	107.5 (3)	Cl2^i—Cu1—Cl1	99.65 (5)
C14—C9—H9	108.3	Cl2^i—Cu1—Cl1^i	129.04 (4)
C9—C10—H10A	108.5	Cl2—Cu1—Cl1	129.04 (4)
C9—C10—H10B	108.5	Cl2^i—Cu1—Cl2	102.97 (9)
H10A—C10—H10B	107.5
O1—C3—C4—C12	179.5 (4)	C9—C10—C11—C1	−167.6 (4)
N1—C9—C10—C11	82.2 (4)	C9—C10—C11—C12	10.2 (6)
N1—C9—C14—C8	171.7 (3)	C10—C9—C14—C8	−64.1 (5)
N1—C9—C14—C13	−63.0 (4)	C10—C9—C14—C13	61.2 (5)
C1—C2—C3—O1	−178.6 (5)	C10—C11—C12—C4	−176.6 (4)
C1—C2—C3—C4	0.9 (8)	C10—C11—C12—C13	−3.6 (6)
C1—C11—C12—C4	1.2 (6)	C11—C1—C2—C3	−0.8 (9)
C1—C11—C12—C13	174.2 (4)	C11—C12—C13—C5	148.6 (4)
C2—C1—C11—C10	177.7 (5)	C11—C12—C13—C14	25.5 (5)
C2—C1—C11—C12	−0.2 (7)	C11—C12—C13—C15	−91.0 (4)
C2—C3—C4—C12	0.1 (7)	C12—C13—C14—C8	71.2 (5)
C3—C4—C12—C11	−1.2 (6)	C12—C13—C14—C9	−53.6 (5)
C3—C4—C12—C13	−174.1 (4)	C12—C13—C15—C16	61.9 (4)
C4—C12—C13—C5	−38.4 (6)	C13—C5—C6—C7	−59.2 (6)
C4—C12—C13—C14	−161.5 (4)	C13—C15—C16—N1	53.3 (4)
C4—C12—C13—C15	82.0 (4)	C14—C9—C10—C11	−39.0 (5)
C5—C6—C7—C8	58.2 (6)	C14—C13—C15—C16	−57.7 (4)
C5—C13—C14—C8	−55.1 (5)	C15—C13—C14—C8	−172.2 (4)
C5—C13—C14—C9	−179.8 (4)	C15—C13—C14—C9	63.1 (4)
C5—C13—C15—C16	−174.4 (3)	C16—N1—C9—C10	−65.5 (4)
C6—C5—C13—C12	−68.5 (5)	C16—N1—C9—C14	58.0 (4)
C6—C5—C13—C14	56.3 (5)	C17—N1—C9—C10	63.5 (5)
C6—C5—C13—C15	172.1 (4)	C17—N1—C9—C14	−173.1 (3)
C6—C7—C8—C14	−57.0 (6)	C17—N1—C16—C15	177.1 (4)
C7—C8—C14—C9	179.7 (4)	C18—O1—C3—C2	173.1 (5)
C7—C8—C14—C13	56.1 (5)	C18—O1—C3—C4	−6.3 (7)
C9—N1—C16—C15	−53.3 (5)

Symmetry code: (i) −x+1, y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.81 (6)	2.46 (6)	3.207 (4)	154 (5)
C10—H10A···Cl2^ii	0.99	2.83	3.754 (5)	156
C17—H17B···Cl2^iii	0.98	2.68	3.590 (5)	156

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