Conformational chirality of dimethyl adamantanoylmalonate

The title mol­ecule, C₁₆H₂₂O₅, is conformationally chiral. The non-ring methine C atom acts as an `asymmetric' atom owing to different orientations of carboxy­methyl groups, and conformational chirality is observed in the solid state. The weak inter­molecular C—H...O hydrogen bonds create a two-dimensional network in the (100) plane.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.048
• wR factor = 0.147
• Data-to-parameter ratio = 11.6

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of Tmax/Tmin expected RT(exp) is > 1.10
            Absorption corrections should be applied.
            Tmin and Tmax expected:      0.817     0.940
            RT(exp) =      1.151
PLAT057_ALERT_3_C Correction for Absorption Required   RT(exp) ...       1.19
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.24 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C2B
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1B    ..  O2A     ..       2.67 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3     ..  O1A     ..       2.62 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          4

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 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
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

dimethyl adamantanoylmalonate

Crystal data

C16H22O5	F(000) = 632
Mr = 294.34	Dx = 1.271 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 11.0158 (11) Å	Cell parameters from 23 reflections
b = 11.4856 (9) Å	θ = 8–16.4°
c = 12.9229 (17) Å	µ = 0.77 mm^−1
β = 109.823 (9)°	T = 293 K
V = 1538.2 (3) Å^3	Plate, light yellow
Z = 4	0.36 × 0.25 × 0.08 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	θmax = 76.6°, θmin = 4.3°
non–profiled ω/2θ scans	h = −13→13
3384 measured reflections	k = −14→0
3236 independent reflections	l = 0→16
2685 reflections with I > 2σ(I)	3 standard reflections every 120 min
Rint = 0.025	intensity decay: 6%

Refinement

Refinement on F^2	All H-atom parameters refined
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0754P)^2 + 0.4441P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.048	(Δ/σ)max < 0.001
wR(F^2) = 0.147	Δρmax = 0.38 e Å^−3
S = 1.03	Δρmin = −0.19 e Å^−3
3236 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
279 parameters	Extinction coefficient: 0.0049 (7)
0 restraints

Special details

Experimental. 1H NMR and 13 C NMR spectra were recorded on Bruker AV 300 MHz, and IR spectrum was recorded on FT—IR ABB Bomem MB 102.

IR (KBr): ν 2919, 2905, 2853, 1754, 1739, 1715, 1456, 1435 cm^-1. IR (C₂Cl₄): ν 2908, 2852, 1765, 1745, 1714, 1452, 1435. IR (CH₂Cl₂): ν 1759, 1738, 1708, 1436.

¹H NMR (CDCl₃, 300 MHz): δ 1.68 (d, J = 12.5 Hz, 3H), 1.77 (d, J = 12.5 Hz, 3H), 1.80–1.88 (m, 6H), 2.07 (bs, 3H), 3.78 (s, 6H), 4.98 (s, 1H). ¹H NMR (DMSO, 300 MHz): 1.63–1.68 (m, 6H), 1.72–1.74 (m, 6H), 1.98 (bs, 3H), 3.67 (s, 6H), 5.51 (s, 1H). ¹³C NMR (CDCl₃, 75 MHz): 27.41, 35.99, 37.27, 47.61, 52.91, 58.39, 164.97, 202.75.

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.

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

	x	y	z	Uiso*/Ueq
C1A	0.2746 (2)	0.9097 (2)	0.1234 (2)	0.0709 (6)
C1B	0.6051 (3)	1.3447 (2)	0.0241 (2)	0.0718 (6)
C2A	0.47300 (16)	1.01045 (15)	0.18463 (13)	0.0480 (4)
C2B	0.54324 (16)	1.18233 (15)	0.10431 (13)	0.0489 (4)
C3	0.58019 (15)	1.05971 (14)	0.14881 (13)	0.0437 (4)
C4	0.70804 (16)	1.05394 (14)	0.24579 (12)	0.0460 (4)
C5	0.78800 (14)	0.94408 (13)	0.25748 (12)	0.0411 (3)
C6	0.85854 (18)	0.95186 (16)	0.17242 (16)	0.0533 (4)
C7	0.70634 (17)	0.83267 (14)	0.23380 (16)	0.0492 (4)
C8	0.8889 (2)	0.93753 (19)	0.37310 (16)	0.0629 (5)
C9	0.94495 (19)	0.84474 (19)	0.18337 (18)	0.0639 (5)
C10	0.8635 (2)	0.73563 (18)	0.16109 (18)	0.0621 (5)
C11	0.7931 (2)	0.72604 (16)	0.24412 (17)	0.0570 (5)
C12	0.8903 (3)	0.72017 (19)	0.36027 (18)	0.0715 (6)
C13	0.9741 (2)	0.8296 (2)	0.38260 (18)	0.0749 (7)
C14	1.0436 (2)	0.8394 (2)	0.2985 (2)	0.0798 (7)
H1A*	0.224 (4)	0.973 (4)	0.140 (3)	0.149 (14)*
H1A'	0.220 (3)	0.873 (2)	0.054 (2)	0.092 (8)*
H1A	0.300 (3)	0.851 (3)	0.173 (3)	0.109 (10)*
H1B'	0.532 (3)	1.342 (3)	−0.039 (3)	0.117 (11)*
H1B	0.599 (3)	1.399 (3)	0.075 (3)	0.125 (12)*
H1B*	0.684 (3)	1.365 (3)	0.010 (3)	0.119 (11)*
H3	0.5874 (17)	1.0124 (16)	0.0906 (15)	0.046 (4)*
H6A	0.790 (2)	0.9581 (17)	0.0942 (18)	0.059 (5)*
H6B	0.910 (2)	1.024 (2)	0.1860 (19)	0.074 (6)*
H7A	0.659 (2)	0.8263 (19)	0.2864 (18)	0.068 (6)*
H7B	0.643 (2)	0.8328 (19)	0.1584 (19)	0.064 (6)*
H8A	0.941 (2)	1.014 (2)	0.3899 (19)	0.073 (6)*
H8B	0.8418 (19)	0.9336 (17)	0.4245 (18)	0.059 (6)*
H9	0.991 (2)	0.8528 (19)	0.1276 (19)	0.073 (6)*
H10A	0.803 (2)	0.739 (2)	0.088 (2)	0.070 (6)*
H10B	0.920 (2)	0.663 (2)	0.167 (2)	0.081 (7)*
H11	0.740 (2)	0.656 (2)	0.2267 (19)	0.075 (7)*
H12A	0.844 (2)	0.715 (2)	0.413 (2)	0.082 (7)*
H12B	0.943 (2)	0.650 (2)	0.369 (2)	0.083 (7)*
H13	1.038 (3)	0.828 (2)	0.454 (2)	0.100 (9)*
H14A	1.097 (2)	0.909 (2)	0.312 (2)	0.076 (7)*
H14B	1.102 (2)	0.769 (2)	0.305 (2)	0.081 (7)*
O1A	0.38412 (12)	0.95893 (12)	0.10115 (10)	0.0583 (4)
O1B	0.63474 (13)	1.23158 (11)	0.07644 (11)	0.0594 (4)
O2A	0.46905 (15)	1.01790 (15)	0.27537 (11)	0.0734 (4)
O2B	0.44016 (16)	1.22377 (15)	0.09022 (18)	0.0925 (6)
O3	0.74092 (15)	1.13528 (12)	0.30795 (11)	0.0726 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.0696 (13)	0.0654 (13)	0.0845 (16)	−0.0163 (11)	0.0352 (12)	0.0024 (12)
C1B	0.0872 (17)	0.0588 (12)	0.0686 (13)	0.0008 (11)	0.0253 (13)	0.0174 (10)
C2A	0.0547 (9)	0.0475 (8)	0.0439 (8)	0.0066 (7)	0.0194 (7)	0.0013 (7)
C2B	0.0489 (9)	0.0529 (9)	0.0448 (8)	0.0077 (7)	0.0158 (7)	0.0022 (7)
C3	0.0477 (8)	0.0451 (8)	0.0379 (7)	0.0045 (6)	0.0141 (6)	−0.0037 (6)
C4	0.0528 (9)	0.0438 (8)	0.0385 (7)	0.0015 (7)	0.0114 (6)	−0.0037 (6)
C5	0.0430 (8)	0.0401 (8)	0.0378 (7)	0.0005 (6)	0.0108 (6)	−0.0022 (6)
C6	0.0520 (9)	0.0539 (10)	0.0587 (10)	−0.0036 (8)	0.0247 (8)	0.0049 (8)
C7	0.0501 (9)	0.0423 (8)	0.0595 (10)	−0.0009 (7)	0.0244 (8)	0.0004 (7)
C8	0.0697 (12)	0.0620 (12)	0.0438 (9)	0.0151 (9)	0.0021 (9)	−0.0068 (8)
C9	0.0551 (10)	0.0745 (13)	0.0731 (12)	0.0082 (9)	0.0361 (10)	0.0030 (10)
C10	0.0710 (12)	0.0579 (11)	0.0595 (11)	0.0146 (9)	0.0251 (10)	−0.0069 (9)
C11	0.0663 (11)	0.0410 (9)	0.0674 (11)	0.0032 (8)	0.0274 (9)	0.0013 (8)
C12	0.0960 (16)	0.0589 (12)	0.0619 (12)	0.0297 (11)	0.0297 (11)	0.0156 (9)
C13	0.0754 (13)	0.0748 (14)	0.0534 (11)	0.0276 (11)	−0.0058 (10)	−0.0038 (10)
C14	0.0462 (11)	0.0823 (16)	0.1020 (18)	0.0114 (11)	0.0136 (11)	−0.0083 (13)
O1A	0.0574 (7)	0.0663 (8)	0.0532 (7)	−0.0118 (6)	0.0213 (6)	−0.0028 (6)
O1B	0.0603 (7)	0.0531 (7)	0.0680 (8)	0.0041 (6)	0.0262 (6)	0.0092 (6)
O2A	0.0834 (10)	0.0947 (11)	0.0510 (7)	−0.0063 (8)	0.0344 (7)	−0.0052 (7)
O2B	0.0728 (10)	0.0812 (11)	0.1372 (16)	0.0318 (8)	0.0537 (10)	0.0417 (10)
O3	0.0888 (10)	0.0489 (7)	0.0589 (8)	0.0116 (7)	−0.0027 (7)	−0.0177 (6)

Geometric parameters (Å, º)

C1A—H1A*	0.98 (4)	C8—H8A	1.02 (3)
C1A—H1A'	0.99 (3)	C9—C14	1.517 (3)
C1A—H1A	0.91 (3)	C9—H9	1.01 (2)
C1B—H1B*	0.98 (4)	C10—C9	1.511 (3)
C1B—H1B	0.93 (4)	C10—C11	1.527 (3)
C1B—H1B'	0.93 (4)	C10—H10A	0.95 (2)
C2B—O2B	1.187 (2)	C10—H10B	1.03 (3)
C3—C2A	1.516 (2)	C11—C12	1.521 (3)
C3—C2B	1.524 (2)	C11—H11	0.98 (2)
C3—C4	1.537 (2)	C12—C13	1.528 (4)
C3—H3	0.953 (19)	C12—H12A	0.98 (3)
C4—C5	1.517 (2)	C12—H12B	0.98 (3)
C5—C8	1.532 (2)	C13—H13	0.96 (3)
C5—C6	1.549 (2)	C14—C13	1.530 (4)
C6—C9	1.532 (3)	C14—H14B	1.02 (3)
C6—H6A	1.04 (2)	C14—H14A	0.98 (3)
C6—H6B	0.99 (2)	O1A—C1A	1.447 (2)
C7—C5	1.534 (2)	O1A—C2A	1.325 (2)
C7—C11	1.531 (2)	O1B—C1B	1.450 (2)
C7—H7B	0.99 (2)	O1B—C2B	1.308 (2)
C7—H7A	0.99 (2)	O2A—C2A	1.191 (2)
C8—C13	1.535 (3)	O3—C4	1.205 (2)
C8—H8B	0.97 (2)
H1A*—C1A—H1A'	107 (3)	C9—C14—H14A	109.2 (14)
H1A*—C1A—H1A	117 (3)	C10—C11—C7	109.40 (15)
H1A'—C1A—H1A	106 (3)	C10—C11—H11	107.9 (14)
H1B—C1B—H1B'	114 (3)	C10—C9—C14	109.55 (19)
H1B*—C1B—H1B	105 (3)	C10—C9—C6	109.78 (16)
H1B*—C1B—H1B'	114 (3)	C10—C9—H9	110.2 (13)
H6A—C6—H6B	107.3 (17)	C11—C12—C13	109.15 (17)
H7B—C7—H7A	108.5 (17)	C11—C12—H12A	109.4 (15)
H8B—C8—H8A	106.4 (18)	C11—C7—C5	110.08 (14)
H10A—C10—H10B	107.9 (19)	C11—C7—H7B	107.3 (13)
H12A—C12—H12B	108 (2)	C11—C7—H7A	109.9 (13)
H14B—C14—H14A	108.0 (19)	C11—C10—H10A	110.4 (14)
C2A—O1A—C1A	116.62 (16)	C11—C10—H10B	109.0 (13)
C2A—C3—C2B	108.92 (13)	C12—C13—C14	110.00 (19)
C2A—C3—C4	109.16 (13)	C12—C13—C8	109.6 (2)
C2A—C3—H3	108.1 (11)	C12—C13—H13	111.5 (17)
C2B—C3—C4	113.67 (13)	C12—C11—C10	109.95 (18)
C2B—O1B—C1B	116.31 (17)	C12—C11—C7	109.33 (16)
C2B—C3—H3	108.2 (11)	C12—C11—H11	110.9 (14)
C4—C3—H3	108.7 (11)	C13—C12—H12A	110.1 (15)
C4—C5—C8	110.04 (13)	C11—C12—H12B	110.0 (15)
C4—C5—C7	113.11 (13)	C13—C12—H12B	110.7 (15)
C4—C5—C6	107.19 (13)	C13—C8—H8B	111.2 (12)
C5—C8—H8A	109.4 (13)	C13—C8—H8A	112.9 (13)
C5—C8—C13	109.84 (15)	C13—C14—H14B	109.7 (14)
C5—C8—H8B	106.9 (12)	C13—C14—H14A	110.5 (14)
C5—C6—H6B	108.7 (14)	C14—C9—C6	109.80 (18)
C5—C4—C3	117.25 (12)	C14—C9—H9	109.8 (13)
C5—C7—H7B	111.5 (13)	C14—C13—H13	107.9 (17)
C5—C7—H7A	109.6 (13)	C14—C13—C8	108.9 (2)
C5—C6—H6A	108.9 (12)	O1A—C2A—C3	110.79 (13)
C6—C9—H9	107.6 (13)	O1A—C1A—H1A*	109 (2)
C7—C5—C6	107.93 (13)	O1A—C1A—H1A'	106.3 (16)
C7—C11—H11	109.4 (14)	O1A—C1A—H1A	110 (2)
C8—C13—H13	108.9 (17)	O1B—C1B—H1B*	103 (2)
C8—C5—C7	109.63 (15)	O1B—C1B—H1B	109 (2)
C8—C5—C6	108.82 (15)	O1B—C1B—H1B'	111 (2)
C9—C14—C13	109.59 (17)	O1B—C2B—C3	111.81 (14)
C9—C6—C5	109.49 (14)	O2A—C2A—O1A	124.75 (17)
C9—C6—H6A	111.5 (11)	O2A—C2A—C3	124.46 (16)
C9—C6—H6B	110.9 (13)	O2B—C2B—O1B	124.79 (17)
C9—C10—C11	109.65 (16)	O2B—C2B—C3	123.22 (17)
C9—C10—H10A	109.2 (14)	O3—C4—C5	123.06 (15)
C9—C10—H10B	110.7 (13)	O3—C4—C3	119.69 (15)
C9—C14—H14B	109.8 (14)
O3—C4—C3—C2a	−90.9 (2)	C4—C3—C2a—O1a	−147.9 (1)
O3—C4—C3—C2b	30.9 (2)	C4—C3—C2b—O1b	55.3 (2)
C4—C3—C2a—O2a	32.6 (2)	C5—C4—C3—C2a	89.7 (2)
C4—C3—C2b—O2b	−129.5 (2)	C5—C4—C3—C2b	−148.5 (1)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1a—H1a···O3^i	0.91 (3)	2.54 (3)	3.294 (3)	140 (3)
C1b—H1b···O2a^ii	0.93 (4)	2.67 (4)	3.574 (4)	164 (3)
C7—H7a···O2b^i	0.99 (2)	2.51 (3)	3.439 (3)	156 (2)
C3—H3···O1a^iii	0.95 (2)	2.62 (2)	3.391 (2)	138 (2)

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